JP2000136495A - Composition for processing paper and processed paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a composition for processing paper, capable of imparting excellent water resistance, oil resistance and water repellency to paper by mixing a specific (meth)acrylic copolymer with a surfactant and an aqueous medium. SOLUTION: This composition for processing paper is prepared by mixing 1-30 wt.% polymer based on the weight of the composition with both at least one kind selected from a group consisting of an anionic surfactant, a cationic one and an ampholytic one and an aqueous medium such as water or a mixture of water with a water-soluble organic solvent. The polymer consists of (A) 30-90 wt.% polymer from a polyfluoroalkyl group-including (meth)acrylate and a vinylidene halide as essential monomers, (B) 0.01-50 wt.% polymer from a polyfluoroalkyl group-including (meth)acrylate and a vinyl halide as essential monomers and (C) 0.01-50 wt.% polymer from a cycloalkyl (meth)acrylate [and/ or an alkyl (meth)acrylate] and a polyfluoroalkyl group-including (meth)acrylate as essential monomers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a composition for paper treatment and a treated paper treated with the composition.

[0002]

2. Description of the Related Art In recent years, interest in environmental protection has increased, and plastic food containers and plastic confectionery containers have been replaced with paper containers. BACKGROUND ART A paper container or paper used for the container is subjected to a water- and oil-resistant treatment for the purpose of imparting a property (water- and oil-resistance) that prevents oil and moisture contained in food and confectionery from seeping out.

Conventionally, as a water- and oil-resistant finishing agent for paper, 1) a phosphoric ester compound having a polyfluoroalkyl group (hereinafter referred to as ^Rf group) (JP-A-64-6).
196, JP-A-3-123786), 2) A copolymer essentially comprising a polymer unit of an acrylate having an ^Rf group, a polymer unit of an alkyl (meth) acrylate, and a polymer unit of a methacrylate having a polyethylene oxide side chain (JP-A-Hei. 8-59751), 3) Copolymers essentially comprising a polymerized unit of an acrylate having an ^Rf group and a polymerized unit of vinylidene chloride (JP-A-55-069697, JP-A-51-133)
511, JP-B-53-22547), and the like.

[0004]

However, in the processing agent of 1), since the phosphate compound having an R ^f group is a water-soluble compound, water repellency, which is a property of repelling water, cannot be imparted to paper. There was a problem. Further, when the phosphate compound having an R ^f group is treated together with a sizing agent, there is also a problem that oil repellency, which is a property of repelling oil, is significantly reduced.

[0005] In addition, there is an external addition method in which a base paper is impregnated or coated with a processing agent as a general method of water and oil resistance processing of paper. In the external addition method, a size press or various coaters are used, and drying is performed at 80 to 100 ° C. for a short time of several seconds to several tens of seconds. When a processing agent is used in this external addition method, it is necessary to impart high water and oil resistance by drying at a low temperature for a short time, and for that purpose, a component having good film forming properties at a low temperature and drying for a short time is used. There is a need.

However, when the processing agent of 2) is used,
There was a problem of not exhibiting sufficient performance. The processing agent of 3) is stable when a mechanical force is applied to the processing liquid by, for example, diluting with water at the time of processing into paper, dipping the paper at a high speed, performing a squeezing step, or circulating the processing liquid. And the problem of scum and roll contamination was observed. In addition, the processing agents 1) to 3) were insufficiently adsorbed on paper, and a problem that water resistance, oil resistance, and water repellency were not sufficiently exhibited was recognized.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and is intended for paper processing which is excellent in mechanical stability and imparts excellent water repellency and water and oil resistance to paper. The following invention provides a composition.

That is, the present invention relates to a paper comprising the following polymer (B) and / or polymer (C), polymer (A), surfactant (D), and aqueous medium (E) as essential components. A treatment composition is provided. Polymer (A): a polymer essentially comprising a polymerized unit of a (meth) acrylate having an R ^f group and a polymerized unit of vinylidene halide. Polymer (B): a polymer which essentially contains a polymerized unit of a (meth) acrylate having a R ^f group and a polymerized unit of vinyl halide and does not contain a polymerized unit of vinylidene halide. Polymer (C): a polymer unit of a cycloalkyl (meth) acrylate and / or a polymer unit of an alkyl (meth) acrylate and a polymer unit of a (meth) acrylate having a polyfluoroalkyl group are indispensable. Polymer containing no polymerized units and polymerized units of vinylidene halide.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid, and the same applies to notations such as (meth) acrylate. Hereinafter, terms used in the present specification will be described.

