Oil-resistant compounds for paper.

Abstract

DEPCT64 This invention provides an oil-resistant substance that can offer good oil and water resistance. This innovative paper technology reveals an oil-resistant substance for paper, which is non-fluorine-based. Repeating copolymer formed from (a) acrylic monomer with long-chain hydrocarbon group containing 7- 40 carbon atoms and repeating units which are formed from (b) acrylic monomer with hydrophilic resistance groups. This paper oil uses a liquid medium consisting of water and / or other organic solvents. What should be used is water, or a mixture (aqueous medium) of water and the organic solvent that should be used is... The non-fluorine copolymer has repeating units formed from (c) monomers that have an ionizing group other than Repeating units formed from monomers (a) and (b). -----------------------------------------------------------

Description

Oil-resistant agent for paper

[0001] The present disclosure relates to greaseproofing agents for paper and paper treated with the greaseproofing agents for paper.

[0002] Food packaging materials and food containers made of paper are required to prevent the seepage of moisture and oil from food, and therefore greaseproofing agents are applied to the paper either internally or externally.

[0003] Patent Document 1 (JP 2013-237941 A) describes an oil-resistant layer containing starch, a styrene-acrylic resin having an alkyl (meth)acrylate group having 8 to 24 carbon atoms, and wax, and having an Oken air permeability of 2000 seconds or less and a solid content of the oil-resistant layer of 2.0 to 10.0 g / m ２ Patent Document 2 (International Publication No. 2013 / 008938) discloses an greaseproof paper in which an aqueous varnish containing a filler and an acid-containing copolymer as a main component, the copolymer being formed from one or more (meth)acrylate monomers and one or more vinyl monomers and having a glass transition temperature of -10°C to 50°C, is applied to the paper in a weight ratio of 19 to 700 g / m. ２ Patent Document 3 (JP 2006-028697 A) discloses a food packaging paper having a coating layer formed by coating and drying the paper by a flexographic printing method. In the oil-resistant food paper, an acrylic synthetic resin emulsion is applied to a paper substrate to form an oil-resistant synthetic resin layer, and the oil-resistant synthetic resin layer has an undercoat layer formed on the surface of the paper substrate and an overcoat layer which becomes a surface layer, and the glass transition temperature Tg １ -30 to 0°C, the glass transition temperature Tg ２ The paper discloses a food-grade greaseproof paper having a temperature of 0 to 30°C.

[0004] JP 2013-237941 A International Application Publication No. 2013 / 008938 A Japanese Patent Application Publication No. 2006-028697 A

[0005] An object of the present disclosure is to provide an oil-proofing agent that can impart excellent oil resistance and water resistance to paper.

[0006] The present disclosure relates to an grease-proofing agent for paper comprising a non-fluorine-containing copolymer having: (a) repeating units formed from an acrylic monomer having a long-chain hydrocarbon group with 7 to 40 carbon atoms; and (b) repeating units formed from an acrylic monomer having a hydrophilic group. The grease-proofing agent for paper also contains a liquid medium that is water and / or an organic solvent, preferably water or a mixture of water and an organic solvent (aqueous medium). The present disclosure also provides grease-resistant paper that has been treated with the grease-proofing agent for paper. The paper treatment can be external or internal. The grease-resistant paper has an grease-resistant layer containing the grease-proofing agent and starch, which is formed by an external treatment method using the grease-proofing agent for paper. Alternatively, the grease-resistant paper contains the grease-proofing agent inside the paper, which is formed by an internal treatment method using the grease-proofing agent for paper.

[0007] Preferred aspects of the present disclosure are as follows: [1] An oil-proofing agent for paper comprising a non-fluorine-containing copolymer having: (a) repeating units formed from an acrylic monomer having a long-chain hydrocarbon group with 7 to 40 carbon atoms; and (b) repeating units formed from an acrylic monomer having a hydrophilic group. [2] The acrylic monomer (a) having a long-chain hydrocarbon group is a repeating unit represented by the formula: CH2=C(-X １ )-C(=O)-Y １ (R １ ) ｋ [In the formula, R １ are each independently a hydrocarbon group having 7 to 40 carbon atoms; １ is a hydrogen atom, a monovalent organic group or a halogen atom, １ represents a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ [3] The oil-proofing agent for paper according to claim 1, which is a monomer represented by the formula: [3] In the acrylic monomer (a) having a long-chain hydrocarbon group, X is a group consisting of at least one selected from - and -NH- (excluding hydrocarbon groups), and k ... １ [4] The oil-proofing agent for paper according to [1] or [2], wherein the long-chain hydrocarbon group-containing acrylic monomer (a) is a monomer represented by the formula (a1): CH2=C(-X ４ )-C(=O)-Y２ -R ２ [In the formula, R ２ is a hydrocarbon group having 7 to 40 carbon atoms, and X ４ is a hydrogen atom, a monovalent organic group or a halogen atom, ２ is —O— or —NH—.] and / or (a2) an acrylic monomer represented by the formula: CH═C(—X ５ )-C(=O)-Y ３ -Z (-Y ４ -R ３ ) ｎ [In the formula, R ３ are each independently a hydrocarbon group having 7 to 40 carbon atoms; ５ is a hydrogen atom, a monovalent organic group or a halogen atom, ３ is —O— or —NH—, and Y ４ are each independently a direct bond, —O—, —C(═O)—, or —S(═O) ２ - or -NH-, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2.], and the acrylic monomer (b) having a hydrophilic group is represented by the formula: CH ２ =CX ２ C(=O)-O-(RO) ｎ -X ３ (b1) and / or CH ２ =CX ２ C(=O)-O-(RO) ｎ -C(=O)CX ２ =CH ２ (b2) [wherein, X ２ represents a hydrogen atom or a methyl group, X ３ is a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R is an alkylene group having 2 to 6 carbon atoms, and n is an integer of 1 to 90. [5] The oil-proofing agent for paper according to any one of [1] to [3], which is at least one oxyalkylene (meth)acrylate represented by the formula: １ or Y ４represents -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'-, wherein each Y' independently represents a direct bond, -O-, -NH-, or -S(=O) ２ - and R' is -(CH ２ ) ｍ -(m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -(CH ２ ) ｌ -C ６ H ４ -(CH ２ ) ｌ - (each l is independently an integer of 0 to 5; -C ６ H ４- is a phenylene group).] [6] The oil-proofing agent for paper according to any one of [1] to [5], wherein the fluorine-free copolymer further contains a repeating unit formed from a monomer (c) other than the monomers (a) and (b) having an olefinic carbon-carbon double bond, and an anionic donor group or a cationic donor group. [7] The oil-proofing agent for paper according to [6], wherein the anionic donor group is a carboxyl group, or the cationic donor group is an amino group. [8] The oil-proofing agent for paper according to any one of [1] to [7], wherein the amount of the repeating unit formed from the acrylic monomer (a) having a long-chain hydrocarbon group is 30 to 95% by weight based on the copolymer. [9] The oil-proofing agent for paper according to any one of [1] to [8], wherein the amount of repeating units formed from the acrylic monomer (a) having a long-chain hydrocarbon group is 30 to 90% by weight, based on the copolymer, the amount of repeating units formed from the acrylic monomer (b) having a hydrophilic group is 5 to 70% by weight, based on the copolymer, and the amount of repeating units formed from the monomer (c) having an anionic donor group or a cationic donor group is 0.1 to 30% by weight, based on the fluorine-free copolymer, and the fluorine-free copolymer is a random copolymer.

[10] The oil-proofing agent for paper according to any one of [1] to [9], wherein the non-fluorine-free copolymer has a melting point or glass transition point of 20°C or higher and / or a dynamic viscoelasticity (complex viscosity) of 10 to 5000 Pa s at 90°C.

[11] The oil-proofing agent for paper according to any one of [1] to

[10] , further comprising a liquid medium which is water or a mixture of water and an organic solvent.

[12] Grease-resistant paper having an oil-resistant layer on the surface of the paper, the oil-resistant agent for paper according to any one of [1] to

[11] and starch or modified starch.

[13] The solid content of the oil-resistant agent for paper in the oil-resistant layer is 2 g / m ２ The grease-resistant paper according to

[12] below.

[14] Grease-resistant paper containing the non-fluorinated copolymer of the grease-proofing agent for paper according to any one of [1] to

[11] inside the paper.

[15] The grease-resistant paper according to any one of

[12] to

[14] , which is a food packaging material or a food container.

[16] A paper treatment method, in which the paper is treated with the grease-proofing agent for paper according to any one of [1] to

[11] by external addition or internal addition.

[0008] In the oil-proofing agent, the non-fluorine copolymer is well dispersed in an aqueous medium, particularly water, and the oil-proofing agent imparts high oil resistance and water resistance to paper.

[0009] 1 is a graph showing the complex viscosity of non-fluorinated copolymers of Synthesis Examples 1, 10 and 11.

[0010] The fluorine-free copolymer has (a) repeating units formed from an acrylic monomer having a long-chain hydrocarbon group with 7 to 40 carbon atoms, and (b) repeating units formed from an acrylic monomer having a hydrophilic group. Furthermore, the fluorine-free copolymer preferably has repeating units formed from (c) a monomer having an ion-donating group, in addition to the monomers (a) and (b). The fluorine-free copolymer may have repeating units formed from (d) another monomer, in addition to the monomers (a), (b), and (c).

[0011] (a) Acrylic Monomer Having a Long-Chain Hydrocarbon Group The acrylic monomer (a) having a long-chain hydrocarbon group has a long-chain hydrocarbon group having 7 to 40 carbon atoms. The long-chain hydrocarbon group having 7 to 40 carbon atoms is preferably a linear or branched hydrocarbon group having 7 to 40 carbon atoms. The long-chain hydrocarbon group preferably has 10 to 40 carbon atoms, for example, 12 to 30 carbon atoms, and particularly preferably 15 to 30 carbon atoms. Alternatively, the long-chain hydrocarbon group may have 18 to 40 carbon atoms.

[0012] The acrylic monomer (a) having a long chain hydrocarbon group has the formula: CH2=C(-X １ )-C(=O)-Y １ (R １ ) ｋ [In the formula, R １ are each independently a hydrocarbon group having 7 to 40 carbon atoms; １ is a hydrogen atom, a monovalent organic group or a halogen atom, １ represents a divalent to tetravalent hydrocarbon group having one carbon atom (particularly, —CH ２ -, -CH=), -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２- or -NH- (excluding hydrocarbon groups), and k is 1 to 3.

