KR100481334B1 - Oil, water and solvent resistant paper treated with fluorocompound copolymer - Google Patents

Abstract

The present invention,

(a) about 60% to about 90% by weight of at least one monomer of formula (I);

(b) about 10% to about 40% by weight of at least one monomer of Formula II; And

(c) a copolymer composition for treating paper and paper products for providing water repellency, oil repellency or oil repellency, comprising at least one monomer of formula III or IV or a monomer copolymerized from about 1% to about 7% by weight thereof. It is about.

<Formula I>

R _f -QAC (O) -C (R) = C ₂

<Formula II>

(R ₁ ) ₂ N-CH ₂ CH ₂ -OC (O) -C (R ₂ ) = CH ₂

<Formula III>

<Formula IV>

Cl-CH ₂ -CH (OH) CH ₂ -OC (O) -C (R ₄ ) = CH ₂

In the formula,

R _f is a straight or branched chain perfluoroalkyl group having 2 to about 20 carbon atoms,

R is H or CH ₃ ,

A is O, S or N (R '), wherein R' is H or alkyl having 1 to about 14 carbon atoms,

Q is alkylene having 1 to about 15 carbon atoms, hydroxyalkylene having 3 to about 15 carbon atoms,-(C _n H _2n ) (OC _q H _2q ) _m- , -SO ₂ -NR '(C _n H _2n )-or -CONR '(C _n H _2n )-(where R' is H or alkyl having 1 to about 4 carbon atoms, n is 1 to 15, q is 2 to 4, m Is 1 to 15),

R ₁ is an alkyl group having 1 to about 3 carbon atoms,

R ₂ is H or an alkyl radical having 1 to about 4 carbon atoms,

Nitrogen in formula (II) is about 40% to 100% salted,

R ₃ and R ₄ are each independently H or the same or different alkyl radicals having 1 to about 4 carbon atoms.

Description

Oil, water and solvent resistant papers treated with fluorocompound copolymers

The present invention relates to fluorocompound copolymers and their use in paper and similar products for imparting resilience to water, oils or fats and oils.

The paper industry has a wide variety of uses for the packaging of food. Paper that comes in contact with oily, oily or aqueous foods will need an antifouling or leakproof barrier layer. Polymer barrier layers, such as polyethylene, are expensive to use on paper, prevent re-pulping or regeneration of paper after use as the intended use, and are increasingly limited by the related regulations. Fluorine-containing compounds and copolymers, collectively called fluoro compounds, have been used for years to add water resistance, oil resistance and oil resistance to paper-like substrates, due to their effect at low concentrations and their applicability to conventional papermaking methods. come. For example, US Pat. No. 4,147,851, issued to Raynolds on April 3, 1979, discloses 50 to 85 weight percent of perfluoroaliphatic acrylate / methacrylate monomers and dialkylaminoalkyl acrylates / meta. It is described that copolymers consisting of 50 to 15% by weight of acrylate monomers or corresponding amine salts, quaternary amine or amine oxide monomers are useful for oil and water repellency. EP 234601 teaches fluorocompound copolymers useful as papermaking additives that provide oil and water repellency and food contamination resistance to oven heated cardboard. Japanese Patent No. 50010820 teaches polyurethane coating compositions containing polar fluorine compounds for providing good gloss and weather resistance to mixed sponges.

In general, fluoro compounds can be applied to these materials by applying them to the paper surface or by adding them to paper pulp before the paper is formed. Surface application can be carried out by methods such as spraying, depositing, roller-coating or padding to apply the fluorocompound to one or both sides of the essentially finished product. This type of treatment has the advantage of being able to directly control the total amount of fluoro compound on the paper, since the possibility of loss at this stage of the process is extremely limited. This has the disadvantage that the fluoro compound is mainly applied to the surface of the paper making it only limited protection against deeper liquid penetration.