[(Meth) acrylate having R ^f group]
The (meth) acrylate having R ^f group means a compound ^the R ^f group is present in the alcohol residue portion of the (meth) acrylate. The R ^f group refers to a group in which two or more hydrogen atoms of an alkyl group have been substituted with fluorine atoms. The ^Rf group preferably has 2 to 20 carbon atoms, particularly preferably 6 to 16 carbon atoms. Further, the R ^f group may have a linear structure or a branched structure, and particularly preferably has a linear structure. In the case of a branched structure, the branched portion is preferably present at the terminal of the R ^f group, and is preferably a short chain having about 1 to 4 carbon atoms. The R ^f group may contain another halogen atom other than a fluorine atom.
As another halogen atom, a chlorine atom is preferable.

An etheric oxygen atom or a thioetheric sulfur atom may be inserted between the carbon-carbon bonds in the R ^f group. The structure of the terminal portion of the ^Rf group is -C
_{F 2 CF 3, -CF (CF} 3) 2, -CF 2 H, -CF
H _2, include -CF ₂ Cl and the like, -CF ₂ CF ₃ are preferred.

[0012] The number of fluorine atoms in the R ^f groups, [(R ^f number of fluorine atoms in the group) / (R ^f number of hydrogen atoms contained in the alkyl group corresponding same carbon number and group)] × 100 (%)
When expressed by, it is preferably 60% or more, particularly 80%
The above is preferred. Further, the R ^f group is preferably a perfluoroalkyl group in which all of the hydrogen atoms of the alkyl group have been substituted with fluorine atoms, or a group having a perfluoroalkyl group at the terminal portion.

The perfluoroalkyl group has 2 to 2 carbon atoms.
0 is preferable, and especially 6 to 16 is preferable. When the number of carbon atoms is less than 6, water repellency and oil repellency tend to decrease, and when it exceeds 16, the polymer becomes a solid at room temperature, has high sublimability, and may be difficult to handle. There is.

R^f Specific examples of the group include the following groups
Can be C_Four F₉ − [F (CF_Two )_Four −, (CF_Three )_Two 
CFCF_Two −, (CF_Three )_Three C- and CF_Three CF_Two 
CF (CF_Three )-Etc.], C_Five F₁₁
-[For example, F (CF_Two )_Five −], C₆ F₁₃-[Parable
BA F (CF_Two )₆ −], C₇ F_Fifteen-[For example, F (CF
_Two )₇ −], C₈ F₁₇-[For example, F (CF_Two ) ₈ 
−], C₉ F₁₉-[For example, F (CF_Two )₉ −], C_Ten
F_{twenty one}-[For example, F (CF_Two )_Ten−], C₁₂F_{twenty five}-[T
For example, F (CF_Two )₁₂−], C₁₄F₂₉-[Eg F
(CF_Two )₁₄−], C₁₆F₃₃-[For example, F (CF_Two )
₁₆−], Cl (CF_Two )_s -(Where s is 2 to 16
Integer), H (CF_Two )_t -(Where t is an integer of 2 to 16)
Number), (CF_Three )_Two CF (CF_Two )_y − (Where y is
Integer from 1 to 14) and the like.

When the R ^f group is a group having an etheric oxygen atom inserted between carbon-carbon bonds or a thioetheric sulfur atom inserted between carbon-carbon bonds, the following groups may be mentioned. .

F (CF ₂ ) ₅ OCF (CF ₃ ) —, F
[CF (CF ₃ ) CF ₂ O] _r CF (CF ₃ ) CF ₂ C
F ₂ −, F [CF (CF ₃ ) CF ₂ O] _z CF (CF
_{3) -, F [CF (} CF 3) CF 2 O] u CF 2 CF 2
−, F (CF ₂ CF ₂ CF ₂ O) _v CF ₂ CF ₂ −, F
(CF ₂ CF ₂ O) _w CF ₂ CF _2- (r and z are 1 to 1
An integer of 0, u is an integer of 2 to 6, v is an integer of 1 to 11, w
Is an integer of 1 to 11).

