Paper felts or mats

Abstract

A paper felt or mat is made from an aqueous slurry or dispersion of kraft wood pulp, a number of compounding ingredients such as finely divided inorganic pigments and fillers, a binder, an anionic latex of a copolymer wherein the core of the copolymer comprises a copolymer of a vinyl aryl monomer and a dicarboxylic acid monomer such as fumaric acid and/or itaconic acid and wherein the shell comprises a copolymer or a vinyl aryl monomer, a conjugated diene monomer, a glycidyl monomer such as glycidyl acrylate and/or glycidyl methacrylate and optionally a monocarboxylic acid monomer such as acrylic acid and/or methacrylic acid. The mat of this invention exhibits improved properties over mats made from other latex binders.

Description

This invention relates to a polymeric binder, to a method for making said binder and to felts or paper mats.

BACKGROUND

Paper felts or mats are formed from an aqueous slurry of kraft wood pulp, a predominant amount of finely divided inorganic fillers, a latex binder and other ingredients such as antioxidants, biocides and flocculants. The slurry is cast onto a fourdrinier machine or rotary drum machine from a head box where the water is largely removed, pressed to form a sheet which is then passed over drying cans, cooling cans, calendered and wound on a reel.

To form a flooring tile, the felt or mat is unwound from the reel, passed to a conveyor where the top layer of the mat is coated with a vinyl plastisol which is fluxed and cooled to form a vinyl coating which is then printed to form a design on the vinyl coating of the mat sheet. The design is then overcoated with a hot melt vinyl coating composition and cooled to form an abrasion-resistant top coating.

An object of this invention is to provide a novel polymeric binder for paper felts or mats.

Another object of this invention is to provide a method for making a novel polymeric binder.

Still another object of this invention to provide an improved paper felt or mat.

These and other objects and advantages of the present invention will become more apparent to those skilled in the art from the following description and examples.

SUMMARY OF THE INVENTION

According to the present invention, an improved paper felt or mat is provided wherein the latex or polymeric binder used in the paper making process comprises an anionic emulsion of a polymeric binder comprising a core-shell copolymer wherein the core comprises a copolymer of a vinyl aryl monomer and fumaric and/or itaconic acid and a shell of a copolymer of a vinyl aryl monomer, a conjugated diene, glycidylacrylate and/or glycidylmethacrylate and optionally acrylic acid and/or methacrylic acid.

The core-shell copolymer latex is then mixed with the kraft wood pulp and compounding ingredients for the paper felt or mat, dewatered, dried and compressed to form a paper felt or mat.

DISCUSSION OF DETAILS AND PREFERRED EMBODIMENTS

In the core the vinyl aryl monomer having from 8 to 10 carbon atoms may be selected from the group consisting of styrene, alphamethyl styrene, paramethyl styrene, methylvinyl toluene, p-vinyl toluene and s-ethyl styrene. Styrene is preferred. The styrene is used in an amount of from 6 to 8 parts by weight and the fumaric and/or itaconic acid are used in an amount of from 0.50 to 8 parts. Fumaric acid is preferred.

In the shell, the conjugated diene monomer has from 4 to 6 carbon atoms selected from the group consisting of 1,3-butadiene (preferred), isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, pentadiene and hexadiene and where the vinyl aryl monomer has from 8to 10 carbon atoms and can be selected from the group consisting of styrene (preferred), alphamethyl styrene, paramethyl styrene, methylvinyl toluene, p-vinyl toluene and 3-ethyl styrene. The vinyl aryl monomer is used in a amount of from about 40 to 60 parts by weight and the conjugated diene monomer is used in an amount of from 60 to 40 parts. The glycidyl acrylate and/or glycidyl methacrylate (preferred) is used in the amount of from 1.5 to 5.0 parts. The acrylic and/or methacrylic acid (if used, it is preferred) are employed in an amount of 0 to 2.0 parts.

The copolymer core is first formed by free radical emulsion polymerization, followed by the addition of monomers to form the shell copolymer.

Of the core-shell copolymer, the core comprises about 7.5 to 10.5 and the shell comprises from 92.5 to 89.5 parts.