Alternatively, the fluorocompound may be added to the paper pulp under suitable conditions retained in the paper after all or most of the fluorocompound has been dehydrated. In this type of treatment, the fluorocompound is applied throughout the paper thickness, not just on the surface. This more uniform treatment is particularly important in that it provides resistance to the penetrating liquid when any part of the paper is wrinkled or worn out. A disadvantage of this type of treatment is that special conditions must be established to ensure that the fluoro compound is retained in the paper, i.e., that it is not lost in the water removal step during paper formation. In these two application methods, the main measurement performance of these fluoro compounds is their ability to exhibit repulsion or resistance at low fluorine content against substances such as oils, fats and oils and similar materials.

Another important feature for these fluoro compounds is their stability under high shear stress conditions. In paper mills, these compounds are often transferred to the application area by high shear stress pumps. In addition, they are typically applied to paper from rollers operating under high shear stress conditions. If the fluorocompound is unstable under these conditions and deposits a condensation on the roller or pump, it will lead to machine outages and generally poor performance.

Fluorine-containing copolymers used in these applications often contain cationic groups in order to bind to cellulosic fibers that are anionic under most conditions. These copolymers can be prepared by emulsion polymerization or solution polymerization. In emulsion polymerization, the monomers are dispersed using a surfactant in an aqueous continuous phase, and polymerization is initiated to form an emulsion of droplets in which the surfactant is dispersed. Products of this type may have the problem that these emulsions often become unstable (ie, solidify) under the extreme high shear stress conditions encountered on a commercial scale. In solution polymerization, one or more monomers are solubilized without the need for a surfactant. Products of this type can form solutions or emulsions, which can be more stable under extreme conditions than products in which the surfactant is dispersed. The use of such fluorocompound copolymers requires a careful balance between the hydrophilicity of dissolving or dispersing it in water and the hydrophobicity desired in the finished paper product.

Thus, in addition to their dispersion stability under high shear stress conditions, another important criterion of performance for fluorocompound copolymers is the hydrophobicity and oleophobicity of the finished paper product. Another criterion is to achieve these benefits while minimizing the amount of volatiles released into the air during application to paper or paper products. Accordingly, there is a need for compositions that provide improved water and oil repellency or oil repellency for paper and paper products, are stable under high shear stress conditions, and release a minimum amount of volatile material into the air during application. The fluorocompound copolymers of the present invention meet these requirements and exhibit some important performance advantages over other fluorocompound copolymers already used for this purpose.

Summary of the Invention

The present invention

(a) about 60% to about 90% by weight of at least one monomer of formula (I);

(b) about 10% to about 40% by weight of at least one monomer of Formula II; And

(c) a copolymer composition for providing water and oil repellency or oil repellency to paper and paper products comprising at least one monomer of formula III or IV or a monomer copolymerized from about 1% to about 7% by weight thereof. Include.

<Formula I>

R _f -QAC (O) -C (R) = CH ₂

<Formula II>

(R ₁ ) ₂ N-CH ₂ CH ₂ -OC (O) -C (R ₂ ) = CH ₂

<Formula III>

<Formula IV>

Cl-CH ₂ -CH (OH) CH ₂ -OC (O) -C (R ₄ ) = CH ₂

In the formula,

R _f is a straight or branched chain perfluoroalkyl group having 2 to about 20 carbon atoms,

R is H or CH ₃ ,

A is O, S or N (R '), wherein R' is H or alkyl having 1 to about 4 carbon atoms,

Q is alkylene having 1 to about 15 carbon atoms, hydroxyalkylene having 3 to about 15 carbon atoms,-(C _n H _2n ) (OC _q H _2q ) _m- , -SO ₂ -NR '(C _n H _2n )-or -CONR '(C _n H _2n )-(where R' is H or alkyl having from 1 to about 4 carbon atoms, n is from 1 to about 15, q is from 2 to about 4 m is 1 to about 15),

R ₁ is an alkyl group having 1 to about 3 carbon atoms,

R ₂ is H, or an alkyl radical having 1 to about 4 carbon atoms,

About 40% to 100% of the nitrogen in formula (II) is salted,

R ₃ and R ₄ are each independently H or the same or different alkyl radicals having 1 to about 4 carbon atoms.