[0013] X １ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. １ Examples of X are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. １ is preferably a hydrogen atom, a methyl group, or a chlorine atom. １ is particularly preferably a hydrogen atom.

[0014] Y １ is a divalent to tetravalent group. １ is preferably a divalent group. １ represents a hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ A group consisting of at least one selected from - and -NH- (excluding hydrocarbon groups) is preferred. Examples of hydrocarbon groups having one carbon atom include -CH ２ -, a branched -CH=, or a branched -C≡.

[0015] Y １ -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [Wherein, Y' is a direct bond, -O-, -NH- or -S(=O) ２ - and R' is -(CH ２ ) m - (m is an integer of 1 to 5) or -C ６ H ４ -(phenylene group).

[0016] Y １Specific examples include -O-, -NH-, -O-C(=O)-, -C(=O)-NH-, -NH-C(=O)-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C ６ H ４ -, -O-(CH ２ ) m -O-, -NH-(CH ２ ) m -NH-, -O-(CH ２ ) m -NH-, -NH-(CH ２ ) m -O-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m -C(=O)-O-, -NH-(CH ２ ) m -O-C(=O)-, -NH-(CH ２ ) m -C(=O)-O-, -O-(CH ２ ) m -O-C(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-O-, -O-(CH ２ ) m -C(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-, -O-(CH ２ ) m -NH-C(=O)-NH-, -O-(CH ２ ) m -O-C ６ H ４ -, -O-(CH ２ ) m -NH-S(=O) ２ -, -O-(CH ２ ) m -S(=O) ２ -NH-, -NH-(CH ２ ) m -O-C(=O)-NH-, -NH-(CH ２ ) m -NH-C(=O)-O-, -NH-(CH ２ ) m -C(=O)-NH-, -NH-(CH２ ) m -NH-C(=O)-, -NH-(CH ２ ) m -NH-C(=O)-NH-, -NH-(CH ２ ) m -O-C ６ H ４ -, -NH-(CH ２ ) m -NH-C ６ H ４ -, -NH-(CH ２ ) m -NH-S(=O) ２ -, or -NH-(CH ２ ) m -S(=O) ２ -NH-, wherein m is 1 to 5, particularly 2 or 4.

[0017] Y １ is -O-, -NH-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m -NH-C(=O)-, -O-(CH ２ ) m -OC(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-O-, -O-(CH ２ ) m -NH-C(=O)-NH-, -O-(CH ２ ) m -NH-S(=O) ２ -, -O-(CH ２ ) m -S(=O) ２ -NH-, -NH-(CH ２ ) m -NH-S(=O) ２ -, or -NH-(CH ２ ) m -S(=O) ２ -NH- [wherein m is an integer of 1 to 5, particularly 2 or 4] is preferred. １ is -O- or -O-(CH ２ ) m —NH—C(═O)—, particularly —O—(CH ２ )m It is more preferably —NH—C(═O)—.

[0018] R １ is preferably a linear or branched hydrocarbon group. The hydrocarbon group may particularly be a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 or 15 to 26, particularly 18 to 22 or 17 to 22 carbon atoms.

[0019] Examples of the acrylic monomer (a) having a long chain hydrocarbon group include (a1) a monomer represented by the formula: CH2=C(-X ４ )-C(=O)-Y ２ -R ２ [In the formula, R ２ is a hydrocarbon group having 7 to 40 carbon atoms, and X ４ is a hydrogen atom, a monovalent organic group or a halogen atom, ２ is —O— or —NH—.], and (a2) an acrylic monomer represented by the formula: CH═C(—X ５ )-C(=O)-Y ３ -Z (-Y ４ -R ３ ) ｎ [In the formula, R ３ are each independently a hydrocarbon group having 7 to 40 carbon atoms; ５ is a hydrogen atom, a monovalent organic group or a halogen atom, ３ is —O— or —NH—, and Y ４ are each independently a direct bond, —O—, —C(═O)—, or —S(═O) ２ - or -NH-, Z is a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2.

[0020] (a1) Acrylic Monomer The acrylic monomer (a1) is a monomer represented by the formula: CH2=C(-X ４ )-C(=O)-Y ２ -R ２ [In the formula, R ２is a hydrocarbon group having 7 to 40 carbon atoms, and X ４ is a hydrogen atom, a monovalent organic group or a halogen atom, ２ is —O— or —NH—.]

[0021] The acrylic monomer (a1) is Y ２ a long chain acrylate ester monomer in which Y is —O—; ２ is a long chain acrylamide monomer in which R is —NH—. ２ is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. ２ In the formula (I), the number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example, 16 to 26, and particularly preferably 18 to 22. ４ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0022] Preferred examples of the long-chain acrylate ester monomer include lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, icosyl α-chloroacrylate, and behenyl α-chloroacrylate. Preferred examples of the long-chain acrylamide monomer include stearyl (meth)acrylamide, icosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0023] (a2) Acrylic Monomer The acrylic monomer (a2) is a monomer different from the acrylic monomer (a1). The acrylic monomer (a2) is a monomer selected from the group consisting of —O—, —C(═O)—, and —S(═O) ２ The acrylic monomer (a2) is a (meth)acrylate or (meth)acrylamide having at least one group selected from the group consisting of -, -, -NH-, - ... ５ )-C(=O)-Y ３ -Z (-Y ４ -R ３ ) ｎ [In the formula, R ３are each independently a hydrocarbon group having 7 to 40 carbon atoms; ５ is a hydrogen atom, a monovalent organic group or a halogen atom, ３ is —O— or —NH—, and Y ４ are each independently a direct bond, —O—, —C(═O)—, or —S(═O) ２ - or -NH-, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2.

[0024] R ３ is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. ３ In the formula (I), the hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 or 15 to 26, and particularly preferably 18 to 22 or 17 to 22 carbon atoms.

[0025] X ５ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0026] Y ４ represents -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'-, wherein each Y' independently represents a direct bond, -O-, -NH-, or -S(=O) ２ - and R' is -(CH ２ ) ｍ -(m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -(CH ２ ) ｌ -C ６ H ４ -(CH ２ ) ｌ- (each l is independently an integer of 0 to 5; -C ６ H ４ - is a phenylene group.

[0027] Y ４ Specific examples include direct bond, -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O) ２ -, -S(=O) ２ -NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -OC ６ H ４ -, -NH-C ６ H ４ -, -O-(CH ２ ) m -O-, -NH-(CH ２ ) m -NH-, -O-(CH ２ ) m -NH-, -NH-(CH ２ ) m -O-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m -C(=O)-O-, -NH-(CH ２ ) m -OC(=O)-, -NH-(CH ２ ) m -C(=O)-O-, -O-(CH ２ ) m -OC(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-O-, -O-(CH ２ ) m -C(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-, -O-(CH ２ ) m -NH-C(=O)-NH-, -O-(CH ２ ) m -O-C ６ H ４ -, -NH-(CH ２ ) m-OC(=O)-NH-, -NH-(CH ２ ) m -NH-C(=O)-O-, -NH-(CH ２ ) m -C(=O)-NH-, -NH-(CH ２ ) m -NH-C(=O)-, -NH-(CH ２ ) m -NH-C(=O)-NH-, -NH-(CH ２ ) m -O-C ６ H ４ -, -NH-(CH ２ ) m -NH-C ６ H ４ wherein m is an integer of 1 to 5.

[0028] Y ４ is -O-, -NH-, -O-C(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O) ２ -, -S(=O) ２ -NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -OC ６ H ４ - is preferred. ４ is more preferably —NH—C(═O)—, —C(═O)—NH—, —O—C(═O)—NH—, —NH—C(═O)—O— or —NH—C(═O)—NH—.

[0029] Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a linear or branched structure. Z preferably has 2 to 4 carbon atoms, and particularly preferably 2. Specific examples of Z include a direct bond, -CH ２ -, -CH ２ CH ２ -, -CH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ CH ２ -, -CH ２ CH ２ CH２ CH ２ CH ２ -, -CH having a branched structure ２ CH=, -CH having a branched structure ２ (CH-)CH ２ -, -CH having a branched structure ２ CH ２ CH=, -CH having a branched structure ２ CH ２ CH ２ CH ２ CH=, -CH having a branched structure ２ CH ２ (CH-)CH ２ -, -CH having a branched structure ２ CH ２ CH ２ It is preferred that Z is not a direct bond, and Y ４ and Z cannot simultaneously be a direct bond.

[0030] The acrylic monomer (a2) is CH═C(-X ５ )-C(=O)-O-(CH ２ ) m -NH-C(=O)-R ３ , C.H. ２ =C(-X ５ )-C(=O)-O-(CH ２ ) ｍ -OC(=O)-NH-R ３ , C.H. ２ =C(-X ５ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-OR ３ , C.H. ２ =C(-X ５ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-NH-R ３ Preferably, R ３ and X ５ has the same meaning as above.] The acrylic monomer (a2) is CH2=C(-X ５ )-C(=O)-O-(CH ２ ) m -NH-C(=O)-R３ It is particularly preferred that:

[0031] The acrylic monomer (a2) can be produced by reacting a hydroxyalkyl (meth)acrylate or a hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate. Examples of long-chain alkyl isocyanates include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate. Alternatively, the acrylic monomer (a2) can be produced by reacting a (meth)acrylate having an isocyanate group in the side chain, such as 2-methacryloyloxyethyl methacrylate, with a long-chain alkylamine or a long-chain alkyl alcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of long-chain alkyl alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0032] Preferred examples of the long-chain hydrocarbon group-containing acrylic monomer are as follows: stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, behenyl α-chloroacrylate; stearyl (meth)acrylamide, behenyl (meth)acrylamide;

[0033]

[0034]

[0035]

[0036]

[0037] [In the above formula, n is a number from 7 to 40, and m is a number from 1 to 5.] The compound of the above chemical formula is an acrylic compound in which a hydrogen atom is at the α-position, but specific examples may be a methacryl compound in which a methyl group is at the α-position, and an α-chloroacrylic compound in which a chlorine atom is at the α-position.

