HK1096131B - Fluorochemical finishes for paint applicators - Google Patents

Description

Fluorochemical finishes for paint applicators

Technical Field

The present invention relates to the field of paint applicators having improved properties and to a method of treating a paint-carrying surface of an applicator with a fluorochemical finish.

Background

Paint rollers, paint brushes and other applicators are widely used as applicators as a means of applying paint to a surface. However, after use of these applicators, cleaning thereof becomes an unpleasant task because it is difficult to remove all paint between the paint carrying fibers. Failure to remove all of the paint results in the fibers being too stiff to provide a smooth painted surface and the individual fibers being excessively stained and improperly separated to provide adequate paint carrying capability. On the other hand, very adequate cleaning usually requires a lot of washing liquid and additional washing of the hands and containers used, resulting in a lot of contaminated washing solvent to be disposed of.

Many mechanical devices have been patented to make the cleaning work easier, see, for example, U.S. patent 6,450,185. These devices are complex and even rarely purchase, use and/or maintain them.

U.S. patent 5,462,798 discloses a brush for applying thick liquid cosmetics to a surface. It uses a monofilament fibre made of a plastic containing 0.2 to 15% by weight of an agent for improving the sliding properties of the fibre and for reducing its wettability by water and/or other solvents. These components are incorporated into the fiber body, so that the disclosed brush requires the use of expensive custom-made paint brush filaments.

In the production of synthetic fibers for use as textiles and carpets, it is known that synthetic fibers can be treated with polymeric fluorine protectant compositions to improve stain resistance, oil and water repellency. No reference was found to apply these fluorine protectant compositions to fabrics or filaments used in paint applicators, nor was there any teaching of such application to make it easier to remove paint from such applicators.

There is a need for paint applicators such as paint roller covers (paint rollers) and paint brushes that are easier to clean. It would be further advantageous if these applicators surprisingly had increased paint carrying capacity during use. The present invention provides such a paint applicator.

Summary of the invention

The present invention includes a paint applicator comprising a paint-carrying surface coated or treated with a fluoroacrylate polymer or copolymer, a fluorourethane polymer or copolymer, or mixtures thereof. The invention further includes a method of treating a paint applicator comprising applying to its paint-carrying surface, or a precursor thereof, a fluoroacrylate polymer or copolymer, a fluorourethane polymer or copolymer, or a mixture thereof.

Detailed description of the invention

Trademarks are indicated herein in capitals.

The present invention includes a paint applicator having improved painting capabilities and/or increased cleanability and a method of producing the same. Paint applicators, such as paint rollers, paint brushes or other applicators, are prepared in which a paint-carrying surface is coated with a fluoroacrylate and/or fluorourethane polymer or copolymer using techniques such as spraying, foaming, skimming and dipping, followed by curing. Curing of the fabric, fiber, or filament comprising such a surface is typically carried out at a temperature of about 100 ℃ to about 190 ℃ for at least 30 seconds. Paint-carrying fibers, such as finishes on fabrics or silk (finish), typically contain from about 0.05% to about 20% of active ingredient, based on the weight of the fiber.

The invention further includes a method of treating a paint applicator, or a fabric, fiber or filament forming a paint-carrying surface, with various fluoroacrylate polymers or copolymers or fluorourethane polymers or copolymers, or mixtures thereof.

The present invention provides paint applicators having improved paint carrying capabilities and/or increased cleanability, and methods of making the same. The paint applicators of the present invention include embodiments such as paint rollers, paint brushes, cotton batts for rubbing (paint pads), patterned paint rollers, patterned pads, paint sponges, paint cloths and other physical forms in which the paint-carrying surface has been coated or treated with a fluoroacrylate and/or fluorourethane polymer or copolymer, or mixtures thereof.

One embodiment of the paint applicator of the present invention includes a paint roller. The painting roller comprises a collapsible roller sleeve made of pile fabric placed on a roller mechanism with a handle. Typically, the sleeve is made by a manufacturing process such as: first, one or more short fibers are blended, brushed, carded, and knitted. The knit fabric is then fed to a backing machine where a latex backing is applied and cured. The fabric is then cut and wound onto a plastic roll where it is held in place with glue or by melting the backing onto the fabric. It is then combed and sheared and cut into piecesAt a suitable length of the roll. The pile length of the fabric may be 1/4 inches (0.6cm) to about 1¹/₂Inches (3.8 cm). The fabric is typically made of nylon or polyester fibers, but may also include other synthetic or natural fibers. The roll surface may be flat or patterned. The sleeve useful in the present invention may be made by the above manufacturing process, or by any other manufacturing process.

