TW202106949A - Oil-resistant agent composition for paper - Google Patents

Abstract

This invention provides an oil-resistant agent capable of providing excellent oil-resistant properties for paper.

The oil-resistant agent composition for paper includes (1) non-fluoro polymer and (2) at least one particle selected from inorganic particle or organic particle , and is added inside of paper, wherein, with respect to the total weight of non-fluoro polymer(1) and (2) particle, the amount of particle (2) is 1 to 99.9 weight%.

Description

Oil resistant agent for paper

This disclosure relates to an oil-resistant agent for paper and paper treated with the oil-resistant agent for paper.

Paper is required to have oil resistance.

For example, food packaging materials and food containers made of paper are required to prevent the leakage of water and oil from the food. Therefore, oil-resistant agents are applied to paper by internal or external additions.

Several groups of proposals have been proposed for imparting oil resistance to paper.

Patent Document 1 (Japanese Patent Application Laid-Open No. 2015-129365) discloses a method for forming a cellulose article, which comprises: blending a formulation containing an aqueous dispersion with cellulose fibers, the aqueous dispersion containing selected from the group consisting of ethylene At least one polymer in the group consisting of a thermoplastic polymer, a propylene-based thermoplastic polymer and a mixture of these, at least one polymer stabilizer, and water.

Patent Document 2 (International Application Publication No. 2015/008868) discloses a fine cellulose fiber sheet composed of fine cellulose fibers having an average fiber diameter of 2 nm to 1000 nm, and the weight ratio of the fine cellulose fibers is 50 The weight percentage is greater than or equal to 99% by weight, relative to the weight of the above-mentioned fine cellulose fibers, the aggregate of blocked polyisocyanates is contained in a weight ratio of 1 to 100% by weight.

Patent Document 3 (Japanese Patent Application Laid-Open No. 2004-148307) discloses a method of manufacturing a coated support, which includes: a) a composite multilayer curtain (Curtain) comprising at least two layers of barrier function-imparting layers The forming step and b) the step of bringing the above-mentioned curtain into contact with the continuous web support to obtain the coating support.

[Prior Technical Literature]

[Technical Literature]

[Technical Document 1] Japanese Patent Application Publication No. 2015-129365

[Technical Document 2] International Application Publication 2015/008868 Bulletin

[Technical Document 3] JP 2004-148307 A

The purpose of this disclosure is to provide an oil resistant agent that can impart excellent oil resistance to paper.

This disclosure relates to an oil resistant agent, which comprises (1) a non-fluoropolymer and (2) particles selected from inorganic particles and/or organic particles. In the treatment of paper, the oil-resistant agent can be added externally or internally, but it is better to add the oil-resistant agent internally.

The preferred aspects of the present disclosure are as follows.

[1] An oil resistant agent for paper, which contains:

(1) Non-fluoropolymer, and

(2) At least one kind of particles selected from inorganic particles or organic particles,

The oil resistant agent for paper is added to the inside of the paper,

among them,

The amount of the particles (2) is 1 to 99.9% by weight relative to the total weight of the non-fluoropolymer (1) and the particles (2).

[2] The oil-resistant agent for paper according to [1], wherein the non-fluoropolymer (1) is an acrylic polymer.

[3] The oil-resistant agent for paper as described in [1] or [2], wherein the non-fluoropolymer has a repeating unit formed from an acrylic monomer (a) having a long-chain hydrocarbon group,

The acrylic monomer (a) having a long-chain hydrocarbon group is a monomer represented by the following formula:

CH ₂ =C(-X ¹ )-C(=O)-Y ¹ (R ¹ ) _k where,

R ^{1 is} each independently a hydrocarbon group having 7 to 40 carbon atoms;

X ¹ is a hydrogen atom, a monovalent organic group or a halogen atom;

Y ¹ is a hydrocarbon group with a carbon number of 1 selected from 2 to 4, -C ₆ H ₄ -, -O-, -C(=O)-, -S(=O) ₂ -or -NH- A group consisting of at least one of the above (except for the hydrocarbon group);

k is 1 to 3.

[4] The oil-resistant agent for paper according to [3], wherein, in the acrylic monomer (a) having a long-chain hydrocarbon group, X ¹ is a hydrogen atom or a methyl group.

[5] The oil-resistant agent for paper according to any one of [1] to [4], wherein in the acrylic monomer (a) having a long-chain hydrocarbon group, the carbon number of the long-chain hydrocarbon group is 18 or more.

[6] The oil resistant agent for paper according to any one of [3] to [5], wherein the acrylic monomer (a) having a long-chain hydrocarbon group is an acrylic monomer represented by formula (a1) and/or The acrylic monomer represented by formula (a2), formula (a1):

CH ₂ =C(-X ⁴ )-C(=O)-Y ² -R ²

In the formula, R ² is a hydrocarbon group with 7 to 40 carbons;

X ⁴ is a hydrogen atom, a monovalent organic group or a halogen atom;

Y ² is -O- or -NH-(a2) formula:

CH ₂ =C(-X ⁵ )-C(=O)-Y ³ -Z(-Y ⁴ -R ³ ) _n

In the formula, R ^{3 is} each independently a hydrocarbon group having 7 to 40 carbon atoms;

X ⁵ is a hydrogen atom, a monovalent organic group or a halogen atom;

Y ³ is -O- or -NH-;

Y ^{4 is} each independently a direct bond, or a group consisting of at least one 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;

n is 1 or 2.

[7] The oil resistant agent for paper according to any one of [3] to [6], wherein the acrylic monomer (b) having a hydrophilic group is the following formula (b1), (b2) or (b3) ) Shows at least one oxyalkylene(meth)acrylate, CH ₂ =CX ² C(=O)-O-(RO) _n -X ³ (b1), CH ₂ =CX ² C(=O)-O-(RO) _n -C(=O)CX ² =CH ₂ (b2), or CH ₂ =CX ² C(=O)-NH-(RO) _n -X ³ (b3) where

X ² is a hydrogen atom or a methyl group;

X ³ is a hydrogen atom or an unsaturated or saturated hydrocarbon group with 1 to 22 carbon atoms;

R is each independently an alkylene group having 2 to 6 carbon atoms;

n is an integer from 1 to 90.

[8] The oil-resistant agent for paper according to any one of [3] to [7], wherein the non-fluoropolymer further includes monomers (a) and (b) other than monomers (a) and (b), which are made of olefinic carbon-carbon double The repeating unit formed by the monomer (c) of the bond and the anionic donor group or the cationic donor group.

[9] The oil resistant agent for paper according to [8], wherein the anionic donor group is a carboxyl group, or the cationic donor group is an amino group.

[10] The oil-resistant agent for paper according to any one of [3] to [9], wherein the amount of repeating units formed from the acrylic monomer (a) having a long-chain hydrocarbon group relative to the copolymer is 30 to 90% by weight, relative to the copolymer, the amount of repeating units formed from the acrylic monomer (b) having a hydrophilic group is 5 to 70% by weight.

[11] The oil resistant agent for paper according to any one of [1] to [10], wherein the inorganic particles are selected from calcium carbonate, talc, kaolin, clay, mica, aluminum hydroxide, barium sulfate, silicon It is made of at least one of calcium acid, calcium sulfate, silicon oxide, zinc carbonate, zinc oxide, titanium oxide, bentonite, and white carbon. The organic particles are made of at least one selected from polysaccharides and thermoplastic resins. to make.

[12] The oil-resistant agent for paper according to any one of [1] to [11], wherein the organic particles have a property of being insoluble in water at 40°C.

[13] The oil resistant agent for paper according to any one of [1] to [12], wherein the inorganic particles are calcium carbonate and the organic particles are starch.

[14] The oil-resistant agent for paper according to any one of [1] to [13], wherein the particles (2) contain organic particles.

[15] The oil resistant agent for paper according to any one of [1] to [14], wherein the oil resistant agent for paper further contains water or a liquid medium that is a mixture of water and an organic solvent.

[16] An oil-resistant paper containing the oil-resistant agent for paper according to any one of [1] to [15] in the inside of the paper.

[17] The oil-resistant paper as described in [16], which is a molded pulp product.

[18] The oil-resistant paper as described in [16] or [17], which is a food packaging material or food container.

[19] A method for producing oil-resistant paper, comprising: adding the oil-resistant agent for paper described in any one of [1] to [15] to a slurry prepared by dispersing the pulp in an aqueous medium, Prepare a blended pulp slurry, paper-made oil-resistant paper intermediate, dehydrated and dried to obtain oil-resistant paper.

Among the oil-resistant agents, the non-fluoropolymer is well dispersed in an aqueous medium, especially in water.

The oil resistance agent imparts high oil resistance to the paper. The oil resistance agent can impart high water resistance and high gas barrier properties.

The oil resistant agent system includes (1) a non-fluorine polymer, and (2) particles. The oil resistance agent can be one liquid or two liquids or three liquids. When it is a liquid, it is a liquid containing non-fluoropolymer (1) and particles (2). When it is two liquids (two components), it is a combination of a liquid containing a non-fluoropolymer (1) and a liquid containing particles (2) (or only particles (2)). Among the three liquids (three components), a liquid containing paper additives is added for use. The liquid containing the particles (2) may be solid (for example, only particles).

(1) Non-fluoropolymer

The non-fluorine polymer may be acrylic polymer, polyester polymer, polyether polymer, silicone polymer, urethane polymer, etc. A polymer having an ester bond, amide bond and/or urethane bond is preferred. An acrylic polymer (that is, a non-fluorine acrylic polymer) is particularly preferred. The acrylic polymer is preferably one having an ester bond and/or an amide bond.

The non-fluoropolymer can be a homopolymer or a copolymer. Non-fluoropolymers are preferably copolymers.

The homopolymer has only a repeating unit formed from one type of monomer. The homopolymer is preferably one formed only of acrylic monomers having a long-chain hydrocarbon group having 7 to 40 carbon atoms.

The copolymer has repeating units formed from two or more monomers.

Non-fluorine polymer system to have

(a) A repeating unit formed from an acrylic monomer having a long-chain hydrocarbon group with a carbon number of 7 to 40, and

(b) A repeating unit formed from an acrylic monomer having a hydrophilic group is preferred.

Furthermore, in addition to monomers (a) and (b), non-fluoropolymers are

(c) Monomers with ion-donating groups

The formed repeating unit is preferred.

In addition to monomers (a), (b) and (c), non-fluoropolymers may have

(d) Other monomers

The repeating unit formed.

(a) Acrylic monomers with long-chain hydrocarbon groups

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 long-chain or branched hydrocarbon group having 7 to 40 carbon atoms. The carbon number of the long-chain hydrocarbon group is preferably 10-40, for example 12-30, especially 15-30. Alternatively, the carbon number of the long-chain hydrocarbon group may be 18-40.

The acrylic monomer (a) having a long-chain hydrocarbon group is preferably a monomer represented by the following formula.

CH ₂ =C(-X ¹ )-C(=O)-Y ¹ (R ¹ ) _k [where,

R ^{1 is} each independently a hydrocarbon group having 7 to 40 carbon atoms;

X ¹ is a hydrogen atom, a monovalent organic group or a halogen atom;

Y ¹ is selected from a hydrocarbon group with a carbon number of 1 from 2 to 4 (especially -CH ₂ -, -CH=), -C ₆ H ₄ -, -O-, -C(=O)-,- A group consisting of at least one of S(=O) ₂ -or -NH- (except for hydrocarbon groups);

k is 1 to 3. ]

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

Y ¹ is a base of 2 to 4 valence. Y ¹ is preferably based on 2 valence.