Polymerization of the monomers to form the core and shell is effected by free-radical initiators (free-radical formers or free-radical forming systems, catalysts) such as ammonium, potassium or sodium persulfate, H.sub.2 O.sub.2 and the like in an amount sufficient for polymerization of the monomers and to obtain the desired molecular weight. Other free-radical initiators can be used which decompose or become active at the temperature used during polymerization. Examples of some other free-radical initiators are cumene hydroperoxide, dibenzoyl peroxide, diacetyl peroxide, didecanoyl peroxide, di-t-butyl peroxide, dilauroyl peroxide, bis (p-methoxy benzoyl) peroxide, t-butyl peroxy pivalate, dicumyl peroxide, isopropyl percarbonate, di-sec-butyl, peroxydicarbonate, azobis-dimethyl-valeronitrile, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile and 2,2'-azobis (methylisobutyrate) and the like and mixtures of the same. Only minor amounts of initiators are necessary to effect polymerization.

Emulsifiers such as soaps, surfactants or dispersing agents are used in an amount sufficient to obtain an aqueous emulsion of the water and monomers and resulting polymers. Examples of some emulsifiers are potassium laurate, potassium soap of disproportionated rosin, potassium stearate, potassium oleate, sodium lauryl sulfate, na-dodecyldiphenyloxide disulfonate, di-iso butylsodiumsulfosuccinate, sodium dodecylsulfonate, sodiumdecylsulfate, sodium salt of condensed naphthalene sulfonic acid and sodium rosinate and the like and mixtures thereof. Other well know surfactants can be used.

Chain transfer agents or modifiers are well known in the emulsion copolymerization of vinyl and diene monomers to make polymers. They are used generally to modify the molecular weight and to reduce cross-linking. While many types have been proposed, it is preferred to use the alkyl and/or alkylaryl mercaptans having from 8 to 18 carbon atoms. Of these, the tertiary alkyl mercaptans are much preferred. Examples of some mercaptans are n-octyl mercaptan, n-dodecyl mercaptan (preferred), t-octyl mercaptan, t-dodecyl mercaptan, p-tridecyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan and so forth and the mixtures thereof.

NaOH, KOH, NH.sub.4 OH and so forth may be added to the polymerization reactor before, during or after polymerization to control the pH as desired.

The water should be free of deleterious materials, and preferably should be distilled or ion exchanged. Sufficient water is used to enable formation of the emulsions and to enable proper mixing or stirring of the ingredients during polymerization to obtain the desired rate and degree of polymerization, heat transfer and so forth. The solids content of the resulting aqueous alkaline latices or dispersions or copolyers may vary from about 35 to 55% by weight, and the pH can be from about 7.0 to 11.5.

Stabilizers, antioxidants and chelating agents may be used during polymerization. Also the use of shortstops at the end of free radical polymerization is well known; they are not only used to stop the polymerization in the reactor at the desired conversion but also to prevent further polymerization, cross-linking, etc. during stripping, work-up and so forth. Examples of some shortstops are hydroquinone, sodium sulfide, hydroxyl ammonium acid sulfate, hydroxyl ammonium sulfate, sodium diethyl dithiocarbamate, diethylhydroxylamine (preferred), sodium dimethyl dithiocarbamate, potassium dimethyl dithiocarbamate, dimethylammonium dimethyldithiocarbamate, hydroxylamine sulfate plus sodium hydrosulfite and so forth.

Temperatures used during polymerization should be sufficient to effect polymerization by activation of the initiator and double bonds of the monomers. They should not be too high to cause a run-away reaction and not too low to retard polymerization. In general, the temperature may be from about 125to 175.degree. F.

Polymerization should be conducted in a pressure reactor, fitted with a stirrer or other agitating means, heating and cooling means, with means to flush with or pump in an inert gas such as nitrogen, helium, argon, neon and the like in order to polymerize preferably under inert or non-reactive conditions, with means to charge the monomers, water, initiators and so forth, venting means, and with means to recover the polymer and so forth. The reactor should be cleaned or flushed out between polymerization runs to remove traces of shortstops, initiators, modifiers, residues and so forth which might interfere with subsequent polymerizations. There should be sufficient agitation or stirring of the polymerization media to ensure thorough mixing, diffusion, contact and so forth. All of the polymerization ingredients except the shortstop may be charged to the reactor at the same time, intermittently, incrementally or continuously. Also, the ingredients may be added separately or in a mixture.

The polymers are, thus, made in water using free radical initiators, chelating agents, modifiers, emulsifiers, surfactants, stabilizers, fungicides, short stopping agents and so forth by known techniques. Polymerization may be carried to about 100% conversion.