F (CF ₂ ) ₅ SCF (CF ₃ )-, F
[CF (CF ₃ ) CF ₂ S] _r CF (CF ₃ ) CF ₂ C
_{F 2 -, F [CF (} CF 3) CF 2 S] z CF (CF
_{3) -, F [CF (} CF 3) CF 2 S] u CF 2 CF 2
−, F (CF ₂ CF ₂ CF ₂ S) _v CF ₂ CF ₂ −, F
(CF ₂ CF ₂ S) _w CF ₂ CF _2- (r and z are 1 to 1
An integer of 0, u is an integer of 2 to 6, v is an integer of 1 to 11, w
Is an integer of 1 to 11).

As the (meth) acrylate having an R ^f group, a compound represented by the following formula 1 is preferable. Here, in Formula 1, R ^f represents an R ^f group, Q represents a divalent organic group, and R ¹ represents a hydrogen atom or a methyl group. R ^f -Q-OCOCR ¹ = CH ₂ Formula 1

The R ^f group in the formula (1) is preferably an R ^f group containing neither an etheric oxygen atom nor a thioetheric sulfur atom, more preferably a perfluoroalkyl group, and particularly preferably-
(CF ₂ ) _n F (where n is an integer of 1 to 16,
An integer of 4 to 16 is preferred, and an integer of 6 to 12 is particularly preferred. ) Is preferred.

In the formula 1, Q is-(CH ₂ )
_{p + q -, - (CH} 2) p CONH (CH 2) q -, -
(CH ₂ ) _p OCONH (CH ₂ ) _q -,-(CH ₂ )
^{_{p SO 2 NR a (CH 2}} ) q -, - (CH 2) p NHC
_{ONH (CH 2) q -,} - (CH 2) p CH (OH)
(CH ₂ ) _q- and the like are preferable. Here, Ra represents ^a hydrogen atom or an alkyl group. P and q each represent an integer of 0 or more, and p + q is an integer of 1 to 22.

Of these, Q is-(CH ₂ ) _{p + q-} ,
-(CH ₂ ) _p CONH (CH ₂ ) _q- or-(C
H ₂ ) _p SO ₂ NR ^a (CH ₂ ) _q — and q
Is preferably an integer of 2 or more, and p + q is preferably 2 to 6, particularly preferably-(CH ₂ ) when p + q is 2 to 6.
_{p + q-} , that is, Q in the case of an ethylene group to a hexamethylene group is preferable. Further, it is preferable that a fluorine atom is bonded to a carbon atom of R ^f bonded to Q.

The following compounds may be mentioned as (meth) acrylates having an R ^f group. Here, R ¹ represents a hydrogen atom or a methyl group.

[0023]

Embedded image F (CF ₂ ) ₅ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₆ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , H (CF ₂ ) ₆ CH ₂ OCOCR ¹ = CH ₂ , H ( CF ₂ ) ₈ CH ₂ OCOCR ¹ = CH ₂ , H (CF ₂ ) ₁₀ CH ₂ OCOCR ¹ = CH ₂ , H (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₈ CH ₂ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₁₀ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₁₂ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₁₄ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₁₆ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₈ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₈ (CH ₂ ) ₄ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₈ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₈ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₈ CONHCH ₂ CH ₂ OCOCR ¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ (CH ₂ ) ₃ OCOCR ¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OCOCH ₃ ) OCOCR ¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OH) CH ₂ OCOCR ¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₇ CH ₂ CH (OH) CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₉ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₉ CONHCH ₂ CH ₂ OCOCR ¹ = CH ₂ .

[Other polymerizable monomers] In the present specification, the other polymerizable monomers include (meth) acrylate having an ^Rf group, vinylidene halide, vinyl halide, and cycloalkyl (meth) acrylate. And polymerizable monomers other than alkyl (meth) acrylate. Examples of the other polymerizable monomer include known or well-known polymerizable monomers, and a polymerizable monomer having one or two polymerizable unsaturated groups is preferable. A polymerizable monomer having one is preferred.