Y ¹ is selected from at least one of a hydrocarbon group with carbon number 1, -C ₆ H ₄ -, -O-, -C(=O)-, -S(=O) ₂ -or -NH- The constituted base (except for the hydrocarbyl group) is preferred. Examples of the hydrocarbon group with a carbon number of 1 include -CH ₂ -, -CH= with a branched structure, or -CH≡ with a branched structure.

Y ¹ can be -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 Y'is a direct bond, -O-, -NH- or -S(=O) ₂ -; R'is -(CH ₂ ) _m- (m is an integer from 1 to 5) or -C ₆ H _4- (phenylene). ].

Specific examples of Y ¹ can be -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=O)- NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -OC 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 -OC(=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 -OC ₆ H ₄ -, -O-(CH ₂ ) _m -NH-S(=O) ₂ -, -O-(CH ₂ ) _m -S(=O) ₂ -NH-, -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- OC 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-[In the formula, m is 1 to 5, especially 2 or 4. ].

The preferable ones of Y ¹ are -O-, -NH-, -O-(CH ₂ ) _m -OC(=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 from 1 to 5, especially 2 or 4. ]. The better Y ¹ is -O- or -O-(CH ₂ ) _m -NH-C(=O)-, especially -O-(CH ₂ ) _m -NH-C(=O)-.

R ¹ is preferably a linear or branched hydrocarbon group. In particular, the hydrocarbon group may be a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group, especially an alkyl group. The carbon number of the hydrocarbon group is preferably 12 to 30, for example, 16 to 26 or 15 to 26, especially 18 to 22 or 17 to 22.

Examples of the acrylic monomer (a) having a long-chain hydrocarbon group are the acrylic monomer represented by the following formula (a1) and the acrylic monomer represented by the following formula (a2),

(a1) Formula:

CH ₂ =C(-X ⁴ )-C(=O)-Y ² -R ² [In the formula, R ² is a hydrocarbon group with 7 to 40 carbon ^{atoms; X 4} is a hydrogen atom, a monovalent organic group or a halogen atom; Y ² is -O- or -NH-. ]

(a2) Formula:

CH ₂ =C(-X ⁵ )-C(=O)-Y ³ -Z(-Y ⁴ -R ³ ) _n [wherein, R ^{3 is} each independently a hydrocarbon group with 7 to 40 carbon atoms; X ⁵ is A hydrogen atom, a monovalent organic group or a halogen atom; Y ³ is -O- or -NH-; Y ^{4 is} each independently a direct bond, or is selected from -O-, -C(=O)-, -S (=O) _{A group consisting of at least one of 2} -or -NH-; Z is a divalent or trivalent hydrocarbon group with 1 to 5 carbon atoms; n is 1 or 2. ].

(a1) Acrylic monomer:

The acrylic monomer (a1) is a compound represented by the following formula,

CH ₂ =C(-X ⁴ )-C(=O)-Y ² -R ² [In the formula, R ² is a hydrocarbon group with 7 to 40 carbon ^{atoms; X 4} is a hydrogen atom, a monovalent organic group or a halogen atom; Y ² is -O- or -NH-. ].

The acrylic monomer (a1) is a long-chain acrylate monomer ^{whose Y 2} is -O-, or a long-chain acrylamide monomer whose ^{Y 2 is -NH-.}

R ² is preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group, especially an alkyl group. In R ² , the carbon number of the hydrocarbon group is preferably 12 to 30, for example, 12 to 26, and 18 to 22 is particularly preferred.

X ⁴ may be a hydrogen atom, a methyl group, a halogen atom excluding a fluorine atom, a substituted or unsubstituted benzyl group, and a substituted or unsubstituted phenyl group. A hydrogen atom, a methyl group or a chlorine atom is preferred.

Preferred specific examples of long-chain acrylate monomers are lauryl (meth)acrylate, stearyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, Stearyl α-chloroacrylate, eicosanyl chloroacrylate, and behenyl chloroacrylate.

Preferred specific examples of the long-chain acrylamide monomer are stearyl (meth)acrylamide, eicosyl (meth)acrylamide, and behenyl (meth)acrylamide.

(a2) Acrylic monomer:

The acrylic monomer (a2) is a monomer different from the acrylic monomer (a1). The acrylic monomer (a2) is a (meth)acrylic acid having a group consisting of at least one selected from -O-, -C(=O)-, -S(=O) _{2-or -NH-} Ester or (meth)acrylamide.

The acrylic monomer (a2) may be a compound represented by the following formula,

CH ₂ =C(-X ⁵ )-C(=O)-Y ³ -Z(-Y ⁴ -R ³ ) _n [wherein, R ^{3 is} each independently a hydrocarbon group with 7 to 40 carbon atoms; X ⁵ is A hydrogen atom, a monovalent organic group or a halogen atom; Y ³ is -O- or -NH-; Y ^{4 is} each independently a direct bond, or is selected from -O-, -C(=O)-, -S (=O) _{A group consisting of at least one of 2} -or -NH-; Z is a direct bond, or a divalent or trivalent hydrocarbon group with 1 to 5 carbon atoms; n is 1 or 2. ].

R ³ is preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group, especially an alkyl group. In R ³ , the carbon number of the hydrocarbon group is preferably 12 to 30, for example, 16 to 26 or 15 to 26, and 18 to 22 or 17 to 22 is particularly preferred.

X ⁵ may be a hydrogen atom, a methyl group, a halogen atom excluding a fluorine atom, a substituted or unsubstituted benzyl group, and a substituted or unsubstituted phenyl group. A hydrogen atom, a methyl group or a chlorine atom is preferred.

Y ⁴ can be -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, Y'is each independently direct Bonding, -O-, -NH- or -S(=O) ₂ -; R'is -(CH ₂ ) _m- (m is an integer from 1 to 5), unsaturated bond with carbon number 1 to 5 A straight-chain hydrocarbon group having a carbon number of 1 to 5, a hydrocarbon group having a branched structure with a carbon number of 1 to 5, or -(CH ₂ ) _l -C ₆ H ₄ -(CH ₂ ) _l -(l is each independently an integer from 0 to 5; ₆ H ₄ -is phenylene). ].

Specific examples of Y ⁴ are direct bonding, -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 -OC(=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 -OC 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 -OC ₆ H ₄ -, -NH-(CH ₂ ) _m -NH-C ₆ H _4- [In the formula, m is an integer of 1 to 5. ].

Y ^{4 is} based on -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 -are preferred. Y ^{4 is} based on -NH-C(=O)-, -C(=O)-NH-, -OC(=O)-NH-, -NH-C(=O)-O- or -NH-C (=O)-NH- is better.

Z is a direct bond, or a divalent or trivalent hydrocarbon group of 1 to 5 carbons, and may have a linear structure or a branched structure. The carbon number of Z is preferably 2 to 4, and 2 is particularly preferred. Specific examples of Z are direct bonding, -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH= with branch structure, -CH ₂ (CH-)CH ₂ -with branch structure, -CH ₂ CH ₂ CH= with branch structure, -CH ₂ CH _{2 with branch structure} CH ₂ CH ₂ CH=, -CH ₂ CH ₂ (CH-)CH ₂ -with branch structure, -CH ₂ CH ₂ CH ₂ CH= with branch structure.

Z is preferably not directly bonded, and Y ⁴ and Z are not directly bonded at the same time.

Acrylic monomer (a2) is based on CH ₂ =C(-X ⁵ )-C(=O)-O-(CH ₂ ) _m -NH-C(=O)-R ³ , CH ₂ =C(-X ⁵ )-C(=O)-O-(CH ₂ ) _m -OC(=O)-NH-R ³ 、CH ₂ =C(-X ⁵ )-C(=O)-O-(CH ₂ ) _m -NH-C(=O)-OR ³ 、CH ₂ =C(-X ⁵ )-C(=O)-O-(CH ₂ ) _m -NH-C(=O)-NH-R ³ is Good [where R ³ and X ⁵ are synonymous with the above].

The acrylic monomer (a2) is particularly preferably CH ₂ =C(-X ⁵ )-C(=O)-O-(CH ₂ ) _m -NH-C(=O)-R ³ .

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 are: lauryl isocyanate, myristate isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, behenyl isocyanate Ester etc.

Alternatively, the acrylic monomer (a2) can also be a (meth)acrylate having an isocyanate group in the side chain, for example: 2-methacryloyloxyethyl methacrylate and long-chain alkylamine or Long-chain alkyl alcohol is produced by reaction. Examples of long-chain alkyl amines include: lauryl amine, myristyl amine, cetyl amine, stearyl amine, oleyl amine, behenyl amine and the like. Examples of long-chain alkyl alcohols include: lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol and the like.

Preferred examples of acrylic monomers containing long-chain hydrocarbon groups are as follows.

Stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl alpha-chloroacrylate, behenyl alpha-chloroacrylate;

Stearyl (meth)acrylamide, behenyl (meth)acrylamide;

[上述式中，n為7至40之數，m為1至5之數。]。

[In the above formula, n is a number from 7 to 40, and m is a number from 1 to 5. ].

[Alpha] position based compound of the above formula is a hydrogen atom of the acrylate compound, specific examples may be α - [alpha] compounds and methacrylic acid para-chlorine atom in the para-methyl α - acrylic acid chloride compound.

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

The acrylic monomer (a) having a long-chain hydrocarbon group is preferably an acrylate in which X ¹ , X ⁴ and X ⁵ are hydrogen atoms.

The acrylic monomer (a2) is preferably an amide group-containing monomer represented by the following formula,

R ¹² -C(=O)-NH-R ¹³ -OR ¹¹ [In the formula, R ¹¹ is an organic residue having an ethylenically unsaturated polymerizable group, R ¹² is a hydrocarbon group with 7 to 40 carbons, and R ¹³ is A hydrocarbon group having 1 to 5 carbon atoms].

R ¹¹ is an organic residue having an ethylenically unsaturated polymerizable group, and it is not particularly limited as long as there is a double bond between carbon and carbon. Specific examples include: -C(=O)CR ¹⁴ =CH ₂ , -CHR ¹⁴ =CH ₂ , -CH ₂ CHR ¹⁴ =CH ₂ and other organic residues having ethylenically unsaturated polymerizable groups, R ¹⁴ can be Examples include hydrogen atoms or alkyl groups with 1 to 4 carbon atoms. Furthermore, R ¹¹ may have various organic groups in addition to the ethylenically unsaturated polymerizable group. Examples thereof include organic groups such as chain hydrocarbon groups, cyclic hydrocarbon groups, polyoxyalkylene groups, and polyoxyalkylene groups. Such organic groups can be substituted with various substituents. R ¹¹ is preferably -C(=O)CR ¹⁴ =CH ₂ .

R ¹² 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 them, a chain hydrocarbon group is preferred, and a linear saturated hydrocarbon group is particularly preferred. The carbon number of R ¹² is from 7 to 40, preferably from 11 to 27, and particularly preferably from 15 to 23.

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 linear or branched, and may have an unsaturated bond, but is preferably linear. The carbon number of R ¹³ is preferably 2 to 4, and 2 is particularly preferred. R ¹³ is preferably an alkylene group.

The monomer containing an amide group can be ^{one type of R 12} (for example: only R ¹² is a compound with 17 carbons), or a ^{combination of R 12 with} plural numbers (for example: a compound with 17 carbons for ^{R 12 and} R ¹² is a mixture of compounds with 15 carbon atoms).

An example of the monomer containing an amido group is alkyl carboxy amido (meth)acrylate.

