JP2020056023A - Water-resistant oil-resistant composition, article and water-resistant oil-resistant paper - Google Patents

Abstract

To provide a water-resistant oil-resistant composition capable of imparting excellent oil resistance to a base material and excellent in workability during use, to provide an article excellent in oil resistance and to provide a water-resistant oil-resistant paper.SOLUTION: The water-resistant oil-resistant composition includes: a polymer A containing 60 to 98 mass% of a unit a, 1 to 20 mass% of a unit b and 1 to 30 mass% of a unit c and having an acrylate unit in a ratio of 0 mol% to less than 40 mol% based on the total units; and a polymer B containing 50 to 98 mass% of a unit a, 0 to 21 mass% of a unit b and 2 to 30 mass% of a unit c and having an acrylate unit in a ratio of 40 to 80 mol% based on the total units. A unit a: a unit based on a monomer having 1-6C perfluoroalkyl group; a unit b: a unit based on a monomer having an oxyalkylene group; and a unit c: a unit based on a monomer having an amino group; and an acrylate unit: a unit based on an acrylate.SELECTED DRAWING: None

Description

  The present invention relates to a water and oil resistant composition, an article, and a water and oil resistant paper.

  BACKGROUND ART Water- and oil-resistant compositions which impart water resistance and oil resistance to a substrate such as paper are known (Patent Documents 1 to 3 and the like). Treating pulp or paper with a water and oil resistant composition results in a water and oil resistant paper. Examples of a method of treating pulp or paper with the water and oil resistant composition include a method of applying or impregnating the paper with the water and oil resistant composition (external addition), and a method of making a pulp slurry containing the water and oil resistant composition. (Internal addition).

Patent Document 1 describes a water and oil resistant composition in which a fluorinated copolymer is dispersed in an aqueous medium. The fluorine-containing copolymer of Patent Document 1 has 60 to 98% by mass of units based on a monomer having a perfluoroalkyl group having 6 or less carbon atoms, and 1 to 20% by mass of units based on a monomer having an oxyalkylene group. % And from 1 to 30% by weight of units based on monomers having dialkylamino groups.
Patent Document 2 describes a composition containing a fluorinated copolymer. The fluorine-containing copolymer of Patent Document 2 has a unit based on a monomer having a fluoroalkyl group having 1 to 6 carbon atoms, a unit based on a monomer having an amino group, and a unit based on pyrrolidone.
Patent Document 3 describes a method for preparing a treated article. In the method of Patent Document 3, a mixture of a slurry containing fibers and a first fluorinated composition is produced, at least one sheet is produced from the mixture, and at least one surface of the sheet is coated with a second fluorinated composition.

International Publication No. 2005/090423 International Publication No. 2011/021619 JP-T-2015-507103

However, a water and oil resistant paper obtained by treating pulp or paper with the water and oil resistant composition of Patent Document 1 may have insufficient oil resistance. For example, when the water and oil resistant composition of Patent Document 1 is internally added to a high pH pulp slurry, the obtained oil and water resistant paper has insufficient oil resistance.
The composition described in Patent Literature 2 tends to foam during mixing, dilution, and the like, which may hinder continuous operation. In addition, spots due to foaming may occur. Thus, the composition described in Patent Document 2 has insufficient workability at the time of use.
Patent Literature 3 does not discuss at all about compatibility between workability at the time of using a fluorinated composition and oil resistance imparted to a substrate.

  The present invention provides a water and oil resistant composition which can impart excellent oil resistance to a base material and has excellent workability during use, an article having excellent oil resistance, and a water and oil resistant paper.

The present invention has the following aspects.
[1] 60 to 98% by mass of the unit based on the monomer represented by the following formula 1 and 1 to 20% by mass of the unit based on the monomer represented by the following formula 2 and represented by the following formula 3 1 to 20% by mass of a unit based on one or both of the monomer and the monomer represented by the following formula 4, and the proportion of the unit based on the acrylate is 0 mol% or more based on all units. Less than 40 mol% of polymer A, 50 to 98% by mass of units based on the monomer represented by the following formula 1, and 0 to 21% by mass of units based on the monomer represented by the following formula 2 And 2 to 29% by mass of the unit based on one or both of the monomer represented by the following formula 3 and the monomer represented by the following formula 4, and the proportion of the unit based on the acrylate is totally Polymer B in an amount of 40 to 80 mol% based on units;
A water and oil resistant composition comprising:
^{_{CH 2 = C (R 1)}} C (O) O-Y- (CF 2) n F Formula 1
Here, R ¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom, Y is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 6.
^{_{CH 2 = C (R 2)}} -C (O) O- (R 3 O) q -R 4 Formula 2
However, R ² is a hydrogen atom or a methyl group, R ³ is an alkylene group having 2 to 4 carbon atoms, q is an integer of 1 to 140, and when q is an integer of 2 or more,- (R 3 ^O) - can be identical to each other, or different, R ⁴ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (meth) acryloyl group or a glycidyl group.
CH ₂ ＣC (R ⁵ ) -MQ-NR ⁶ R ⁷ Formula 3
CH ₂ ＣC (R ⁵ ) -MQN (O) R ⁶ R ⁷ Formula 4
However, in Formulas 3 and 4, R ⁵ is a hydrogen atom or a methyl group,
M is -C (O) O- or -C (O) NH-,
Q is an alkylene group having 2 to 4 carbon atoms or an alkylene group having 2 to 3 carbon atoms in which part or all of hydrogen atoms are substituted with a hydroxyl group;
R ⁶ and R ⁷ are each independently a benzyl group, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 2 to 3 carbon atoms in which some or all of the hydrogen atoms have been substituted with hydroxyl groups.
[2] The water- and oil-resistant composition according to [1], wherein the unit based on the monomer represented by the formula 1 in the polymer A is a unit based on the monomer represented by the formula 11.
^{_{CH 2 = C (R 11)}} C (O) O-Y- (CF 2) n F Formula 11
However,
R ¹¹ is an alkyl group having 1 to 3 carbon atoms or a halogen atom,
Y is an alkylene group having 1 to 10 carbon atoms,
n is an integer of 1 to 6.
[3] The water- and oil-resistant composition according to [1] or [2], wherein the proportion of units based on acrylate in the polymer A is 10 mol% or less based on all units.
[4] The water and oil resistant composition according to any one of [1] to [3], wherein the mass ratio of the polymer A to the polymer B is 1/4 to 4/1.
[5] The water- and oil-resistant composition according to any one of [1] to [4], wherein the proportion of units based on acrylate in the polymer B is 42 to 60 mol% based on all units.
[6] Any of [1] to [5], wherein the unit based on the monomer represented by the formula 1 contained in the polymer B is a unit based on the monomer represented by the following formula 5 A water- and oil-resistant composition.
_{CH 2 = CHC (O) O} -Y- (CF 2) n F Formula 5
Here, Y is an alkylene group having 1 to 10 carbon atoms,
n is an integer of 1 to 6.
[7] The water- and oil-resistant composition according to [6], wherein the proportion of the unit based on the compound represented by the formula 5 in the polymer B is 40 to 80 mol% based on all units.
[8] The water- and oil-resistant composition according to any one of [1] to [7], wherein the polymer B further contains a unit based on N-vinylpyrrolidone.
[9] The water and oil resistant composition according to any one of [1] to [8], wherein the defoaming parameter measured by the following defoaming test is 500 mL or less.
Defoaming test: a measuring cylinder having an inner diameter of 65 mm, a temperature control system for maintaining a constant temperature of an aqueous dispersion test liquid obtained by diluting the water and oil resistant composition with water so that the solid content concentration becomes 0.1% by mass, A nozzle having an inner diameter of 9 mm disposed so that the tip is downward at a height of 420 mm from the bottom of the graduated cylinder, and the water dispersion test liquid is withdrawn from the vicinity of the bottom of the graduated cylinder and discharged from the nozzle. The following steps 1 to 7 are sequentially performed using a continuous foam tester having a circulation system for circulating the aqueous dispersion test liquid at a flow rate of 11.5 L / min. Test in which (mL) is measured as the defoaming parameter.
Step 1: The graduated cylinder containing 650 mL of the aqueous dispersion test solution is allowed to stand by the temperature control system until the temperature of the aqueous dispersion test solution reaches 18 ° C. Step 2: Circulation by the circulation system is performed for 30 seconds. Step 3: stopping the circulation by the circulation system for 30 seconds Step 4: performing the circulation by the circulation system for 120 seconds Step 5: stopping the circulation by the circulation system for 60 seconds Step 6: circulation by the circulation system Step 7: Stopping the circulation by the circulation system and measuring the foam volume (mL) on the liquid surface of the aqueous dispersion test liquid 60 seconds after the stop [10] For pulp or paper , [1] to [9].
[11] An article treated with the water / oil resistant composition according to any one of [1] to [10].
[12] A water and oil resistant paper obtained by treating pulp or paper with the water and oil resistant composition of any one of [1] to [10].