The present invention further includes a process for preparing a paint applicator, such as paint roller covers (roller covers), having improved paint carrying capability and/or increased cleanability, wherein the surface of the paint carrying fiber is coated or treated with a fluoroacrylate polymer or copolymer, a fluorourethane polymer or copolymer, or mixtures thereof, at any stage prior to and during the applicator manufacturing process.

A second embodiment of the paint applicator of the present invention comprises a paint brush. The manufacture of the paint brush comprises: mixing filaments of the same or different lengths, braiding them into a tow having parallel filaments, placing the tow in a ferrule with an adhesive such as epoxy or glue, curing or drying the adhesive, and attaching a paint brush handle to the ferrule. The length of the filaments and the number of filaments in the brush will vary depending on the intended use. The filaments are typically nylon or polyester fibers, but may be replaced with other synthetic or natural fibers for some uses. The paint brush of the present invention can be made by the above manufacturing process, or by any other manufacturing process.

The present invention further includes a method for preparing a paint applicator, such as a paint brush, having increased cleanability wherein the surface carrying the paint fibers is coated or treated with a fluoroacrylate polymer or copolymer, a fluorourethane polymer or copolymer, or a mixture thereof at any stage of the paint brush manufacturing process.

Other embodiments of the invention include painted floss balls, mats, cloths, sponges, combs, paper, feathers, needles, knives, and other applicator tools treated with fluoroacrylate and/or fluorourethane polymers or copolymers, or mixtures thereof.

In the present invention, the fluoroacrylate polymer or copolymer is applied to a paint-carrying fiber, filament, or fabric used in the paint-carrying surface of a paint applicator. The term "fluoroacrylate polymer or copolymer" refers herein to a polymer or copolymer that contains perfluoroalkyl (meth) acrylate groups. "meth (acrylate" refers herein to acrylate, methacrylate, or a mixture of the two. Many of the fluoroacrylate polymers or copolymers currently described in the literature contain up to about 50% by weight long chain alkyl (meth) acrylate groups. They may also contain minor percentages of vinyl chloride, vinylidene chloride or other monomers, and/or minor percentages of various crosslinking monomers such as hydroxyethyl (meth) acrylate, ethoxylated (meth) acrylates, and/or N-methylol (meth) acrylamide, in order to modify their properties.

Preferred compositions, alone or in combination with the fluoro-urethane, are the fluoro-acrylate polymers used in the included embodiments. Preferred compositions comprise monomers copolymerized in the following percentages by weight:

(a) from about 50% to about 85% of a monomer having structural formula I:

R₁-CH₂CH₂-OC(O)-C(R)＝CH₂ I

(b) from about 10% to about 25% of a monomer having the structural formula II:

R₂-OC(O)-C(R)＝CH₂ II

(c) 0.1% to about 5% of a monomer having the structure III:

HO-CH₂CH₂-OC(O)-C(R)＝CH₂ III

(d) 0.1% to about 5% of a monomer having structural formula IV:

H-(OCH₂CH₂)_m-O-C(O)-C(R)＝CH₂ IV

(e) 0.1% to about 3% of a monomer having the structure V:

HO-CH₂-NH-C(O)-C(R)＝CH₂ V

wherein R is_fIs a linear or branched perfluoroalkyl group having 2 to about 20 carbon atoms, each R is independently H or CH₃；R₂Is an alkyl chain having from 2 to about 18 carbon atoms; and m is 2 to about 10.