Specific examples of monomers containing amide groups include: palmitoylamide ethyl (meth)acrylate, stearylamine ethyl (meth)acrylate, and behenylamide ethyl (meth)acrylate Ester, ethyl myristamide (meth)acrylate, ethyl lauramide (meth)acrylate, acetamide isostearate (meth)acrylate, acetamide oleate (meth)acrylate , (Meth) acrylate tertiary butyl cyclohexyl hexyl amide ethyl ester, (meth) acrylate adamantane carboxylate acetamide, (meth) acrylate naphthalene carboxy amide ethyl, (meth) anthracene acrylate Ethyl carboxamide, propyl palmitamide (meth)acrylate, propyl stearylamine (meth)acrylate, palmitamide ethyl vinyl ether, stearylamine ethyl vinyl ether, palmitate Amino ethyl allyl ether, stearylamine ethyl allyl ether, or a mixture of these.

The single system containing an amido group is preferably stearyl ethyl (meth)acrylate. The monomer containing an amido group may be a mixture containing stearyl ethyl (meth)acrylate. In the mixture containing stearyl ethyl (meth)acrylate, the amount of stearyl ethyl (meth)acrylate can be, for example, 55 to 99 weight with respect to the total weight of the monomers containing amide groups. %, preferably 60 to 85% by weight, more preferably 65 to 80% by weight. The remaining monomer may be palmitamide ethyl (meth)acrylate, for example.

(b) Acrylic monomers with hydrophilic groups

The acrylic monomer (b) having a hydrophilic group may be a monomer other than a monomer, and is a hydrophilic monomer. The hydrophilic group is preferably an oxyalkylene group (the alkylene group has a carbon number of 2 to 6). In particular, the acrylic monomer (b) having a hydrophilic group is based on polyalkylene glycol mono(meth)acrylate and/or polyalkylene glycol di(meth)acrylate, polyalkylene glycol mono(meth) ) Acrylamide is preferred. Polyalkylene glycol mono(meth)acrylate and polyalkylene glycol di(meth)acrylate, polyalkylene glycol mono(meth)acrylamide are preferably those represented by the following formula, CH ₂ =CX ² C(=O)-O-(RO) _n -X ³ (b1), CH ₂ =CX ² C(=O)-O-(RO) _n -C(=O)CX ² =CH ₂ (b2 ), or CH ₂ =CX ² C(=O)-NH-(RO) _n -X ³ (b3) [In the formula, X ^{2 is} each independently a hydrogen atom or a methyl group; X ^{3 is} each independently a hydrogen atom Or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms; R is each independently an alkylene group having 2 to 6 carbon atoms; n is an integer from 1 to 99. ].

n can be, for example, 1 to 50, especially 1 to 30, especially 1 to 15 or 2 to 15. Alternatively, n may be 1, for example.

R can be a linear or branched alkylene group, for example, the formula -(CH ₂ ) _x -or -(CH ₂ ) _x1 -(CH(CH ₃ )) _x2 -[where, x1 and x2 are 0 to 6, for example, 2 to 5, and the total of x1 and x2 is 1 to 6. The order of -(CH ₂ ) _x1 -and -(CH(CH ₃ )) _x2 -is not limited to the formula described, and may be random. ] The base shown.

In -(RO) _n -, R can be two or more kinds (for example: 2 to 4 kinds, especially two kinds), -(RO) _n -can be -(R ¹ O) _{n1 -and} -(R ² O) _n2 -[In the formula, R ¹ and R ² are different from each other, and are an alkylene having 2 to 6 carbon atoms, n1 and n2 are numbers greater than 1, and the total of n1 and n2 is 2 to 90. ] Combination.

R in the general formulas (b1), (b2), (b3) is particularly preferably ethylene, propylene or butylene. R in the general formulas (b1), (b2), and (b3) may be a combination of two or more alkylene groups. In this case, at least one of R is preferably ethylene, propylene or butylene. The combination of R can be exemplified as: ethylene/propylidene group Combinations, ethylene/butylene combinations, and propylene/butylene combinations. The monomer (b) may be a mixture of two or more kinds. In this case, at least one of the monomers (b) is preferably one in which R in the general formulas (b1), (b2), (b3) is ethylene, propylene or butylene. Moreover, when the polyalkylene glycol di(meth)acrylate represented by the general formula (b2) is used, it is not suitable to be used as the general formula (b) alone, and it is preferable to use it in combination with the monomer (b1). In this case, the amount of the compound represented by the general formula (b2) is preferably less than 30% by weight of the monomer (b) used.

Specific examples of the acrylic monomer (b) having a hydrophilic group include the following, but are not limited to these.