The water and oil resistant composition of the present invention can impart excellent oil resistance to a substrate, and is excellent in workability during use.
The article of the present invention has excellent oil resistance.
The water and oil resistant paper of the present invention has excellent oil resistance.

In the present specification, the compound represented by Formula 1 is referred to as Compound 1. The same applies to compounds represented by other formulas.
The meanings of the following terms in the present specification are as follows.
“Monomer” means a compound having a polymerization-reactive carbon-carbon double bond.
The “unit based on a monomer” is a general term for an atomic group formed directly by polymerization of one monomer molecule and an atomic group obtained by chemically converting a part of the atomic group.
“(Meth) acrylate” is a generic term for acrylate and methacrylate.
“(Meth) acryloyl group” is a general term for an acryloyl group and a methacryloyl group.
The “unit ratio” is a value determined from NMR (nuclear magnetic resonance) analysis and elemental analysis. It may be calculated based on the charged amount of the monomer during the production of the polymer.
"Mass average molecular weight" is a molecular weight in terms of polymethyl methacrylate obtained by measurement by gel permeation chromatography using a calibration curve prepared using a standard polymethyl methacrylate sample.
“Glass transition temperature” is a midpoint glass transition temperature measured by a differential scanning calorimetry (DSC) method according to JIS K 7121-1987 (corresponding international standard ISO 3146).
The “solid content concentration” is defined as solid mass / sample mass × 100, where the mass of the sample before heating is the mass of the sample, and the mass after drying the sample with a convection dryer at 120 ° C. for 4 hours is the mass of the solid content. The value to be calculated.
The “average particle size” is a value calculated by a cumulant method analysis from an autocorrelation function obtained by a dynamic light scattering method for a sample obtained by diluting a water and oil resistant composition to a solid concentration of 5% by mass with water.
"-" Indicating a numerical range means that the numerical values described before and after that are included as the lower limit and the upper limit.

<Water and oil resistant composition>
The water and oil resistant composition of the present invention contains a specific polymer A and a specific polymer B.
The water and oil resistant composition may further comprise an aqueous medium.
The water and oil proofing agent composition of the present invention may further contain components other than the polymer A, the polymer B and the aqueous medium, if necessary, as long as the effects of the present invention are not impaired.

(Polymer A)
The polymer A includes a unit based on the monomer a described below (hereinafter, referred to as “unit a”), a unit based on the monomer b described below (hereinafter, referred to as “unit b”), and a polymer A described below. And a unit based on one or both of the monomer c1 and the monomer c2 described below (hereinafter, referred to as “unit c”) in a specific ratio.
The polymer A may contain a unit based on acrylate (hereinafter referred to as “acrylate unit”) as needed.

Monomer a is compound 1.
^{_{CH 2 = C (R 1)}} C (O) O-Y- (CF 2) n F Formula 1
Here, R ¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom, Y is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 6.
The monomer a in the polymer A is preferably a compound 11.
^{_{CH 2 = C (R 11)}} C (O) O-Y- (CF 2) n F Formula 11
Here, R ¹¹ is an alkyl group having 1 to 3 carbon atoms or a halogen atom, and Y and n are the same as described above.
When the polymer A contains the unit a, water resistance and oil resistance can be imparted to the article and the water and oil resistant paper obtained by treating the substrate with the water and oil resistant composition.

R ¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a halogen atom. When R ¹ is a hydrogen atom, the unit a is an acrylate unit.
As the halogen atom, a fluorine atom and a chlorine atom are preferable.
As R ¹ in the polymer A, an alkyl group having 1 to 3 carbon atoms or a halogen atom is preferable, a methyl group or a chlorine atom is more preferable, the stability of the water and oil resistant composition, the water resistance of the article and the water and oil resistant paper, and A methyl group is more preferred from the viewpoint of excellent oil resistance.

Y is an alkylene group having 1 to 10 carbon atoms. Y may be linear or branched.
Specific examples of Y include, for example, the following groups.
-CH ₂ -,
—CH ₂ CH ₂ —,
— (CH ₂ ) ₃ —,
—CH ₂ CH ₂ CH (CH ₃ ) —,
-CH = _CH-CH 2 -.

  n is an integer of 1 to 6. N is preferably from 2 to 6, more preferably from 4 to 6, and even more preferably 6, from the viewpoint that the article and the water and oil resistant paper are more excellent in water resistance and oil resistance.

Specific examples of the monomer a include the following compounds.
_{CH 2 = C (CH 3)} C (O) OCH 2 CH 2 (CF 2) 6 F,
CH ₂ ＣＨCHC (O) OCH ₂ CH ₂ (CF ₂ ) ₆ F,
_{CH 2 = C (Cl) C} (O) OCH 2 CH 2 (CF 2) 6 F,
_{CH 2 = C (CH 3)} C (O) OCH 2 CH 2 (CF 2) 4 F,
CH ₂ ＣＨCHC (O) OCH ₂ CH ₂ (CF ₂ ) ₄ F,
_{CH 2 = C (Cl) C} (O) OCH 2 CH 2 (CF 2) 4 F.
As the monomer a, one type may be used alone, or two or more types may be used in combination.
As the monomer a in the polymer (A), CH ₂ ＣC (CH ₃ ) C (O) OCH ₂ CH ₂ (CF ₂ ) ₆ F, CH ₂ ＣC (Cl) C (O) OCH ₂ CH _{2 (CF 2) 6 F,} CH 2 = C (CH 3) C (O) OCH 2 CH 2 (CF 2) 4 F and _{CH 2 = C (Cl) C} (O) OCH 2 CH 2 (CF 2) ₄ F is preferable.

Monomer b is compound 2.
^{_{CH 2 = C (R 2)}} -C (O) O- (R 3 O) q -R 4 Formula 2
However, R ² is a hydrogen atom or a methyl group, R ³ is an alkylene group having 2 to 4 carbon atoms, q is an integer of 1 to 140, and when q is an integer of 2 or more,- (R 3 ^O) - can be identical to each other, or different, R ⁴ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (meth) acryloyl group or a glycidyl group.
When the polymer A contains the unit b, the dispersibility of the polymer A contained in the water and oil resistant composition is further improved, and the stability of the water and oil resistant composition is further improved.

R ² is a hydrogen atom or a methyl group. When R ² is a hydrogen atom, unit b is an acrylate unit.
R ³ is an alkylene group having 2 to 4 carbon atoms. One molecule of compound 2 may contain two or more oxyalkylene groups having different numbers of carbon atoms. The arrangement of two or more oxyalkylene groups having different carbon numbers may be block-like or random.
q is an integer of 1 to 140, preferably 1 to 50, more preferably 1 to 9, and still more preferably 1 to 4.
R ⁴ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a (meth) acryloyl group or a glycidyl group. R ⁴ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

Specific examples of the monomer b include the following compounds.
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Acrylate, methoxypolyethylene glycol (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, acryloyl polyethylene glycol methacrylate, poly (oxypropylene-oxybutylene) Glycol (meth) acrylate, poly (oxyethylene-oxypropylene) glycol (meth) acrylate, poly (oxy) Ethylene-oxybutylene) glycol (meth) acrylate, poly (oxyethylene-oxytetramethylene) (meth) acrylate, poly (oxypropylene-oxybutylene) glycol di (meth) acrylate, poly (oxyethylene-oxypropylene) glycol di (Meth) acrylate, poly (oxyethylene-oxybutylene) glycol di (meth) acrylate, and the like.

As the monomer b, triethylene glycol di (meth) acrylate or 2-ethylene glycol is preferred from the viewpoint of achieving both the water dispersibility and stability of the water and oil resistant composition and the water and oil resistance of the article and the water and oil resistant paper. Hydroxyethyl (meth) acrylate is preferred.
As the monomer b, one type may be used alone, or two or more types may be used in combination.

Monomer c1 is compound 3, and monomer c2 is compound 4.
CH ₂ ＣC (R ⁵ ) -MQ-NR ⁶ R ⁷ Formula 3
CH ₂ ＣC (R ⁵ ) -MQN (O) R ⁶ R ⁷ Formula 4
However, in Formulas 3 and 4, R ⁵ is a hydrogen atom or a methyl group, M is —C (O) O— or —C (O) NH—, and Q is an alkylene group having 2 to 4 carbon atoms or R ⁶ and R ⁷ are each independently a benzyl group, an alkyl group having 1 to 8 carbon atoms, or a hydrogen atom, in which a part or all of the hydrogen atoms are substituted with a hydroxyl group. A part or the whole is an alkyl group having 2 to 3 carbon atoms substituted with a hydroxyl group.
When the polymer A contains the unit c, the water dispersion stability of the polymer A contained in the water and oil resistant composition is further improved, and the affinity with pulp is improved.

