# US 8,771,470 B2 · Method of preparing a treated article and treated article formed therefrom

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 8,771,470 B2
- Document ID: US8771470B2
- Status: Granted
- Kind: B2
- Application number: 13/351,286
- Filed: 2012-01-17
- Published: 2013-07-18
- Granted: 2014-07-08
- Earliest claimed: 2012-01-17
- Assignees: Agc Chemicals Americas, Inc.
- Applicants: Michael J. Sanchez; James L. Scott
- Inventors: Michael J. Sanchez; James L. Scott
- Web page: https://patentgrep.com/patent/US8771470B2

## CPC

- D21H 17/33: Synthetic macromolecular compounds
- B32B 27/10: of paper or cardboard
- D21H 11/04: Kraft or sulfate pulp
- D21H 17/34: obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H 19/20: comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H 21/16: Sizing or water-repelling agents
- D21H 23/02: characterised by the manner in which substances are added
- D21H 23/04: Addition to the pulp; After-treatment of added substances in the pulp
- D21H 23/24: during paper manufacture
- D21H 23/72: Plural serial stages only
- D21H 27/00: Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H 27/10: Packing paper (packaging materials of special type or form B65D65/38)
- B65D 65/42: Applications of coated or impregnated materials
- D21H: PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B65D: CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES

## Abstract

A method of preparing a treated article comprises the step of providing a slurry comprising fibers. The method further comprises the step of combining the slurry and a first fluorinated composition to form a mixture. In addition, the method comprises the step of forming at least one sheet from the mixture. Finally, the method comprises the step of applying a second fluorinated composition on at least one surface of the at least one sheet to prepare the treated article.

## Claims

### Claim 1

A method of preparing a treated article, said method comprising the steps of:
providing a slurry comprising fibers;
combining the slurry and a first fluorinated composition to form a mixture;
forming at least one sheet from the mixture; and
applying a second fluorinated composition on at least one surface of the at least one sheet to prepare the treated article;
wherein the first fluorinated composition is further defined as an anionic fluorinated composition and wherein the second fluorinated composition is further defined as a cationic fluorinated composition.

### Claim 2 (depends on 1)

A method as set forth in claim 1 wherein the fibers are further defined as cellulosic fibers and the treated article is further defined as a treated cellulosic article.

### Claim 3 (depends on 1)

A method as set forth in claim 1 wherein the anionic fluorinated composition comprises a first fluorinated copolymer comprising from 40 to 98 mass % of polymerized units (a′) based on monomer (a), from 1 to 50 mass % of polymerized units (b′) based on monomer (b) and from 1 to 10 mass % of polymerized units (c′) based on monomer (c);
wherein monomer (a) comprises a compound represented by (Z—Y)aX, wherein Z is a C1-6 perfluoroalkyl group or a monovalent group represented by CbF2b+1O(CFWCF2O)cCFK—, wherein b is an integer of from 1 to 6, c is an integer of from 1 to 4, and each of W and K which are independent of each other, is a fluorine atom or a trifluoromethyl group, Y is a single bond or a bivalent organic group containing no fluorine atom, a is 1 or 2, provided that when a is 1, X is —CR═CH2, —COOCR═CH2, —OCOCR═CH2, —OCH2-φ-CR═CH2 or —OCH═CH2, and when a is 2, X is —CH[—(CH2)dCR═CH2]—, —CH[—(CH2)dCOOCR═CH2]—, —CH[—CH2)dOCOCR═CH2]— or —OCOCH═CHCOO—, R is a hydrogen atom, a methyl group or a halogen atom, φ is a phenylene group, d is an integer of from 0 to 4, and when a is 2, two (Z—Y) present in one molecule may be the same or different from each other;
wherein monomer (b) comprises a compound represented by CH2═CR1-G-(R2O)c—R3, wherein R1 is a hydrogen atom or a methyl group, R2 is a C2-4 alkylene group, or a C2-3 alkylene group having some or all of its hydrogen atoms substituted by hydroxyl groups, e is an integer of from 1 to 10, G is —COO(CH2)f— or —COO(CH2)g—NHCOO—, wherein f is an integer of from 0 to 4, and g is an integer of from 1 to 4, and R3 is a hydrogen atom, a methyl group, an acryloyl group, a methacryloyl group or an allyl group; and
wherein monomer (c) comprises a compound represented by CH2═C(COOH)-Q-COOH, wherein Q is a C1-4 alkylene group, or a C2-3 alkylene group having some or all of its hydrogen atoms substituted by hydroxyl groups, and in the monomer (c), some or all of the carboxyl groups may form at least one salt selected from an ammonium salt and an organic amine salt.