CH ₂ =CHCOO-CH ₂ CH ₂ OH

CH ₂ =CHCOO-CH ₂ CH ₂ CH ₂ OH

CH ₂ =CHCOO-CH ₂ CH(CH ₃ )OH

CH ₂ =CHCOO-CH(CH ₃ )CH ₂ OH

CH ₂ =CHCOO-CH ₂ CH ₂ CH ₂ CH ₂ OH

CH ₂ =CHCOO-CH ₂ CH ₂ CH(CH ₃ )OH

CH ₂ =CHCOO-CH ₂ CH(CH ₃ )CH ₂ OH

CH ₂ =CHCOO-CH(CH ₃ )CH ₂ CH ₂ OH

CH ₂ =CHCOO-CH ₂ CH(CH ₂ CH ₃ )OH

CH ₂ =CHCOO-CH ₂ C(CH ₃ ) ₂ OH

CH ₂ =CHCOO-CH(CH ₂ CH ₃ )CH ₂ OH

CH ₂ =CHCOO-C(CH ₃ ) ₂ CH ₂ OH

CH ₂ =CHCOO-CH(CH ₃ )CH(CH ₃ )OH

CH ₂ =CHCOO-C(CH ₃ )(CH ₂ CH ₃ )OH

CH ₂ =CHCOO-(CH ₂ CH ₂ O) ₂ -H

CH ₂ =CHCOO-(CH ₂ CH ₂ O) ₄ -H

CH ₂ =CHCOO-(CH ₂ CH ₂ O) ₅ -H

CH ₂ =CHCOO-(CH ₂ CH ₂ O) ₆ -H

CH ₂ =CHCOO-(CH ₂ CH ₂ O) ₅ -CH ₃

CH ₂ =CHCOO-(CH ₂ CH ₂ O) ₉ -CH ₃

CH ₂ =CHCOO-(CH ₂ CH ₂ O) ₂₃ -CH ₃

CH ₂ =CHCOO-(CH ₂ CH ₂ O) ₉₀ -CH ₃

CH ₂ =CHCOO-(CH ₂ CH(CH ₃ )O) ₉ -H

CH ₂ =CHCOO-(CH ₂ CH(CH ₃ )O) ₉ -CH ₃

CH ₂ =CHCOO-(CH ₂ CH(CH ₃ )O) ₁₂ -CH ₃

CH ₂ =CHCOO-(CH ₂ CH ₂ O) ₅ -(CH ₂ CH(CH ₃ )O) ₂ -H

CH ₂ =CHCOO-(CH ₂ CH ₂ O) ₅ -(CH ₂ CH(CH ₃ )O) ₃ -CH ₃

CH ₂ =CHCOO-(CH ₂ CH ₂ O) ₈ -(CH ₂ CH(CH ₃ )O) ₆ -CH ₂ CH(C ₂ H ₅ )C ₄ H ₉

CH ₂ =CHCOO-(CH ₂ CH ₂ O) ₂₃ -OOC(CH ₃ )C=CH ₂

CH ₂ =CHCOO-(CH ₂ CH ₂ O) ₂₀ -(CH ₂ CH(CH ₃ )O) ₅ -CH ₂ -CH=CH ₂

CH ₂ =CHCOO-(CH ₂ CH ₂ O) ₉ -H

CH ₂ =C(CH ₃ )COO-CH ₂ CH ₂ OH

CH ₂ =C(CH ₃ )COO-CH ₂ CH ₂ CH ₂ OH

CH ₂ =C(CH ₃ )COO-CH ₂ CH(CH ₃ )OH

CH ₂ =C(CH ₃ )COO-CH(CH ₃ )CH ₂ OH

CH ₂ =C(CH ₃ )COO-CH ₂ CH ₂ CH ₂ CH ₂ OH

CH ₂ =C(CH ₃ )COO-CH ₂ CH ₂ CH(CH ₃ )OH

CH ₂ =C(CH ₃ )COO-CH ₂ CH(CH ₃ )CH ₂ OH

CH ₂ =C(CH ₃ )COO-CH(CH ₃ )CH ₂ CH ₂ OH

CH ₂ =C(CH ₃ )COO-CH ₂ CH(CH ₂ CH ₃ )OH

CH ₂ =C(CH ₃ )COO-CH ₂ C(CH ₃ ) ₂ OH

CH ₂ =C(CH ₃ )COO-CH(CH ₂ CH ₃ )CH ₂ OH

CH ₂ =C(CH ₃ )COO-C(CH ₃ ) ₂ CH ₂ OH

CH ₂ =C(CH ₃ )COO-CH(CH ₃ )CH(CH ₃ )OH

CH ₂ =C(CH ₃ )COO-C(CH ₃ )(CH ₂ CH ₃ )OH

CH ₂ =C(CH ₃ )COO-(CH ₂ CH ₂ O) ₂ -H

CH ₂ =C(CH ₃ )COO-(CH ₂ CH ₂ O) ₄ -H

CH ₂ =C(CH ₃ )COO-(CH ₂ CH ₂ O) ₅ -H

CH ₂ =C(CH ₃ )COO-(CH ₂ CH ₂ O) ₆ -H

CH ₂ =C(CH ₃ )COO-(CH ₂ CH ₂ O) ₉ -H

CH ₂ =C(CH ₃ )COO-(CH ₂ CH ₂ O) ₅ -CH ₃

CH ₂ =C(CH ₃ )COO-(CH ₂ CH ₂ O) ₉ -CH ₃

CH ₂ =C(CH ₃ )COO-(CH ₂ CH ₂ O) ₂₃ -CH ₃

CH ₂ =C(CH ₃ )COO-(CH ₂ CH ₂ O) ₉₀ -CH ₃

CH ₂ =C(CH ₃ )COO-(CH ₂ CH(CH ₃ )O) ₉ -H

CH ₂ =C(CH ₃ )COO-(CH ₂ CH(CH ₃ )O) ₉ -CH ₃

CH ₂ =C(CH ₃ )COO-(CH ₂ CH(CH ₃ )O) ₁₂ -CH ₃

CH ₂ =C(CH ₃ )COO-(CH ₂ CH ₂ O) ₅ -(CH ₂ CH(CH ₃ )O) ₂ -H

CH ₂ =C(CH ₃ )COO-(CH ₂ CH ₂ O) ₅ -(CH ₂ CH(CH ₃ )O) ₃ -CH ₃

CH ₂ =C(CH ₃ )COO-(CH ₂ CH ₂ O) ₈ -(CH ₂ CH(CH ₃ )O) ₆ -CH ₂ CH(C ₂ H ₅ )C ₄ H ₉

CH ₂ =C(CH ₃ )COO-(CH ₂ CH ₂ O) ₂₃ -OOC(CH ₃ )C=CH ₂

CH ₂ =C(CH ₃ )COO-(CH ₂ CH ₂ O) ₂₀ -(CH ₂ CH(CH ₃ )O) ₅ -CH ₂ -CH=CH ₂

CH ₂ =CH-C(=O)-NH-CH ₂ CH ₂ OH

CH ₂ =CH-C(=O)-NH-CH ₂ CH ₂ CH ₂ OH

CH ₂ =CH-C(=O)-NH-CH ₂ CH(CH ₃ )OH

CH ₂ =CH-C(=O)-NH-CH(CH ₃ )CH ₂ OH

CH ₂ =CH-C(=O)-NH-CH ₂ CH ₂ CH ₂ CH ₂ OH

CH ₂ =CH-C(=O)-NH-CH ₂ CH ₂ CH(CH ₃ )OH

CH ₂ =CH-C(=O)-NH-CH ₂ CH(CH ₃ )CH ₂ OH

CH ₂ =CH-C(=O)-NH-CH(CH ₃ )CH ₂ CH ₂ OH

CH ₂ =CH-C(=O)-NH-CH ₂ CH(CH ₂ CH ₃ )OH

CH ₂ =CH-C(=O)-NH-CH ₂ C(CH ₃ ) ₂ OH

CH ₂ =CH-C(=O)-NH-CH(CH ₂ CH ₃ )CH ₂ OH

CH ₂ =CH-C(=O)-NH-C(CH ₃ ) ₂ CH ₂ OH

CH ₂ =CH-C(=O)-NH-CH(CH ₃ )CH(CH ₃ )OH

CH ₂ =CH-C(=O)-NH-C(CH ₃ )(CH ₂ CH ₃ )OH

CH ₂ =CH-C(=O)-NH-(CH ₂ CH ₂ O) ₂ -H

CH ₂ =CH-C(=O)-NH-(CH ₂ CH ₂ O) ₄ -H

CH ₂ =CH-C(=O)-NH-(CH ₂ CH ₂ O) ₅ -H

CH ₂ =CH-C(=O)-NH-(CH ₂ CH ₂ O) ₆ -H

CH ₂ =CH-C(=O)-NH-(CH ₂ CH ₂ O) ₉ -H

CH ₂ =CH-C(=O)-NH-(CH ₂ CH ₂ O) ₅ -CH ₃

CH ₂ =CH-C(=O)-NH-(CH ₂ CH ₂ O) ₉ -CH ₃

CH ₂ =CH-C(=O)-NH-(CH ₂ CH ₂ O) ₂₃ -CH ₃

CH ₂ =CH-C(=O)-NH-(CH ₂ CH ₂ O) ₉₀ -CH ₃

CH ₂ =CH-C(=O)-NH-(CH ₂ CH(CH ₃ )O) ₉ -H

CH ₂ =CH-C(=O)-NH-(CH ₂ CH(CH ₃ )O) ₉ -CH ₃

CH ₂ =CH-C(=O)-NH-(CH ₂ CH(CH ₃ )O) ₁₂ -CH ₃

CH ₂ =CH-C(=O)-NH-(CH ₂ CH ₂ O) ₅ -(CH ₂ CH(CH ₃ )O) ₂ -H

CH ₂ =CH-C(=O)-NH-(CH ₂ CH ₂ O) ₅ -(CH ₂ CH(CH ₃ )O) ₃ -CH ₃

CH ₂ =CH-C(=O)-NH-(CH ₂ CH ₂ O) ₈ -(CH ₂ CH(CH ₃ )O) ₆ -CH ₂ CH(C ₂ H ₅ )C ₄ H ₉

CH ₂ =C(CH ₃ )-C(=O)-NH-CH ₂ CH ₂ OH

CH ₂ =C(CH ₃ )-C(=O)-NH-CH ₂ CH ₂ CH ₂ OH

CH ₂ =C(CH ₃ )-C(=O)-NH-CH ₂ CH(CH ₃ )OH

CH ₂ =C(CH ₃ )-C(=O)-NH-CH(CH ₃ )CH ₂ OH

CH ₂ =C(CH ₃ )-C(=O)-NH-CH ₂ CH ₂ CH ₂ CH ₂ OH

CH ₂ =C(CH ₃ )-C(=O)-NH-CH ₂ CH ₂ CH(CH ₃ )OH

CH ₂ =C(CH ₃ )-C(=O)-NH-CH ₂ CH(CH ₃ )CH ₂ OH

CH ₂ =C(CH ₃ )-C(=O)-NH-CH(CH ₃ )CH ₂ CH ₂ OH

CH ₂ =C(CH ₃ )-C(=O)-NH-CH ₂ CH(CH ₂ CH ₃ )OH

CH ₂ =C(CH ₃ )-C(=O)-NH-CH ₂ C(CH ₃ ) ₂ OH

CH ₂ =C(CH ₃ )-C(=O)-NH-CH(CH ₂ CH ₃ )CH ₂ OH

CH ₂ =C(CH ₃ )-C(=O)-NH-C(CH ₃ ) ₂ CH ₂ OH

CH ₂ =C(CH ₃ )-C(=O)-NH-CH(CH ₃ )CH(CH ₃ )OH

CH ₂ =C(CH ₃ )-C(=O)-NH-C(CH ₃ )(CH ₂ CH ₃ )OH

CH ₂ =C(CH ₃ )-C(=O)-NH-(CH ₂ CH ₂ O) ₂ -H

CH ₂ =C(CH ₃ )-C(=O)-NH-(CH ₂ CH ₂ O) ₄ -H

CH ₂ =C(CH ₃ )-C(=O)-NH-(CH ₂ CH ₂ O) ₅ -H

CH ₂ =C(CH ₃ )-C(=O)-NH-(CH ₂ CH ₂ O) ₆ -H

CH ₂ =C(CH ₃ )-C(=O)-NH-(CH ₂ CH ₂ O) ₉ -H

CH ₂ =C(CH ₃ )-C(=O)-NH-(CH ₂ CH ₂ O) ₅ -CH ₃

CH ₂ =C(CH ₃ )-C(=O)-NH-(CH ₂ CH ₂ O) ₉ -CH ₃

CH ₂ =C(CH ₃ )-C(=O)-NH-(CH ₂ CH ₂ O) ₂₃ -CH ₃

CH ₂ =C(CH ₃ )-C(=O)-NH-(CH ₂ CH ₂ O) ₉₀ -CH ₃

CH ₂ =C(CH ₃ )-C(=O)-NH-(CH ₂ CH(CH ₃ )O) ₉ -H

CH ₂ =C(CH ₃ )-C(=O)-NH-(CH ₂ CH(CH ₃ )O) ₉ -CH ₃

CH ₂ =C(CH ₃ )-C(=O)-NH-(CH ₂ CH(CH ₃ )O) ₁₂ -CH ₃

CH ₂ =C(CH ₃ )-C(=O)-NH-(CH ₂ CH ₂ O) ₅ -(CH ₂ CH(CH ₃ )O) ₂ -H

CH ₂ =C(CH ₃ )-C(=O)-NH-(CH ₂ CH ₂ O) ₅ -(CH ₂ CH(CH ₃ )O) ₃ -CH ₃

CH ₂ =C(CH ₃ )-C(=O)-NH-(CH ₂ CH ₂ O) ₈ -(CH ₂ CH(CH ₃ )O) ₆ -CH ₂ CH(C ₂ H ₅ )C ₄ H ₉

Monomer (b) is preferably an acrylate or acrylamide ^{with X 2 being a hydrogen atom.} Especially hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethacrylamide is preferred.

(c) Monomers with ion-donating groups

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 olefin carbon-carbon double bond and an ion-donating group. The ion donor group is an anion donor group and/or a cation donor group.

Examples of the monomer having an anion donating group include monomers having a carboxyl group, a sulfonic acid group or a phosphoric acid group. Specific examples of monomers having anion donor groups are (meth)acrylic acid, crotonic acid, and maleic acid Acid, fumaric acid, methylene succinic acid, methyl maleic acid, vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, phosphoric acid (meth)acrylate , Vinylbenzene sulfonic acid, acrylamide tertiary butyl sulfonic acid, etc., or their salts.

Examples of salts of the anion donor group include alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methylammonium salt, ethanolammonium salt, triethanolammonium salt, and the like.

Among monomers having a cation-donating group, examples of the cation-donating group are an amino group, and preferably a tertiary amino group and a quaternary amino group. In the tertiary amine group, the two groups bonded to the nitrogen atom are the same or different aliphatic groups (especially alkyl groups) with 1 to 5 carbon atoms, and aromatic groups (aryl groups) with 6 to 20 carbon atoms. Or an aromatic aliphatic group having 7 to 25 carbon atoms (especially an aralkyl group, such as benzyl (C ₆ H ₅ -CH ₂ -)) is preferred. In the quaternary amino group, the three groups bonded to the nitrogen atom are the same or different aliphatic groups (especially alkyl groups) with carbon numbers of 1 to 5, and aromatic groups (aryl groups) with carbon numbers of 6 to 20. Or an aromatic aliphatic group having 7 to 25 carbon atoms (especially an aralkyl group, such as benzyl (C ₆ H ₅ -CH ₂ -)) is preferred. In the tertiary amino group and the quaternary amino group, the remaining one group bonded to the nitrogen atom may have a carbon-carbon double bond. The cation donor group can be in the form of a salt.

The cation donor group belonging to the salt is a salt formed with an acid (organic acid or inorganic acid). The organic acid is preferably a carboxylic acid having 1 to 20 carbon atoms (especially monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid). Preferred are dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and their salts.

Specific examples of the monomer having a cation-donating group are as follows.

CH ₂ =CHCOO-CH ₂ CH ₂ -N(CH ₃ ) ₂ and its salts (e.g. acetate)

CH ₂ =CHCOO-CH ₂ CH ₂ -N(CH ₂ CH ₃ ) ₂ and its salts (e.g. acetate)

CH ₂ =C(CH ₃ )COO-CH ₂ CH ₂ -N(CH ₃ ) ₂ and its salts (e.g. acetate)

CH ₂ =C(CH ₃ )COO-CH ₂ CH ₂ -N(CH ₂ CH ₃ ) ₂ and its salts (e.g. acetate)

CH ₂ =CHC(O)N(H)-CH ₂ CH ₂ CH ₂ -N(CH ₃ ) ₂ and its salts (e.g. acetate)

CH ₂ =CHCOO-CH ₂ CH ₂ -N(-CH ₃ )(-CH ₂ -C ₆ H ₅ ) and its salts (e.g. acetate)

CH ₂ =C(CH ₃ )COO-CH ₂ CH ₂ -N(-CH ₂ CH ₃ )(-CH ₂ -C ₆ H ₅ ) and its salts (e.g. acetate)

_{CH 2 = CHCOO-CH 2 CH} 2 -N + (CH 3) 3 Cl -

_{CH 2 = CHCOO-CH 2 CH} 2 -N + (-CH 3) 2 (-CH 2 -C 6 H 5) Cl -

_{CH 2 = C (CH 3)} COO-CH 2 CH 2 -N + (CH 3) 3 Cl -

_{CH 2 = CHCOO-CH 2 CH} (OH) CH 2 -N + (CH 3) 3 Cl -

_{CH 2 = C (CH 3)} COO-CH 2 CH (OH) CH 2 -N + (CH 3) 3 Cl -

_{CH 2 = C (CH 3)} COO-CH 2 CH (OH) CH 2 -N + (-CH 2 CH 3) 2 (-CH 2 -C 6 H 5) Cl -

_{CH 2 = C (CH 3)} COO-CH 2 CH 2 -N + (CH 3) 3 Br -

_{CH 2 = C (CH 3)} COO-CH 2 CH 2 -N + (CH 3) 3 I -

CH ₂ =C(CH ₃ )COO-CH ₂ CH ₂ -N ⁺ (CH ₃ ) ₃ O ^- SO ₃ CH ₃

_{CH 2 = C (CH 3)} COO-CH 2 CH 2 -N + (CH 3) (- CH 2 -C 6 H 5) 2 Br -

The monomer (c) having an ion-donating group is preferably methacrylic acid, acrylic acid and dimethylaminoethyl methacrylate, and more preferably methacrylic acid and dimethylaminoethyl methacrylate.