[0038] The melting point of the acrylic monomer (a) having a long-chain hydrocarbon group is preferably 10°C or higher, more preferably 25°C or higher.

[0039] The acrylic monomer (a) having a long chain hydrocarbon group is preferably X １ , X ４ and X ５ is preferably an acrylate in which is a hydrogen atom.

[0040] The acrylic monomer (a2) is represented by the formula: １２ -C(=O)-NH-R １３ -O-R １１ [In the formula, R １１ represents an organic residue having an ethylenically unsaturated polymerizable group, R １２ represents a hydrocarbon group having 7 to 40 carbon atoms, R １３ is a hydrocarbon group having 1 to 5 carbon atoms.]

[0041] R １１ is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has a carbon-carbon double bond. １４ =CH ２ , -CHR １４ =CH ２ , -CH ２ CHR １４ =CH ２ and the like. １４ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. １１ R may have various organic groups in addition to the ethylenically unsaturated polymerizable group, such as organic groups of chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups, and these organic groups may be substituted with various substituents. １１ is -C(=O)CR１４ =CH ２ It is preferable that:

[0042] R １２ R is a hydrocarbon group having 7 to 40 carbon atoms, preferably an alkyl group, and examples thereof include chain hydrocarbon groups and cyclic hydrocarbon groups. Among these, a chain hydrocarbon group is preferred, and a linear saturated hydrocarbon group is particularly preferred. １２ has 7 to 40 carbon atoms, preferably 11 to 27 carbon atoms, and particularly preferably 15 to 23 carbon atoms.

[0043] R １３ is a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group. The hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched, and may have an unsaturated bond, but is preferably linear. １３ The number of carbon atoms in R is preferably 2 to 4, and particularly preferably 2. １３ is preferably an alkylene group.

[0044] The amide group-containing monomer is R １２ is one type (for example, R １２ is only a compound having 17 carbon atoms), or R １２ A combination of multiple １２ a compound having 17 carbon atoms, and R １２ and a compound having 15 carbon atoms.

[0045] An example of the amide group-containing monomer is carboxylic acid amide alkyl (meth)acrylate.Specific examples of the amide group-containing monomer include palmitic acid amide ethyl (meth)acrylate, stearic acid amide ethyl (meth)acrylate, behenic acid amide ethyl (meth)acrylate, myristate amide ethyl (meth)acrylate, laurate amide ethyl (meth)acrylate, isostearate ethyl amide (meth)acrylate, oleic acid ethyl amide (meth)acrylate, tertiary butylcyclohexyl caproate amide ethyl (meth)acrylate, adamantanecarboxylic acid ethyl amide (meth)acrylate, naphthalenecarboxylic acid amide ethyl (meth)acrylate, anthracenecarboxylic acid amide ethyl (meth)acrylate, palmitic acid amide propyl (meth)acrylate, stearic acid amide propyl (meth)acrylate, palmitic acid amide ethyl vinyl ether, stearic acid amide ethyl vinyl ether, palmitic acid amide ethyl allyl ether, stearic acid amide ethyl allyl ether, or mixtures thereof.

[0046] The amide group-containing monomer is preferably stearamidoethyl (meth)acrylate. The amide group-containing monomer may be a mixture containing stearamidoethyl (meth)acrylate. In the mixture containing stearamidoethyl (meth)acrylate, the amount of stearamidoethyl (meth)acrylate may be, for example, 55 to 99 wt %, preferably 60 to 85 wt %, and more preferably 65 to 80 wt %, based on the total weight of the amide group-containing monomers, and the remaining monomer may be, for example, palmitamidoethyl (meth)acrylate.

[0047] (b) Acrylic Monomer Having a Hydrophilic Group The acrylic monomer (b) having a hydrophilic group is a monomer other than the monomer (a) and is a hydrophilic monomer. The hydrophilic group is preferably an oxyalkylene group (the alkylene group has 2 to 6 carbon atoms). In particular, the acrylic monomer (b) having a hydrophilic group is preferably a polyalkylene glycol mono(meth)acrylate and / or a polyalkylene glycol di(meth)acrylate, or a polyalkylene glycol mono(meth)acrylamide. The polyalkylene glycol mono(meth)acrylate, polyalkylene glycol di(meth)acrylate, and polyalkylene glycol mono(meth)acrylamide are represented by the general formula: CH ２ =CX ２ C(=O)-O-(RO) ｎ -X ３ (b1) and CH ２ =CX ２ C(=O)-O-(RO) ｎ -C(=O)CX ２ =CH ２ (b2), CH ２ =CX ２ C(=O)-NH-(RO) ｎ -X ３ (b3) wherein X ２ each independently represents a hydrogen atom or a methyl group, X ３ are each independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R is an alkylene group having 2 to 6 carbon atoms, and n is an integer from 1 to 90. ] n may be, for example, 1 to 50, particularly 1 to 30, and especially 1 to 15 or 2 to 15. Alternatively, n may be, for example, 1. R may be a linear or branched alkylene group, for example, a group represented by the formula -(CH ２ ) ｘ - or - (CH ２ ) ｘ１ -(CH(CH ３ )) ｘ２ - [wherein x1 and x2 are 0 to 6, for example, 2 to 5, and the sum of x1 and x2 is 1 to 6. -(CH ２ ) ｘ１- and - (CH (CH ３ )) ｘ２ The order of - is not limited to the illustrated formula and may be random. ｎ In -, R may be two or more types (for example, two to four types, particularly two types), and -(RO) ｎ - is, for example, -(R １ O) ｎ１ - and - (R ２ O) ｎ２ - [wherein, R １ and R ２ are different from each other and are alkylene groups having 2 to 6 carbon atoms, n1 and n2 are numbers of 1 or more, and the sum of n1 and n2 is 2 to 90.

[0048] In general formulas (b1), (b2), and (b3), R is preferably an ethylene group, a propylene group, or a butylene group. R in general formulas (b1), (b2), and (b3) may be a combination of two or more alkylene groups. In such a case, it is preferable that at least one of R is an ethylene group, a propylene group, or a butylene group. Examples of R combinations include an ethylene / propylene combination, an ethylene / butylene combination, and a propylene / butylene combination. Monomer (b) may be a mixture of two or more types. In such a case, it is preferable that at least one of the monomers (b) is an ethylene group, a propylene group, or a butylene group in general formula (b1), (b2), or (b3). Furthermore, when using a polyalkylene glycol di(meth)acrylate represented by general formula (b2), it is not preferable to use it alone as the monomer (b), but rather it is preferable to use it in combination with monomer (b1). In this case, it is also preferable that the compound represented by the general formula (b2) is contained in an amount of less than 30% by weight of the monomer (b) used.

[0049] Specific examples of the acrylic monomer (b) having a hydrophilic group include, but are not limited to, the following: CH2=CHCOO-CH2CH2O-H CH2=CHCOO-CH2CH2CH2O-H CH2=CHCOO-CH2CH(CH3)OH CH2=CHCOO-CH(CH3)CH2O-H CH2=CHCOO-CH2CH2CH2CH2O-H CH2=CHCOO-CH2CH2CH(CH3)OH CH2=CHCOO-CH2CH(CH3)CH2O-H CH2=CHCOO-CH(CH3)CH2CH2O-H CH2=CHCOO-CH2CH(CH2CH3)OH CH2=CHCOO-CH2C(CH3)2O-H CH2=CHCOO-CH(CH2CH3)CH2O-H CH2=CHCOO-C(CH3)2CH2O-H CH2=CHCOO-CH(CH3)CH(CH3)OH CH2=CHCOO-C(CH3)(CH2CH2O)OH CH2=CHCOO-(CH2CH2O)2-H CH2=CHCOO-(CH2CH2O)4-H CH2=CHCOO-(CH2CH2O)5-H CH2=CHCOO-(CH2CH2O)6-H CH2=CHCOO-(CH2CH2O)5-CH3 CH2=CHCOO-(CH2CH2O)9-CH3 CH2=CHCOO-(CH2CH2O) 23 -CH3 CH2=CHCOO-(CH2CH2O) 90 -CH3

[0050] CH2=CHCOO-(CH2CH(CH3)O)9-H CH2=CHCOO-(CH2CH(CH3)O)9-CH3 CH2=CHCOO-(CH2CH(CH3)O) 12 -CH3 CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=CHCOO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9 CH2=CHCOO-(CH2CH2O) 23 -OOC(CH3)C=CH2 CH2=CHCOO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0051] CH2=CHCOO-(CH2CH2O)9-H CH2=C(CH3)COO-CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH3)O-H CH2=C(CH3)COO-CH(CH3)CH2O-H CH2=C(CH3)COO-CH2CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH(CH3)O-H CH2=C(CH3)COO-CH2CH(CH3)CH2O-H CH2=C(CH3)COO-CH(CH3)CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH2CH3)O-H CH2=C(CH3)COO-CH2C(CH3)2O-H CH2=C(CH3)COO-CH(CH2CH3)CH2O-H CH2=C(CH3)COO-C(CH3)2CH2O-H CH2=C(CH3)COO-CH(CH3)CH(CH3)O-H CH2=C(CH3)COO-C(CH3)(CH2CH3)O-H CH2=C(CH3)COO-(CH2CH2O)2-H CH2=C(CH3)COO-(CH2CH2O)4-H CH2=C(CH3)COO-(CH2CH2O)5-H CH2=C(CH3)COO-(CH2CH2O)6-H CH2=C(CH3)COO-(CH2CH2O)9-H CH2=C(CH3)COO-(CH2CH2O)5-CH3 CH2=C(CH3)COO-(CH2CH2O)9-CH3 CH2=C(CH3)COO-(CH2CH2O) 23 -CH3 CH2=C(CH3)COO-(CH2CH2O) 90 -CH3 CH2=C(CH3)COO-(CH2CH(CH3)O)9-H

[0052] CH2=C(CH3)COO-(CH2CH(CH3)O)9-CH3 CH2=C(CH3)COO-(CH2CH(CH3)O) 12-CH3 CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=C(CH3)COO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9 CH2=C(CH3)COO-(CH2CH2O) 23 -OOC(CH3)C=CH2 CH2=C(CH3)COO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0053] CH2=CH-C(=O)-NH-CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH3)OH CH2=CH-C(=O)-NH-CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH(CH3)OH CH2=CH-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH3)OH CH2=CH-C(=O)-NH-CH2C(CH3)2O-H CH2=CH-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=CH-C(=O)-NH-C(CH3)2CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH(CH3)OH CH2=CH-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=CH-C(=O)-NH-(CH2CH2O)2-H CH2=CH-C(=O)-NH-(CH2CH2O)4-H CH2=CH-C(=O)-NH-(CH2CH2O)5-H CH2=CH-C(=O)-NH-(CH2CH2O)6-H CH2=CH-C(=O)-NH-(CH2CH2O)9-H CH2=CH-C(=O)-NH-(CH2CH2O)5-CH3 CH2=CH-C(=O)-NH-(CH2CH2O)9-CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 23-CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 90 -CH3

[0054] CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-H CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-CH3 CH2=CH-C(=O)-NH-(CH2CH(CH3)O) 12 -CH3 CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=CH-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0055] CH2=C(CH3)-C(=O)-NH-CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-CH2C(CH3)2O-H CH2=C(CH3)-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-C(CH3)2CH2O-H CH2=C(CH3)-C(=O)-NH-CH(CH3)CH(CH3)OH CH2=C(CH3)-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-(CH2CH2O)2-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)4-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)6-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 23 -CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 90 -CH3

[0056] CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O) 12-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0057] The monomer (b) may be X ２ is a hydrogen atom. In particular, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide is preferred.