### Claim 4 (depends on 3)

A method as set forth in claim 3 wherein the anionic fluorinated composition comprises the first fluorinated copolymer in an amount of from 0.01 to 1.50 percent by weight based on the total dry weight of the fibers.

### Claim 5 (depends on 1)

A method as set forth in claim 1 wherein the anionic fluorinated composition comprises a second fluorinated copolymer comprising repeating units derived from:
(a) a fluorine-containing monomer having a fluoroalkyl group represented by the general formula:
CH2═C(—X′)—C(═O)—Y′—Z′—Rf
wherein X′ represents a hydrogen atom, a linear or branched C1 to C21 alkyl group, a halogen atom, a CFX1X2 group wherein X1 and X2 are a hydrogen atom, a halogen atom, a cyano group, a linear or branched C1-C21 fluoroalkyl group, a substituted or non-substituted benzyl group, or a substituted or non-substituted phenyl group;
Y′ is —O— or —NH—;
Z′ is a C1-C10 aliphatic group, a C6-C10 aromatic or cyclic aliphatic group, a —CH2CH2N(R4)SO2— group wherein R4 is a C1-C4 alkyl group, a —CH2CH(OZ1)CH2— group wherein Z1 is a hydrogen atom or an acetyl group, a —(CH2)h—SO2—(CH2)i— group or a —(CH2)h—S—(CH2)i— group wherein h is 1-10 and i is 0-10; and
Rf is a C1-C6 linear or branched fluoroalkyl group;
(b) a hydrophilic monomer, and
(c) a monomer having an anion-donating group,
wherein a weight average molecular weight of the second fluorinated copolymer is 100,000 or more.

### Claim 6 (depends on 5)

A method as set forth in claim 5 wherein the anionic fluorinated composition comprises the second fluorinated copolymer in an amount of from 0.01 to 1.50 percent by weight based on the total dry weight of the fibers.

### Claim 7 (depends on 1)

A method as set forth in claim 1 wherein the cationic fluorinated composition comprises a third fluorinated copolymer comprising:
(1) a monomer unit based on a (meth)acrylate having a polyfluoroalkyl group;
(2) a monomer unit based on an alkyl(meth)acrylate having a C16-C12 alkyl group;
(3) a monomer unit based on an alkyl(meth)acrylate having a C1-C22 alkyl group; and
(4) a monomer unit based on at least one compound selected from the group consisting of 2-isocyanate ethyl methacrylate, 1,3,3-trimethyl-4 ocyanate cyclohexylmethylamidoxyethyl methacrylate of general formula 1 and 1,3,3-trimethyl-4-isocyanate cyclohexylmethylamidoxyethyl acrylate of general formula 2, the isocyanate group of which is blocked;
wherein general formula 1 is
and
wherein general formula 2 is

### Claim 8 (depends on 7)

A method as set forth in claim 7 wherein the cationic fluorinated composition comprises the third fluorinated copolymer in an amount of from 0.01 to 1.50 percent by weight based on the total weight of the cationic fluorinated composition.

### Claim 9 (depends on 1)

A method as set forth in claim 1 wherein the cationic fluorinated composition comprises a fourth fluorinated copolymer comprising 60 to 98 mass % of polymerized units (d)′ based on monomer (d), from 1 to 20 mass % of polymerized units (e)′ based on monomer (e) and from 1 to 30 mass % of polymerized units (f)′ based on monomer (f);
wherein monomer (d) comprises a compound represented by (Z″—Y″)jX″,
wherein Z″ is a C1-6 perfluoroalkyl group or a group represented by CkF2k+1O(CFW′CF2O)lCFK′—, wherein k is an integer of from 1 to 6, l is an integer of from 1 to 4, and each of W′ and K′ is independently a fluorine atom or —CF3, Y″ is a bivalent organic group or a single bond, j is 1 or 2, and X″ is a polymerizable unsaturated group provided that when j is 1, X″ is —CR5═CH2, —COOCR5═CH2, —OCOCR5═CH2, —OCH2-φ-CR5═CH2 or —OCH═CH2, and when j is 2, X″ is ═CH(CH2)mCR5═CH2, ═CH(CH2)mCOOCR5═CH2, ═CH(CH2)mOCOCR5═CH2 or —OCOCH═CHCOO—, wherein R5 is a hydrogen atom, a methyl group or a halogen atom, φ is a phenylene group, and m is an integer of from 0 to 4;
wherein monomer (e) comprises a compound represented by CH2═CR6-G′-(R7O)n—R8,
wherein R6 is a hydrogen atom or a methyl group, R7 is a C2-4 alkylene group or an otherwise C2-3 alkylene group in which some or all of the hydrogen atoms have been replaced by hydroxyl groups, n is an integer of from 1 to 50, G′ is —COO(CH2)o— or —COO(CH2)s—NHCOO—, wherein o is an integer of from 0 to 4, and s is an integer of from 1 to 4, and R8 is at least one of an acryloyl group and a methacryloyl group; and
wherein monomer (f) comprises a compound represented by CH2═CR9-M-Q′—NR10R11 or CH2═CR9-M-Q′-N(O)R10R11, wherein R9 is a hydrogen atom or a methyl group, M is —COO— or —CONH—, Q′ is a C2-4 alkylene group or an otherwise C2-3 alkylene group in which some or all of the hydrogen atoms have been replaced by hydroxyl groups, and each of R10 and R11 comprises a benzyl group, a C1-8 alkyl group or an otherwise C2-3 alkylene group in which some of the hydrogen atoms have been replaced by hydroxyl groups, or R10 and R11 may form a morpholino group, a piperidino group or a pyrrolidinyl group, together with a nitrogen atom.