The present invention also provides for imparting water, oil or fat repellency, comprising applying an effective amount of the copolymer composition of the invention as described above to the surface of a paper or paper product, or applying to the pulp prior to forming the paper or paper product. Method for treating paper or paper products.

The present invention is also treated with the composition by a method of treatment comprising applying the copolymer composition of the invention as described above to the surface of a paper or paper product, or adding the composition to pulp prior to the formation of the paper or paper product. Paper or paper products. The treated paper or paper product has a fluorine content of about 0.04% to about 0.10% by weight.

1A, 1B and 1C show three black filter cloths through which Commercial Sample A, and the copolymer solutions of Examples 1 and 2, respectively, were filtered through. Figure 1A (Sample A) shows a white polymer precipitated solid, while Figures 1B and 1C (Examples 1 and 2) show complete filtration with no residue.

The present invention includes improved fluorocompound copolymers useful for providing water, oil and oil resistance to paper and paper products. By paper product is meant paper, cardboard, cardboard, and similar products made by dewatering wood or cellulosic aqueous pulp (including cotton). The following description applies to paper as an example, and may generally include other paper products.

The fluorocompound copolymer composition of the present invention is added to provide excellent water and oil repellency or oil retention for paper and paper products. The composition is added to the paper or paper product in the form of a self dispersion emulsion, or suspension in water or other solvent. The composition is added to paper pulp prior to paper formation, or applied to essentially the final processed paper. The copolymer composition of the present invention is based on the total weight of the copolymer

(a) about 60% to about 90% by weight of at least one monomer of formula (I);

(b) about 10% to about 40% by weight of at least one monomer of Formula II; And

(c) monomers copolymerized from about 1% to about 7% by weight of one or more monomers of Formula III or IV or mixtures thereof.

<Formula I>

R _f -QAC (O) -C (R) = CH ₂

(In the meal,

R _f is a straight or branched chain perfluoroalkyl group having 2 to about 20 carbon atoms,

R is H or CH ₃ ,

A is O, S or N (R '), wherein R' is H or alkyl having 1 to about 4 carbon atoms,

Q is alkylene having 1 to about 15 carbon atoms, hydroxyalkylene having 3 to about 15 carbon atoms,-(C _n H _2n ) (OC _q H _2q ) _m- , -SO ₂ -NR '(C _n H _2n )-or -CONR '(C _n H _2n )-(where R' is H or alkyl having 1 to about 4 carbon atoms, n is 1 to 15, q is 2 to 4, m Is 1 to 15)

<Formula II>

(R ₁ ) ₂ N-CH ₂ CH ₂ -OC (O) -C (R ₂ ) = CH ₂

(In the meal,

R ₁ is an alkyl group having 1 to about 3 carbon atoms,

R ₂ is H or an alkyl radical having 1 to about 4 carbon atoms,

40% to 100% of nitrogen is salted)

<Formula III>

<Formula IV>

Cl-CH ₂ -CH (OH) CH ₂ -OC (O) -C (R ₄ ) = CH ₂

(In the meal,

R ₃ and R ₄ are each independently H, or the same or different alkyl radicals having 1 to about 4 carbon atoms)

In the composition of the present invention, in formula (I), R ₄ is a straight-chain perfluoroalkyl group having 2 to about 20 carbon atoms, A is O, and Q is alkylene having 1 to about 15 carbon atoms. The monomer of formula (I) is a perfluoroalkylethyl having the formula CF ₃ CF ₂ (CF ₂ ) _x C ₂ H ₄ OC (O) -C (H) = CH ₂ , where x is an even number from 4 to 18. It is more preferable that it is an acrylate or a mixture thereof. It is most preferred that the carbon chain length distribution (x) is about 50 wt% C ₈ , about 29 wt% C ₁₀ , about 11 wt% C ₁₂ , and a smaller percentage at C ₆ , C ₁₄ and longer chain lengths. It is preferred that the monomer of formula (II) is diethylaminoethyl methacrylate and the monomer of formula (III) be glycidyl methacrylate.