Examples of other polymerizable monomers include the following polymerizable monomers. Monoolefin, vinyl carboxylate, styrene, substituted styrene, (meth) acrylamide, N-substituted (meth) acrylamide, alkyl vinyl ether, (substituted alkyl) vinyl ether, vinyl alkyl ketone, diolefin, glycidyl (meth) acrylate, aziridinyl (meth) A) acrylate, substituted alkyl (meth) acrylate, polyoxyalkylene mono (meth) acrylate, polyoxyalkylene monomethyl ether mono (meth) acrylate, polyoxyalkylene di (meth) acrylate, (meth) acrylate having a polydimethylsiloxane group, Triallyl cyanurate, allyl glycidyl ether, allyl carboxylate, N-vinylcarbazole, N-methylmaleimide,
Maleic anhydride, monoalkyl maleate, dialkyl maleate, blocked isocyanate group-containing (meth) acrylate, diacetone (meth) acrylamide, and (meth) acrylate having a quaternary ammonium base in the side chain.

Here, the (meth) acrylate containing a blocked isocyanate group is a (meth) acrylate having at least one blocked isocyanate group,
A compound having a structure in which the isocyanate group of the (meth) acrylate having an isocyanate group is blocked by a blocking agent is preferable. (Meth) acrylate having an isocyanate group refers to 2-isocyanateethyl (meth) acrylate or (meth) acrylate having a functional group capable of binding to an isocyanate group and polyisocyanate, in which one or more isocyanate groups remain Is preferred.

The (meth) acrylate having a functional group capable of binding to an isocyanate group is preferably a (meth) acrylate having a hydroxyl group, and particularly preferably a monoester or diester of (meth) acrylic acid and a polyhydric alcohol. Examples of the polyhydric alcohol include ethylene glycol, polyoxyethylene glycol, propylene glycol, polyoxypropylene glycol, glycerin, trimethylolpropane-alkylene oxide adduct, and pentaerythritol.

As the polyisocyanate, 4,4'-
Diphenylmethane diisocyanate, aromatic isocyanates such as tolylene diisocyanate, aliphatic isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, alicyclic isocyanates such as norbornene diisocyanate, and Modified products such as modified nurate, modified prepolymer and modified burette are preferred. Above all, aliphatic isocyanates, alicyclic isocyanates, and nurate-modified, prepolymer-modified, and burette-modified products of these polyisocyanates are more preferable.

Examples of the blocking agent for the isocyanate group of the isocyanate group-containing (meth) acrylate include alkyl ketoximes, phenols, alcohols, β-
Diketones or lactams are preferred, and methyl ethyl ketoxime, ε-caprolactam, phenol, cresol, acetylacetone, diethyl malonate, isopropanol, t-butyl alcohol, and maleic imide are particularly preferred. In particular, dissociation temperatures of alkyl ketoximes such as methyl ethyl ketoxime and lactams such as ε-caprolactam are 120 to 18;
Blocking agents consisting of compounds at 0 ° C. are preferred.

Blocked isocyanate group-containing (meth)
Specific examples of the acrylate include the following. Compound in which the isocyanate group of 2-isocyanatoethyl (meth) acrylate is blocked with methyl ethyl ketoxime, 2-isocyanatoethyl (meth)
Compound in which isocyanate group of acrylate is blocked with ε-caprolactam, 1: 1 of isophorone diisocyanate and 2-hydroxyethyl (meth) acrylate
(Molar ratio) a compound in which an isocyanate group of a reactant is blocked with methyl ethyl ketoxime, a compound in which an isocyanate group of a 1: 1 (molar ratio) of isophorone diisocyanate and 2-hydroxypropyl (meth) acrylate is blocked with methyl ethyl ketoxime, A compound in which a 1: 1 (molar ratio) reaction product of norbornene diisocyanate and 2-hydroxyethyl (meth) acrylate is blocked with methyl ethyl ketoxime.

[Polymer (A)] The polymer (A) is a polymer having a (meth) acrylate polymer unit having an R ^f group and a vinylidene halide polymer unit as essential components. R ^f
The polymerization unit of the (meth) acrylate having a group may be one type or two or more types. When two or more (meth) acrylate polymerized units having an R ^f group are contained,
It is preferably a polymerized unit of a (meth) acrylate having an R ^f group having a different number of carbon atoms.

As the polymerized units of vinylidene halide, vinylidene fluoride or vinylidene chloride is preferred, and vinylidene chloride is particularly preferred. The polymerization unit of the vinylidene halide may be one type or two or more types. The polymer (A) may be composed of only a polymerized unit of a (meth) acrylate having an R ^f group and a polymerized unit of vinylidene chloride, and a polymerized unit other than the polymerized unit (hereinafter referred to as another polymerized unit (a ).)).