Preferred copolymer compositions optionally further comprise:

(f) from 0% to about 10% of vinylidene chloride (formula VI) or vinyl acetate (formula VII), or mixtures thereof:

CH₂＝CCl₂ VI

CH₃-(O)COCH＝CH₂ VII

the term "fluoro-urethane polymer or copolymer" refers herein to a polymer or copolymer having perfluoroalkyl-containing groups that react with any polyisocyanate having three or more isocyanate groups to form a polyurethane. The perfluoroalkyl-containing groups are attached to the polymer network through any number of nucleophilic atoms such as nitrogen, oxygen, and sulfur. To improve polymer properties, the polymer may also contain a small percentage of polyethylene/polypropylene glycol or a mixture of both or other monomers containing one or more terminal reactive groups reactive with isocyanates. The polymer network is then formed by crosslinking the residual isocyanate groups with a specific amount of water.

In general, the fluoro-urethane polymers used in combination with or alone with fluoroacrylates in embodiments of the present invention comprise at least one urea group, and are the reaction product of (a), (B), (C), and (D):

(A) at least one organic polyisocyanate or mixture of organic polyisocyanates containing at least three isocyanate groups per molecule. Preferred polyisocyanates are selected from commercially available polyisocyanate resins such as DESMODUR N-100, DESMODUR N-3200, and DESMODUR N-3300. DESMODUR-type resins are available from Bayer Corporation, Pittsburg, Pa.

(B) At least one fluorochemical compound having the following composition:

R_f-X-Y-H, wherein R_fIs C₂-C₂₀A linear or branched fluoroalkyl radical, X is- (CH)₂)_n-，-(CH₂)₈SO₂(CH₂)_t-or-SO₂N(R₁)CH₂CH₂-, and Y is-O-, -S-, -N (R)₂) -; wherein R is₂Is H or an alkyl group containing 1-6 carbons.

(C) One or more hydrophilic, water-solvatable agents comprising a monofunctional group having at least one reactive H. Examples are Carbowax 750, methoxypolyethylene glycol with a molecular weight of about 750, available from Union Carbide Co; danbury, CT.

(D) And (3) water.

Reactants (B) and (C) are reacted with 55-95% of the isocyanate groups in reactant (a), and then water is reacted with the remaining 5% to 100% of the isocyanate groups.

Fluoroacrylates and fluorourethanes suitable for coating or treating the surface of paint-carrying fabrics, filaments, or fibers are available under the trade names such as "TEFLON", "DURATECH", and ZONYL "from E.I.du Pont DE Nemours and Company, Wilmington, DE, available as" OLEPHOBOOL "from Ciba Specialty Chemicals, High Point, NC, available as" MILEASE "from ICI, Wilmington, DE, available as" ASAHIGARD "from Asahi, Japan, available as" SCOTCHGARD "from 3M, Minneapolis, MN, available as" SOFTTECH ", Dalton, GA, available as" TEX-TEL "from Atocm, France, available as" NKGARD "from Nicca, Japan, and available as" Nanotex, OPherbro, and other sources.

The fluoroacrylate polymer or copolymer, the fluorourethane polymer or copolymer, or mixtures thereof are used in the form of an aqueous emulsion (aqueous emulsion). The polymer or copolymer is applied to the paint-carrying fabric, yarn, or fiber, either alone or in admixture with other treating agents or finishes. For example, the fluoroacrylate and/or fluorourethane may also be blended with a blocked isocyanate extender such as hydrophopol XAN (Ciba specialty chemicals, High Point, NC) and a wetting agent such as ALKANOL 6112(e.i. du pont de Nemours and Company, Deepwater, NJ) to increase the durability of the finish and increase the spreading of the polymer on the surface of the fiber during the application process. Fluorochemical is applied to paint-carrying fabrics, filaments, or fibers by spraying, foaming, dipping, padding (padding), or other well-known methods commonly used to impart oil-, soil-, and water-repellency to textiles and carpets.

For painting roller cover fabrics, the preferred method of applying the polymer is to apply the polymer emulsion to a precursor of the paint-carrying fibers of the roller, which precursor is a fiber, filament, or fabric prior to being attached to the roller. Preferably, the polymer or copolymer emulsion is applied to the knitted fabric on a back-coating machine with a pressure roller against the measuring force. This method is an improvement over the method disclosed in U.S. patent 5,558,916 with respect to applying certain other repellent finishes to the secondary backing of the carpet. This patent includes a detailed description of the mechanism of the process, which is incorporated herein by reference in its entirety. After excess liquid has been removed, for example by squeeze rolls, the treated sleeve fabric is dried and then cured by heating at, for example, about 100 ℃ to about 190 ℃ for at least about 30 seconds, typically about 60 to about 180 seconds. Such curing increases coating durability. While these curing conditions are typical, some industrial devices may operate outside of these ranges due to their specific design characteristics. The treated sleeve fabric comprises from about 0.05% to about 20% of a fluoroacrylate or fluorourethane polymer or copolymer, based on the weight of the fiber or substrate. Preferably, the amount is from about 0.1% to about 6%.