[0058] (c) Monomer Having an Ion-Donating Group The monomer (c) having an ion-donating group is a monomer other than the monomer (a) and the monomer (b). The monomer (c) is preferably a monomer having an olefinic carbon-carbon double bond and an ion-donating group. The ion-donating group is an anion-donating group and / or a cation-donating group.

[0059] Examples of the monomer having an anion donating group include a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Specific examples of the monomer having an anion donating group include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acrylate phosphate, vinylbenzenesulfonic acid, acrylamido-tertiarybutylsulfonic acid, and salts thereof.

[0060] Salts of anion-donating groups include alkali metal salts, alkaline earth metal salts, and ammonium salts, such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0061] In the monomer having a cation donating group, examples of the cation donating group are amino groups, preferably tertiary amino groups and quaternary amino groups. In the tertiary amino group, two groups bonded to the nitrogen atom may be the same or different and may be an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example a benzyl group (C ６ H ５ -CH ２ In the quaternary amino group, the three groups bonded to the nitrogen atom are the same or different and are an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example a benzyl group (C ６ H ５ -CH ２ In the tertiary amino group and the quaternary amino group, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cation-donating group may be in the form of a salt.

[0062] The cation-donating group in the form of a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid), are preferred. Dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate and salts thereof are preferred.

[0063] Specific examples of the monomer having a cation donor group are as follows: CH2=CHCOO-CH2CH2-N(CH3)2 and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (e.g., acetate) CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (e.g., acetate) CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (e.g., acetate) CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (e.g., acetate) CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH2-N + (-CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (-CH2CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Br - CH2=C(CH3)COO-CH2CH2-N + (CH3)3I - CH2=C(CH3)COO-CH2CH2-N + (CH3)3O - SO3CH3 CH2=C(CH3)COO-CH2CH2-N + (CH3)(-CH2-C6H5)2Br -

[0064] As the monomer (c) having an ion-donating group, methacrylic acid, acrylic acid and dimethylaminoethyl methacrylate are preferred, and methacrylic acid and dimethylaminoethyl methacrylate are more preferred.

[0065] (d) Other Monomers The other monomers (d) are monomers other than the monomers (a), (b) and (c). Such other monomers include ethylene, vinyl acetate, vinyl chloride, vinyl fluoride, halogenated vinylstyrene, α-methylstyrene, p-methylstyrene, polyoxyalkylene mono(meth)acrylate, (meth)acrylamide, diacetone (meth)acrylamide, methylolated (meth)acrylamide, N-methylol (meth)acrylamide, alkyl vinyl ether, halogenated alkyl vinyl ether, alkyl vinyl ketone, butadiene, isoprene, chloroprene, glycidyl (meth)acrylate, aziridinyl (meth)acrylate, benzyl (meth)acrylate, isocyanatoethyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, short-chain alkyl (meth)acrylate, maleic anhydride, (meth)acrylate having a polydimethylsiloxane group, and N-vinylcarbazole.

[0066] The amount of the repeating unit formed from monomer (a) (repeating unit (a)) may be 30 to 95% by weight or 30 to 90% by weight, preferably 40 to 88% by weight (or 45 to 95% by weight), more preferably 50 to 85% by weight, based on the non-fluorinated copolymer (or the total of the repeating unit (a) and the repeating unit (b)). The amount of the repeating unit formed from monomer (b) (repeating unit (b)) may be 5 to 70% by weight or 10 to 70% by weight, preferably 8 to 50% by weight, more preferably 10 to 40% by weight, based on the non-fluorinated copolymer (or the total of the repeating unit (a) and the repeating unit (b)). The amount of the repeating unit formed from monomer (c) may be 0.1 to 30% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight, based on the non-fluorinated copolymer. The amount of repeating units formed from the monomer (d) may be 0 to 20% by weight, for example 1 to 15% by weight, particularly 2 to 10% by weight, based on the fluorine-free copolymer.

[0067] The weight average molecular weight of the non-fluorinated copolymer may be 1,000 to 1,000,000 or 10,000,000, preferably 5,000 to 800,000 or 8,000,000, and more preferably 10,000 to 400,000 or 4,000,000. The weight average molecular weight is a value determined by gel permeation chromatography in terms of polystyrene. In this specification, "(meth)acrylic" means acrylic or methacrylic. For example, "(meth)acrylate" means acrylate or methacrylate.

[0068] From the viewpoint of oil resistance, the non-fluorine copolymer is preferably a random copolymer rather than a block copolymer. The melting point or glass transition point of the non-fluorine copolymer is preferably 20°C or higher, more preferably 30°C or higher, particularly preferably 35°C or higher, for example, 40°C or higher. The dynamic viscoelasticity (complex viscosity) of the non-fluorine copolymer at 90°C is preferably 10 to 5000 Pa s, for example, 20 to 3000 Pa s, and particularly 50 to 1000 Pa s. The dynamic viscoelasticity (complex viscosity) of the non-fluorine copolymer at 70°C is preferably 500 to 100,000 Pa s, and particularly 1000 to 50,000 Pa s. Furthermore, the dynamic viscoelasticity (complex viscosity) of the non-fluorine copolymer is preferably 10 to 5000 Pa s, for example, 20 to 3000 Pa s, and particularly 50 to 1000 Pa s, at 80 to 90°C.

[0069] The polymerization of the non-fluorine-containing copolymer is not particularly limited, and various polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, and radiation polymerization can be selected. For example, solution polymerization using an organic solvent or emulsion polymerization using water or a combination of an organic solvent and water is generally selected. After polymerization, the polymer is diluted with water and emulsified in water to prepare a treatment liquid. In the present disclosure, after polymerization (e.g., solution polymerization or emulsion polymerization, preferably solution polymerization), water is added and the solvent is removed to disperse the polymer in water. A self-dispersing product can be produced without the need to add an emulsifier.

[0070] Examples of organic solvents include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and methyl acetate, glycols such as propylene glycol, dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone (NMP), dipropylene glycol, tripropylene glycol, and low-molecular-weight polyethylene glycol, and alcohols such as ethyl alcohol and isopropanol.

[0071] Examples of polymerization initiators that can be used include peroxides, azo compounds, and persulfate compounds. Polymerization initiators are generally water-soluble and / or oil-soluble. Specific examples of oil-soluble polymerization initiators include 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-isobutyronitrile), benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and t-butyl perpivalate.

[0072] Specific examples of the water-soluble polymerization initiator preferably include 2,2'-azobisisobutylamidine dihydrochloride, 2,2'-azobis(2-methylpropionamidine) hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]sulfate hydrate, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]hydrochloride, potassium persulfate, barium persulfate, ammonium persulfate, hydrogen peroxide, etc. The polymerization initiator is used in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the monomer.

[0073] Furthermore, for the purpose of molecular weight control, a chain transfer agent such as a mercapto group-containing compound may be used, specific examples of which include 2-mercaptoethanol, thiopropionic acid, alkyl mercaptan, etc. The mercapto group-containing compound is used in an amount of 10 parts by weight or less, in the range of 0.01 to 5 parts by weight, per 100 parts by weight of the monomer.

[0074] Specifically, the fluorine-free copolymer can be produced as follows. In solution polymerization, a method is adopted in which the monomers are dissolved in an organic solvent, the solvent is purged with nitrogen, a polymerization initiator is added, and the mixture is heated and stirred at a temperature in the range of 40 to 120°C for 1 to 10 hours, for example. The polymerization initiator may generally be an oil-soluble polymerization initiator.

[0075] The organic solvent is one that is inactive to the monomers and dissolves them, and examples of the organic solvent include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and methyl acetate, glycols such as propylene glycol, dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone (NMP), dipropylene glycol, tripropylene glycol, and low-molecular-weight polyethylene glycol, alcohols such as ethyl alcohol and isopropanol, and hydrocarbon solvents such as n-heptane, n-hexane, n-octane, cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane, methylpentane, 2-ethylpentane, isoparaffin hydrocarbons, liquid paraffin, decane, undecane, dodecane, mineral spirits, mineral turpentine, and naphtha. Preferred examples of the solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, N-methyl-2-pyrrolidone (NMP), dipropylene glycol monomethyl ether (DPM), etc. The organic solvent is used in an amount of 50 to 2000 parts by weight, for example, 50 to 1000 parts by weight, per 100 parts by weight of the total of the monomers.