On a dry weight basis the aqueous slurry to form the paper felt or mat comprises from about parts by weight:

Kraft wood pulp 5.0 to 20.0 Polyethylene particles 0.5 to 3.0 to improve pulping Finely divided clay 60.0 to 85.0 or talc (clay preferred) Glass fibers, chopped 1.0 to 2.0 inches Antioxidant 0.01 to 0.0015 Water clarifier 0.01 to 0.02 Latex copolymer 8.0 to 16.0

Surfactants, fungicides and defoamers also may be added to the slurry.

The following examples will serve to illustrate the invention with more particularity to those skilled in the art.

EXAMPLE 1 A. Preparation of core or seed copolymer

______________________________________Charge ChargeInstructions Order Material Parts______________________________________Initial charge Deionized water 89.25heat to 135.degree. F. Hampene Na 3 (40%) 0.05 1 Dowfax 2A1 (15%) 0.195 Monawet MB45 (45%) 2.25 Fumaric Acid 0.75 Potassium Persulfate 0.30React for 45 min. @ 2 Styrene 7.50135.degree. F. then charge______________________________________

B. Preparation of coverpolymer or shell copolymer

______________________________________Charge ChargeInstruction Order Material Parts______________________________________React 75 min. Styrene 7.33then charge 3 Sulfole 120 0.06 4 Butadiene 7.58Charge @ 16 .+-. 1% Styrene 7.33T.S.C. 5 Sulfole 120 0.06Raise temp to 160.degree. F. Butadiene 7.58 6 Glycidyl Methacrylate 0.38 7 Deionized Water 2.00Charge @ 22% .+-. 1 8 Styrene 7.33T.S.C. Sulfole 120 0.06 Butadiene 7.58 9 GMA 0.38 10 Deionized Water 2.00Charge @ 27% .+-. 1 Styrene 7.33T.S.C. Sulfole 120 0.06 11 Methacrylic Acid 0.75 Butadiene 7.58Charge @ 32% .+-. 1 Styrene 7.33T.S.C. 12 Sulfole 120 0.06 Butadiene 7.58 13 GMA 0.38 14 Deionized Water 2.00Charge @ 35% .+-. 1 Styrene 7.33T.S.C. 15 Sulfole 120 0.06 Butadiene 7.58 16 GMA 0.38 17 Deionized Water 2.00Charge @ 37% .+-. 1 18 Deionized Water 2.74 Potassium Persulfate 0.10 Deionized Water 3.62 19 Drew L-198 0.15 DEHA (85%) 0.20______________________________________PHYSICAL PROPERTIES Blowover Stripped% TSC 46.19 38.5pH 3.01 353S.T. 50.6 446B.V. 69.0 20% Turb. 58 57Prefloc 1.9%Filterability goodTotals: Core 8.21 parts Shell 91.75 parts Bd 45.48 parts Sty 51.48 parts GMA 1.52 Parts MAA .75 FA .75______________________________________

EXAMPLE 2

A. Preparation or core or seed copolymer

______________________________________Charge ChargeInstruction Order Material Parts______________________________________Initial charge Deionized water 89.25heat to 135.degree. F. Hampene Na 3 (40%) 0.05 1 Dowfax 2A1 (15%) 0.195 Monawet MB45 (45%) 2.25 Fumaric Acid 0.75 Potassium Persulfate 0.30React for 45 min.@ 2 Styrene 7.50135.degree. F. then charge______________________________________