The preferred method of applying the polymer emulsion to the paint brush filaments is by applying the polymer emulsion to the filaments by a spraying mechanism just prior to and during mixing of the filaments. The filaments are thoroughly coated with the emulsion and then thoroughly mixed as they are typically found during mixing in the paint brush manufacturing process. These filaments constitute the precursor of the paint-carrying fibers of the paint brush prior to assembly of the paint brush. The treated filaments comprise about 0.05% to about 20% of a fluoroacrylate or fluorourethane polymer or copolymer, preferably about 0.1% to about 2%, based on the weight of the fiber.

The class of paints for which the present invention is intended is water-based latex paints. Typically, these paints contain resins such as acrylic resins, epoxy resins, vinyl resins, and the like. Such paints are readily available on the market under a number of major brands.

The paint applicators of the present invention have enhanced cleanability as compared to conventional applicators that are not surface treated with fluoroacrylate or fluorourethane polymers or copolymers. In addition, the paint applicator of the present invention has improved paint carrying capabilities as compared to such conventional applicators. This is unexpected because these properties require opposite effects. Easier cleaning requires improved paint release properties, while increased paint carrying capacity requires improved paint attraction properties. The paint applicators of the present invention provide both easier cleaning performance and increased paint carrying capability. Other advantages of the present invention include: the painted surface is smoother and improved durability due to less lint from the paint applicator. Thus, the paint applicator of the present invention can be used for more efficient surface painting and faster cleaning.

Examples

Example 1

The initial application is carried out on the finished paint roller sleeve. Immersing the sleeve in a pad bath (water) comprising 10g/L hydrophopool XAN, 2g/L ALKANOL 6112, and 40g/L as described hereinPage 3 line 28 to page 4 line 16, wherein R_fIs CF₃CF₂(CF₂)_rWherein x is 6, 8, 10, 12, 14, 16 and 18, in respective amounts of about 3%, 50%, 31%, 10%, 3%, 2% and 1%, R is H, R₂Is C₁₈H₃₇M is 7, and comprises 6% vinylidene chloride, said emulsion comprising 25-31% polymer, 5-9% dipropylene glycol, and the balance water, the sum being 100%. HYDROPHOBOL XAN is a blocked isocyanate extender available from Ciba specialty Chemicals, High Point, NC. ALKANOL 6112 is a wetting agent available from e.i. du Pont DE Nemours and company, Wilmington, DE. Once the roll is uniformly treated, it is "wrung out" to remove excess solution. The moisture absorption of the roll is about 80-100%. The pile height (pile height) on the treated roll was 1/2 inches (0.6cm) to 1 inch (2.5 cm).

Example 2

Polyester fabrics used for the treatment were obtained from Rock Valley textile (Janesville, WI). Two different types of fabrics were treated (1/2 inches (0.6cm) of fluff and 3/4 inches (1.9cm) of fluff). The fabric is 2³/₄Inches (7.0cm) wide and 90 inches (228.6cm) long. The fabric is treated by spray application. The surface of the fabric was sprayed with two different pad baths (paddath) at two different concentration levels. Two padding baths (compositions 1 and 2) containing the fluoroacrylate polymer of example 1 at a concentration of 40 or 80g/L, 7.5g/L of LHYDROPHOBO XAN and 2g/L of ALKANOL 6112, each obtained as described in example 1.

The other two padding water baths (compositions 3 and 4) contained 80 or 160g/L of the fluoro urethane polymer emulsion as described herein page 4, line 24 to page 5, line 6, wherein the polyisocyanate is DESMODUR N-100; r_f-X-Y-H is F (CF)₂)_yCH₂CH₂OH wherein Y is 4, 6, 8, 10, 12, 14, 16 and 18, in respective amounts of about 0-3%, 27-37%, 28-32%, 14-20%, 5-11%, 2-5%, 0-2% and 0-1%; and the water-solvatable agent is Carbowax 750, saidThe emulsion contains 10-15% polymer and the balance water, totaling 100%. These compositions are given in table 1 below.