The proportion of monomers of formula (I) is at least about 60% based on the total weight of the copolymer. If present in lesser amounts, the repulsion is unacceptably small. The percentage should be less than about 90%. When present in higher amounts, the amounts of monomers of formula (II) and monomers of formula (III) or (IV) or mixtures thereof are too small, resulting in poor dispersibility. The percentage of monomers of formula (I) in the copolymer is preferably from about 79% to about 85% by weight in view of the best balance of dispersion stability, solubility and reaction performance.

The monomer of formula (II) is preferably diethylaminoethyl methacrylate, which has undergone partial or total salting or quaternization. At least about 40% salt should be salted for a suitable dissolution effect, but can be salted 100%. Although fully salted materials are satisfactory in performance, when the polymer is heated and cured, an unnecessary amount of salting agent is removed. The degree of salt formation is preferably about 50% to 100%. The free amine portion of the resulting copolymer can be reacted with a salt forming agent such as acetic acid to convert some or all of the amine residues into the corresponding acetates. Alternatively, the salt formation process can be carried out on amine groups prior to the polymerization reaction to obtain equally good results. The hydrophobic quaternization group can be an acetate, halide, sulphate or other known salting quaternization group.

The monomer proportion of formula (II) is at least about 10% for proper dissolution. A ratio above about 40% will inhibit oil and water repellency. The percentage of monomers of formula (II) in the copolymer is preferably from about 13% to about 19% by weight (as salted).

Without wishing to be bound by theory, it is believed that the monomers of Formula III or IV can act as reaction sites for the polymer to covalently bond to the surface of the support. Preferably, the monomer of formula III is glycidyl methacrylate. Existing at a rate of about 1% or more has a significant effect. An amount of about 7% or more cannot further improve performance. The proportion of monomers of formula III or IV, or mixtures thereof, in the copolymer is from about 1% by weight to about 5% by weight.

Polymerization of the comonomers of formulas (I), (II), and (III) or (IV) or mixtures thereof to prepare the compositions of the present invention may be achieved by subjecting monomers to acetone, methylisobutyl ketone, ethyl acetate, isopropanol and other ketones, esters and alcohols, or It is carried out by contact with a solvent such as a mixture thereof. The polymerization is initiated by any free radical initiator, such as 2,2'-azobis (2,4-dimethylvaleronitrile, for convenience .. These are E. I. Dupont di Nemo, Wilmington, Delaware, USA. Commercially available under the names "VAZO" 67, 52 and 64 from EI Du Pont De Nemours and Co. or "V-501" from Wako Chemicals USA, Ltd. It is marketed under the name.

The following tests were used to evaluate the properties of the treated paper using the inventive copolymers and comparative examples:

The Cobb Size test as described in TAPPI 441 os-77 measures the absorbance (g) per square meter of paper surface using a water height pressure of 1 cm and a time of 120 seconds. In addition, a turpentine test for maintenance resistance is described in TAPPI T454 os-77, which measures the number of seconds that elapsed before the red colored turpentine penetrates the paper. Higher numbers indicate greater sustainability. Ralston-Purina resistance test for pet food ingredients is described in Volume 6 of the packaging container of Ralston-Purina. It measures paper contamination using specially supplied synthetic oils designed to double the effects of ingredients in pet foods. Higher numbers indicate a greater degree of contamination, ie poor maintenance. The Kit Test described in TAPPI UM 557 was used to drop 1 drop from a series of specific castor oil, toluene and heptane mixtures numbered from 1 to 12 at a height of 2.5 cm (1 inch) to the fluorochemical reagent. The repellency and semi-absorbance properties of the treated paper are measured. The kit test grade is the highest numbered solution that does not indicate paper contamination, and the higher number indicates good oil resistance.