In Formulas 3 and 4, M is preferably -C (O) O-. Q is preferably an alkylene group having 2 to 4 carbon atoms. Preferably, R ⁶ and R ⁷ are each independently an alkyl group having 1 to 8 carbon atoms.
In the formulas 3 and 4, when R ⁵ is a hydrogen atom and M is —C (O) O—, the compounds 3 and 4 are acrylates, and the unit c contained in the polymer A is an acrylate unit. Is included.

As the monomer c1, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) ) Acrylate, N, N-diisopropylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpepyridine are preferred, and N, N- Dimethylaminoethyl methacrylate and N, N-diethylaminoethyl (meth) acrylate are more preferred.
As the monomer c1, one type may be used alone, or two or more types may be used in combination.
As the monomer c2, N, N-dimethylaminooxideethyl (meth) acrylate and N, N-diethylaminooxideethyl (meth) acrylate are preferable.
As the monomer c2, one type may be used alone, or two or more types may be used in combination.

The polymer A is a unit (hereinafter, referred to as “monomer d”) based on a monomer other than the monomer a, the monomer b, the monomer c1, and the monomer c2 as necessary (hereinafter, referred to as “monomer d”). , "Unit d") may be further contained.
Examples of the monomer d include olefins (eg, ethylene), fluorine-containing monomers (eg, vinylidene fluoride), and vinyl esters (eg, vinyl acetate, vinyl propionate, vinyl isobutanoate, vinyl isodecanoate, and vinyl stearate). , Vinyl ether (cetyl vinyl ether, dodecyl vinyl ether, isobutyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, etc.), aromatic vinyl (styrene, α-methylstyrene, p-methylstyrene, etc.), vinyl alkyl ketone, diene (butadiene, isoprene) , Chloroprene, etc.), (meth) acrylic acid, (meth) acrylate (benzyl (meth) acrylate, (meth) acrylate having polysiloxane, etc.), allyl ester (allyl acetate, etc.), N-vinylpyrrolidone, N Vinylacetamide, N- vinyl carbazole, an imido group-containing monomer (maleimide, N- methylmaleimide, etc.).
As the monomer d, one type may be used alone, or two or more types may be used in combination.

The ratio of each unit of the polymer A is as follows.
The proportion of the acrylate unit is from 0 mol% to less than 40 mol%, preferably from 0 mol% to 20 mol%, more preferably from 0 mol% to 10 mol%, of the total unit 100 mol% in the polymer A. More preferably does not contain an acrylate unit. Since the ratio of the acrylate unit in the polymer A is 0 mol% or more, the oil resistance of the article and the water- and oil-resistant paper is improved. Since the proportion of the acrylate unit in the polymer A is less than 40 mol%, foaming of the water and oil resistant composition is reduced, and workability at the time of using the water and oil resistant composition is improved.
The content ratio of the unit based on the compound in which R ¹ of the formula (1) in the polymer A is a hydrogen atom is preferably less than 40 mol%, preferably 0 to 20 mol%, of 100 mol% of all units in the polymer A. Is more preferable, and 0 to 10 mol% is further preferable. It is particularly preferred that the polymer A does not contain a unit based on the compound of the formula (1) wherein R ¹ is a hydrogen atom. When the content of the unit based on the compound in which R ¹ of the formula (1) in the polymer A is a hydrogen atom in the polymer A is within the above range, the oil resistance of the article and the water and oil resistant paper is improved, and the water and oil resistant composition of the water and oil resistant composition is improved. Less foaming. The proportion of the unit a is 60 to 98% by mass, preferably 66 to 86% by mass, more preferably 70 to 82% by mass, and more preferably 74 to 78% by mass based on 100% by mass of all units in the polymer A. More preferred. Since the ratio of the unit a is 60% by mass or more, the water resistance and oil resistance of the article and the water and oil resistant paper are improved. Since the ratio of the unit a is 98% by mass or less, the dispersibility of the polymer A contained in the water and oil resistant composition becomes good, and the stability of the water and oil resistant composition becomes good.
The proportion of the unit b is 1 to 20% by mass, preferably 7 to 17% by mass, more preferably 9 to 15% by mass, and preferably 11 to 13% by mass based on 100% by mass of all units in the polymer A. More preferred. Since the proportion of the unit b is 1% by mass or more, the dispersibility of the polymer A contained in the water and oil resistant composition is improved, and the stability of the water and oil resistant composition is improved. Since the ratio of the unit b is 20% by mass or less, the water resistance and oil resistance of the article and the water and oil resistant paper are excellent.
The proportion of the unit c is 1 to 20% by mass, preferably 7 to 17% by mass, more preferably 9 to 15% by mass, and preferably 11 to 13% by mass based on 100% by mass of all units in the polymer A. More preferred. Since the ratio of the unit c is 1% by mass or more, the aqueous dispersion stability of the polymer A is improved. Since the ratio of the unit c is 20% by mass or less, the water resistance and oil resistance of the article and the water and oil resistant paper are excellent.
The proportion of the unit d is preferably from 0 to 38% by mass, more preferably from 0 to 20% by mass, and still more preferably from 0 to 12% by mass based on 100% by mass of all units in the polymer A. When the ratio of the unit d is equal to or less than the upper limit of the above range, the effect of the present invention is hardly impaired.

  The weight average molecular weight of the polymer A is preferably 400,000 or less, more preferably 10,000 to 300,000, still more preferably 20,000 to 200,000, and particularly preferably 30,000 to 150,000. When the weight average molecular weight of the polymer A is at least the lower limit of the above range, the dispersibility of the polymer A contained in the water and oil resistant composition will be further improved, and the stability of the water and oil resistant composition will be further improved. When the weight average molecular weight of the polymer A is equal to or less than the upper limit of the above range, the water and oil resistant composition will have excellent stability.

The glass transition temperature of the polymer A is preferably 35 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 50 ° C. or higher. When the glass transition temperature of the polymer A is equal to or higher than the lower limit of the above range, an article and a water- and oil-resistant paper having further excellent water resistance and oil resistance can be obtained. In particular, foaming hardly occurs during mixing, dilution, and the like, and continuous operation is hardly hindered. In addition, the occurrence of spots due to foaming is easily suppressed.
The higher the glass transition temperature of the polymer A, the better. The upper limit of the glass transition temperature of the polymer A is usually 100 ° C. from the viewpoint of easy production of the polymer A.

When the polymer A contains a unit based on the monomer c1 as the unit c (hereinafter, referred to as “unit c1”), the water dispersion stability of the polymer A and the affinity with pulp are further improved. Therefore, it is preferable that part or all of the unit c1 is in a state of being salified by an acid. What is salified by the acid is the amino group in the unit c1.
In order to convert a part or all of the unit c1 into a state of being salified by an acid, an acid may be used when dispersing the polymer A in an aqueous medium.
Examples of the acid include an inorganic acid and an organic acid. As the acid, an organic acid is preferable because the polymer A is easily dispersed in water.
Examples of the inorganic acid include hydrochloric acid, hydrobromic acid, sulfonic acid, nitric acid, and phosphoric acid.
Examples of the organic acid include acetic acid, formic acid, propionic acid, lactic acid, citric acid, malic acid, itaconic acid, tartaric acid, fumaric acid, succinic acid, adipic acid, oxalic acid, and maleic acid. As the organic acid, acetic acid, lactic acid, and malic acid are preferable, and acetic acid is more preferable, from the viewpoint that the polymer A is easily dispersed in water and the safety in operation.

The polymer A is obtained, for example, by polymerizing a mixture a containing a monomer a, a monomer b, and one or both of a monomer c1 and a monomer c2. The mixture a may further include a monomer d as needed.
Examples of the polymerization method of the polymer A include a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. Solution polymerization is preferred from the viewpoint of polymerization stability. The solution polymerization method is a method of polymerizing the mixture a in a polymerization solvent in the presence of a polymerization initiator. In the solution polymerization method, a chain transfer agent may be used as necessary.