TABLE 1

Test compositions

Composition number	1	2	3	4
					Fluoroacrylate esters	40g	80g
Fluorocarbamates			80g	160g
					HYDROPHOBOL XAN	7.5g	7.5g
ALKANOL 6112	2g	2g
					Water (W)	950.5g	910.5g	920.0	840.0

After spraying the pad bath onto the surface of the fabric, the fabric is passed between press rolls. The surface of the fabric is then re-sprayed to achieve the desired 50-60% moisture pick-up.

The fabric was dried at 180 ° F (82 ℃) for 1 hour and then cured at 330 ° F (166 ℃) for 3 minutes.

Example 3

Polyester fabric was obtained as in example 2. The fabrics were treated with each of the above described pad bath compositions disclosed in table 1 using a laboratory scale lick coating padder. The fabric side was exposed to a padding bath and the fabric was then pressed between two rolls at constant pressure. The fabric moisture pick-up is about 42%. The fabric was dried/cured in one step at 330 ° F (166 ℃) for 5 minutes.

Example 4

Polyester fabric samples were obtained from Rock Valley textile (Janesville, WI). The fabric samples were approximately 24 inches (61.0cm) wide and 65 inches (214.9cm) long. The fabric was treated with a pad bath using a spray application as in example 2; the moisture absorption of the fabric was 10%. The pad bath contained 600g/L of the fluoroacrylate polymer of example 1 and 10g/L of 70% isopropanol and was treated prior to latex back-coating of the fabric. The fabric was finally used to make a roll cover having a pile height of 1/2 inches (1.3 cm).

Example 5

Samples of polyester fabric were obtained, treated and made into rolls as in example 4 except that the moisture pick-up of the fabric was 20%.

Example 6

Polyester fabric samples were obtained, treated and made into rolls as in example 4, except that the fabric side was treated with a pad bath using foam application; the moisture absorption of the fabric was 10%. The pad bath contained 600g/L of the fluoroacrylate polymer of example 1 and 10g/L of 70% isopropyl alcohol and was treated prior to latex back coating of the fabric.

Example 7

Samples of polyester fabric were obtained, treated and made into rolls as in example 6 except that the backside of the fabric was treated with the pad bath of example 6 using foam application; the moisture absorption of the fabric was 10%.

Example 8

Samples of polyester fabric were obtained, treated and rolled as in example 6 except that the moisture pick-up of the fabric was 20%.

Example 9

Samples of polyester fabric were obtained, treated and made into rolls as in example 7 except that the moisture pick-up of the fabric was 20%. It is difficult to manufacture the sleeve and therefore no data is collected for this process.

Example 10

The sleeves of examples 2-9 and the control sleeve not treated with any fluorochemical were tested for paint carrying and cleanability as described below.

First, the paint roller sleeve is "break in" to ensure that all air is removed from the sleeve before any pick up or release weight is determined. ASTM method No. D5069-92 used herein is briefly described below.

The rolls were mounted on a stand and then weighed. This weight was recorded and used to calculate the maximum paint pick-up and release from the roll. The paint tray is filled with latex paint so that the liquid surface is no higher than the pile height of the fabric. For example, if the sleeve is 1/2 inches (1.3cm) fluff height, the depth of paint in the pan does not exceed 1/2 inches (1.3 cm). The roller is then rolled into the paint so that the entire periphery is covered. The roll is then pulled vertically out onto the smooth primed stone chip surface. The paint was applied to an area no more than 2 feet (61.0cm) long and 14 inches (35.6cm) wide. The roller applies multiple passes in this area, releasing the paint to the location where the suction is heard. This means that air is present in the fibres. The roll was reloaded as described above and repeatedly coated on the same painted area. Eventually, after the repeated loading, the roller does not produce the suction sound any more. At this point, the assembly was weighed and recorded before the rollers were reloaded. The sleeve was reloaded and used to paint in the same area in 6 passes up and down. The assembly is weighed again. The sleeve reaches a saturation point where it is no longer able to release paint to the surface. This is evident when the last weight measurement differs from the current weight measurement by 5 grams or less. At this point, the sleeve was fully worn in and tested.