Example 1

A vessel equipped with a stirrer, thermometer and reflux cooler

CF ₃ CF ₂ (CF ₂ ) _x C ₂ H ₄ Formula I with OC (O) -C (H) = CH ₂ , wherein x is 6, 8, 10, 12, 14, 16, 18, each The relative amounts of are about 3%, 50%, 31%, 10%, 3%, 2% and 1%) of fluoromonomer (weight average molecular weight 569) 673.5 parts; 119.5 parts of N, N-diethylaminoethyl methacrylate as a monomer of Formula II; 19 parts glycidyl methacrylate as a monomer of Formula III; And 505 parts of methyl isobutyl ketone (MIBK). The charge was purged with nitrogen at 40 ° C. for 30 minutes. Subsequently, E.I., Wilmington, Delaware, USA. Polymerization was initiated by addition of "Vazo" 67 (0.6 parts) commercially available from Dupont Di Nemoir and Company, and the charge was stirred at 70 ° C. under nitrogen for 16 hours.

A mixture of water (2435 parts) and acetic acid (59.5 parts) at room temperature was added to the copolymer mixture at 70 ° C. The reflux condenser was replaced with a distillation tube and the MIBK was removed under reduced pressure. A total of 3103 parts of copolymer solution was obtained. The copolymer solids (23.1%) contained 82.2% perfluoroalkylethyl methacrylate units, 15.4% N, N-diethylaminoethyl methacrylate units and 2.4% glycidyl methacrylate units.

The polymer from above was applied to the paper by immersing the wet paper 15 kg / 288 m 2 (34 lb / 3000 sq ft) in several treatment solutions and then passing the treated paper through a compression roller. The treatment solution was prepared by dispersing the copolymer in 50 ppm of hard water and hydroxyethylated starch. The concentration of copolymer in the treatment solution was adjusted to deposit 0.04%, 0.05%, 0.06%, 0.07%, 0.08% or 0.10%, and 2.4% starch, respectively, on paper. The treated paper was cured in a heat press at 127 ° C. (260 ° F.) for 2 minutes and evaluated for oil repellency, oil repellency, solvent repellency and water repellency. Oil repellency, oil repellency, solvent repellency and water repellency results for Example 1 and conventional Sample A for comparison are summarized in Table 1 below. Based on data from the FDA registration table, Commercial Sample A is a fluoro acrylate, 2-ethoxyethyl acrylate, diethylaminoethyl methacrylate polymerized using an ethoxylated amine salt as an emulsifier and a water-soluble free radical initiator. Emulsion copolymers of late methyl chloride salt, glycidyl methacrylate, and octyl mercaptan. It is marketed as "SCOTCHBAN" FC845 from Minnesota Mining and Manufactu Ring Co, (3M), Minneapolis, Minnesota, USA.

Cove size test results are the average of two tests. The Ralston-purina retention test is the average of four tests. The turbin test is the average of two trials. A "+" is displayed after the result indicating that at least one trial has yielded a frequency of at least 1800 seconds.

TABLE 1

Oil repellency, water repellency, solvent repellency and oil repellency on 15 kg of damp paper

The copolymer of Example 1 clearly shows excellent oil and solvent repellency at similar fluorine concentrations in the terebin test for oil repellency at low concentrations of fluorine applied and in the ralston-purina resistance test. Cove size test results show no difference for the two fluoropolymers.

Example 2

This example illustrates the comparative performance of copolymers prepared according to the teachings of U.S. Patent No. 4,147,815, ie copolymers prepared without the monomer of Formula III or IV, or a mixture thereof, of the third component (c) above.