Examples of the polymerization solvent include ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone), alcohols (eg, isopropyl alcohol), diacetone alcohol, esters (eg, ethyl acetate, butyl acetate), ethers (eg, diisopropyl ether, tetrahydrofuran), and fats. Group hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons (perchloroethylene, trichloro-1,1,1-ethane, trichlorotrifluoroethane, dichloropentafluoropropane, etc.), N, N-dimethylformamide, N-methyl -2-pyrrolidone, butylacetone, dimethyl sulfoxide, glycol ether (propylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol, Polypropylene glycol, etc.), and water.
As the polymerization solvent, a hydrophilic organic solvent is preferable because the polymer A is easily dispersed in water. In addition, an organic solvent having a relatively low boiling point and an organic solvent capable of forming an azeotropic mixture with water are preferable because the polymerization solvent is easily removed from the dispersion described below.

  The hydrophilic organic solvent is a solvent that can be uniformly mixed with water at an arbitrary ratio. Specific examples of the hydrophilic organic solvent include ketones (eg, acetone, methyl ethyl ketone), alcohols (eg, methanol, ethanol, 2-propanol), esters (eg, ethyl acetate, butyl acetate), and ethers (eg, diisopropyl ether, tetrahydrofuran). Is mentioned. As the hydrophilic organic solvent, ketones are preferable, and acetone or methyl ethyl ketone is more preferable, from the viewpoint of solubility of each monomer.

As the organic solvent having a relatively low boiling point, an organic solvent having a boiling point of 80 ° C. or less is preferable. Specific examples include acetone, methanol, and ethanol.
Specific examples of organic solvents capable of forming an azeotrope with water include propylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, diacetone alcohol, methanol, ethanol, propanol, acetone , Methyl isobutyl ketone and methyl ethyl ketone.

As the polymerization solvent, ketone is preferable, and acetone or methyl ethyl ketone is more preferable, since the polymer A is easily dispersed in water, has a relatively low boiling point, and can form an azeotropic mixture with water.
One type of polymerization solvent may be used alone, or two or more types may be used in combination.

Examples of the polymerization initiator include ammonium persulfate, potassium persulfate, peroxide, and azo compound.
Examples of the peroxide include benzyl peroxide, lauryl peroxide, succinyl peroxide, and tert-butylperoxypivalate.
Examples of the azo compound include dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobis (2-methylbutyronitrile), and 4,4′-azobis (4-cyanonova). Relic acid), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4 -Dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobisisobutyi Lonitrile, 1,1'-azobis (2-cyclohexane-1-carbonitrile), 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propion Bromide), and the like.
As the polymerization initiator, tert-butyl peroxypivalate is preferable among peroxides from the viewpoint of monomer reactivity. Among the azo compounds, dimethyl-2,2'-azobis (2-methylpropionate) is preferable.

  Examples of the chain transfer agent include alkyl mercaptans (tert-dodecyl mercaptan, n-dodecyl mercaptan, stearyl mercaptan, etc.), aminoethanethiol, mercaptoethanol, thioglycolic acid, 3-mercaptopropionic acid, 2,4-diphenyl-4. -Methyl-1-pentene. However, when the mixture a is polymerized, it is preferable not to use a chain transfer agent because the formation of oligomers having a low degree of polymerization is easily suppressed.

The ratio of each monomer in the mixture a is the same as the ratio of each unit in the polymer A, and the preferable range is also the same.
The concentration of the mixture a is preferably from 5 to 70% by mass, more preferably from 10 to 60% by mass based on 100% by mass of all the raw materials (including the polymerization solvent).
The amount of the polymerization initiator is preferably from 0.1 to 2.0 parts by mass based on 100 parts by mass of the mixture a.
The amount of the chain transfer agent is preferably from 0 to 1 part by mass with respect to 100 parts by mass of the mixture a.
The polymerization temperature is preferably equal to or higher than the half-life temperature of the polymerization initiator, and more preferably 30 to 90 ° C., from the viewpoint of efficiently using the polymerization initiator.

When the mixture a contains the monomer c1, after the mixture a is polymerized, a solution containing the polymer A, an acid and water are mixed, and a part or all of the units c1 in the polymer A is salified with an acid. Then, the polymer A may be dispersed in an aqueous medium to obtain a dispersion A. At this time, an acid and water may be added to the solution containing the polymer A, or a solution containing the polymer A may be added to the acid and water.
The amount of the acid used at the time of mixing is 0.1 to the amount of the unit c1 in the polymer A, that is, the amount of the amino group, from the viewpoint of the aqueous dispersion stability of the polymer A and the affinity for pulp. -20 equivalents are preferred, and 0.5-10 equivalents are more preferred.
The amount of water (excluding water for dilution) used in the salification is preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the polymer A from the viewpoint of the stability of the aqueous dispersion of the polymer A. Preferably, 100 to 600 parts by mass is more preferable.

  When the mixture a contains the monomer c1, the amino group in the unit c1 may be oxidized after the polymerization reaction from the viewpoint of further improving the aqueous dispersion stability of the polymer A and the affinity with pulp. When oxidized, hydrogen chloride may be mixed and oxidized after salification or removal of the organic solvent. Oxidation is preferably performed on some or all of the amino groups, and more preferably on all of the amino groups, since the water- and oil-resistant composition under high pH conditions tends to be stable. When the amino group is oxidized, it does not become salified by the acid. Therefore, when a part of the amino group is oxidized, it is preferable to salify the non-oxidized amino group with an acid.

The dispersion A contains an organic solvent such as a polymerization solvent used when synthesizing the polymer A. It is preferable to remove at least a part of the organic solvent from the dispersion A.
Examples of the method for removing the organic solvent from the dispersion A include methods such as stripping (volatilization), distillation, and bubbling. In order to increase the removal rate of the organic solvent, when removing the organic solvent, the pressure may be reduced, heated, or a combination of reduced pressure and heating.
When the organic solvent is a hydrophilic organic solvent, it is preferable to remove the organic solvent from the dispersion A by the following removal method from the viewpoint that the organic solvent can be removed efficiently.
Removal method: Dispersion liquid A is filled in a closed container having a gas outlet to form a liquid phase and a gas phase, and a part of the liquid in the liquid phase is formed into small droplets and brought into contact with the gas phase to remove the liquid. A method of reducing the amount of an organic solvent in a liquid phase by vaporizing an organic solvent and extracting a gaseous gas containing the vaporized organic solvent from a gas outlet of a closed container. Here, the small droplet is a droplet having a particle diameter of 1000 μm or less.

In order to make a part of the liquid in the liquid phase small and contact with the gas phase, a circulation system for circulating the liquid in the inside or outside of the closed vessel is provided, and a part of the liquid in the liquid is circulated by the circulation system. It is preferable to take out the liquid, adjust the temperature of the liquid, and make the liquid into small droplets for discharge. In particular, a liquid outlet for introducing the liquid in the liquid phase and a liquid inlet for introducing the liquid into the gas phase are provided in the closed container, and the circulation system is formed as an external circulation system formed between the liquid outlet and the liquid inlet. More preferably, the external circulation system has means for adjusting the temperature and pressure of the liquid flowing therein. The organic solvent can be more efficiently removed by adjusting the temperature and pressure of the liquid in the circulating system to conditions under which the organic solvent is easily vaporized.
Other components described below may be added to the dispersion A, or may be diluted with an aqueous medium or the like. As the aqueous medium for dilution, water is preferable.

(Polymer B)
The polymer B contains the unit a and the unit c at a specific ratio. The polymer B contains an acrylate unit in a specific ratio. In the polymer B, at least a part of the units a and c is preferably an acrylate unit.
The polymer B may further contain a unit b as needed.
The polymer B may further contain a unit d as long as the effects of the present invention are not impaired. Specific examples of the monomers a to d in the polymer B are the same as those described for the specific examples of each monomer in the polymer A.

The unit a contained in the polymer B is preferably a unit based on the compound 5 from the viewpoint of further improving the oil resistance of the article and the water and oil resistant paper.
_{CH 2 = CHC (O) O} -Y- (CF 2) n F Formula 5
Here, Y is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 6.
In Formula 5, the details and preferred embodiments of Y and n are the same as those described for the polymer A.

The unit a contained in the polymer B is CH ₂ ＣC (CH ₃ ) C (O) OCH ₂ CH ₂ (CF ₂ ) ₆ F, CH ₂ from the viewpoint that the oil resistance of the article and the water and oil resistant paper is significantly improved. _{= CHC (O) OCH 2 CH} 2 (CF 2) units based on ₆ F are preferred.

  When the polymer B contains the unit b, the water dispersion stability of the polymer B is further improved by the hydroxyl group, the main chain of the polymer B is softened, the glass transition temperature is lowered, and the article and the water- and oil-resistant paper The unit b is preferably a unit based on 2-hydroxyethyl acrylate in that oil resistance is significantly improved.