The performance of the rolls was then tested using a generalized version of the ASTM method above. The painted surface used for the test was a smooth stone chip sealed with a white primer. When the maximum weight is reached as described above, the sleeve is brought to the paint substrate. A rectangle of a specific area is painted. Each tested roll was coated with the same number of passes to ensure the same chance of paint removal. After finishing the oblong painting, the assembly is weighed again, the difference between this value and the full load value being the amount of discharge of the sleeve in a given area. All emission values are plotted against the respective surface areas.

The roll cover was tested for cleanability as follows.

Cleaning is a test judged on a subjective basis because it is a timed cleaning in the sense that the technician decides that the roll is "comfortable" to clean. Consider how fast the paint is released by simply moving under water. The rollers always require some agitation of the fibers to push the paint from the bottom surface of the fibers near the backing yarn.

The resulting data for the above tests are given in tables 2 and 3. The data for the paint roller sleeve used are the following table.

"square feet of paint" is the size of the area painted for each test. The area was painted as described above.

The "grams of sleeve and frame" is the total weight of the roller before any paint is drawn up onto the fabric.

The "grams after load" is the weight of the paint roller after the roller has "run-in" and possibly most of the paint has been placed on the fabric of the roller shell.

"grams sucked" is the exact weight of paint sucked by the roller, equal to (wt) "grams after load" minus (wt) "grams of sleeve and cage" — "grams sucked".

"grams after painting" is the weight of the paint roller after it has been used to paint a specified square foot area.

The "grams of unloaded paint" is the exact weight of paint released from the roller onto the wall during the painting process. "grams after loading" minus "grams after painting" is "grams of unloaded paint".

"percent change" is the improvement in paint released from the treated sleeve to the wall as compared to the untreated sleeve, equal to "grams of paint unloaded (treated)" minus "grams of paint unloaded (untreated)" divided by "grams of paint unloaded (untreated)".

TABLE 2

The sleeves of examples 2 and 3, treated by spraying and licking respectively, performed very well with respect to the grams of paint added during paint suction and released during painting. The "hand" of the sleeve fabric treated by lick application is significantly harder than the "hand" of spray applicators. "handle" herein refers to softness or hardness when touched. The stiffer hand is due to the larger amount of product applied for lick application versus spray application.

TABLE 3

The sleeves of examples 4 and 5 were treated by spray application, while the sleeves of examples 6 to 8 were treated by foam application to the sleeve fabric, with a moisture pick-up of 10-20%. The amount of paint picked up by the sleeve and released onto the wall is increased with both application methods compared to an untreated sleeve. The sleeve fabrics of examples 4 and 5 (spray application) retained lower amounts of the treatment product (due to excessive shearing of fiber length during manufacture of the sleeve) compared to the initial spray application data of examples 2 and 3 in table 2, resulting in slightly lower values in terms of paint release and pick-up. Example 6 a polymer treatment was prepared using a 10% moisture pick-up and applied to the face side of the fabric such that the shearing of the fiber length during the manufacture of the sleeve removed more of the treated fiber, resulting in a lower% change. Example 7 was prepared using a 10% moisture pick-up and treatment was applied to the back of the fabric so that the fiber length had less effect on shear during manufacture, thus resulting in better performance expressed as% change. Example 8 was prepared using 20% moisture absorption and the treatment was applied to the front side of the fabric so that it had better performance due to higher moisture absorption.

On average, the cleaning time for the treated sleeve was 45-55 seconds, while for the untreated sleeve 60-70 seconds. A 25% reduction in cleaning time was found. This is based on the average of several different rolls.

Example 11

Compositions 5-8 as shown in table 4 were applied to the surface of the paint brush. The initial application was carried out on a 0.5 g polybutylene terephthalate (PBT) strand. The PBT filaments were immersed in a padding bath containing the amounts of polymer, hydrophopol XAN, and water shown in table 4 below. The polymer composition is a blend of 7-9% of the fluoroacrylate polymer of example 1, 5-6% of the fluorourethane polymer of example 2, 0-1% of sodium dodecylbenzenesulfonate and the balance water, to total 100%. HYDROPHOBAL XAN is a blocked isocyanate extender available from Ciba specialty Chemicals, High Point, NC. The filaments were then cured at 100 ℃ for 10 minutes.