(d) Other monomers

Other monomers (d) are monomers other than monomers (a), (b) and (c). Such other monomers can be enumerated such as: ethylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinyl halide, styrene, α -methylstyrene, p-methylstyrene, polyoxyalkylene mono(methyl) Acrylate, (meth)acrylamide, diacetone (meth)acrylamide, methylolated (meth)acrylamide, N-methylol (meth)acrylamide, alkyl vinyl Ether, haloalkyl vinyl ether, alkyl vinyl ketone, butadiene, isoprene, chloroprene, glycidyl (meth)acrylate, aziridinyl (meth)acrylate, Benzyl (meth)acrylate, isocyanate (meth)ethyl acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, short-chain alkyl (meth)acrylate, maleic anhydride , (Meth) acrylate with polydimethylsiloxane, N-vinyl carbazole.

Relative to non-fluoropolymers (especially acrylic polymers), the amount of repeating units formed by monomer (a) can be 30 to 95% by weight, preferably 40 to 88% by weight, and 50 to 85% by weight % Is better.

Relative to the non-fluoropolymer, the amount of repeating units formed by the monomer (b) can be 5 to 70% by weight, preferably 8 to 50% by weight, and more preferably 10 to 40% by weight.

Relative to the non-fluoropolymer, the amount of repeating units formed by the monomer (c) can be 0.1 to 30% by weight, preferably 0.5 to 20% by weight, and more preferably 1 to 15% by weight.

Relative to the non-fluoropolymer, the amount of the repeating unit formed by the monomer (d) may be 0 to 20% by weight, for example, 1 to 15% by weight, especially 2 to 10% by weight.

The weight average molecular weight of the non-fluoropolymer can be 1,000 to 10,000,000, preferably 5,000 to 8,000,000, and more preferably 10,000 to 4,000,000. The weight average molecular weight is a value obtained by gel permeation chromatography in terms of polystyrene.

In this specification, "(meth)acrylic acid" means acrylic or methacrylic acid. For example: "(meth)acrylate" means acrylate or methacrylate.

Non-fluorine polymers (especially acrylic polymers), from the standpoint of oil resistance, are preferably random copolymers compared to block copolymers.

The polymerization of the non-fluoropolymer 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 organic solvent and water is generally selected. After the polymerization, it is diluted with water and emulsified into water to prepare a treatment liquid.

In the present disclosure, it is preferable to add water and remove the solvent after polymerization (for example, solution polymerization or emulsion polymerization, preferably solution polymerization) to disperse the polymer in water. It is possible to manufacture self-dispersing products without adding emulsifiers.

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

As the polymerization initiator, for example, peroxides, azo compounds, or persulfuric acid compounds can be used. The polymerization initiator is generally water-soluble and/or oil-soluble.

Preferable specific examples of the oil-soluble polymerization initiator 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-nitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-isobutyronitrile), Benzyl peroxide, di-tertiary butyl peroxide, lauryl peroxide, cumene hydroperoxide, tertiary butyl peroxytrimethyl acetate, diisopropyl peroxydicarbonate, tri-peroxide Tertiary butyl methyl acetate and so on.

In addition, preferred specific examples of the water-soluble polymerization initiator include: 2,2'-azobisisobutamidine 2 hydrochloride, 2,2'-azobis(2-methylpropionamidine) salt Acid salt, 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, persulfuric acid Ammonium, hydrogen peroxide, etc.

The polymerization initiator is used in the range of 0.01 to 5 parts by weight relative to 100 parts by weight of the monomer.

Furthermore, for the purpose of molecular weight adjustment, a chain transfer agent such as a mercapto group-containing compound can be used. Specific examples thereof include 2-mercaptoethanol, thiopropionic acid, and alkyl mercaptan. Relative to 100 parts by weight of the monomer, the mercapto group-containing compound is used in the range of less than 10 parts by weight and 0.01 to 5 parts by weight.

Specifically, the non-fluoropolymer system can be manufactured in the following manner.

In the solution polymerization, a method of dissolving the monomer in an organic solvent, replacing with nitrogen, adding a polymerization initiator, and heating and stirring for 1 to 10 hours in the range of, for example, 40 to 120°C is adopted. The polymerization initiator may generally be an oil-soluble polymerization initiator.

Organic solvents are those that are inert to monomers and dissolve them. They are ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and methyl acetate; propylene glycol, dipropylene glycol monomethyl ether, N- Methyl-2-pyrrolidone (NMP), dipropylene glycol, tripropylene glycol, low molecular weight polyethylene glycol and other glycols; ethanol, isopropanol and other alcohols; n-heptane, n-hexane, n-octane, Cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane, methylpentane, 2-ethylpentane, isoalkane hydrocarbons, liquid paraffin, decane, undecane, dodecane , Mineral spirits, terpene minerals, naphtha and other hydrocarbon solvents. Preferred examples of solvents include, for example: acetone, chloroform, HCHC225, isopropanol, 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, trichloroethane Vinyl chloride, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, N-methyl-2-pyrrolidone (NMP), dipropylene glycol monomethyl ether (DPM), etc. The organic solvent is used in the range of 50 to 2000 parts by weight, for example, 50 to 1000 parts by weight with respect to 100 parts by weight of the total monomers.

In the emulsion polymerization, the monomer is emulsified in water in the presence of an emulsifier, etc., after nitrogen replacement, a polymerization initiator is added, and the mixture is stirred at 40 to 80°C for 1 to 10 hours to polymerize. The polymerization initiator is a water-soluble polymerization initiator, for example: 2,2'-azobisisobutamidine 2 hydrochloride, 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 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-nitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-isobutyronitrile), benzyl peroxide, Di-tertiary butyl peroxide, lauryl peroxide, cumene hydroperoxide, trimethyl acetic acid tertiary butyl peroxide, diisopropyl dicarbonate peroxide, trimethyl acetic acid Tertiary butyl peroxide. The polymerization initiator is used in the range of 0.01 to 10 parts by weight relative to 100 parts by weight of the monomer.

In order to obtain an aqueous polymer dispersion with excellent storage stability, it is desirable to use an emulsification device such as a high-pressure homogenizer or an ultrasonic homogenizer that can impart powerful crushing energy, to form monomers into particles in water, and then use oil-soluble polymerization to start The agent is polymerized. In addition, various emulsifiers of anionic, cationic, or nonionic properties can be used as the emulsifier, and it is used in the range of 0.5 to 20 parts by weight relative to 100 parts by weight of the monomer. It is better to use anionic and/or nonionic and/or cationic emulsifiers. When the monomers are completely incompatible, it is better to add a compatibilizer that makes the monomers fully compatible, such as water-soluble organic solvents or low molecular weight monomers. The addition of compatibilizer can improve emulsification and copolymerization.

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 or isoprene glycol, etc., can be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, relative to 100 parts by weight of water. By adding NMP or DPM or 3-methoxy-3-methyl-1-butanol or isoprenediol (relative to the composition, the preferred amount is, for example, 1 to 20% by weight, especially 3 to 10% by weight) %) to improve the stability of the composition (especially emulsion). Moreover, low molecular weight monomers include, for example, methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., relative to 100 parts by weight of the total monomers, It can be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight.

The amount of the non-fluoropolymer (1) is 0.1 to 99% by weight relative to the total weight of the non-fluoropolymer (1) and the particles (2). The lower limit of the amount of the non-fluoropolymer (1) may be 1% by weight, for example 5% by weight, especially It is 10% by weight, especially 20% by weight or 30% by weight. The upper limit of the amount of the non-fluoropolymer (1) may be 90% by weight, for example 70% by weight, especially 60% by weight, especially 50% by weight or 40% by weight.

(2) Particles

The particles (2) contain at least one of inorganic particles and organic particles. The particles (2) preferably contain organic particles. It is more preferable that the particle (2) contains both inorganic particles and organic particles.

Inorganic particles are particles made of inorganic substances. Examples of inorganic substances constituting inorganic particles include: calcium carbonate, talc, kaolin (and fired kaolin), clay (and fired clay), mica, aluminum hydroxide, barium sulfate, calcium silicate, calcium sulfate, and dioxide Silicon, zinc carbonate, zinc oxide, titanium oxide, bentonite, white carbon. It is better to use calcium carbonate, silicon dioxide, and fired clay. Calcium carbonate is particularly preferred.

Organic particles are particles made of organic matter. Examples of organic substances constituting organic particles include polysaccharides and thermoplastic resins (for example, polyvinyl alcohol, polyolefin, and polystyrene). Organic particles (e.g., polysaccharide particles, thermoplastic resin particles) can be modified (e.g., cationic or anionic). Polysaccharides are preferred.

Polysaccharides are biopolymers synthesized in biological systems through the condensation of various monosaccharides, and they also include those that have been chemically modified (modified). Examples of polysaccharides include starch, cellulose, modified cellulose, amylose, amylopectin, triglucose, Cattleya polysaccharide, xanthan gum, chitin, and chitosan. Examples of modified cellulose include hydroxymethyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose.

The polysaccharide is preferably starch. The dispersibility of starch particles in pulp slurry is excellent. Examples of starches include rice flour starch, wheat starch, corn starch, potato starch, tapioca starch, sweet potato starch, red bean starch, mung bean starch, kudzu root starch, and chestnut (pig tooth flower) starch. The starch may be unmodified starch. Starch can be modified by enzyme, thermochemical, acetic acid esterification, phosphoric acid esterification, Carboxyl etherification modification, hydroxyl etherification modification, cationization modification, etc. Since it provides high air permeability and high oil resistance, the starch is preferably amphoteric starch (starch with cationic and anionic groups) or cationized starch (starch with cationic groups). Since the water resistance is also increased, a combination of amphoteric starch and cationized starch (preferably weight ratio is 0.1:9.9 to 4:6 or 0.5:9.5 to 2:8) is preferred.

In the particle (2), the cationic group (especially the cationic group in amphoteric starch or cationized starch) is the same cationic group as the cationic group in the monomer (c) having an ion-donating group, for example, it can be an amine The anionic group (especially the anionic group in the amphoteric starch) is the same anionic group as the anionic group in the monomer (c) having an ion-donating group, for example, a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

The shape of the particles (2) can be powder, granular, fibrous, scaly, etc.

The particles (inorganic particles and organic particles) are preferably those that are insoluble in water at 40°C. The property of being insoluble in water means that the solubility in 100 g of water at 40°C is 1 g or less, for example, 0.5 g or less.

The average particle size of the particles may be 0.01 to 100 μm, for example, 0.1 to 50 μm, especially 1.0 to 2.0 μm.

The average particle size can be measured by using a particle size distribution measuring device (applying light scattering theory) by laser diffraction using an aqueous dispersion of particles.

For organic particles, the temperature of dissolution in water is preferably about 55°C or higher (for example, 60°C to 100°C). "Dissolution temperature" means that, under atmospheric pressure, it is observed with the naked eye, while stirring, after adding 5 parts by weight of organic particles (the initial addition may be a turbid liquid) to 100 parts by weight of water maintained at the target temperature, while stirring Keep the temperature for 30 minutes, check whether the appearance of the liquid has changed from turbid to transparent, and check the meaning of the highest temperature among the temperatures at which it becomes transparent.

Examples of such water-soluble organic particles are unmodified starch, modified starch (for example, cationized starch), locust bean gum, carboxymethyl cellulose, and polyvinyl alcohol.

The organic particles may be ionic or non-ionic. When the pulp is ionic, the organic particles are preferably ionic particles that can be easily fixed in the pulp slurry and on the pulp in the product, especially anionic, cationic or amphoteric organic particles. Especially when the pulp is ionic, it is advisable to use organic particles with an ionic part opposite to that of the pulp. This can effectively fix the organic particles (preferably used with an oil-resistant agent) on the pulp and improve the final The gas barrier properties of the obtained molded pulp container. Pulp is generally anionic. For this kind of pulp, it is preferable that organic particles have cationic sites, and more specifically, those that are cationized or amphotericized.