  The unit c contained in the polymer B is a unit based on N, N-dimethylaminoethyl (meth) acrylate or N, N-diethylaminoethyl (meth) acrylate from the viewpoint of further improving the water dispersion stability of the polymer B. Is preferred.

  When the polymer B contains the unit d, the unit d is the same as that described for the polymer A. When the polymer B contains the unit d and does not contain the unit b, the unit d is preferably a hydrophilic monomer, and is preferably N-vinylacetamide from the viewpoint of water dispersion stability and oil resistance of the water- and oil-resistant paper. And a unit based on N-vinylpyrrolidone is preferred, and a unit based on N-vinylpyrrolidone is more preferred.

The ratio of each unit of the polymer B is as follows.
The proportion of the acrylate unit is 40 to 80 mol%, preferably 41 to 70 mol%, and more preferably 42 to 60 mol%, based on 100 mol% of all units in the polymer B. Since the proportion of the acrylate unit in the polymer B is 40 mol% or more, the oil resistance of the article and the water- and oil-resistant paper is improved. In particular, when a water- and oil-resistant agent composition is internally added to a high-pH pulp slurry, a water- and oil-resistant paper having further excellent water resistance and oil resistance can be obtained. Since the proportion of the acrylate unit in the polymer B is 80 mol% or less, the stability of the reaction solution after polymerization and the stability after dispersion in water are improved.
The content ratio of the unit based on the compound represented by the formula (5) in the polymer B is preferably 40 to 80 mol%, more preferably 41 to 70 mol%, out of 100 mol% of all units in the polymer B. , 42 to 60 mol% is more preferred. When the content ratio of the unit based on the compound represented by the formula (5) is within the above range, the oil resistance of the article and the water and oil resistant paper becomes better, and in particular, the water and oil resistant composition is added to a high pH pulp slurry. When added internally, a water- and oil-resistant paper having even better water resistance and oil resistance is obtained, and the reaction solution after polymerization and the solution after water dispersion are more stable.
The proportion of the unit a is 50 to 98% by mass, preferably 54 to 93% by mass, more preferably 59 to 87% by mass, and more preferably 64 to 79% by mass of 100% by mass of all units in the polymer B. More preferred. Since the ratio of the unit a is 50% by mass or more, an article excellent in water resistance and oil resistance and a water-resistant oil-resistant paper can be obtained. Since the ratio of the unit a is 98% by mass or less, the polymer B is excellent in water dispersion stability.
The proportion of the unit b is 0 to 21% by mass, preferably 5 to 21% by mass, more preferably 10 to 21% by mass, and preferably 17 to 21% by mass based on 100% by mass of all units in the polymer B. More preferred. Since the proportion of the unit b is 0% by mass or more, the dispersibility of the polymer B contained in the water and oil resistant composition is further improved, and the stability of the water and oil resistant composition is further improved. Since the ratio of the unit b is 21% by mass or less, the water resistance and oil resistance of the article are improved.
The proportion of the unit c is 2 to 29% by mass, preferably 2 to 25% by mass, more preferably 3 to 20% by mass, and preferably 4 to 15% by mass based on 100% by mass of all units in the polymer B. More preferred. Since the ratio of the unit c is 2% by mass or more, the polymer B has excellent water dispersion stability. Since the ratio of the unit c is 30% by mass or less, an article excellent in water resistance and oil resistance and a water-resistant oil-resistant paper can be obtained.
The proportion of the unit d is preferably from 0 to 48% by mass, more preferably from 0 to 39% by mass based on 100% by mass of all units in the polymer B. When the ratio of the unit d is equal to or less than the upper limit of the above range, the effect of the present invention is hardly impaired.

The mass average molecular weight of the polymer B is preferably from 80,000 to 300,000, more preferably from 90,000 to 200,000. When the mass average molecular weight of the polymer B is equal to or more than the lower limit of the above range, the water dispersion stability of the polymer B is further excellent. In addition, an article and a water- and oil-resistant paper which are more excellent in water resistance and oil resistance can be obtained. When the mass average molecular weight of the polymer B is equal to or less than the upper limit of the above range, an article and a water- and oil-resistant paper having more excellent water resistance and oil resistance can be obtained.
When the molecular weight of the polymer B is from 80,000 to 300,000, the aqueous dispersion stability of the polymer B is further improved.

The glass transition temperature of the polymer B is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, and further preferably 35 ° C. or lower. When the glass transition temperature of the polymer B is equal to or lower than the upper limit of the above range, an article and a water- and oil-resistant paper having further excellent water resistance and oil resistance can be obtained. In particular, when a water- and oil-resistant agent composition is internally added to a high-pH pulp slurry, a water- and oil-resistant paper having further excellent water resistance and oil resistance can be obtained.
The lower the glass transition temperature of the polymer B, the better. From the viewpoint of ease of production of the polymer B, the lower limit of the glass transition temperature of the polymer B is usually −10 ° C.

When the polymer B contains the unit c1, a part or all of the unit c1 of the polymer B is salified by an acid from the viewpoint of further improving the water dispersion stability of the polymer B and the affinity with pulp. Preferably, it is in the state.
In order to convert a part or all of the unit c1 into a state of being salified by an acid, an acid may be used when dispersing the polymer B in water. The details and preferred embodiments of the acid are the same as those described for the polymer A.

The polymer B contains, for example, one or both of the monomer a and the monomer c1 and the monomer c2, and at least a part of the monomer a, the monomer c1 and the monomer c2 is an acrylate. It is obtained by polymerizing a certain mixture b. The mixture b may further include a monomer b and a monomer d as needed.
The polymerization method is the same as that described for the polymerization of the mixture a, and the preferred polymerization method is also the same. If necessary, a chain transfer agent may be used.

  Examples of the polymerization solvent for polymerizing the mixture b include the same compounds as those described for the polymerization of the mixture a. Preferred embodiments of the polymerization solvent used for the polymerization of the mixture b are the same. One type of polymerization solvent may be used alone, or two or more types may be used in combination.

Examples of the polymerization initiator include the same compounds as those described for the polymerization of the mixture a, and preferred embodiments are also the same.
Examples of the chain transfer agent include the same compounds as those described for the polymerization of the mixture a. It is preferable not to use a chain transfer agent because oligomer components having a low degree of polymerization can be easily suppressed.

The proportion of each monomer in the mixture b is the same as the proportion of each unit in the polymer B, and the preferred embodiment is also the same.
The details of the concentration of the mixture b, the amount of the chain transfer agent, and the polymerization temperature are the same as the polymerization method of the mixture a, and the preferred embodiments are also the same.
In the polymerization of the mixture b, the amount of the polymerization initiator is preferably from 0.1 to 3.0 parts by mass based on 100 parts by mass of the mixture b.

When the mixture b contains the monomer c1, after the mixture b is polymerized, a solution containing the polymer B, an acid and water are mixed, and a part or all of the amino group of the unit c1 in the polymer B is acidified. The polymer B may be dispersed in an aqueous medium to obtain a dispersion B in the same manner as in the dispersion A described above.
The amount of acid used for mixing and the amount of water used for salification are the same as those described for the dispersion A, and the preferred embodiments are also the same.

  When the mixture b contains the monomer c1, the amino group in the unit c1 may be oxidized from the viewpoint of further improving the aqueous dispersion stability of the polymer B and the affinity with pulp. When the unit c1 in the polymer B is oxidized, the polymer B may be oxidized by mixing with hydrogen peroxide after salification or after removing the organic solvent. The details and preferred embodiments of the oxidization are the same as those described above for the polymer A.

Dispersion B contains an organic solvent such as a polymerization solvent used for synthesizing polymer B. It is preferable to remove at least a part of the organic solvent from the dispersion B.
Examples of the method for removing the organic solvent from the dispersion B include the same method as the method for removing the organic solvent from the dispersion A described above, and a preferable embodiment is also the same.

  The dispersion B may be added with other components described below as in the case of the dispersion A, or may be diluted with an aqueous medium or the like. When the polymer B contains the unit c1, the amino group in the unit c1 may be oxidized in order to improve the aqueous dispersion stability of the polymer B and the affinity with pulp.

(Aqueous medium)
The aqueous medium is a liquid medium containing water as a main component. In the water and oil resistant composition, the aqueous medium may contain an organic solvent. The aqueous medium in the water and oil resistant composition may include, for example, an organic solvent that can form an azeotrope with water.