TABLE 4

Composition 5 in table 4 was the least tacky and did not adhere to the filaments themselves. Compositions 6 to 8 were very viscous and the filaments tended to adhere to themselves. Composition 5 was used in the other examples.

Example 12

Composition 5 of Table 4 was applied to about 172g of bulk polybutylene terephthalate (PBT) filaments prior to brushing. The PBT filaments were sprayed (ensuring no coating of the roots of the filaments) and mixed by hand using a spray bottle containing a pad bath containing 70g/L of the polymer blend of example 11, 10g/L of LHYDROPHOBOOL XAN and water (composition 5). This process was repeated 3 times and the filaments were then dried. A total of five pounds of filaments were processed and put into a brush. The filaments were mixed, placed in a ferrule, epoxy added, followed by a curing step (150 ℃) and the handle attached. The filaments have a bath moisture pick-up of about 10-20% and a filament weight gain of 0.5-1.0%.

Example 13

The polymer blend of example 11 was applied to a 2.5 pound batch of PBT filament during the brushing process. The PBT filaments were sprayed during the mixing step of manufacture (ensuring that the roots of the filaments were not covered) using a sprayer similar to an insecticide applicator containing a 70g/L pad bath of the polymer blend of example 11. The wire was then placed in the ferrule, epoxy was added, followed by a curing step (150 ℃) and the handle was attached.

Example 14

The paint brush tests of examples 12 and 13 are as follows. After assembling the paint brush, the brush is weighed. The silk was then partially dipped into latex paint for 15 seconds and drained for 30 seconds. The brush was weighed again and then a piece of stone was painted with a brush 30 times. The brush was then weighed again. It was found that there was a weight difference in the amount of paint released from and absorbed onto the brush after draining. The treated brushes were directly compared to untreated brushes. The following results apply to examples 12 and 13.

The amount of paint released from the paint brush and the amount of paint picked up by the paint brush is not reduced by treatment with fluorochemical. Fluorochemical treatments produced slight improvements. Cleaning of the brush was tested immediately after use, 5 hours after use, and 15 hours after use. After all three periods, the cleaning time of the untreated brush was compared to that of the treated brush. The cleaning time of the treated brush is significantly improved over the untreated brush, with the benefit of increasing the duration of time before cleaning. The cleaning time of the fresh wet paint from the brush was not significantly improved for the treated brush compared to the untreated brush. But after 5 hours, an average of 1 minute removed the semi-dried paint from the filaments of the treated brush and an average of 3 minutes for the untreated brush. But after 15 hours the semi-dry paint was removed from the filaments of the treated brush for an average of 3 minutes and for an average of 7 minutes for the untreated brush.

Claims (10)

1. A paint applicator comprising a paint-carrying surface coated or treated with a fluoroacrylate polymer or copolymer, a fluorourethane polymer or copolymer, or mixtures thereof;

wherein the fluoroacrylate polymer or copolymer comprises monomers copolymerized in the following weight percentages:

(a) from about 50% to about 85% of a monomer having structural formula I:

R_f-CH₂CH₂-OC(O)-C(R)＝CH₂ I

(b) from about 10% to about 25% of a monomer having the structural formula II:

R₂-OC(O)-C(R)＝CH₂ II

(c) 0.1% to about 5% of a monomer having the structure III:

HO-CH₂CH₂-OC(O)-C(R)＝CH₂ III

(d) 0.1% to about 5% of a monomer having structural formula IV:

H-(OCH₂CH₂)_m-O-C(O)-C(R)＝CH₂ IV

(e) 0.1% to about 3% of a monomer having the structure V:

HO-CH₂-NH-C(O)-C(R)＝CH₂ V

wherein R is_fIs a linear or branched perfluoroalkyl group having 2 to about 20 carbon atoms, each R is independently H or CH₃；R₂Is an alkyl chain having from 2 to about 18 carbon atoms; and m is 2 to about 10;

wherein the fluoro urethane polymer has at least one urea group and is the reaction product of:

(A) at least one organic polyisocyanate or mixture of organic polyisocyanates containing at least three isocyanate groups per molecule,