A vessel equipped with a stirrer, thermometer and reflux cooler

CF ₃ CF ₂ (CF ₂ ) _x C ₂ H ₄ COC (O) -C (CH ₃ ) = CH ₂ , wherein x is 4, 6, 8, 10, 12, 14, 16, 18 , 20, each of the relative amounts of about 5%, 35%, 30%, 14%, 6%, 4%, 3%, 2%, and 1%) of fluoromonomer (weight average molecular weight 543) 70 minutes; 30 parts of N, N-diethylaminoethyl methacrylate as a monomer of Formula (II); And 100 parts of isopropanol. The charge was purged with nitrogen at 30 ° C. for 30 minutes. Subsequently, E.I., Wilmington, Delaware, USA. "Bazo" 67 (0.5 parts) commercially available from Dupont di Nemoir & Co., Ltd. was added to initiate polymerization and the charge was stirred at 65 ° C. under nitrogen for 18 hours.

Peracetic acid (24.3 parts of a 42% solution in acetic acid) was added dropwise to the copolymer solution at 65 ° C. Upon completion of the dropwise addition, the reaction was further stirred at 65 ° C. for an additional hour. Water (200 parts) was added to the copolymer mixture to contain about 70% perfluoroalkylethyl methacrylate units and about 30% N, N-diethylaminoethyl methacrylate amine oxide units (24% A total of 414 parts of a copolymer solution with) were obtained. The polymer solution was used by itself or distilled under air or reduced pressure.

The polymer of Example 2 immersed 25 kg / 288 m 2 (56 Ib / 3000 sq ft) of unbleached kraft paper in the treatment solution, then passed the treated paper between the compression rollers and at 127 ° C. (260 ° F.) The paper was applied by curing for 2 minutes in a hot press. The treatment solution was prepared by dispersing the copolymer in 50 ppm of hard water (no starch). Wet impregnation of the paper was adjusted to deposit 0.06%, 0.08% and 0.10% of fluorine. Oil and water repellent results are summarized in Table 2. Table 2 contains data obtained by similar application of Example 1 and Commercial Sample A.

TABLE 2

Oil repellency, water repellency, solvent repellency and oil repellency on unbleached kraft paper

The table shows that the copolymer of the present invention from Example 1 was inferior at a fluorine concentration of 0.04% in the Ralston-Furina retention test, but significantly higher than that prepared in Example 2 in the oil kit test and the terebin resistance test. It is excellent. In general, the copolymer of Example 1 exhibits similar overall performance to Sample A on this particular paper.

The most significant difference in the performance of the copolymers is their dispersion stability under high shear stress conditions. This was tested in the following manner. Each copolymer solution in water was prepared to add a dispersion containing 10 parts of polymer solids to 90 parts of distilled water. It was circulated through a Viking variable speed pump for 3.5 hours at a rate of approximately 1200 ml / min and a temperature of 30 ° C.

The recycled copolymer solution was then filtered through black filter cloth and tested for insoluble residue. A copy of the resulting filter cloth is shown in FIG. 1. The copolymers from Examples 1 and 2 were filtered completely through the filter cloth without leaving residue. Recycled Commercial Sample A showed excess white polymer precipitates and poor dispersion stability under these high shear stress conditions.

Examples 3-9

Examples 3 to 9 use acrylates, methacrylates or other fluoromonomers of formula (I), add a third component (c) (monomers of formula III or IV, or mixtures thereof), And a copolymer produced according to the general method exemplified in Example 1 or 2 by appropriately changing as necessary depending on whether the resulting copolymer is reacted with acetic acid or peracetic acid. The compositions of the copolymers of Examples 3-9 thus prepared are summarized in Table 3 as weight percent. For reference, the composition of the copolymer prepared in Example 1 is also included.

TABLE 3

Composition of the Copolymers of Examples 3-9

Note: The peracetic acid used was a 32 wt% solution in acetic acid. The monomer of formula (I) used in Examples 8 and 9 was fluoromonomer FX-14, available from 3M Company, Minneapolis, Minn. Acryl stands for acrylate. Meth stands for methacrylate. DEAM stands for diethylaminoethyl methacrylate. GMA stands for glycidyl methacrylate.