The organic particles with cationic sites include cationized starch, amphoteric starch, cationic modified polyvinyl alcohol, and the like.

The amount of the particles (2) is 1 to 99.9% by weight relative to the total weight of the non-fluoropolymer (1) and the particles (2). The lower limit of the amount of particles (2) may be 10% by weight, for example 30% by weight or 40% by weight, especially 50% by weight or 60% by weight, especially 65% by weight or 70% by weight. The upper limit of the amount of particles (2) may be 99% by weight or 98% by weight, for example, 97% by weight or 95% by weight, especially 90% by weight, especially 80% by weight or 70% by weight. Or, relative to the total weight of the non-fluoropolymer (1) and the particles (2), the amount of the particles (2) can be 60 to 99% by weight, for example, 65% or 98% by weight, especially 70 to 97% by weight %.

(3) Other ingredients

The oil-resistant agent may contain other components other than the non-fluoropolymer (1) and particles (2). Examples of other components include aqueous media, emulsifiers, and the like.

The aqueous medium is water, or a mixture of water and an organic solvent (an organic solvent mixed with water). The amount of the aqueous medium may be 50% to 99.99% by weight relative to the total amount of the non-fluoropolymer (1) (and particles (2) if necessary) and the aqueous medium.

The amount of the emulsifier may be 0 to 30 parts by weight relative to 100 parts by weight of the non-fluoropolymer (1), for example, it may be 0.1 to 10 parts by weight.

[Oil Resistant Agent]

The oil resistant agent can be in the form of a solution, emulsion or mist (aerasol, also known as aerosol). The oil-resistant agent system may include a non-fluoropolymer (1) and a liquid medium. The liquid medium is, for example, an organic solvent and/or water, and an aqueous medium is preferred. The aqueous medium is water, or a mixture of water and an organic solvent (for example, polypropylene glycol and/or its derivatives).

In the form of dispersion (emulsification), the non-fluoropolymer is a water-dispersible type in which the non-fluoropolymer (1) is dispersed in an aqueous medium, which can emulsify the non-fluoropolymer (1) by itself, and can also be in the form of a neutralized salt It may be dispersed in an aqueous medium, or an emulsifier may be used for emulsification.

The particles (2) can be used in solid form or dispersed in a liquid medium. The non-fluoropolymer (1) and the particles (2) can be dispersed in the same liquid medium or in different liquid media. In the oil resistant agent, the concentration of the non-fluoropolymer can be, for example, 0.01 to 50% by weight. The oil resistance agent may contain or not contain an emulsifier, but the one that does not contain an emulsifier is preferred.

Oil-resistant agents can be used to treat paper substrates. "Treatment" refers to the application of an oil-resistant agent to the inside and/or outside of the paper.

The oil-resistant agent can be applied to the object to be treated by a conventional method. The oil resistance agent can be added internally and mainly exists in the interior of the paper.

Examples of the paper substrate of the processed object include paper, paper containers, paper molded articles (for example, pulp molding), and the like.

Non-fluoropolymers can adhere well to paper substrates.

If the amount of the non-fluoropolymer (1) and the particles (2) is 0.01 to 75 parts by weight relative to 100 parts by weight of the solid content of the pulp, for example, 0.1 to 60 parts by weight, it is better to use an oil-resistant agent.

[Paper making (that is, paper making)]

The paper can be manufactured by conventional papermaking methods. The internal treatment method of adding oil-resistant agent to the pulp slurry before papermaking can be used, or the external treatment method of applying oil-resistant agent to the paper after papermaking. The treatment method of the oil-resistant agent in this disclosure is preferably an internal addition treatment method. Even if the oil resistant agent of the present disclosure is used in the internal addition treatment, no new device is required.

In the internal addition treatment, the oil-resistant agent is mixed with the pulp slurry to make paper, and the paper treated with the oil-resistant agent can be produced. The paper treated with oil resistant agent is oil resistant paper with oil resistance. Grease-resistant paper can be thin paper, thick paper or pulp molded.

After the paper thus treated is simply dried at room temperature or high temperature, depending on the nature of the paper, it is rendered by heat treatment with a temperature range of up to 300°C, for example up to 200°C, especially 80°C to 180°C. Excellent oil resistance and water resistance.

The present disclosure can be used for gypsum board base paper, coated base paper, medium-quality paper, ordinary lining paper and core paper, neutral pure white roll paper, neutral lining paper, anti-rust lining paper, metal lining paper, kraft paper, etc. Moreover, it can also be used for neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure sensitive paper, neutral inkjet paper and neutral information paper.

The pulp used as a raw material (pulp raw material) can be bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp; bleached or unbleached high-quality pulp such as ground wood pulp, mechanical pulp or thermomechanical pulp Pulp produced; old paper pulp such as old newspapers, old magazine paper, old corrugated paper or deinked old paper; bagasse pulp, kenaf pulp, bamboo pulp and other non-wood pulps, or one or two of them A combination of the above. Furthermore, it is also possible to use one or a mixture of two or more kinds of pulp raw materials, and synthetic fibers such as asbestos, polyamide, polyimide, polyester, and polyolefin.

In the internal addition treatment, the pulp slurry with a pulp concentration of 0.5 to 5.0% by weight (for example, 2.5 to 4.0% by weight) is preferably used for papermaking. Additives (such as sizing agents, paper strength enhancers, flocculants, retention aids or coagulants, etc.) and non-fluoropolymers can be added to the pulp slurry. Since pulp is generally anionic, in order to fix the additives and non-fluoropolymers on the paper well, at least one of the additives and non-fluoropolymers is preferably cationic or amphoteric. Preferably, the additives are cationic or amphoteric and the non-fluoropolymer is negative, the additive is anionic and the non-fluoropolymer is positive or amphoteric, and the additive and non-fluoropolymer are cationic or amphoteric. combination.

In addition to oil resistant agents, other ingredients (additives) can also be used. Examples of other components include cationic coagulants, water-resistant agents, paper strength enhancers, flocculants, fixatives, retention aids, and the like.

Cationic coagulants, paper strength enhancers, flocculants, fixatives, and retention aids can use cationic or amphoteric polymers or inorganic substances. With cationic coagulant, paper strength enhancer, flocculant, fixing agent, retention aid, the oil resistant agent composed of non-fluoropolymer (1) and particles (2) can be effectively fixed to the generally anionic On the pulp, the gas barrier and/or water and oil resistance of the final molded pulp container can be improved.

Examples of cationic coagulants, paper strength enhancers, flocculants, fixatives, and retention aids include: polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, cationic polyacrylamide (acrylamide) -Allylamine copolymer, acrylamide-dimethylaminoethyl (meth)acrylate copolymer, acrylamide-diethylaminoethyl (meth)acrylate copolymer, acrylamide- Quaternary (meth)acrylic dimethylamine Ethyl ester copolymer, acrylamide-quaternary (meth)acrylic acid diethyl amino ethyl copolymer, etc.), polydiallyldimethylammonium chloride, polyallylamine, polyvinylamine , Polyethyleneimine, N-vinylformamide-vinylamine copolymer, melamine resin, polyamide epoxy resin, aluminum sulfate, PAC (polychlorinated aluminum), aluminum chloride, ferric chloride, etc. . In particular, polyamide polyamine-epichlorohydrin (PAE), polydiallyl dimethyl ammonium chloride (poly-DADMAC), polypropylene amide (PAM), etc. can be used.

In addition to oil-resistant agents, water-resistant agents can also be used. In the present disclosure, "water resistant agent" refers to a component that can improve the water resistance of a molded pulp product by adding it to the pulp slurry compared to when it is not added (except for the above-mentioned oil resistant agent). The water resistance of the finally obtained pulp molded container can be improved by the water resistance agent. Moreover, the above-mentioned cationic coagulant generally cannot improve the water resistance alone, and it can be understood that it is different from the water resistance agent.

The water-resistant agent can be used as a sizing agent in general papermaking. Examples of water-resistant agents include cationic sizing agents, anionic sizing agents, and rosin-based sizing agents (for example, acidic rosin-based sizing agents, neutral rosin-based sizing agents), and cationic sizing agents are preferred. Among them, styrene-containing polymers such as styrene-(meth)acrylate copolymers, alkenyl succinic anhydride, and alkyl ketene dimers are preferred.

In addition, according to other needs, dyes, fluorescent dyes, slime control agents, anti-slip agents, defoamers, asphalt control agents, etc. that are generally used in paper treatment agents as papermaking chemicals can be used.

The paper system is preferably a pulp molded product. The production of molded pulp products can be obtained by including: adding an oil-resistant agent to a slurry in which the pulp is dispersed in an aqueous medium to prepare a blended pulp slurry, making a pulp molding intermediate, dewatering, and then at least drying it. Pulp molded products are manufactured by the method of manufacturing.

The preparation of the blended pulp slurry is preferably carried out by maintaining the presence of organic particles in a solid state. For example: the blended pulp slurry is prepared at a temperature lower than the melting temperature of the organic particles, for example, at least 5°C lower. In the prepared blended pulp slurry, the organic particles maintain a solid state (depending on The organic particles used as a raw material are present in powder, granular, fibrous, scaly, etc.). For example, when powdered starch is used as a raw material, the powdered starch can be dispersed in an aqueous medium.

The order of adding oil-resistant agent, organic particles, and cationic coagulant and/or water-resistant agent depending on the situation to the pulp slurry can be in any order as long as the organic particles remain in a solid state.

The content ratio of each component in the blended pulp slurry (on a whole basis) can be appropriately selected to have a high degree of freeness suitable for papermaking and dehydration, and can be adapted to the physical properties required for the pulp molded product, for example, the following can be :

˙Aqueous medium 89.5 to 99.89% by weight, especially 94.5 to 99.69% by weight

˙Pulp 0.1 to 5% by weight, especially 0.3 to 2.5% by weight

˙Oil resistance agent (solid content) 0.00001 to 1% by weight, especially 0.0001 to 0.5% by weight

˙Cationic coagulant (solid content) 0.1 to 1% by weight, especially 0 to 0.5% by weight (when added, for example, 0.00005% by weight or more)

˙Water resistant agent (solid content) 0 to 1% by weight, especially 0 to 0.5% by weight (when added, for example, 0.00005% by weight or more)

In addition, in the above, when each component is in the form of a dispersion or the like, the content ratio of the solid content of each component in the blended pulp slurry (as a whole) is shown.

From another point of view, relative to the aqueous medium in the blended pulp slurry, the content ratio of the pulp and the oil resistance agent can be appropriately selected to have a high degree of freeness suitable for papermaking and dehydration, for example, the following can be:

˙Pulp 0.1 to 5.58% by weight, especially 0.3 to 2.64% by weight

˙Oil resistance agent (solid content) 0.001 to 2.79% by weight, especially 0.005 to 1.05% by weight

When organic particles are dissolved in an aqueous medium (or when an aqueous solution in which organic particles such as starch have been dissolved in an aqueous medium is added to the pulp slurry), the freeness of the resulting aqueous composition will decrease. On the other hand, in the blended pulp slurry, when the organic particles do not dissolve in the aqueous medium but exist in a solid state, compared to when the organic particles are dissolved in the aqueous medium, the freeness of the blended pulp slurry can be maintained at a high level. At the same time, a large amount of organic particles are added.

Secondly, a pulp molding intermediate is made from the above-prepared blended pulp slurry, and after dehydration, at least it is dried to obtain a pulp molded product.