B. Preparation of coverpolymer or shell copolymer

______________________________________Charge ChargeInstruction Order Material Parts______________________________________React 75 min. Styrene 7.2then charge 3 Sulfole 120 0.06 4 Butadiene 7.47Charge @ 1 h % .+-. 1 Styrene 7.2T.S.C. 5 Sulfole 120 0.06Raise temp to 160.degree. F. Butadiene 7.47 6 Glycidyl Methacrylate 0.75 7 Deionized Water 2.00Charge @ 22% .+-. 1 Styrene 7.2T.S.C. 8 Sulfole 120 0.06 Butadiene 7.47 9 GMA 0.75 10 Deionized Water 2.00Charge @ 27% .+-. 1 Styrene 7.2T.S.C. Sulfole 120 0.06 11 Methacrylic Acid 0.75 Butadiene 7.47Charge @ 32% .+-. 1 Styrene 7.2T.S.C. 12 Sulfole 120 0.06 Butadiene 7.47 13 GMA 0.75 14 Deionized Water 2.00Charge @ 35% .+-. 1 Styrene 7.2T.S.C. 15 Sulfole 120 0.06 Butadiene 7.47 16 GMA 0.75 17 Deionized Water 2.00Charge @ 37% .+-. 1 18 Deionized Water 2.74 Potassium Persulfate 0.10React to 47-49% T.S.C. then add post Deionized Water 3.62 19 Drew L-198 0.15 DEHA (85%) 0.20______________________________________PHYSICAL PROPERTIES Blowover Stripped% TSC 46.61 53.0pH 3.71 3.45S.T. 47.1 47.2B.V. 59 159% Turb. 54 51Prefloc 3.1%Filterability goodTotals: Core 8.25 parts Shell 91.75 parts Bd 44.82 parts Sty 50.70 parts GMA 3.00 Parts MAA .75 FA .75______________________________________

EXAMPLE 3

A. Preparation of core or seed copolymer

______________________________________Charge ChargeInstruction Order Material Parts______________________________________Initial charge Deionized water 89.25heat to 135.degree. F. Hampene Na3 (40%) 0.05 1 Dowfax 2A1 (15%) 0.195 Monawet MB45 (45%) 2.25 Fumaric Acid 1.50 Potassium Persulfate 0.30React for 45 min.@ 2 Styrene 7.50135.degree. F. then charge______________________________________

B. Preparation of over copolymer or shell copolymers:

______________________________________Charge ChargeInstruction Order Material Parts______________________________________React 75 min. Styrene 7.2then charge 3 Sulfole 120 0.06 4 Butadiene 7.47Charge @ 27% .+-. 1 Styrene 7.2T.S.C. 5 Sulfole 120 0.06Raise temp to 160.degree. F. Butadiene 7.47 6 Glycidyl Methacrylate 0.75 7 Deionized Water 2.00Charge @ 22% .+-. 1 8 Styrene 7.2T.S.C. Sulfole 120 0.06 Butadiene 7.47 9 GMA 0.75 10 Deionized Water 2.00Charge @ 27% .+-. 1 Styrene 7.2T.S.C. 11 Sulfole 120 0.06 Butadiene 7.47Charge @ 32% .+-. 1 Styrene 7.2T.S.C. 12 Sulfole 120 0.06 Butadiene 7.47 13 GMA 0.75 14 Deionized Water 2.00Charge @ 35% .+-. 1 Styrene 7.2T.S.C. 15 Sulfole 120 0.06 Butadiene 7.47 16 GMA 0.75 17 Deionized Water 2.00Charge @ 37% .+-. 1 18 Deionized Water 2.74T.S.C. Potassium Persulfate 0.10React to 47-49% T.S.C. then add post Deionized Water 3.62 19 Drew L-198 0.15 DEHA (85%) 0.20______________________________________PHYSICAL PROPERTIES Blowover Stripped% TSC 47.16 52.0pH 3.19 3.26S.T. 43.8 43.7B.V. 72.5 121% Turb. 53 55Prefloc 15.7%Filterability goodTotals: Core 9.00 parts Shell 91.02 parts Bd 44.82 parts Sty 50.70 parts GMA 3.00 parts FA 1.50______________________________________

EXAMPLE 4

A. Preparation of core of seed copolymer

______________________________________Charge ChargeInstruction Order Material Parts______________________________________Charge to reactor 1 Deionized water 73.419Set agitation to Itaconic Acid 0.50250 RPM, purge well Hampene Na3 (40%) 0.05 Potassium Persulfate 0.25 Dowfax 2A1 (15%) 0.14 Monawet MB45 (45%) 0.50 Di Sodium Phosphate 0.50Heat reactor to 135.degree. F., 2 Styrene 7.50then pull full vacuumand charge______________________________________