[0076] In emulsion polymerization, a method is employed in which a monomer is emulsified in water in the presence of an emulsifier or the like, and after nitrogen substitution, a polymerization initiator is added and polymerization is carried out by stirring for 1 to 10 hours at a temperature in the range of 40 to 80° C. The polymerization initiator is a water-soluble polymerization initiator, for example, 2,2′-azobisisobutylamidine dihydrochloride, 2,2′-azobis(2-methylpropionamidine) hydrochloride, 2,2′-azobis[2-(2-imidazolin-2-yl)propane] hydrochloride, 2,2′-azobis[2-(2-imidazolin-2-yl)propane] sulfate hydrate, 2,2′-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] hydrochloride, potassium persulfate, barium persulfate, ammonium persulfate, hydrogen peroxide, and the like. Oil-soluble polymerization initiators such as 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-isobutyronitrile), benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and t-butyl perpivalate are used. The polymerization initiator is used in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the monomer.

[0077] To obtain a polymer aqueous dispersion with excellent shelf stability, it is desirable to atomize the monomer in water using an emulsifying device capable of applying powerful crushing energy, such as a high-pressure homogenizer or ultrasonic homogenizer, and then polymerize using an oil-soluble polymerization initiator. Furthermore, various anionic, cationic, or nonionic emulsifiers can be used as emulsifiers, and are used in a range of 0.5 to 20 parts by weight per 100 parts by weight of monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely compatible, it is preferable to add a compatibilizer, such as a water-soluble organic solvent or a low-molecular-weight monomer, that will fully compatibilize these monomers. Adding a compatibilizer can improve emulsifiability and copolymerizability.

[0078] Examples of water-soluble organic solvents include acetone, propylene glycol, dipropylene glycol monomethyl ether (DPM), dipropylene glycol, tripropylene glycol, ethanol, N-methyl-2-pyrrolidone (NMP), 3-methoxy-3-methyl-1-butanol, and isoprene glycol. These may be used in an amount of 1 to 50 parts by weight, e.g., 10 to 40 parts by weight, per 100 parts by weight of water. The addition of NMP, DPM, 3-methoxy-3-methyl-1-butanol, or isoprene glycol (preferably in an amount of, e.g., 1 to 20% by weight, particularly 3 to 10% by weight, based on the composition) improves the stability of the composition (e.g., emulsion). Examples of low-molecular-weight monomers include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate. These may be used in an amount of 1 to 50 parts by weight, e.g., 10 to 40 parts by weight, per 100 parts by weight of the total amount of monomers.

[0079] The oil-proofing agent is preferably in the form of a solution, emulsion, or aerosol. The oil-proofing agent comprises a non-fluorinated copolymer and a medium (for example, a liquid medium such as an organic solvent or water). The oil-proofing agent is preferably an aqueous dispersion of the non-fluorinated copolymer. In the oil-proofing agent, the concentration of the non-fluorinated copolymer may be, for example, 0.01 to 50% by weight. The oil-proofing agent preferably does not contain an emulsifier.

[0080] The organic solvent in the polymer solution can be removed by heating the polymer solution (preferably under reduced pressure) (for example, to 30° C. or higher, for example, 50 to 120° C.).

[0081] The oil-proofing agent can be used to treat (e.g., surface treat) a paper substrate. The oil-proofing agent can be applied to the object to be treated by a conventionally known method. Typically, the oil-proofing agent is dispersed and diluted in an organic solvent or water, and then applied to the surface of the object to be treated by a known method such as dip coating, spray coating, or foam coating, followed by drying (surface treatment). Examples of the paper substrate to be treated include paper, paper containers, and paper molded articles (e.g., pulp molds). The non-fluorine copolymer of the present disclosure adheres well to the paper substrate.

[0082] The paper can be produced by a conventional papermaking method. An internal treatment method in which an oil-proofing agent is added to a pulp slurry before papermaking, or an external treatment method in which an oil-proofing agent is applied to paper after papermaking, can be used. The external treatment method is preferred as the oil-proofing agent treatment method in the present disclosure.

[0083] Size presses using external additive treatment methods can also be divided into the following categories based on the application method. One application method is the so-called pond-type two-roll size press, in which a coating liquid (size liquid) is supplied to the nip formed by passing paper between two rubber rolls, creating a pool of coating liquid called a pond, and the paper is passed through this pool of coating liquid to apply the size liquid to both sides of the paper. Other application methods include the gate roll type, in which the size liquid is applied using a surface transfer method, and the rod metering size press. In the pond-type two-roll size press, the size liquid easily penetrates into the paper, while in the surface transfer type, the size liquid components tend to remain on the paper surface. In the surface transfer type, the coating layer tends to remain on the paper surface compared to the pond-type two-roll size press, and the oil-resistant layer formed on the surface is larger than in the pond-type two-roll size press. In the present disclosure, oil resistance can be imparted to paper even when the former pond-type two-roll size press is used. Papers treated in this way, after simple drying at room temperature or elevated temperature, optionally followed by a heat treatment which may range in temperature up to 300°C, for example up to 200°C, especially between 80°C and 180°C, depending on the nature of the paper, exhibit excellent oil and water resistance.

[0084] The present disclosure can be used in gypsum board base paper, coated base paper, medium paper, general liners and corrugating media, neutral pure white roll paper, neutral liners, anti-rust liners and metal interleaving paper, kraft paper, etc. It can also be used in neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper.

[0085] Pulp raw materials that can be used include bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulps such as groundwood pulp, mechanical pulp or thermomechanical pulp, and recycled paper pulp such as recycled newspapers, recycled magazines, recycled corrugated cardboard, and deinked recycled paper. Mixtures of the above pulp raw materials with synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, and polyvinyl alcohol can also be used.

[0086] A sizing agent can be added to improve the water resistance of paper. Examples of sizing agents include cationic sizing agents, anionic sizing agents, and rosin-based sizing agents (e.g., acidic rosin-based sizing agents and neutral rosin-based sizing agents). The amount of sizing agent may be 0.01 to 5% by weight of the pulp.

[0087] If necessary, the paper can contain additives used in paper production, such as paper strength agents such as starch, modified starch, carboxymethyl cellulose, and polyamide polyamine-epichlorohydrin resin, as well as flocculants, fixing agents, retention aids, dyes, fluorescent dyes, slime control agents, and antifoaming agents, to the extent that they are commonly used. Starch and modified starch are preferably used. If necessary, oil-resistant agents can be applied to the paper using starch, polyvinyl alcohol, dyes, coating colors, anti-slip agents, etc., using a size press, gate roll coater, bill blade coater, calendar, etc.

[0088] In the external addition, the amount of the non-fluorine copolymer contained in the oil-resistant layer is 0.01 to 2.0 g / m ２ , particularly 0.1 to 1.0 g / m ２ The oil-resistant layer is preferably formed from an oil-proofing agent and starch and / or modified starch. The solid content of the oil-proofing agent for paper in the oil-resistant layer is preferably 2 g / m. ２ In the internal addition, the oil-proofing agent is preferably mixed with the pulp so that the amount of the oil-proofing agent is 0.01 to 50 parts by weight or 0.01 to 30 parts by weight, for example 0.01 to 10 parts by weight, particularly 0.2 to 5.0 parts by weight, per 100 parts by weight of the pulp forming the paper. In the external addition and internal addition, the weight ratio of the starch or modified starch to the non-fluorinated copolymer may be 10:90 to 98:2.

[0089] In the external addition, oil resistance can also be imparted to paper by using a so-called pond-type two-roll size press treatment, in which a treatment solution is accumulated between rolls and the base paper is passed through the treatment solution between the rolls at any roll speed and nip pressure.

[0090] The fluorine-free copolymer may be nonionic, cationic, anionic, or amphoteric. In the external additive treatment, the paper substrate may contain additives such as sizing agents, strength agents, flocculants, retention agents, or coagulants. The additives may be nonionic, cationic, anionic, or amphoteric. The ionic charge density of the additives may be -10,000 to 10,000 μeq / g, preferably -4,000 to 8,000 μeq / g, and more preferably -1,000 to 7,000 μeq / g. Additives (solids or active ingredients) such as sizing agents, strength agents, flocculants, retention agents, or coagulants can generally be used in an amount of 0.1 to 10% by weight (e.g., 0.2 to 5.0% by weight) based on the pulp. In the case of a paper substrate containing cationic additives (e.g., sizing agents, strength agents, flocculants, retention agents, or coagulants), the greaseproofing agent is preferably anionic.

[0091] In the internal addition treatment, it is preferable to make paper using a pulp slurry having a pulp concentration of 0.5 to 5.0% by weight (e.g., 2.5 to 4.0% by weight). Additives (e.g., sizing agents, paper strength agents, flocculants, retention agents, or coagulants) and a fluorine-free copolymer can be added to the pulp slurry. Since pulp is generally anionic, it is preferable that at least one of the additive and the fluorine-free copolymer be cationic or amphoteric so that the additive and the fluorine-free copolymer are well fixed to the paper. It is preferable to use a combination in which the additive is cationic or amphoteric and the fluorine-free copolymer is anionic, a combination in which the additive is anionic and the fluorine-free copolymer is cationic or amphoteric, or a combination in which the additive and the fluorine-free copolymer are cationic or amphoteric. It is more preferable to make paper with an ionic charge density of additives such as sizing agents, paper strength agents, flocculants, retention agents, or coagulants of -1000 to 7000 μeq / g, and even more preferable to make paper with an ionic charge density of 100 to 1000 μeq / g (for example, 330 μeq / g, 420 μeq / g, or 680 μeq / g).

[0092] Examples of additives (for example, sizing agents, paper strength agents, flocculants, retention agents, or coagulants) include alkylketene dimers, alkenyl succinic anhydrides, styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylenepolyamines, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0093] In the present disclosure, an article to be treated is treated with an oil-resistant agent. "Treatment" means applying the oil-resistant agent to the article to be treated by immersion, spraying, coating, or the like. Through the treatment, the non-fluorinated copolymer, which is the active ingredient of the oil-resistant agent, penetrates into the interior of the article to be treated and / or adheres to the surface of the article to be treated.

[0094] The present disclosure will now be described in detail with reference to examples, comparative examples, and test examples. However, these examples are not intended to limit the scope of the present disclosure. In the following, parts, percentages, and ratios represent parts by weight, percentages by weight, and ratios by weight unless otherwise specified.