### Claim 10 (depends on 9)

A method as set forth in claim 9 wherein the cationic fluorinated composition comprises the fourth fluorinated copolymer in an amount of from 0.01 to 1.50 percent by weight based on the total weight of the cationic fluorinated composition.

### Claim 11 (depends on 1)

A method as set forth in claim 1 wherein the first fluorinated composition further comprises water and a water-soluble solvent selected from the group of propylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glyocol monomethyl ether, dipropylene glycol monoether ether, tripropylene glycol monomethyl ether, and combinations thereof.

### Claim 12 (depends on 1)

A method as set forth in claim 1 wherein the second fluorinated composition further comprises water and a water-soluble solvent selected from the group of propylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glyocol monomethyl ether, dipropylene glycol monoether ether, tripropylene glycol monomethyl ether, and combinations thereof.

### Claim 13 (depends on 1)

A method as set forth in claim 1 wherein the first fluorinated composition and the second fluorinated composition each independently further comprise a starch.

### Claim 14 (depends on 1)

A method as set forth in claim 1 wherein the step of applying the second fluorinated composition on at least one surface of the at least one sheet comprises applying the second fluorinated composition by spraying, brushing, padding, size press coating, metering size press coating, film press coating, gravure coating, flexo coating, roller coating, rotor dampening, foaming, gate roll coating, bill blade coating, bar coating, intaglio coating, reverse roll coating, skid roll coating, transfer (offset) roll coating, knife coating, knife-over-roll coating, J-coating, air knife coating, curtain coating, and combinations thereof.

### Claim 15 (depends on 1)

A method as set forth in claim 1 further comprising the step of refining the fibers by subjecting the fibers to a shear force.

### Claim 16 (depends on 1)

A method as set forth in claim 1 further comprising the step of drying the sheet prior to the step of applying the second fluorinated composition on at least one surface of the sheet.

### Claim 17 (depends on 1)

A method as set forth in claim 1 wherein the step of applying the second fluorinated composition comprises applying the second fluorinated composition on all major surfaces of the at least one sheet.

### Claim 18 (depends on 1)

A method as set forth in claim 1 further comprising the step of drying the sheet after the step of applying the second fluorinated composition on at least one surface of the sheet.

### Claim 19

A method of preparing a treated cellulosic article, said method comprising the steps of:
providing a slurry comprising cellulosic fibers;
combining the slurry and an anionic fluorinated composition to form a mixture;
forming at least one sheet from the mixture; and
applying a cationic fluorinated composition on at least one surface of the at least one sheet to prepare the treated cellulosic article.

### Claim 20

A method of preparing a treated article, said method comprising the steps of:
providing a slurry comprising fibers;
combining the slurry and a first fluorinated composition to form a mixture;
forming at least one sheet from the mixture; and
applying a second fluorinated composition on at least one surface of the at least one sheet to prepare the treated article;
wherein the first fluorinated composition is further defined as an anionic fluorinated composition comprising from 0.1 to 0.7 wt. % of a first fluorinated copolymer, and wherein the second fluorinated composition is further defined as a cationic fluorinated composition comprising from 0.1 to 0.7 wt. % of a second fluorinated copolymer.

### Claim 21 (depends on 20)

A treated article formed in accordance with the method of claim 20.

### Claim 22 (depends on 20)

A treated sheet of paper formed in accordance with the method of claim 20.