(Other ingredients)
Other components include, for example, conventionally known additives.
Specific examples of the additives include paper strength agents other than the polymer A and the polymer B, a waterproofing agent, a resin, a sizing agent, a crosslinking agent, a catalyst, an organic filler, an inorganic filler, a support agent, a flocculant, and a buffering agent. Germicides, biocides, sequestering agents, surfactants, defoamers, volatile organic solvents. However, examples of the additives are not limited to these.

In the water and oil resistant composition, the solid content concentration of the polymer A and the polymer B is preferably from 10 to 60% by mass, and more preferably from 10 to 50% by mass.
In the water and oil resistant composition, the mass ratio of the polymer A to the polymer B (polymer A / polymer B) is preferably 1/4 to 4/1, more preferably 1/3 to 2/1, and 1 to 4. / 2 to 1/1 are more preferred. When the mass ratio of the polymer A to the polymer B is 4/1 or less, an article having more excellent oil resistance and a water-resistant oil-resistant paper can be obtained. When the mass ratio of the polymer A to the polymer B is within the above range, the foaming of the water and oil proofing agent composition is further reduced, and the workability during use is further improved.

The content of water in the water and oil resistant composition is preferably from 150 to 100,000 parts by mass, more preferably from 150 to 1,000 parts by mass, based on 100 parts by mass of the polymer A and the polymer B in total.
The content of the organic solvent in the water and oil resistant composition is preferably 30% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less. Organic solvents may affect the human body, so if the composition contains a large amount of organic solvent, it is not only unfavorable for food contact applications, but also volatilizes in the water- and oil-resistant paper manufacturing process. May not be desirable.

The defoaming parameter of the water and oil proofing agent composition is measured by the defoaming test described below. The defoaming parameter is preferably 500 mL or less, more preferably 400 mL or less, and even more preferably 300 mL or less. The defoaming parameter is measured by the following defoaming test. If the defoaming parameter measured based on the following defoaming test is 500 mL or less, foaming of the water and oil resistant composition is small, and workability at the time of using the water and oil resistant composition is further improved.
Defoaming test: a measuring cylinder having an inner diameter of 65 mm, a temperature control system for maintaining a constant temperature of an aqueous dispersion test liquid obtained by diluting the water and oil resistant composition with water so that the solid content concentration becomes 0.1% by mass, A nozzle having an inner diameter of 9 mm disposed so that the tip is downward at a height of 420 mm from the bottom of the graduated cylinder, and the water dispersion test liquid is withdrawn from the vicinity of the bottom of the graduated cylinder and discharged from the nozzle. The following steps 1 to 7 are sequentially performed using a continuous foam tester having a circulation system for circulating the aqueous dispersion test liquid at a flow rate of 11.5 L / min. Test in which (mL) is measured as the defoaming parameter.
Step 1: The measuring cylinder containing 650 mL of the aqueous dispersion test solution is allowed to stand by the temperature control system until the temperature of the aqueous dispersion test solution reaches 18 ° C. Step 2: Circulation by the circulation system is performed for 30 seconds. Step 3: stopping the circulation by the circulation system for 30 seconds Step 4: performing the circulation by the circulation system for 120 seconds Step 5: stopping the circulation by the circulation system for 60 seconds Step 6: circulation by the circulation system Step 7: Stopping the circulation by the circulation system and measuring the foam volume (mL) on the liquid surface of the aqueous dispersion test solution 60 seconds after the stop.

  The pH of the water and oil resistant composition is preferably 2 to 12, and more preferably 3 to 11. When the pH of the water and oil proofing agent composition is within the above range, the polymer A and polymer B contained in the water and oil proofing agent composition do not undergo sedimentation due to poor dispersion, and do not cause ester hydrolysis by alkali. Excellent stability of objects.

In the water and oil resistant composition, it is preferable that the polymer A and the polymer B are each dispersed as particles in an aqueous medium.
The average particle diameter of the water and oil resistant composition is preferably from 5 to 250 nm, more preferably from 10 to 200 nm. If the average particle size of the water and oil resistant composition is not less than the lower limit of the above range, the water resistance and oil resistance of the article and the water and oil resistant paper are further improved. If the average particle size of the water and oil proofing agent composition is equal to or less than the upper limit of the above range, the dispersibility of the polymer A and the polymer B contained in the water and oil proofing agent composition is further improved, and the water and oil proofing agent composition Stability is further improved.

  The water and oil resistant composition can be prepared, for example, by blending the aforementioned dispersion A and the aforementioned dispersion B. When blending the dispersion A and the dispersion B, the above-mentioned other components may be blended as necessary, or may be diluted with an aqueous medium or the like to form a water and oil resistant composition.

  The water and oil resistant composition can be applied to the treatment of various substrates and the production of water and oil resistant paper. The treatment of the base material and the water and oil resistant paper will be described later.

  Since the water and oil resistant composition of the present invention described above contains the polymer A and the polymer B, a water and oil resistant paper excellent in oil resistance can be obtained even when internally added to a high pH pulp slurry. Further, according to the water and oil resistant composition of the present invention, foaming at the time of dilution is reduced, so that the occurrence of spots due to foaming is suppressed, and workability at the time of using the water and oil resistant composition is improved.

<Article>
The article of the present invention has been treated with the water and oil resistant composition of the present invention.
By treating a substrate with the water and oil resistant composition of the present invention, an article having water resistance and oil resistance can be obtained.

  As the base material, for example, a paper base material (paper, paperboard, pulp mold, synthetic paper using synthetic fiber as at least a part of raw material and its related products); woven or nonwoven fabric based on cellulose or regenerated cellulose; Or woven or non-woven fabric based on artificial fibers (cotton, cellulose acetate, wool, silk, etc.); based on artificial fibers or synthetic fibers (polyamide fibers, polyester fibers, polyolefin fibers, polyurethane fibers, polyacrylonitrile fibers, etc.) Woven or non-woven fabric; leather, artificial leather, resin, plastic material such as film, glass, wood, metal, concrete, stone, tile, ceramic, brick, painted surface.

  Examples of the treatment method include a method of applying or impregnating the substrate with the water and oil resistant composition of the present invention, drying the substrate in an environment of 60 ° C. or higher, and performing heat treatment as necessary. By performing drying, heat treatment, and the like, more excellent water resistance and oil resistance can be imparted to the substrate.

  As the article, a water-resistant oil-resistant paper and a water-resistant oil-resistant pulp mold are preferable because the water-resistant oil-resistant composition of the present invention is suitable for treating a paper substrate.

  The article of the present invention has excellent oil resistance because it is treated with the water and oil resistant composition of the present invention.

<Water and oil resistant paper>
The water and oil resistant paper of the present invention is pulp or paper treated with the water and oil resistant composition of the present invention.
As a method for producing the water and oil resistant paper, a method of applying or impregnating the water and oil resistant composition of the present invention to a paper substrate (external addition) or a method of making a pulp slurry containing the water and oil resistant composition of the present invention ( Internal addition).
In the external addition step and the internal addition step, the water and oil resistant composition of the present invention may be diluted with water or an aqueous medium before use. The solid concentration of the water and oil resistant composition used in the production method of the present invention is preferably from 10 to 30% by mass, more preferably from 20 to 25% by mass.

(Outside additive)
As the paper base material, one kind of pulp slurry in which pulp is dispersed in water is used alone, or two or more kinds are mixed at an arbitrary mixing ratio, beaten, and a chemical is added, and then a paper is made using a wire. One. Examples of the form include a continuous long web, a sheet-like sheet obtained by cutting the web, and a molded article (a container or the like) obtained by a pulp mold molding machine. Basis weight, for ^example, may be ^{10g / m 2 ~500g / m 2} .

Specific examples of pulp raw materials include, for example, wood such as conifers and hardwoods; herbs such as bagasse, rice straw, bamboo, reeds, and palms; and used paper. Of the pulp raw materials, pulp made from wood and herbs is called fresh pulp, and pulp made from waste paper is called recycled pulp.
Fresh pulp is called by different names depending on the manufacturing method. Examples of the name of the fresh pulp include kraft pulp (KP), sulfite pulp (SP), soda pulp, mechanical pulp (MP), thermomechanical pulp (TMP), and chemithermomechanical pulp (CTMP). As the fresh pulp, one subjected to single or plural bleaching treatments as necessary may be used.
As the recycled pulp, pulp produced by performing one of the steps of defibration, dust removal, deinking, and bleaching, or combining a plurality of steps, as necessary, may be used.

  The paper base material may contain a sizing agent, a fixing agent, a dry strength agent, a wet strength agent, a sulfuric acid band, a retention enhancer, a dye, a pigment, a filler, and the like, as long as the effects of the present invention are not impaired.