[0095] The test methods used below are as follows:

[0096] Dynamic Viscoelasticity (Complex Viscosity) A non-fluorinated copolymer aqueous dispersion was dried in an oven at approximately 130°C for 30 minutes to obtain a sample copolymer for measurement. The complex viscosity (H*) of the copolymer was measured using a dynamic viscoelasticity measuring device RHEOSOL-G3000 (manufactured by UBM Co., Ltd.) at a heating rate of 1°C / min. Measurement of Weight-Average Molecular Weight The weight-average molecular weight of the fluorinated copolymer was determined by GPC (gel permeation chromatography) (polystyrene equivalent). Oil Resistance (KIT) Oil resistance (KIT method) was measured according to TAPPI T-559cm-02. The KIT test liquid was a mixture of castor oil, toluene, and heptane in the ratios shown in Table 1. A drop of the test liquid shown in Table 1 was placed on paper, and the state of oil penetration was observed after 15 seconds. The highest oil resistance score given by the KIT test liquid showing no penetration was defined as oil resistance. The higher the KIT test liquid number, the higher the oil resistance.

[0097]

[0098] Water resistance (Cobb value) Water resistance (Cobb value) was measured in accordance with JIS P 8140. The weight (g) of water absorbed in one minute by a 100 cm2 piece of paper supporting a height of 1 cm of water was measured, and the value was expressed as the weight per square meter (g / m ２ ) and converted to oil resistance. Oil resistance (Practical Oil Test 1) Approximately 1 g of commercially available olive oil (approximately 0.1 g for treated paper) was dripped onto the resulting paper plate or treated paper, and after leaving it at room temperature (20°C) for 15 minutes, the degree to which the oil had soaked into the back of the paper plate or treated paper was observed. The following evaluation values ​​were set depending on the degree of soaking into the back: 5: 0-5% 4: 6-20% 3: 21-50% 2: 51-75% 1: 76-100% Oil resistance (Practical Oil Test 2) The same method as in Practical Oil Test 1 was used for evaluation, except that the treated paper or paper plate onto which olive oil had been dripped was placed in a 70°C oven, removed after 7 minutes, and the degree of soaking was observed.

[0099] Synthesis Example 1 A 500 ml reactor equipped with a stirrer, thermometer, reflux condenser, dropping funnel, nitrogen inlet, and heating device was prepared, and 100 parts of methyl ethyl ketone (MEK) solvent was added. Subsequently, under stirring, 78 parts of stearyl acrylate (StA, melting point: 30°C), 16 parts of hydroxyethyl acrylate (HEA), and 6 parts of methacrylic acid (MAA) (total of 100 parts of monomers), and 1.2 parts of initiator perbutyl PV (PV) were added in this order, and the mixture was mixed and stirred for 12 hours under a nitrogen atmosphere at 65-75°C to carry out copolymerization. The solids concentration of the resulting copolymer-containing solution was 50 wt%. The molecular weight of the resulting copolymer was analyzed by gel permeation chromatography, and the weight average molecular weight in terms of polystyrene was 230,000. As a post-treatment, 142 g of 0.3% NaOH aqueous solution was added to 50 g of the obtained copolymer solution and dispersed. MEK was then removed under reduced pressure while heating using an evaporator, yielding a milky-white copolymer aqueous dispersion (volatile organic solvent content: 1 wt% or less). Ion-exchanged water was further added to this aqueous dispersion to obtain an aqueous dispersion with a solids concentration of 15 wt%. The melting point of this copolymer was 48°C. The complex viscosity of this copolymer was measured. The results are shown in Figure 1. This copolymer was dissolved in chloroform and spin-coated onto a PET film. After air-drying, the contact angle of the surface was measured; the contact angle with water was 108°, and the contact angle with n-hexadecane was 57-59°.

[0100] Synthesis Example 2: A 500 ml reactor equipped with a stirrer, thermometer, reflux condenser, dropping funnel, nitrogen inlet, and heating device was prepared, and 100 parts of methyl ethyl ketone (MEK) solvent was added. Subsequently, with stirring, a monomer mixture consisting of 78 parts of stearyl acrylate (StA, melting point: 30°C), 16 parts of hydroxyethyl acrylate (HEA), and 6 parts of dimethylaminoethyl methacrylate (DM) (total of 100 parts of monomers), and 1.2 parts of the initiator Perbutyl PV (PV) were added in this order, and the mixture was mixed and stirred under a nitrogen atmosphere at 65-75°C for 12 hours to carry out copolymerization. The solids concentration of the resulting copolymer-containing solution was 50 wt%. As a post-treatment, 142 g of a 0.4% aqueous acetic acid solution was added to 50 g of the obtained copolymer solution, and the mixture was dispersed. The mixture was then heated using an evaporator and the MEK was removed under reduced pressure to obtain a milky white copolymer aqueous dispersion (containing 1 wt% or less of a volatile organic solvent). Ion-exchanged water was further added to this aqueous dispersion to obtain an aqueous dispersion with a solids concentration of 15 wt%. This copolymer was dissolved in chloroform and spin-coated onto a PET film. The contact angles of the air-dried surface were measured, revealing a contact angle of 106° with water and a contact angle of 62° with n-hexadecane.

[0101] Synthesis Example 3 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 2, except that 60 parts of StA and 34 parts of HEA were used, to obtain an aqueous dispersion with a solid concentration of 15% by weight.

[0102] Synthesis Example 4 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 1, except that 6 parts of acrylic acid (AA) was used instead of methacrylic acid (MAA) in Synthesis Example 1, to obtain an aqueous dispersion with a solid content of 15% by weight.

[0103] Synthesis Example 5: Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 1, except that 16 parts of hydroxylethyl methacrylate (HEMA) was used instead of the hydroxylethyl acrylate (HEA) in Synthesis Example 1, to obtain an aqueous dispersion with a solids concentration of 15% by weight. This copolymer was dissolved in chloroform and spin-coated onto a PET film. After air-drying, the contact angles of the surface were measured, and the contact angle with water was 102°, and the contact angle with n-hexadecane was 48°.

[0104] Synthesis Example 6 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 1, except that 78 parts of lauryl methacrylate (LMA, melting point: −7° C.) was used instead of StA in Synthesis Example 1, to obtain an aqueous dispersion with a solid content concentration of 15% by weight.

[0105] Synthesis Example 7 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 1, except that 78 parts of stearyl methacrylate (StMA, melting point: 18°C) was used instead of StA in Synthesis Example 1, to obtain an aqueous dispersion with a solid content concentration of 15% by weight.

[0106] Synthesis Example 8 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 1, except that 78 parts of stearic acid amide ethyl acrylate (C18AmEA, melting point: 70°C) was used instead of StA in Synthesis Example 1, to obtain an aqueous dispersion with a solid content concentration of 15 wt%.

[0107] Synthesis Example 9 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 8, except that 39 parts of C18AmEA and 39 parts of StA were used instead of 78 parts of StA in Synthesis Example 1, to obtain an aqueous dispersion having a solids concentration of 15% by weight.

[0108] Synthesis Example 10: Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 8, except that 6 parts of DM were used instead of MAA, to obtain an aqueous dispersion with a solids concentration of 15% by weight. The melting point of this copolymer was 64°C. The complex viscosity of this copolymer was measured. The results are shown in Figure 1.

[0109] Synthesis Example 11: Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 10, except that 16 parts of hydroxybutyl acrylate (HBA, Tg: -40°C) was used instead of the HEA used in Synthesis Example 10, to obtain an aqueous dispersion with a solids concentration of 15% by weight. The melting point of this copolymer was 66°C. The complex viscosity of this copolymer was measured. The results are shown in Figure 1.

[0110] Synthesis Example 12 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 11, except that 49 parts of C18AmEA and 27 parts of HBA were used, to obtain an aqueous dispersion with a solid concentration of 15% by weight.

[0111] Comparative Synthesis Example 1 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 1, except that 78 parts of methyl methacrylate (MMA, melting point: -48°C) was used instead of StA in Synthesis Example 1, to obtain an aqueous dispersion having a solid content concentration of 15 wt%. Comparative Synthesis Example 2 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 1, except that 16 parts of N-vinylpyrrolidone (NVP) was used instead of HEA in Synthesis Example 2, to obtain an aqueous dispersion having a solid content concentration of 15 wt%. Comparative Synthesis Example 3 Copolymerization and post-treatment were carried out in the same manner as in Synthesis Example 1, except that 78 parts of tertiary butyl methacrylate (TBMA, melting point: -60°C) was used instead of StA in Synthesis Example 1, to obtain an aqueous dispersion having a solid content concentration of 15 wt%.

[0112] [Evaluation by external addition method] Example 1 A pulp slurry was prepared using wood pulp in a weight ratio of 60% by weight of LBKP (hardwood bleached kraft pulp) and 40% by weight of NBKP (softwood bleached kraft pulp) and the pulp had a freeness of 400 ml (Canadian Standard Freeness). A wet strength agent and a sizing agent were added to the pulp slurry, and the slurry was run on a Fourdrinier paper machine to produce a paper with a density of 0.58 g / cm. ３ Basis weight 45g / m ２ The paper was used as the base paper for external treatment (size press treatment). The oil resistance (KIT value) of this base paper was 0, and the water resistance (Cobb value) was 52 g / m ２ It was.

[0113] The aqueous dispersion of the copolymer obtained in Synthesis Example 1 was used as an oil-proofing agent to obtain grease-resistant paper (processed paper) according to the following recipe. The treatment liquid was prepared by adjusting the aqueous dispersion of the copolymer obtained in Synthesis Example 1 to a solids concentration of 2.4 wt % and a starch solids concentration of 7%, and the treatment liquid was processed in a size press and then dried in a drum dryer to obtain grease-resistant paper (processed paper). The coating weight of the starch and copolymer solids of the obtained grease-resistant paper was 1.1 g / m ２ (The coating amount of the copolymer was 0.28 g / m ２ The obtained base paper was used as a test paper to carry out the above kit test. The evaluation results are shown in Table 2.

[0114] The starch used was a common hydroxyethylated starch (Penford 290, manufactured by Penford). The size press treatment (using a size press machine manufactured by Mathis) was a so-called pond-type two-roll size press treatment in which a treatment solution was pooled between rolls and the base paper was passed through the treatment solution between the rolls at a given roll speed and nip pressure.