B. Preparation of over copolymer or shell copolymer

______________________________________Charge ChargeInstruction Order Material Parts______________________________________React 90 min., take Styrene 6.667TSC sample and charge 3 Sulfole 120 0.09Raise temp. to 170.degree. F. Butadiene 8.083 Deionized Water 5.328React 65 min. 4 Dowfax 2A1 (15%) 0.20Take sample for % Sodium Hydroxide 0.05T.S.C., then charge (50%) Styrene 6.667 Sulfole 120 0.09 5 Glycidyl Methacrylate 1.50 Butadiene 8.083 6 Deionized Water 4.426React 62 min. Dowfax 2A1 (15%) 0.10then take sample for Styrene 6.667% T.S.C. and charge 7 Sulfole 120 0.09 Butadiene 8.083 8 Deionized Water 2.566 Dowfax 2A1 (15%) 0.10React 65 min. then Styrene 6.667take sample for % 9 Sulfole 120 0.09T.S.C. and charge Methacrylic Acid 0.50 Butadiene 8.083 10 Deionized Water 4.71 Dowfax 2A1 (15%) 0.15React 66 min. then Styrene 6.667take sample for % 11 Sulfole 120 0.09T.S.C. and charge Glycidyl Methacrylate 1.50 Butadiene 8.083 12 Deionized Water 4.993 Dowfax 2A1 (15%) 0.20React 65 min. then Sulfole 120 0.09take sample for % 13 Butadiene 8.083T.S.C. and chargeReact 90 min., take 14 Deionized Water 4.74T.S.C sample and Potassium Persulfate 0.10charge Deionized Water 0.113React 2 hrs, then 15 Sodium Hydroxide 0.39charge and mix 15 (50%)min. Cool to room Dowfax 2A1 (15%) 0.35temp. and add DEHA Drew L-198 0.15filter and run B/Oprop. 16 Deionized Water 2.17 DEHA (85%) 0.20Rotovac 1 qt @ 150.degree.- 17 Deionized Water 0.575160.degree. F. Proxel GXL (25%) 0.05then cool and add postfilter and run strippedpropertiesBatch charged and followed to complete in 10.7 hours.______________________________________PHYSICAL PROPERTIES Blowover Stripped% TSC 43.14 42.96pH 8.48 8.38S.T. 47.6 47.6B.V. 18.5 20% Turb. 48 48Prefloc .24%Filterability very goodTotals: Core 8.00 parts Shell 92.00 parts 100.00 Butadiene 48.498 parts Styrene 47.502 parts Itaconic acid 0.50 parts Glycidyl Methacrylate 3.00 parts Methacrylic acid .50 parts 100.00______________________________________

For Examples 1 to 4 conversions of monomers to polymers were about 98 to 100%. After stripping, total solids were about 38 to 53%.

NOTES FOR EXAMPLES 1 to 4

Hampene Na3--Ethylenediaminetetraacetic acid-sodium salt, sequestrant or chelating agent. Dowfax 2A1--Na-dodecyldipheylacid-disulfonate. Monawet MB45--Di-isobutylsodiumsulfosuccinate. Sulfole 120--T-dodecyl mercaptan, Phillips Petroleum Co. Drew L-198--Defoamer, Drew Chemical Co. DEHA--Diethylhydroxylamine, Shortstop. PROXEL GXL--Fungicide/bactericide, ICI Americas (1-2-benzisothiazolin-3-one). Bd--Butadiene. Sty--Styrene. GMA--Glycidyl methacrylate. MAA--Methacrylic acid. FA--Fumaric acid. IA--Itaconic acid.

EXAMPLE 5

Aqueous slurries were prepared from, on a dry parts-by-weight basis:

______________________________________Kraft wood pulp 13.0Compounding ingredientsPulpex P, Grade A-DC 1.00polyethylene particlesNARVON F-3 clay 15.70Afton clay 36.60Dicalite (not clay) 18.00Glass fibers 1.50Antioxidant 0.1Water clarifier, KYMENE 0.0125Latexes 14.0Latex copolymer (various)

The slurries containing also a fungicide were flocculated with a cationic flocculant and then cast onto wire screens to remove the water to form sheets which were compressed, heated, and cooled to form felts or mats which were then tested.