The water and oil resistant composition of the present invention may contain a concomitant agent.
Examples of the concomitant agent in the external additive include a paper strength enhancer (various starches, resins, etc.), a sizing agent, a penetrant, a defoaming agent, a chelating agent, a dye, a pigment, a dye, a binder, an acid, an alkali, an alginate, Sulfate band.

The application or impregnation of the water and oil proofing agent composition may be performed at any stage after papermaking, and may be at the stage of papermaking, size pressing after passing through a wet press and a former dryer, and a coater after the size press. The stage of use may be sufficient.
A coating machine may be used for applying the water and oil resistant composition.
Examples of the coating machine include a size press machine, a coater, and a printing machine.
Examples of the size press include a two-roll size press, a film transfer size press, and a calender size press.
Examples of the coater include a roll coater, an air knife coater, a die coater, a blade coater, a bar coater, a bill blade coater, and a short dwell blade coater.
Examples of the printing press include a gravure printing press, a flexographic printing press, and an offset printing press.

After applying or impregnating the water and oil resistant composition, the paper substrate is dried. The drying method may be a method of drying with heat or a method of drying without applying heat (air drying).
The drying temperature is preferably from 20 to 300 ° C, more preferably from 20 to 250 ° C.

(Internal addition)
Pulp slurries include water and pulp dispersed in water.
The raw material of the pulp is the same as the content described for the external addition. The pulp slurry may be produced by disintegrating dry pulp with a disintegrator, or may be used by diluting wet pulp produced by a pulp production facility. One kind of pulp slurry is used alone, or two or more kinds are mixed at an arbitrary mixing ratio.
The concentration of pulp in the pulp slurry is preferably 0.1 to 10% by mass.

The addition of the water and oil resistant composition of the present invention may be performed at any stage before the pulp slurry is supplied onto the wire of the paper machine.
A concomitant agent may be added to the pulp slurry. Examples of the concomitant agent in the internal addition process include a coagulant, a retention agent, a sizing agent, a paper strength enhancer, a pigment, a dye, and a pH adjuster.

  A paper machine can be used to make the pulp slurry. The paper machine may be any device that can dewater the pulp slurry on the wire. The paper machine may be a continuous paper machine such as a fourdrinier paper machine, or may be a batch pulp mold molding machine. The batch-type pulp mold molding machine is, for example, an apparatus for dewatering a pulp slurry using a molding frame formed of a wire to produce a molded body.

  The water and oil resistant paper of the present invention is excellent in oil resistance because it is pulp or paper treated with the water and oil resistant composition of the present invention.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following description.
Examples 6 to 17 and 23 to 34 are Examples, and Examples 1 to 5 and 18 to 22 are Comparative Examples.

<Abbreviation>
(Monomer a)
_{C6FMA: CH 2 = C (CH} 3) C (O) OCH 2 CH 2 (CF 2) 6 F,
_{C6FA: CH 2 = CHC (O} ) OCH 2 CH 2 (CF 2) 6 F.
(Monomer b)
HEMA: 2-hydroxyethyl methacrylate,
HEA: 2-hydroxyethyl acrylate,
3ED: triethylene glycol dimethacrylate.
(Monomer c1)
DMAEMA: dimethylaminoethyl methacrylate,
DEAEMA: diethylaminoethyl methacrylate.
(Monomer d)
NVP: N-vinylpyrrolidone.
(Polymerization initiator)
V601: dimethyl 2,2'-azobis (2-methylpropionate) (V-601, manufactured by Wako Pure Chemical Industries, Ltd.).
PV: tert-butyl peroxypivalate (NOF Corporation, Perbutyl PV).
(Polymerization solvent)
MEK: methyl ethyl ketone.
(Contents of Polymer A and Polymer B in Water and Oil Resistant Composition)
M1: The solid content concentration (% by mass) of each polymer in the water and oil resistant composition of Examples 1 to 17.
(Contents of Polymer A and Polymer B in Waterproof and Oilproof Paper)
M2: The solid content concentration (% by mass) of each polymer with respect to the dried mass of the pulp in Examples 18 to 34.

<Measurement method>
(Ratio of acrylate unit)
It was calculated from the molar ratio of the composition of the mixture obtained by mixing the respective monomers.

(Workability)
The workability of the water and oil proofing agent composition was evaluated by measuring the defoaming parameters based on the above-described defoaming test and by the following criteria. In Tables 3 and 4, the foam volume (ml) one minute after the start of the defoaming test is also shown.
〇: The defoaming parameter is 500 mL or less.
X: Defoaming parameter is more than 500 mL.

(Oil resistance test 1)
The kit test was performed by the following method according to the TAPPI T559cm-02 method. For the test, a test solution in which castor oil, toluene and n-heptane were mixed at the volume ratio shown in Table 1 was used. The test results are represented by kit numbers, and the larger the number, the better the oil resistance. The kit test allows the user to know the oil resistance of the test paper in a short time (about 20 seconds) and is widely used for evaluating the oil resistance of the paper. The evaluation result has a meaning as an index for the surface tension of the paper surface.

(Oil resistance test 2)
The water- and oil-resistant paper of each of Examples 18 to 34 was cut into a square of 1 cm and used as a test sample. After about 0.5 ml of soybean oil was gently dropped on the test sample, the test sample was allowed to stand in a thermostat set at 80 ° C. for 30 minutes. Next, the test sample was taken out from the thermostat, and the test sample was visually observed for the degree of penetration of soybean oil, and evaluated according to the following evaluation criteria.
〇: No oil has penetrated the test sample at all.
Δ: The oil has permeated a part of the surface where the oil has been dropped, but has not penetrated to the back surface.
×: Oil has penetrated to the back surface of the test sample.

(Water resistance test)
The water- and oil-resistant paper of each of Examples 18 to 34 was cut into a square of 1 cm and used as a test sample. About 0.5 ml of ion-exchanged water having a temperature of 95 ° C. to 100 ° C. was gently dropped on the test sample, and the test sample was allowed to stand in a thermostat set at 60 ° C. for 30 minutes. Next, the sample was taken out from the thermostat, and the test sample was visually observed for the degree of penetration of ion-exchanged water, and evaluated according to the following evaluation criteria.
〇: Water does not penetrate the test sample at all.
Δ: Water permeates a part of the surface where the water is dropped, but does not permeate to the back surface.
×: Water has penetrated to the back surface of the test sample.

(Production of water and oil resistant composition)
In Examples 1 to 34, the water and oil resistant composition of each example was produced as follows.
First, a mixture containing each monomer having the composition shown in Table 2, a polymerization initiator and a polymerization solvent (acetone or MEK) were charged into a glass ampoule container having a volume of about 120 mL, and nitrogen replacement was repeated three times. Sealed with rubber stopper. This was attached to a shaking thermostat heated to a polymerization temperature of 60 ° C., and the number of times of shaking was set to 110 times per minute, and polymerization was performed for 20 hours to obtain a solution of each polymer. The weight average molecular weight of the polymer A1 was about 80,000, and the weight average molecular weights of the polymers B1 to B4 were 130,000 to 150,000.
Next, water and 1.1 eq equivalents of DMAEMA or DEAEMA acetic acid charged to obtain each polymer were charged into a 1 L four-necked flask equipped with stirring blades, and the mixture was kept at 70 ° C. for 30 minutes. The amount of water charged was 7 times the total weight of the monomers and the polymerization initiator charged during the production of the polymer.
The polymer solution was added to the flask and stirred at 200 rpm for 60 minutes to disperse the polymer in water. Next, the remaining polymerization solvent (acetone or MEK) and a part of water were distilled off using an evaporator, and ion-exchanged water was added to obtain a dispersion of the polymer A1 and the polymers B1 to B4, respectively. The polymerization solvent remaining in the dispersion was 1% by mass or less.

(Examples 1 to 17)
In Examples 1 to 17, the dispersions of the polymer A1 and the polymers B1 to B4 were mixed with ion-exchanged water so that the content of each polymer became the solid content concentration (% by mass) shown in Tables 3 and 4. Thus, the water and oil resistant composition of each example was produced. Workability was evaluated by performing a defoaming test on each of the water-resistant and oil-resistant agent compositions in each example. The results are shown in Tables 3 and 4.