[0115] Example 2 The same treatment as in Example 1 was carried out except that the copolymer of Synthesis Example 2 was used. The coating amount of the starch and copolymer solids on the obtained greaseproof paper was 1.1 g / m ２ (The coating amount of the copolymer was 0.28 g / m ２ The results are shown in Table 2. Example 3 The same treatment as in Example 1 was carried out except that the copolymer of Synthesis Example 3 was used. The coating amount of the starch and copolymer solids on the obtained grease-resistant paper was 1.1 g / m ２ (The coating amount of the copolymer was 0.28 g / m ２ The results are shown in Table 2.

[0116] Example 4 The same treatment as in Example 1 was carried out except that the copolymer of Synthesis Example 4 was used. The coating amount of the starch and copolymer solids on the obtained greaseproof paper was 1.1 g / m ２ (The coating amount of the copolymer was 0.28 g / m ２ The results are shown in Table 2. Example 5 The same treatment as in Example 1 was carried out except that the copolymer of Synthesis Example 5 was used. The coating amount of the starch and copolymer solids on the obtained grease-resistant paper was 1.1 g / m ２ (The coating amount of the copolymer was 0.28 g / m ２ The results are shown in Table 2.

[0117] Example 6 The same treatment as in Example 1 was carried out except that the copolymer of Synthesis Example 6 was used. The coating amount of the starch and copolymer solids on the obtained greaseproof paper was 1.1 g / m ２ (The coating amount of the copolymer was 0.28 g / m ２ The results are shown in Table 2. Example 7 The same treatment as in Example 1 was carried out except that the copolymer of Synthesis Example 7 was used. The coating amount of the starch and copolymer solids on the obtained grease-resistant paper was 1.1 g / m ２ (The coating amount of the copolymer was 0.28 g / m ２ The results are shown in Table 2.

[0118] Example 8 The same treatment as in Example 1 was carried out except that the copolymer of Synthesis Example 8 was used. The coating amount of the starch and copolymer solids on the obtained greaseproof paper was 1.1 g / m ２ (Copolymer coating amount: 0.28 g / m ２ The results are shown in Table 3.

[0119] Example 9 The same treatment as in Example 1 was carried out except that the copolymer of Synthesis Example 9 was used. The coating amount of the starch and copolymer solids on the obtained greaseproof paper was 1.1 g / m ２ (Copolymer coating amount: 0.28 g / m ２ The results are shown in Table 3. Example 10 The same treatment as in Example 1 was carried out except that the copolymer of Synthesis Example 10 was used. The coating amount of the starch and copolymer solids on the obtained grease-resistant paper was 1.1 g / m ２ (Copolymer coating amount: 0.28 g / m ２ The results are shown in Table 3. Example 11 The same treatment as in Example 1 was carried out, except that the copolymer of Synthesis Example 10 was used and the treatment solution was prepared so that the solid concentration of starch was 14%. The coating amount of the starch and copolymer solids on the obtained greaseproof paper was 2.2 g / m ２ (Copolymer coating amount: 0.32 g / m ２ The results are shown in Table 3. Example 12 The same treatment as in Example 1 was carried out except that the copolymer of Synthesis Example 11 was used. The coating amount of the starch and copolymer solids on the obtained greaseproof paper was 1.1 g / m ２ (Copolymer coating amount: 0.28 g / m ２ The results are shown in Table 3. Example 13 The same treatment as in Example 1 was carried out except that the copolymer of Synthesis Example 12 was used. The coating amount of the starch and copolymer solids on the obtained grease-resistant paper was 1.1 g / m ２ (Copolymer coating amount: 0.28 g / m ２ The results are shown in Table 3.

[0120] Comparative Example 1 The same treatment as in Example 1 was carried out except that only starch was used without using the copolymer. The coating amount of the solid content of starch and copolymer on the obtained greaseproof paper was 1.0 g / m ２ (The amount of copolymer applied was 0.0 g / m ２The results are shown in Table 4. Comparative Example 2 The same treatment as in Example 1 was carried out except that the copolymer of Comparative Synthesis Example 1 was used. The coating amount of the starch and copolymer solids on the obtained grease-resistant paper was 1.1 g / m ２ (The coating amount of the copolymer was 0.28 g / m ２ The results are shown in Table 4.

[0121] Comparative Example 3 The same treatment as in Example 1 was carried out except that the copolymer of Comparative Synthesis Example 2 was used. The coating amount of the starch and copolymer solids on the obtained greaseproof paper was 1.1 g / m ２ (The coating amount of the copolymer was 0.28 g / m ２ The results are shown in Table 4. Comparative Example 4 The same treatment as in Example 1 was carried out except that the copolymer of Comparative Synthesis Example 3 was used. The coating amount of the starch and copolymer solids on the obtained grease-resistant paper was 1.1 g / m ２ (The coating amount of the copolymer was 0.28 g / m ２ The results are shown in Table 4.

[0122]

[0123]

[0124]

[0125] [Evaluation by Internal Addition Method] Example 14 100% by weight of bagasse pulp was used as wood pulp, and a pulp slurry (pulp concentration 2.5%) with a freeness of 600 cc (Canadian freeness) was prepared using a disintegrator. To this pulp slurry, alkyl ketene dimer (AKD), a type of sizing agent, was added at a solids concentration of 0.8% by weight per pulp weight, and then the copolymer aqueous dispersion obtained in Synthesis Example 1 was added at a solids concentration of 1.0% by weight per pulp weight to prepare a pulp slurry. Using this pulp slurry, a paper plate weighing 7 g was made using an "automatic mold tester." The resulting paper plate was subjected to a KIT test, resulting in a KIT value of 2. The results are shown in Table 5.

[0126] Example 15 Paper plates were prepared in the same manner as in Example 14, except that cationic starch was used in place of the AKD in Example 14 at a solids concentration per pulp weight of 1.0% and the copolymer aqueous dispersion was used at a solids concentration per pulp weight of 2.0%. The obtained paper plates were subjected to practical oil test 1, which gave a value of 3. The results are shown in Table 6. Example 16 Paper plates were prepared in the same manner as in Example 15, except that the copolymer aqueous dispersion obtained in Synthesis Example 2 was used in place of the copolymer aqueous dispersion obtained in Synthesis Example 1. The obtained paper plates were subjected to practical oil test 1, which gave a value of 5. The results are shown in Table 6.

[0127] Example 17 Paper plates were produced in the same manner as in Example 15, except that the copolymer aqueous dispersion obtained in Synthesis Example 8 was used instead of the copolymer aqueous dispersion obtained in Synthesis Example 1. The paper plates obtained were subjected to Practical Oil Test 1, and the value was 5. The results are shown in Table 6.

[0128] Comparative Example 5 Paper plates were prepared in the same manner as in Example 14, except that the aqueous copolymer dispersion obtained in Synthesis Example 1 was not added. The resulting paper plates were subjected to a KIT test, resulting in a KIT value of 0. The results are shown in Table 5. Comparative Example 6 Paper plates were prepared in the same manner as in Example 14, except that after adding AKD, the aqueous copolymer dispersion obtained in Comparative Synthesis Example 1 was added at a solids concentration of 1 wt% per pulp weight. The resulting paper plates were subjected to a KIT test, resulting in a KIT value of 0. The results are shown in Table 5.

[0129] Comparative Example 7 A paper plate was prepared in the same manner as in Example 15, except that the aqueous copolymer dispersion obtained in Synthesis Example 1 was not added. The value of the obtained paper plate in the Practical Oil Test 1 was 1. The results are shown in Table 6.

[0130]

[0131]

[0132] Test Example 1 The grease-resistant papers of Examples 10, 11, 12, Comparative Examples 1 and 2 were subjected to practical oil test 1 and practical oil test 2. The results are shown in Table 7.

[0133]

[0134] The grease-resistant agent of the present disclosure can be applied to paper used in food containers and food packaging materials.

[0135] Examples of aspects of the present disclosure are as follows: [1] An oil-proofing agent for paper comprising a non-fluorine copolymer having: (a) repeating units formed from an acrylic monomer having a long-chain hydrocarbon group of 7 to 40 carbon atoms; and (b) repeating units formed from an acrylic monomer having a hydrophilic group. [2] An oil-proofing agent for paper comprising a non-fluorine copolymer having: (a) repeating units formed from an acrylic monomer having a long-chain hydrocarbon group; and (b) repeating units formed from an acrylic monomer having a hydrophilic group. [3] An oil-proofing agent for paper comprising a non-fluorine copolymer having: (a) repeating units formed from an acrylic monomer having a long-chain hydrocarbon group; １ )-C(=O)-Y １ (R １ ) ｋ [In the formula, R １ are each independently a hydrocarbon group having 7 to 40 carbon atoms; １ is a hydrogen atom, a monovalent organic group or a halogen atom, １ represents a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ and k is a group consisting of at least one selected from the group consisting of -, -, -NH-, - ... １ [4] The oil-proofing agent for paper according to either [1] or [2], wherein is a hydrogen atom and the long-chain hydrocarbon group has 18 or more carbon atoms. [4] The acrylic monomer (a) having a long-chain hydrocarbon group is represented by the formula (a1): CH2=C(-X ４ )-C(=O)-Y ２ -R ２ [In the formula, R ２ is a hydrocarbon group having 7 to 40 carbon atoms, and X ４ is a hydrogen atom, a monovalent organic group or a halogen atom, ２ is —O— or —NH—.] and / or (a2) an acrylic monomer represented by the formula: CH═C(—X ５ )-C(=O)-Y ３ -Z (-Y ４ -R ３ ) ｎ [In the formula, R ３are each independently a hydrocarbon group having 7 to 40 carbon atoms; ５ is a hydrogen atom, a monovalent organic group or a halogen atom, ３ is —O— or —NH—, and Y ４ are each independently a direct bond, —O—, —C(═O)—, or —S(═O) ２ - or -NH-, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2.], and the acrylic monomer (b) having a hydrophilic group is represented by the formula: CH ２ =CX ２ C(=O)-O-(RO) ｎ -X ３ (b1) and / or CH ２ =CX ２ C(=O)-O-(RO) ｎ -C(=O)CX ２ =CH ２ (b2) [wherein, X ２ represents a hydrogen atom or a methyl group, X ３ is a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R is an alkylene group having 2 to 6 carbon atoms, and n is an integer of 1 to 90. [5] The oil-proofing agent for paper according to any one of [1] to [3], which is at least one oxyalkylene (meth)acrylate represented by the formula: １ or Y ４ represents -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'-, wherein each Y' independently represents a direct bond, -O-, -NH-, or -S(=O) ２ - and R' is -(CH ２ ) ｍ -(m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -(CH２ ) ｌ -C ６ H ４ -(CH ２ ) ｌ - (each l is independently an integer of 0 to 5; -C ６ H ４ - is a phenylene group).] [6] The oil-proofing agent for paper according to any of [1] to [5], wherein the fluorine-free copolymer further contains a repeating unit formed from a monomer (c) other than the monomers (a) and (b) having an olefinic carbon-carbon double bond, and an anionic donor group or a cationic donor group. [7] The oil-proofing agent for paper according to [6], wherein the anionic donor group is a carboxyl group, or the cationic donor group is an amino group. [8] The oil-proofing agent for paper according to any of [1] to [7], wherein the amount of the repeating unit formed from the acrylic monomer (a) having a long-chain hydrocarbon group is 30 to 95% by weight based on the copolymer. [9] The oil-proofing agent for paper according to any one of [1] to [8], wherein the amount of repeating units formed from the acrylic monomer (a) having a long-chain hydrocarbon group is 30 to 90% by weight, based on the copolymer, the amount of repeating units formed from the acrylic monomer (b) having a hydrophilic group is 5 to 70% by weight, based on the copolymer, and the fluorine-free copolymer is a random copolymer.