The copolymers from Examples 3-9 immersed 25 kg / 288 m 2 (56 lb / 3000 sq ft) of unbleached kraft paper in the treatment solution, passed the treated paper between the compression rollers, and 127 ° C. (260 Applied to the paper by curing for 2 minutes in a heat press). The treatment solution was prepared by dispersing the copolymer in 50 ppm hard water. Wet impregnation of the paper was adjusted to deposit 0.06%, 0.08% and 0.10% of fluorine. Repulsive results are summarized in Table 4. ND indicates no measurement was taken. Comparative tests from Table 2 for the copolymer of Example 1 are included for convenience.

TABLE 4

Repulsive test for Examples 3-9 on unbleached kraft paper

The copolymer of Example 3 is similar to the copolymer of Example 1 except that it is reacted with peracetic acid instead of acetic acid. Example 3 shows an improvement over Example 1 in the Ralston-Furrina test, while inferior in the kit test and the terebin resistance test.

The copolymer of Example 4 is similar to the copolymer of Example 1 except that methacrylate with a wider distribution of perfluoroalkyl chain lengths is used compared to acrylate. Example 4 is much inferior to Example 1 in oil repellency, terebin resistance and oil repellency.

The copolymers of Examples 5 and 6 lacking the small amount of monomers of Formula III or IV found in Example 1 are inferior in terebin resistance and oil resistance.

The copolymer of Example 7 is prepared according to the teachings of US Pat. No. 4,147,851 and is very insufficient in oil tests, ralston-purina tests and terebin tests.

In addition, the copolymers of Examples 8 and 9 are insufficient in this test compared to Example 1.

Claims (8)