(Examples 18 to 34)
In Examples 18 to 34, the polymers A1 and B1 to B4 were prepared so that the amount of each polymer was the solid content concentration (% by mass) shown in Table 5 or 6 with respect to the mass of the pulp after drying. The dispersion and the ion-exchanged water were blended to produce the water and oil resistant compositions of each example.
After commercially available LBKP (hardwood bleached kraft pulp) and NBKP (softwood bleached kraft pulp) are mixed at a mass ratio of 6: 4, water is added so that the pulp concentration becomes 1% by mass, and the pulp is crushed using a laboratory disintegrator. A slurry was produced. The pulp was concentrated using a 100 mesh wire (wire mesh having 100 holes per inch) until the pulp concentration became 10% by mass, and beaten to a freeness of 400 CSF using a PFI mill (lab beater). Until the pulp concentration was again 1% by mass, an aqueous sodium hydroxide solution having a pH of 8.5 was diluted as diluting water to adjust the pH of the 1% by mass pulp slurry to 8 to 9.
Next, the pulp slurry was defibrated for 1 minute using a laboratory disintegrator, and while the pulp slurry was being stirred, the solid content of the AKD sizing agent for papermaking (manufactured by Solenis, product name "H-79") was reduced by drying the pulp slurry. An AKD sizing agent for papermaking was added to the pulp slurry so that the amount became 0.3% by mass with respect to the mass of the pulp after the above.
After continuing stirring for 3 minutes, the water and oil resistant composition of each example was added to the pulp slurry such that the amount of each polymer was 0.2% by mass based on the mass of the pulp after drying the pulp slurry. Then, stirring was further continued for 3 minutes. This pulp slurry was paper-made using a TAPPI standard handmade machine so that the basis weight was 50 g / m ² . The wet paper thus formed was subjected to a coach (dehydration) and a press (dehydration) in accordance with JIS P8222, and then dried at 100 ° C. for 60 seconds using a cylinder dryer to obtain a water- and oil-resistant paper. After adjusting the humidity of the water-resistant oil-resistant paper in a standard state, the oil resistance tests 1 and 2 and the water resistance test were performed on the water-resistant oil-resistant paper of each example. The results are shown in Tables 5 and 6.

Examples 1 to 5 and 18 to 22 are Comparative Examples containing only one of Polymer A and Polymer B.
In Example 1, which contained the polymer A1 and did not contain the polymer B, the foaming was small and the result of evaluation of workability was good. However, in Example 18, which contained the polymer A1 and did not contain the polymer B, the water and oil resistant paper had poor oil resistance and water resistance.
In Examples 19 to 22, which contained any one of the polymers B1 to B4 and did not contain the polymer A, the evaluation results of the oil resistance and the water resistance of the water and oil resistant paper were good. However, in Examples 2 to 5, foaming was large, and the evaluation results of workability were insufficient. In addition, the polymer B4 corresponds to the polymer described in Examples of International Publication No. 2011/021619.
Examples 6-17 and 23-34 are examples that include both Polymer A and Polymer B. In Examples 6 to 17, good results were obtained with little foaming. Furthermore, in Examples 23 to 34, the evaluation results of the oil resistance and the water resistance of the water and oil resistant paper were good.
From the above results, it was found that according to the water and oil resistant composition of the present invention, excellent oil resistance can be imparted to the substrate and workability is excellent.

The water and oil resistant composition of the present invention can impart water resistance and oil resistance to a substrate such as paper.
The water- and oil-resistant paper of the present invention is useful as a food packaging container, a food packaging paper, a freshness retaining agent packaging paper, an oxygen scavenger packaging paper and the like.

Claims (12)

60 to 98% by mass of the unit based on the monomer represented by the following formula 1, 1 to 20% by mass of the unit based on the monomer represented by the following formula 2, and the monomer represented by the following formula 3 And 1 to 20% by mass of a unit based on one or both of the monomers represented by the following formula 4, and the ratio of the unit based on the acrylate is 0 mol% or more and 40 mol based on all units. % Polymer A,
50 to 98% by mass of the unit based on the monomer represented by the following formula 1, 0 to 21% by mass of the unit based on the monomer represented by the following formula 2, and the monomer represented by the following formula 3 And 2 to 29% by mass of a unit based on one or both of the monomers represented by the following formula 4, and the proportion of the unit based on the acrylate is 40 to 80% by mole based on all units. A certain polymer B;
A water and oil resistant composition comprising:
^{_{CH 2 = C (R 1)}} C (O) O-Y- (CF 2) n F Formula 1
However,
R ¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom,
Y is an alkylene group having 1 to 10 carbon atoms,
n is an integer of 1 to 6.
^{_{CH 2 = C (R 2)}} -C (O) O- (R 3 O) q -R 4 Formula 2
However,
R ² is a hydrogen atom or a methyl group,
R ³ is an alkylene group having 2 to 4 carbon atoms;
q is an integer of 1 to 140, when q is an integer of 2 or more, - ^(R 3 O) - can be identical to each other, it may be different,
R ⁴ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a (meth) acryloyl group or a glycidyl group.
CH ₂ ＣC (R ⁵ ) -MQ-NR ⁶ R ⁷ Formula 3
CH ₂ ＣC (R ⁵ ) -MQN (O) R ⁶ R ⁷ Formula 4
However, in equations 3 and 4,
R ⁵ is a hydrogen atom or a methyl group,
M is -C (O) O- or -C (O) NH-,
Q is an alkylene group having 2 to 4 carbon atoms or an alkylene group having 2 to 3 carbon atoms in which part or all of hydrogen atoms are substituted with a hydroxyl group;
R ⁶ and R ⁷ are each independently a benzyl group, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 2 to 3 carbon atoms in which some or all of the hydrogen atoms have been substituted with hydroxyl groups. The water and oil resistant composition according to claim 1, wherein the unit based on the monomer represented by the formula 1 in the polymer A is a unit based on the monomer represented by the formula 11.
^{_{CH 2 = C (R 11)}} C (O) O-Y- (CF 2) n F Formula 11
However,
R ¹¹ is an alkyl group having 1 to 3 carbon atoms or a halogen atom,
Y is an alkylene group having 1 to 10 carbon atoms,
n is an integer of 1 to 6.   The water and oil resistant composition according to claim 1 or 2, wherein the proportion of units based on acrylate in the polymer A is 10 mol% or less based on all units.   The water and oil resistant composition according to any one of claims 1 to 3, wherein a mass ratio of the polymer A to the polymer B is 1/4 to 4/1.   The water- and oil-resistant composition according to any one of claims 1 to 4, wherein a ratio of the unit based on acrylate in the polymer B is 42 to 60 mol% based on all units. The unit based on the monomer represented by the formula 1 contained in the polymer B is a unit based on the monomer represented by the following formula 5; Water and oil resistant composition.
_{CH 2 = CHC (O) O} -Y- (CF 2) n F Formula 5
However,
Y is an alkylene group having 1 to 10 carbon atoms,
n is an integer of 1 to 6.   The water and oil resistant composition according to claim 6, wherein the proportion of the unit based on the compound represented by the formula 5 in the polymer B is 40 to 80 mol% based on all units.   The water and oil resistant composition according to any one of claims 1 to 7, wherein the polymer B further contains a unit based on N-vinylpyrrolidone. The water and oil resistant composition according to any one of claims 1 to 8, wherein a defoaming parameter measured by the following defoaming test is 500 mL or less.
Defoaming test: a measuring cylinder having an inner diameter of 65 mm, a temperature control system for maintaining a constant temperature of an aqueous dispersion test liquid obtained by diluting the water and oil resistant composition with water so that the solid content concentration becomes 0.1% by mass, A nozzle having an inner diameter of 9 mm disposed so that the tip is downward at a height of 420 mm from the bottom of the graduated cylinder, and the water dispersion test liquid is withdrawn from the vicinity of the bottom of the graduated cylinder and discharged from the nozzle. The following steps 1 to 7 are sequentially performed using a continuous foam tester having a circulation system for circulating the aqueous dispersion test liquid at a flow rate of 11.5 L / min. Test in which (mL) is measured as the defoaming parameter.
Step 1: The measuring cylinder containing 650 mL of the aqueous dispersion test solution is allowed to stand by the temperature control system until the temperature of the aqueous dispersion test solution reaches 18 ° C. Step 2: Circulation by the circulation system is performed for 30 seconds. Step 3: stopping the circulation by the circulation system for 30 seconds Step 4: performing the circulation by the circulation system for 120 seconds Step 5: stopping the circulation by the circulation system for 60 seconds Step 6: circulation by the circulation system Step 7: Stopping the circulation by the circulation system and measuring the foam volume (mL) on the liquid surface of the aqueous dispersion test solution 60 seconds after the stop.   The water and oil resistant composition according to any one of claims 1 to 9, which is for pulp or paper.   An article treated with the water and oil resistant composition according to any one of claims 1 to 10.   A water- and oil-resistant paper obtained by treating pulp or paper with the water- and oil-resistant composition according to any one of claims 1 to 10.