[10] The oil-proofing agent for paper according to any one of [1] to [9], wherein the melting point or glass transition point of the fluorine-free copolymer is 20°C or higher and / or the dynamic viscoelasticity (complex viscosity) of the fluorine-free copolymer is 10 to 5000 Pa s at 90°C.

[11] The oil-proofing agent for paper according to any one of [1] to

[10] , further comprising a liquid medium which is water or a mixture of water and an organic solvent.

[12] Grease-resistant paper having, on its surface, an oil-resistant layer containing the oil-proofing agent for paper according to any one of [1] to

[11] and starch or modified starch.

[13] The solid content of the paper oil-proofing agent in the oil-resistant layer is 2 g / m ２

[14] Greaseproof paper containing the greaseproofing agent for paper according to any one of [1] to

[11] inside the paper.

[15] The greaseproof paper according to any one of

[12] to

[14] , which is a food packaging material or a food container.

[16] A paper treatment method, in which the paper is treated with the greaseproofing agent for paper according to any one of [1] to

[11] by external or internal addition.

Claims

Revised 21 / 05 / 20261. Oil-resistant agent for paper, which is composed of a fluorine-free copolymer containing: (a) repeating units formed from acrylic monomers with long-chain hydrocarbon groups of 7 to 40 carbon atoms, (b) repeating units formed from acrylic monomers with hydrophilic groups, and (c) repeating units formed from olefinic carbon-carbon double bond monomers with anionic or cationic groups, in addition to monomers (a) and (b), where the acrylic monomer (b) with hydrophilic groups The hydrophilic group is at least one type selected from a group of compounds with the formulas (b1) to (b3): ​​CH₄=CX^2C(=O)-O-(RO)n-X^3(bl)CH₂=CX^2C(=O)-O-(RO)nC(=O)CX^2=CH₂(b2), and CH₄=CX^2C(=O)-NH-(RO)nX^3(b3), where each independent X^2 group is a hydrogen atom or a methyl group, each independent X^3 group is a hydrogen atom or an unsaturated or saturated hydrocarbon group with 1 to 22 carbon atoms, R is an alkyl group with 2 to 6 carbon atoms, and n is an integer 1 to 90, where the amount of repeating units formed by the acrylic monomer (6) is 5 to 70% by weight.Based on copolymers revised 30 / 12 / 20251. Oil-resistant agent for paper, which consists of a fluorine-free copolymer containing: (a) repeating units formed from acrylic monomers with long-chain hydrocarbon groups of 7 to 40 carbon atoms, (b) repeating units formed from acrylic monomers with hydrophilic groups, and (c) repeating units formed from olefinic carbon-carbon double bond monomers with anionic or cationic groups, in addition to From monomers(a) and(b), where the acrylic monomer(b) containing at least one hydrophilic group is selected from the group of compounds with formulas(bl) to(b3):CH=CX^2C(=O)-O-(RO)nX^3(bl),CH2=CX^2C(=O)-O-(RO)nC(=O)CX^2=CH2(b2), andCH?=CX^2-C(=O)-NH-(RO)nX^3(b3), where each independent X^2 group is a hydrogen atom or a methyl group, each independent X^3 group is a hydrogen atom or an unsaturated or saturated hydrocarbon group with 1 to 22 carbon atoms, R is an alkyl group with 2 to 6 carbon atoms, and n is an integer from 1 to 90,where the amount of repeating units formed by acrylic monomer(6) is 5 to 70% by weight, based on the copolymer DEPCT641.Oil resistant for paper, which is composed of a fluorine-free copolymer containing:(a) repeating units formed by acrylic monomer with long-chain hydrocarbon groups of 7 to 40 carbon atoms, and (b) repeating units formed by acrylic monomer with hydrophilic groups2.Oil resistant for paper according to claim 1, where the acrylic monomer with long-chain hydrocarbon groups(a) is the monomer denoted by the formula:CH2=C(-X1) -C(=O)-Y1(R1)k where each independent R1 is a hydrocarbon group with 7 to 40 carbon atoms, X1 is a hydrogen atom, monovalent organic group, or halogen atom, Y1 is a divalent to tetravalent group consisting of at least one selected group from hydrocarbon groups with one carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH-, provided that hydrocarbon groups are excluded, and k is 1 to 33. Oil-resistant compounds for paper under claim 1 or 2, where, in acrylic monomers containing long-chain hydrocarbon groups (a), X1 is a hydrogen atom,and long-chain hydrocarbon group with 18 to 40 carbon atoms.

4. Oil-resistant compounds for paper according to any one of Claims 1 through 3, where acrylic monomers containing long-chain hydrocarbon groups (a) are: (a1) acrylic monomers denoted by the formula:CH2=C(-X4)-C(=O)-Y2-R2 where R2 is a hydrocarbon group with 7 to 40 carbon atoms, X4 is a hydrogen atom, monovalent organic group, or halogen atom, and Y2 is -O- or -NH-, and / or (a2) acrylic monomers The polymer is represented by the formula: CH2=C(-X5)-C(=O)-Y3-Z(-Y4-R3)n, where each independent R3 group is a hydrocarbon group with 7 to 40 carbon atoms, X5 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y3 is -O- or -NH-, each independent Y4 group is a direct bond, or a group composed of at least one group selected from -O-, -C(=O)-, -S(=O)2-, or -NH-, Z is a direct bond or a divalent or trivalent hydrocarbon group with 1 to 5 carbon atoms.and n is 1 or 2; and the acrylic monomer containing hydrophilic groups (b) is at least one oxyalkylene(meth)acrylate represented by the formula:CH2=CX2C(=O)-O-(RO)n-X3(b1) and / or CH2=CX2C(=O)-O-(RO)nC(=O)CX2=CH2(b2) where X2 is a hydrogen atom or methyl group, X3 is a hydrogen atom or unsaturated or saturated hydrocarbon group with 1 to 22 carbon atoms, R is an alkyl group with 2 to 6 carbon atoms, and n is an integer 1 to 905. Oil-resistant compounds for paper according to claim 2 or 4, where Y1 or Y4 is a molecule. Denoted by: -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'-, Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- where each Y' group independently is a direct bond, -O-, -NH-, or -S(=O)2-, and R' is -(CH2)m- where m is an integer 1 to 5, linear hydrocarbons with 1 to 5 carbon atoms and unsaturated bonds, hydrocarbons with 1 to 5 carbon atoms and branched structure, or -(CH2)1-C6H4-(CH2)1- where each 1 independently is an integer 0 to 5.and -C6H4- is a phenylene group.

6. An oil-resistant paper under any of Claims 1 through 5, in which the fluorine-free copolymer is further incorporated with repeating units which are formed from (c) olefin double-carbon monomers and which contain anionic or cationic groups, other than monomers (a) and (b).

7. An oil-resistant paper under Claim 6, in which the anionic group is a carboxyl group, or the cationic group is an amino group.

8. An oil-resistant paper under any of Claims 1 through 5, in which the fluorine-free copolymer is incorporated with repeating units which are formed from (c) olefin double-carbon monomers and which contain anionic or cationic groups, other than monomers (a) and (b). Claims 1 through 7, where the amount of repeating units formed from long-chain hydrocarbon acrylic monomer (a) is 30 to 95% by weight, based on a copolymer; 9. Oil-resistant compounds for paper under any of Claims 1 through 8, where the amount of repeating units formed from long-chain hydrocarbon acrylic monomer (a) is 30 to 90% by weight, based on a copolymer, the amount of repeating units formed from hydrophilic acrylic monomer (b) is 5 to 70% by weight, based on a copolymer;The amount of repeating units formed by anionic or cationic monomers (c) is 0.1 to 30% by weight, based on a non-fluorine-free copolymer, and the non-fluorine-free copolymer is a random copolymer10.Oil-resistant paper under any of the claims 1 through 9, where the non-fluorine-free copolymer has a melting point or glass transition point of 20 °C or higher, and / or the non-fluorine-free copolymer has dynamic viscoelasticity.

11. Oil-resistant paper according to any of the claims 1 through 10, which is further incorporated with a liquid medium, namely water or a mixture of water and an organic solvent.

12. Oil-resistant paper with an oil-resistant layer incorporating an oil-resistant paper according to any of the claims 1 through 11, and starch or modified starch, on the paper surface.

13. Oil-resistant paper according to claim 12.Where the oil-resistant compound for paper in the oil-resistant layer has a solid content of 2 g / m² or less.

14. Oil-resistant paper which incorporates a fluorine-free copolymer of the oil-resistant compound for paper as described in any of Claims 1 through 11 within the paper.

15. Oil-resistant paper as described in any of Claims 12 through 14, which is a food packaging material or food container.

16. Methods of treatment of paper, which include treatment of paper with the oil-resistant compound for paper as described in any of Claims 1 through 11 by external application or internal application.