(a) 60% to 90% by weight of one or more monomers of formula (I); (b) 10% to 40% by weight of at least one monomer of Formula II; And (c) A copolymer composition for treating paper and paper products for providing water repellency, oil repellency or oil repellency, comprising 1 to 7% by weight of at least one monomer of formula III or IV or a mixture thereof. <Formula I> R _f -QAC (O) -C (R) = CH ₂ <Formula II> (R ₁ ) ₂ N-CH ₂ CH ₂ -OC (O) -C (R ₂ ) = CH ₂ <Formula III> <Formula IV> Cl-CH ₂ -CH (OH) CH ₂ -OC (O) -C (R ₄ ) = CH ₂ In the formula, R _f is a straight or branched chain perfluoroalkyl group having 2 to 20 carbon atoms, R is H or CH ₃ , A is O, S or N (R '), where R' is H or alkyl having 1 to 4 carbon atoms, Q is alkylene having 1 to about 15 carbon atoms, hydroxyalkylene having 3 to 15 carbon atoms,-(C _n H _2n ) (OC _q H _2q ) _m- , -SO ₂ -NR '(C _n H _2n )-or -CONR '(C _n H _2n )-(where R' is H or alkyl having 1 to 4 carbon atoms, n is 1 to 15, q is 2 to 4, m is 1 To 15), R ₁ is an alkyl group having 1 to 3 carbon atoms, R ₂ is H or an alkyl radical having 1 to 4 carbon atoms, 40% to 100% of nitrogen in formula (II) is salted, R ₃ and R ₄ are each independently H or the same or different alkyl radicals having 1 to 4 carbon atoms. The composition of claim 1, wherein in the monomer of Formula I, R _f is a straight chain perfluoroalkyl group having 2 to 20 carbon atoms, A is O and Q is alkylene having 1 to 15 carbon atoms. The composition of claim 1 wherein the compound of formula I is perfluoroalkylethyl acrylate, the compound of formula II is diethylaminoethyl methacrylate, and the compound of formula III is glycidyl methacrylate. 4. The monomer of claim 3, wherein the monomer of formula I is CF ₃ CF ₂ (CF ₂ ) × C ₂ H ₄ OC (O) —C (H) = CH ₂ , wherein x is an even number from 4 to 18 or a mixture thereof. Phosphorus composition. (a) 60% to 90% by weight of one or more monomers of formula (I); (b) 10% to 40% by weight of at least one monomer of Formula II; And (c) an effective amount of a composition comprising at least one monomer of formula III or IV or a monomer copolymerized from 1% to about 7% by weight of the mixture thereof is applied to the surface of the paper or paper product, or prior to formation of the paper or paper product A method of treating paper or paper product for providing water repellency, oil repellency or oil repellency, comprising adding to pulp. <Formula I> R _f -QAC (O) -C (R) = CH ₂ <Formula B> (R ₁ ) ₂ N-CH ₂ CH ₂ -OC (O) -C (R ₂ ) = CH ₂ <Formula III> <Formula IV> Cl-CH ₂ -CH (OH) CH ₂ -0-C (O) -C (R ₄ ) = CH ₂ In the formula, R _f is a straight or branched chain perfluoroalkyl group having 2 to 20 carbon atoms, R is H or CH ₃ , A is O, S or N (R '), wherein R' is H or alkyl having 1 to about 4 carbon atoms, Q is alkylene having 1 to 15 carbon atoms, hydroxyalkylene having 3 to 15 carbon atoms,-(C _n H _2n ) (OC _q H _2q ) _m- , -SO ₂ -NR '(C _n H _2n )-or -CONR '(C _n H _2n )-(where R' is H or alkyl having 1 to about 4 carbon atoms, n is 1 to 15, q is 2 to 4, m is 1 To 15), R ₁ is an alkyl group having 1 to 3 carbon atoms, R ₂ is H or an alkyl radical having 1 to 4 carbon atoms, 40% to 100% of nitrogen in formula (II) is salted, R ₃ and R ₄ are each independently H or the same or different alkyl radicals having 1 to 4 carbon atoms. The method of claim 5, wherein said effective amount is an amount depositing from 0.04 to 0.10% by weight of fluorine. The method of claim 6, wherein the compound of formula I is perfluoroalkylethyl acrylate, the compound of formula II is diethylaminoethyl methacrylate, and the compound of formula III is glycidyl methacrylate. (a) about 60% to 90% by weight of at least one monomer of formula (I); (b) 10% to 40% by weight of at least one monomer of Formula II; And (c) A paper or paper product having a fluorine content of 0.04% to 0.10% by weight, treated with a composition comprising from 1 to 7% by weight of one or more monomers of formula III or IV or mixtures thereof. <Formula I> R _f -QAC (O) -C (R) = CH ₂ <Formula II> (R ₁ ) ₂ N-CH ₂ CH ₂ -OC (O) -C (R ₂ ) = CH ₂ <Formula III> <Formula IV> Cl-CH ₂ -CH (OH) CH ₂ -OC (O) -C (R ₄ ) = CH ₂ In the formula, R _f is a straight or branched chain perfluoroalkyl group having 2 to 20 carbon atoms, R is H or CH ₃ , A is O, S or N (R '), where R' is H or alkyl having 1 to 4 carbon atoms, Q is alkylene having 1 to about 15 carbon atoms, hydroxyalkylene having 3 to 15 carbon atoms,-(C _n H _2n ) (OC _q H _2q ) m-, -SO ₂ -NR '(C _n H _2n )-or -CONR '(C _n H _2n )-(where R' is H or alkyl having 1 to 4 carbon atoms, n is 1 to 15, q is 2 to 4, m is 1 To 15), R ₁ is an alkyl group having 1 to 3 carbon atoms, R ₂ is H or an alkyl radical having 1 to 4 carbon atoms, About 40% to 100% salt of nitrogen in formula (II), R ₃ and R ₄ are each independently H or the same or different alkyl radicals having 1 to about 4 carbon atoms.