The anionic core-shell copolymer binder latices used were the following copolymers (parts by weight of monomers);

______________________________________I. Control:45.5 Butadiene51.5 Styrene.5 Itaconic acid.5 Methacrylic acid3.0 AcrylamideII. Latex of the Invention:51.5 Styrene45.5 Butadiene.75 Fumaric acid.75 Methacrylic acid1.50 Glycidyl methacrylateIII. Latex of the Invention:50.3 Styrene44.45 Butadiene.75 Fumaric acid1.50 Methacrylic acid3.00 Glycidyl methacrylateIV. Latex of the Invention:50.7 Styrene44.8 Butadiene1.5 Fumaric acid3.0 Glycidyl methacrylateV. Latex of the Invention:51.5 Styrene45.5 Butadiene1.5 Fumaric acid1.5 Glycidyl methacrylate______________________________________

TESTS ON PAPER FELTS OR MATS

TABLE A______________________________________ Wt Flocculant Williams DrainLatex in Slurry Wt in Gms CSF Freeness TimeBinder Gms .degree.C. pH 1st 2nd CC Sec Sec______________________________________I 30.91 37.0 6.89 199 27 540 37 1.58II 36.36 39.2 7.23 179 33 550 28 1.68III 33.67 38.4 7.22 205 42 580 28 1.53IV 26.92 38.5 7.17 229 30 630 18 1.45V 30.46 39.9 7.00 163 30 520 32 1.75______________________________________ Hot HotLatex Sheet Thickness Density Tensile TensileBinder Wt Inches Lbs/Ft.sup.3 Lbs Elong %______________________________________I 22.94 0279 48.67 13.36 2.37II 24.82 0299 49.29 16.47 2.97III 24.91 0289 50.97 17.81 3.44IV 25.07 0271 50.17 16.73 3.12V 22.34 0281 48.51 13.38 2.60______________________________________ Cold Cold HeatLatex Tensile Tensile Split Strength Lb AgingBinder Lbs Elong % Max Mean Sec______________________________________I 21.06 2.42 35 45 109II 25.46 3.87 41 50 102III 30.96 4.49 50 65 76IV 23.72 3.60 41 53 300V 26.20 3.86 49 41 74______________________________________

Other tests on felts using polymeric latices made with glycidyl methacrylate on a co-monomer in the shell of the core-shell copolymer showed heat aging time of 276, 310, 492 and 504 seconds, respectively. These results show unusually high heat aging for latices containing glycidyl methacrylate as compared to a control latex. Also the latices containing glycidyl methacrylate gave felts with higher cold tensile strengths than the control.

Claims

1. A paper felt or mat comprising about, on a dry-weight basis, a predominant amount of finely divided clay or talc particles, minor amounts of polyethylene particles, glass fibers, antioxidants and biocides, from 5 to 20 parts of kraft wood pulp and from 8 to 16 parts of a core-shell copolymer of:

A. A core of copolymer made from about 6 to 8 parts of at least one vinyl aryl monomer having from 8 to 10 carbon atoms and from about 0.5 to about 8 parts of at least one dicarboxylic acid monomer selected from the group consisting of fumaric acid, itaconic acid, or a combination of fumaric acid and itaconic acid; and

B. A shell of a copolymer made from about 40 to 60 parts of at least one vinyl aryl monomer having from 8 to 10 carbon atoms, from 60 to 40 parts of at least one conjugated diene monomer having from 4 to 6 carbon atoms, from 1.5 to 5.0 parts of at least one glycidyl monomer selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, or a combination of the glycidyl acrylate and glycidyl methacrylate, and from 0 to 2.0 parts of at least one monocarboxylic acid monomer selected from the group consisting of acrylic acid, methacrylic acid, or a combination of acrylic acid and methacrylic acid, wherein the core copolymer comprises from about 7.5 to 10.5 parts and where the shell copolymer comprises from about 92.5 to 89.5 parts of the core-shell copolymer, all parts of monomers in the core-shell copolymer adding up to about 100 parts.

2. A paper felt or mat according to claim 1 wherein the core-shell copolymer, the vinyl aryl monomer is selected from the group consisting of styrene, alphamethyl styrene, paramethyl styrene, methyl vinyl toluene, p-vinyl toluene and 3-ethyl styrene and the conjugated diene monomer is selected from the group consisting of 1,3-butadiene, isoprene, piperylene, 2,3-dimethyl-1,30butadiene. pentadiene and hexadine.

3. A paper felt or mat according to claim 2 wherein the core-shell copolymer, the vinyl aryl monomer is styrene, the conjugated diene monomer is 1,3-butadiene the dicarboxylic acid monomer is fumaric acid, the monocarboxylic acid monomer is methacrylic acid and the glycidyl monomer is glycidyl methacrylate.