The papermaking, dewatering, and drying system can be implemented in accordance with a conventionally known method as pulp molding.

For example: the blended pulp slurry is sieved and dewatered (for example, by suction and/or decompression) using a mold with many holes in the desired shape (if necessary, a filter can be arranged in it), so that at least A portion of the aqueous medium is removed from the blended pulp slurry, and a pulp molding intermediate having a shape corresponding to the mold can be obtained.

However, the above-mentioned blended pulp slurry is carried out from preparation to dehydration while maintaining the solid state of the organic particles. For example, the operation until dehydration after preparation is performed at a temperature lower than the dissolution temperature of the organic particles, for example, at least 5°C lower. Papermaking and dewatering is to remove the aqueous medium from the blended pulp slurry through a mold (and in some cases, a filter). Therefore, if the freeness of the blended pulp slurry is excessively reduced due to the dissolution of organic particles, papermaking and dehydration That is, it cannot be implemented substantially, so it is not good. On the other hand, if the organic particles maintain a solid state, the freeness of the blended pulp slurry will not decrease, and papermaking and dehydration can be carried out appropriately.

After dehydration, in the obtained pulp molding intermediate, the organic particles remain in a solid state (depending on whether the organic particles used as the raw material are powder, granular, fibrous, scaly, etc.). For example, powdered starch is used as the raw material. When used, the powdered starch can be dispersed in an aqueous medium.

Drying is a way to keep the organic particles in a solid state without being implemented. It can effectively remove the remaining aqueous medium at a temperature (if this is the case, it can be a temperature above the dissolution temperature of the organic particles), for example: 90 to 250 °C, especially at 100 to 200 °C. The drying time is not particularly limited, and can be selected in such a way that the aqueous medium remaining in the pulp molding intermediate is substantially removed. The dry environment is not particularly limited. For convenience, the surrounding environment (air under normal pressure) can be used.

During and/or after drying, other conventionally known steps in pulp molding, such as compression molding (including hot pressing), etc., may be implemented as necessary.

During drying and/or compression molding, higher gas barrier properties can be obtained by at least partial dissolution of organic particles. However, the organic particles do not need to be completely dissolved, and part of the organic particles can remain in a solid state.

Through the above, a pulp molded product can be manufactured. The pulp molded product contains pulp and an oil resistance agent, and can achieve high gas barrier properties and excellent water and oil resistance.

In the pulp molded product of the present disclosure, the content ratio of organic particles in the pulp is 0.0001 to 75% by weight, for example, 0.1 to 60% by weight, especially 2 to 50% by weight.

In order to improve the strength, when an aqueous solution obtained by pre-dissolving organic particles such as starch in an aqueous medium is added to the pulp slurry to obtain a pulp molded product, even if the content of organic particles in the pulp is relatively low, sufficient Strengthen the effect, without the need to increase the content ratio of organic particles in the pulp.

In the present disclosure, the content ratio of organic particles in the pulp is preferably higher, and the lower limit of the content ratio of organic particles in the pulp may be 3% by weight or 5% by weight, for example, 8% by weight or 10% by weight, especially 15% by weight. The upper limit of the content ratio of the organic particles in the pulp may be 60% by weight, for example, 50% by weight or 40% by weight, especially 30% by weight or 20% by weight. The content ratio of organic particles in the pulp can be 3 to 70 % By weight or 5 to 60% by weight, for example 8 to 50% by weight or 8 to 40% by weight. That is, relative to 100 parts by weight of the pulp, the content ratio of the organic particles may be 3 to 70 parts by weight or 5 to 60 parts by weight, for example, 8 to 50 parts by weight or 8 to 40 parts by weight. With such a high content ratio of organic particles, not only high gas barrier properties can be obtained, but also water resistance and oil resistance can be further improved.

In the pulp molded product, the organic particles may be derived from powdered starch dispersed in an aqueous medium (in the blended pulp slurry).

The ratio of the pulp, organic particles, oil-resistant agent, and the required cationic coagulant and/or water-resistant agent contained in the molded pulp product can be regarded as substantially the solid content of the ingredients used as the raw material. The ratios are equal (usually, the aqueous medium and other liquid medium if present can be removed by drying and compression molding, but solids that have not been removed or decomposed may remain).

In the molded pulp product, the content ratio of each component (the component that can remain in the molded pulp product) to the pulp (solid content) can be appropriately selected according to the physical properties required by the molded pulp product, for example, the following Narrator.

˙Oil resistance agent (solid content) 0.01 to 50% by weight or 0.01 to 20% by weight, especially 0.05 to 10% by weight

˙Cationic coagulant (solid content) 0 to 20% by weight, especially 0 to 10% by weight (if present, for example, 0.001% by weight or more)

˙Water resistant agent (solid content) 0 to 20% by weight, especially 0 to 10% by weight (if present, for example, 0.001% by weight or more)

Pulp molded products are made by adding oil-resistant agents (added to pulp slurry and manufactured by the pulp molding method). Therefore, after using the pulp molded product, the product can be crushed as a whole, which can be restored to the original material, which is suitable for recycling. Further, the pulp molded product can utilize the biodegradability of the pulp itself to minimize the impact on the environment, and it is best to substantially eliminate the impact on the environment. And, in the In the pulp molded product, the texture of the pulp can be maintained on the surface of the product, and when the surface is laminated with the plastic film, the gloss will not appear and the appearance will not be impaired.

The pulp molded product can be suitably used as a container for food (including trays, etc.), for example, as a container for preservation of frozen food and children's food.

Since the pulp molded product of the present disclosure has excellent water resistance and oil resistance, the moisture or oil derived from the food will not impregnate the pulp molded product. Therefore, it can prevent the container from being impregnated with moisture or oil to reduce the strength of the container, or The table top facing the bottom of the container is soiled by water or oil that has penetrated into the container. Moreover, the pulp molded product of the present disclosure has high gas barrier properties and is difficult to penetrate gas and water vapor. Therefore, when storing high-temperature and high-humidity food, or heating in a microwave oven while storing the food, it can prevent the source The gas and water vapor from the food pass through the container and leak out, especially in order to prevent the problem of condensation on the table top facing the bottom of the container. Moreover, since the pulp molded product of the present disclosure has high gas barrier properties and is difficult to penetrate gas and water vapor (or moisture), it can effectively reduce the evaporation of water from the food when it is frozen and stored in the state of storing food. Or the food is exposed to oxygen, and it can effectively prevent the freezer bum caused by these reasons, and can maintain the flavor of the food for a long time.

Above, the implementation type is described, but it should be understood that various changes in type and details can be made without departing from the spirit and scope of the scope of the patent application.

[Example]

Next, examples, comparative examples, and test examples are given to specifically explain the present disclosure. However, this disclosure is not limited by these instructions.

Unless otherwise specified, parts,% or ratios in the following represent parts by weight,% by weight or ratio by weight, respectively.

The test methods used in the following are as follows.

[High temperature oil resistance]

Pour 100ml of evaluation solution (corn oil) at 90°C into the molded pulp product in the shape of a container, let it stand for 30 minutes, discard the evaluation solution, and visually evaluate the evaluation solution in the molded pulp product (container) according to the following criteria The degree of staining.

4: There is almost no oil stains on the inside of the bottom of the molded pulp container

3: No oil stains can be seen on the outside of the bottom of the molded pulp container

2: Oil stains with an area of less than 5% are found on the outside of the bottom of the molded pulp container

1: Oil stains with an area of more than 5% and less than 50% are found on the outside of the bottom of the molded pulp container

0: More than 50% oil stains are found on the outside of the bottom of the molded pulp container

[High temperature water resistance]

Pour 100ml of evaluation solution (tap water) at 90°C into the molded pulp product in the shape of a container, let it stand for 30 minutes, discard the evaluation solution, and visually evaluate the performance of the evaluation solution in the molded pulp product (container) according to the following criteria Degree of stain.

4: There is almost no water stains on the inside of the bottom of the molded pulp container

3: No water stains can be seen on the outside of the bottom of the molded pulp container

2: Water stains with an area of less than 5% are found on the outside of the bottom of the molded pulp container

1: Water stains with an area of more than 5% and less than 50% are found on the outside of the bottom of the molded pulp container

0: More than 50% water stains are found on the outside of the bottom of the molded pulp container

[Air Permeability]

The air permeability (air resistance) at the bottom of the container-shaped pulp molded product is an automatic Galley air permeability tester manufactured by Yasuda Seiki Seisakusho Co., Ltd. (product number 323-AUTO, pore diameter 28.6±0.1mm), Measured in accordance with JIS P8117 (2009). According to the following standards, the measured air permeability values are classified and evaluated.

Evaluation benchmark

◎: More than 500 seconds

○: 300 seconds or more

△: more than 100 seconds

×: less than 100 seconds

Synthesis example 1

Prepare a 500ml reactor with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet and a heating device, and add 100 parts of methyl ethyl ketone (MEK) as a solvent. Then, under stirring, monomers containing 78 parts of stearyl acrylate (StA, melting point: 30°C), 16 parts of hydroxyethyl acrylate (HEA), and 6 parts of methacrylic acid (MAA) were sequentially added (total monomers) 100 parts), and 1.2 parts of tert-Butyl Peroxy Pivalate (PBPV) as the initiator, and then the mixture was mixed and stirred for 12 hours under a nitrogen atmosphere at 65 to 75°C for copolymerization . The solid content concentration of the resulting copolymer-containing solution was 50% by weight. After the molecular weight of the obtained copolymer was analyzed by gel permeation chromatography, the mass 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 to disperse it, and while heating with an evaporator, MEK was distilled off under reduced pressure to obtain a milky white copolymer aqueous dispersion (volatile The organic solvent content is 1% by weight or less). Furthermore, ion-exchanged water was added to the aqueous dispersion to obtain an aqueous dispersion with a solid content of 15% by weight.

The melting point of the copolymer is 48°C.

Synthesis Example 2

Prepare a 500ml reactor with a stirring device, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet and a heating device, and add 100 parts of methyl ethyl ketone (MEK) as a solvent. Next, stir Add in order below 78 parts of stearylamine ethyl acrylate (C18AmEA, melting point: 70℃), 16 parts of hydroxybutyl acrylate (HBA, Tg: -40℃) and dimethylaminoethyl methacrylate (DM) 6 parts of monomer (a total of 100 parts of monomers), and 1.2 parts of tert-Butyl Peroxy Pivalate (PBPV) as the starter, and then mix the mixture at 65 to The copolymerization was carried out by mixing and stirring for 12 hours in a nitrogen atmosphere at 75°C. The resulting solid content concentration of the copolymer-containing solution was 50% by weight.

As a post-treatment, 142 g of 0.4% acetic acid aqueous solution was added to 50 g of the obtained copolymer solution to disperse it, and while heating with an evaporator, MEK was distilled off under reduced pressure to obtain a light brown aqueous copolymer dispersion ( The volatile organic solvent content is 1% by weight or less). Furthermore, ion-exchanged water was added to the aqueous dispersion to obtain an aqueous dispersion with a solid content of 15% by weight.

Example 1

To 550cc of freeness (Canadian freeness), while adding 2400g of beaten 70 parts of hardwood bleached kraft pulp and 30 parts of needle leaf bleached kraft pulp, 0.5% by weight aqueous dispersion was added while stirring and mixing, and then , Add 1.2g of calcium carbonate and continue stirring for 1 minute, then add 2.4g of 5% solids aqueous solution of amphoteric starch and continue stirring for 1 minute, then add 5% solids of alkyl ketene dimer (AKD) After 0.72 g of the aqueous solution, stirring was continued for 1 minute, and then 3.6 g of the aqueous dispersion of the non-fluorinated copolymer of Synthesis Example 2 was diluted with water to a solid content of 10%, and stirring was continued for 1 minute.