The other polymer units (a) are preferably one or more polymer units selected from polymer units of other polymerizable monomers and polymer units of alkyl (meth) acrylate. Further, the other polymerized unit (a) has 1 carbon atom.
At least one selected from an alkyl (meth) acrylate having an alkyl group of from 6 to 6, (meth) acrylamide, diacetone (meth) acrylamide, N-methylolacrylamide, and a (meth) acrylate having a quaternary ammonium base in a side chain. The polymerized unit of the polymerizable monomer is preferable.

(Meth) having R ^f group in polymer (A)
The ratio of the acrylate polymerization unit is preferably 35 to 80% by weight. The ratio of the polymerized units of the vinylidene halide is preferably 20 to 65% by weight. Further, the polymer (A)
When it contains another polymerized unit (a), the content is preferably 0.1 to 10% by weight in the polymer (A).

[Polymer (B)] The polymer (B) is a polymer having a polymerized unit of a (meth) acrylate having an R ^f group and a polymerized unit of vinyl halide as essential components, and a polymerized vinylidene halide. It is a polymer containing no units. The polymer units of the (meth) acrylate having an R ^f group in the polymer (B) may be the same as or different from the polymer units in the polymer (A).

The polymerization unit of the (meth) acrylate having an R ^f group may be one type or two or more types. R ^f
When two or more polymerized units of a (meth) acrylate having a group are included, a (meth) acrylate having an R ^f group having a different number of carbon atoms
It is preferably an acrylate polymerization unit. As the polymerization unit of the vinyl halide, vinyl fluoride or vinyl chloride is preferable, and vinyl chloride is particularly preferable. The polymerization unit of the vinyl halide may be one type or two or more types.

The polymer (B) has a (meth) having an R ^f group.
It may be composed only of a polymerized unit of acrylate and a polymerized unit of vinyl chloride, or may contain a polymerized unit other than the polymerized unit (hereinafter, referred to as another polymerized unit (b)). The other polymer units (b) are preferably selected from polymer units of other polymerizable monomers, and particularly preferably one or more polymer units of the following polymerizable monomers.

Vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, glycidyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, methylolated diacetone (meth) ) Acrylamide,
N-methylol (meth) acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, aziridinylethyl (meth) acrylate, benzyl (meth) acrylate, aziridinyl (meth) acrylate, hydroxyalkyl (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate), polyoxyalkylene mono (meth) acrylate, polyoxyalkylene monomethyl ether mono (meth) acrylate, polyoxyalkylene mono (2-ethylhexyl) mono (meth) acrylate, polyoxyalkylene di ( (Meth) acrylate, (meth) acrylate having a polydimethylsiloxane group, triallyl cyanurate, allyl glycidyl ether, allyl acetate, 2-hydro Shi 3- chloropropyl (meth)
Acrylate, N-vinyl carbazole, maleimide,
N-methylmaleimide, (2-dimethylamino) ethyl (meth) acrylate and the like.

(Meth) having R ^f group in polymer (B)
The ratio of the polymerization unit of the acrylate is preferably 40 to 95% by weight. The ratio of polymerized units of vinyl halide is 5
~ 60% by weight is preferred. Further, when the polymer (B) contains another polymerized unit (b), the polymer (B) may contain 0.1.
The content is preferably set to 1 to 30% by weight.

[Polymer (C)] The polymer (C) comprises polymerized units of cycloalkyl (meth) acrylate and / or polymerized units of alkyl (meth) acrylate, and
It is a polymer which essentially requires a polymerization unit of a (meth) acrylate having an R ^f group and does not include a polymerization unit of a vinyl halide and a polymerization unit of a vinylidene halide.

As the polymer (C), a polymer essentially comprising a polymer unit of cycloalkyl (meth) acrylate and a polymer unit of (meth) acrylate having an R ^f group,
A polymer essentially including a polymer unit of an alkyl (meth) acrylate and a polymer unit of a (meth) acrylate having an R ^f group, a polymer unit of a cycloalkyl (meth) acrylate, a polymer unit of an alkyl (meth) acrylate, and R ^f Any of polymerized units of a (meth) acrylate having a group may be used.