(B) at least one fluorochemical compound having the following composition: r_f-X-Y-H, wherein R_fIs C₂-C₂₀A linear or branched fluoroalkyl radical, X is- (CH)₂)_n-，-(CH₂)_gSO₂(CH₂)_t-or-SO₂N(R₁)CH₂CH₂-, and Y is-O-, -S-, or-N (R)₂) -; wherein R is₂Is H or an alkyl group containing 1 to 6 carbons,

(C) one or more hydrophilic, water-solvatable agents comprising monofunctional groups having at least one reactive H, and thereafter

(D) An amount of water that reacts with about 5% to 100% of the remaining isocyanate groups.

2. The paint applicator of claim 1, wherein the fluoroacrylate polymer or copolymer comprises at least 50% by weight of long chain alkyl (meth) acrylate groups.

3. The paint applicator of claim 1, further comprising from 0% to about 10% of a vinylidene chloride of formula VI

CH₂＝CCl₂ VI

Or vinyl acetate of the formula VII

CH₃-(O)COCH＝CH₂ VII

Or mixtures thereof.

4. The paint applicator of claim 1, comprising a roller, brush, floss ball, sponge, cloth, mat, comb, paper, knife, feather, needle, or applicator tool.

5. The paint applicator of claim 1, wherein the paint-carrying surface has been coated or treated with from about 0.05% to about 20% of a fluoroacrylate or a fluorourethane based on the weight of the fiber.

6. A method of treating a paint applicator comprising applying to a paint-carrying surface thereof, or a precursor to said surface, a fluoroacrylate polymer or copolymer, a fluorourethane polymer or copolymer, or mixtures thereof;

wherein the fluoroacrylate polymer or copolymer comprises monomers copolymerized in the following weight percentages:

(a) from about 50% to about 85% of a monomer having structural formula I:

R_f-CH₂CH₂-OC(O)-C(R)＝CH₂ I

(b) from about 10% to about 25% of a monomer having the structural formula II:

R₂-OC(O)-C(R)＝CH₂ II

(c) 0.1% to about 5% of a monomer having the structure III:

HO-CH₂CH₂-OC(O)-C(R)＝CH₂ III

(d) 0.1% to about 5% of a monomer having structural formula IV:

H-(OCH₂CH₂)m-O-C(O)-C(R)＝CH₂ IV

(e) 0.1% to about 3% of a monomer having the structure V:

HO-CH₂-NH-C(O)-C(R)＝CH₂ V

wherein R is_fIs a linear or branched perfluoroalkyl group having 2 to about 20 carbon atoms, each R is independently H or CH₃；R₂Is an alkyl chain having from 2 to about 18 carbon atoms; and m is 2 to about 10;

wherein the fluoro urethane polymer or copolymer has at least one urea group and is the reaction product of:

(A) at least one organic polyisocyanate or mixture of organic polyisocyanates containing at least three isocyanate groups per molecule,

(B) at least one fluorochemical compound having the following composition: r_f-X-Y-H, wherein R_fIs C₂-C₂₀A linear or branched fluoroalkyl radical, X is- (CH)₂)_n-，-(CH₂)_gSO₂(CH₂)_t-or-SO₂N(R₁)CH₂CH₂-, and Y is-O-, -S-, or-N (R)₂) -; wherein R is₂Is H or an alkyl group containing 1 to 6 carbons,

(C) one or more hydrophilic, water-solvatable agents comprising monofunctional groups having at least one reactive H, and thereafter

(D) An amount of water that reacts with about 5% to 100% of the remaining isocyanate groups.

7. The process of claim 6 further comprising from 0% to about 10% of a vinylidene chloride having the structure VI

CH₂＝CCl₂ VI

Or vinyl acetate of the formula VII

CH₃-(O)COCH＝CH₂ VII

Or mixtures thereof.

8. The method of claim 6, wherein the paint applicator comprises a roller, brush, floss ball, sponge, cloth, mat, comb, paper, knife, feather, needle, or applicator tool.

9. The method of claim 6, wherein the paint-carrying surface has been coated or treated with from about 0.05% to about 20% of a fluoroacrylate or a fluorourethane, based on the weight of the fiber or substrate.

10. A paint applicator treated by the method of claim 6.