Put the above-mentioned pulp slurry into a metal tank. At the bottom of the tank, there is a metal pulp molding mold provided with a large number of suction holes, and the mold is in a state where a mesh body is arranged on the mold. From the side opposite to the side where the network body is equipped with the pulp molding mold, the aqueous composition containing the pulp is pumped and dewatered by the vacuum pump through the pulp molding mold and the network body to make the aqueous composition containing the pulp The solid content (pulp, etc.) contained in the material accumulates on the net-like body to obtain a pulp molded intermediate. Next, the obtained pulp molding intermediate is pressurized up and down on a metal male and female molding die heated to 60 to 200°C and allowed to dry. Thereby, a pulp molded product formed with a container shape is manufactured. Table 1 shows the content ratio of each component in the obtained pulp molded product and the evaluation results of high temperature oil resistance, high temperature water resistance, and air permeability.

Example 2

To 550cc of freeness (Canadian freeness), while adding 2400g of beaten 70 parts of hardwood bleached kraft pulp and 30 parts of needle leaf bleached kraft pulp, 0.5% by weight aqueous dispersion was added while stirring and mixing, and then , Add 0.6g of calcium carbonate and continue to stir for 1 minute, then add 1.2g of powdered cationized starch and continue to stir for 1 minute, then add 2.4g of 5% solid aqueous solution of amphoteric starch and continue to stir for 1 minute. Then add 0.72g of 5% solid content aqueous solution of alkyl ketene dimer (AKD) and continue stirring for 1 minute. Then, add the aqueous dispersion of the non-fluorinated copolymer of Synthesis Example 2 and dilute with water to 10% solid content. After 3.6 g of the obtained product, stirring was continued for 1 minute.

Then, except for using the above-mentioned pulp slurry, the same operation as in Example 1 was performed to produce a pulp molded product. Table 1 shows the content ratio of each component in the obtained pulp molded product and the evaluation results of high temperature oil resistance, high temperature water resistance, and air permeability.

Example 3

The same experiment as in Example 1 was performed except that 1.2 g of calcium carbonate in Example 2 and 2.4 g of powdered cationized starch were added. Table 1 shows the content ratio of each component in the obtained pulp molded product and the evaluation results of high temperature oil resistance, high temperature water resistance, and air permeability.

Example 4

The same experiment as in Example 1 was performed except that 2.4 g of the water dispersion of the non-fluorinated copolymer of Synthesis Example 2 in Example 3 was diluted with water to a solid content of 10%. Each of the obtained pulp molded products The content ratio of the components in the pulp and the evaluation results of high temperature oil resistance, high temperature water resistance, and air permeability are shown in Table 1.

Example 5

Except for adding 4.8 g of powdered cationized starch in Example 4, the same experiment as in Example 1 was performed. Table 1 shows the content ratio of each component in the obtained pulp molded product and the evaluation results of high temperature oil resistance, high temperature water resistance, and air permeability.

Example 6

The same experiment as in Example 1 was performed except that the calcium carbonate in Example 5 was not added, and the aqueous dispersion of the non-fluorinated copolymer of Synthesis Example 2 was diluted with water to a solid content of 10%, and 3.6 g was added. Table 1 shows the content ratio of each component in the obtained pulp molded product and the evaluation results of high temperature oil resistance, high temperature water resistance, and air permeability.

Example 7

The same experiment as in Example 1 was performed except that the 5% solid solution of amphoteric starch in Example 5 and the 5% solid solution of alkyl ketene dimer (AKD) were not added. Table 1 shows the content ratio of each component in the obtained pulp molded product in the pulp, and the evaluation results of high temperature oil resistance, high temperature water resistance, and air permeability.

Example 8

Except for adding 0.6 g of calcium carbonate in Example 1, the same experiment as in Example 1 was performed. Table 1 shows the content ratio of each component in the obtained pulp molded product and the evaluation results of high temperature oil resistance, high temperature water resistance, and air permeability.

Example 9

Except for adding the water dispersion of the non-fluorinated copolymer of Synthesis Example 2 in Example 8 with water to dilute to a solid content of 10%, 3.6 g was kept stirring for 1 minute, and then the non-fluorinated copolymer of Synthesis Example 1 was added. The same experiment as in Example 1 was performed except that 6.0 g of the aqueous dispersion was diluted with water to a solid content of 10%, and stirring was continued for 1 minute. Table 1 shows the content ratio of each component in the obtained pulp molded product and the evaluation results of high temperature oil resistance, high temperature water resistance, and air permeability.

Example 10

The same experiment as in Example 1 was carried out except that the 5% solid solution aqueous solution of the alkyl ketene dimer (AKD) in Example 3 was not added. Table 1 shows the content ratio of each component in the obtained pulp molded product and the evaluation results of high temperature oil resistance, high temperature water resistance, and air permeability.

Comparative example 1

Except for not adding the calcium carbonate in Example 1, but adding styrene-butadiene latex and diluting with water to a solid content of 10%, 3.6 g is substituted for the aqueous dispersion of the non-fluorinated copolymer of Synthesis Example 2 with water The same experiment as in Example 1 was performed except for the product diluted to 10% solid content. Table 1 shows the content ratio of each component in the obtained pulp molded product and the evaluation results of high temperature oil resistance, high temperature water resistance, and air permeability.

Comparative example 2

Except for adding styrene-butadiene latex and diluting it with water to a solid content of 10%, 3.6g is substituted for the water dispersion of the non-fluorinated copolymer of Synthesis Example 2 in Example 2 and diluted with water to a solid content of 10 Except for the% obtained, the same experiment as in Example 1 was performed. Table 1 shows the content ratio of each component in the obtained pulp molded product and the evaluation results of high temperature oil resistance, high temperature water resistance, and air permeability.

[Table 1]

[Industrial availability]

The oil resistant agent of the present disclosure can be applied to various papers, especially paper used for food containers and food packaging materials. By adding externally or internally, especially internally, the oil-resistant agent is incorporated into the paper.

Claims (19)

An oil resistant agent for paper, which contains: (1) Non-fluoropolymer, and (2) At least one kind of particles selected from inorganic particles or organic particles, The oil resistant agent for paper is added to the inside of the paper, among them, The amount of the particles (2) is 1 to 99.9% by weight relative to the total weight of the non-fluoropolymer (1) and the particles (2). The oil-resistant agent for paper according to claim 1, wherein the non-fluoropolymer (1) is an acrylic polymer. The oil-resistant agent for paper according to claim 1 or 2, wherein the non-fluoropolymer has a repeating unit formed from an acrylic monomer (a) having a long-chain hydrocarbon group, The acrylic monomer (a) having a long-chain hydrocarbon group is a monomer represented by the following formula: CH ₂ =C(-X ¹ )-C(=O)-Y ¹ (R ¹ ) _k Where R ^{1 is} each independently a hydrocarbon group having 7 to 40 carbon atoms; X ¹ is a hydrogen atom, a monovalent organic group or a halogen atom; Y ¹ is selected from a hydrocarbon group with a carbon number of 1 from 2 to 4, -C ₆ H ₄ -, -O-, -C(=O)-, -S(=O) ₂ -or -NH- At least one group constituted by more than one group (except hydrocarbyl group); k is 1 to 3. The oil-resistant agent for paper according to claim 3, wherein, in the acrylic monomer (a) having a long-chain hydrocarbon group, X ¹ is a hydrogen atom or a methyl group. The oil-resistant agent for paper according to claim 3 or 4, wherein in the acrylic monomer (a) having a long-chain hydrocarbon group, the carbon number of the long-chain hydrocarbon group is 18 or more. The oil-resistant agent for paper according to any one of claims 3 to 5, wherein the acrylic monomer (a) having a long-chain hydrocarbon group is an acrylic monomer represented by formula (a1) and/or formula (a2) The acrylic monomer shown, (a1) formula: CH ₂ =C(-X ⁴ )-C(=O)-Y ² -R ² Where R ² is a hydrocarbon group with 7 to 40 carbons; X ⁴ is a hydrogen atom, a monovalent organic group or a halogen atom; Y ² is -O- or -NH- (a2) Formula: CH ₂ =C(-X ⁵ )-C(=O)-Y ³ -Z(-Y ⁴ -R ³ ) _n Where R ^{3 is} each independently a hydrocarbon group having 7 to 40 carbon atoms; X ⁵ is a hydrogen atom, a monovalent organic group or a halogen atom; Y ³ is -O- or -NH-; Y ^{4 is} each independently a direct bond, or a group consisting of at least one 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; n is 1 or 2. The oil-resistant agent for paper according to any one of claims 3 to 6, wherein the acrylic monomer (b) having a hydrophilic group is at least one represented by the following formula (b1), (b2) or (b3) 1 oxyethylene (meth)acrylate, CH ₂ =CX ² C(=O)-O-(RO) _n -X ³ (b1), CH ₂ =CX ² C(=O)-O-(RO) _n -C(=O)CX ² =CH ₂ (b2), or CH ₂ =CX ² C(=O)-NH-(RO) _n -X ³ (b3) Where X ² is a hydrogen atom or a methyl group; X ³ is a hydrogen atom or an unsaturated or saturated hydrocarbon group with 1 to 22 carbon atoms; R is each independently an alkylene group having 2 to 6 carbon atoms; n is an integer from 1 to 90. The oil-resistant agent for paper according to any one of claims 3 to 7, wherein the non-fluorine polymer further includes monomers (a) and (b) other than monomers (a) and (b) having olefinic carbon-carbon double bonds and anionic properties. A repeating unit formed by the monomer (c) of the donor group or the cationic donor group. The oil-resistant agent for paper according to claim 8, wherein the anionic donor group is a carboxyl group, or the cationic donor group is an amino group. The oil-resistant agent for paper according to any one of claims 3 to 9, wherein the amount of the repeating unit formed from the acrylic monomer (a) having a long-chain hydrocarbon group is 30 to 90% by weight relative to the copolymer Relative to the copolymer, the amount of repeating units formed by the acrylic monomer (b) having a hydrophilic group is 5 to 70% by weight. The oil resistant agent for paper according to any one of claims 1 to 10, wherein the inorganic particles are selected from calcium carbonate, talc, kaolin, clay, mica, aluminum hydroxide, barium sulfate, calcium silicate, sulfur The organic particles are made of at least one of calcium acid, silicon oxide, zinc carbonate, zinc oxide, titanium oxide, bentonite, and white carbon, and the organic particles are made of at least one selected from polysaccharides and thermoplastic resins. The oil-resistant agent for paper according to any one of claims 1 to 11, wherein the organic particles have a property of being insoluble in water at 40°C. The oil resistance agent for paper according to any one of claims 1 to 12, wherein the inorganic particles are calcium carbonate and the organic particles are starch. The oil-resistant agent for paper according to any one of claims 1 to 13, wherein the particles (2) contain organic particles. The oil-resistant agent for paper according to any one of claims 1 to 14, wherein the oil-resistant agent for paper further contains water or a liquid medium that is a mixture of water and an organic solvent. An oil-resistant paper containing the oil-resistant agent for paper according to any one of claims 1 to 15 inside the paper. The oil-resistant paper according to claim 16, which is a molded pulp product. The oil-resistant paper described in claim 16 or 17, which is a food packaging material or a food container. A method for manufacturing oil-resistant paper, comprising: adding the oil-resistant agent for paper according to any one of claims 1 to 15 to a slurry prepared by dispersing the pulp in an aqueous medium to prepare a blended pulp slurry , Papermaking oil-resistant paper intermediate, dehydrated and dried to obtain oil-resistant paper.