The polymer units of the (meth) acrylate having an R ^f group in the polymer (C) may be the same as or different from the polymer units in the polymer (A) or the polymer (B). The polymerization unit of the (meth) acrylate having an R ^f group may be one type or two or more types.
When the polymer units of the (meth) acrylate having an R ^f group are two or more, the polymer units of the (meth) acrylate having an R ^f group having different carbon numbers are preferable.
The alkyl group in the alkyl (meth) acrylate may have a linear structure or a branched structure.
The alkyl group moiety preferably has 1 to 25 carbon atoms, and particularly preferably 4 to 22 carbon atoms.

Specific examples of the alkyl (meth) acrylate include butyl (meth) acrylate, octadecyl (meth) acrylate, hexadecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, docosyl (meth) acrylate, and the like. Octadecyl (meth) acrylate or hexadecyl (meth) acrylate is preferred. As the cycloalkyl (meth) acrylate, cyclopentyl (meth) acrylate or cyclohexyl (meth) acrylate is preferable.

In the polymer (C), polymerized units other than polymerized units of alkyl (meth) acrylate, polymerized units of cycloalkyl (meth) acrylate, and polymerized units of (meth) acrylate having an R ^f group (hereinafter referred to as “polymerized units”) , Another polymerized unit (c)). The other polymerization unit (c) is preferably selected from the polymerization units of other polymerizable monomers, and particularly preferably selected from the polymerization units exemplified as the other polymerization units (b).

(Meth) having R ^f group in polymer (C)
The ratio of the polymerization unit of the acrylate is preferably 40 to 95% by weight. Further, the ratio of the polymerization unit of the alkyl (meth) acrylate or the cycloalkyl (meth) acrylate is preferably 5 to 60% by weight in total. Further, when the polymer (C) contains another polymerized unit (c), the content is preferably 0.1 to 30% by weight in the polymer (C).

[Surfactant (D)] The surfactant (D) is preferably one or more surfactants selected from nonionic surfactants, cationic surfactants, and amphoteric surfactants. As the nonionic surfactant, a known or well-known nonionic surfactant can be employed. As the nonionic surfactant, the following surfactant (d ¹ )
~ 1 or more nonionic surfactants is preferably selected from (d ^6), the following surfactant ^{(d 1), (d 3} ), and (d ⁵⁾ one or more nonionic surfactants selected from Agents are more preferred. As the cationic surfactant,
The following surfactant (d ⁷ ) is preferable, and the following surfactant (d ⁸ ) is preferable as the amphoteric surfactant.

[Surfactant (d ¹ )] Surfactant (d ¹ )
¹ ) is a polyoxyalkylene monoalkyl ether,
It is a nonionic surfactant composed of polyoxyalkylene monoalkenyl ether or polyoxyalkylene monoalkapolyenyl ether.

An alkyl group in the surfactant (d ¹ ),
The alkenyl group or alkapolyenyl group preferably has 4 to 26 carbon atoms. Further, each of the alkyl group, alkenyl group, and alkapolyenyl group may have a straight-chain structure or a branched structure. In the case of a branched structure, it may be a secondary alkyl group, a secondary alkenyl group, or a secondary alkapolyenyl group.
Specific examples of the alkyl group, alkenyl group, or alkapolyenyl group include octyl, dodecyl, tetradecyl, hexadecyl, octadecyl, hexadecyl, behenyl (docosyl), and oleyl (9-octadecenyl). ) And the like.

The surfactant (d ¹ ) is preferably a polyoxyalkylene monoalkyl ether or a polyoxyalkylene monoalkenyl ether. The polyoxyalkylene portion of the surfactant (d ¹ ) is one or two or more.
It is preferably made of a kind of oxyalkylene group, and when it is made of two kinds, it is preferable that the way of connection is a block. The polyoxyalkylene portion preferably comprises a portion in which two or more oxyethylene groups and / or oxypropylene groups are linked.

As the surfactant (d ¹ ), a compound represented by the following formula 2 is preferable. R ² in the formula 2 where represents an alkyl group or the number 8 or more alkenyl groups of carbon atoms of 8 or more carbon atoms, s represents an integer of 5 to 50, g is 0 to 2
Indicates an integer of 0. When g and S are 2 or more,
The oxyethylene group and the oxypropylene group in the formula 2 are connected in a block shape.

[0051]

Embedded image R ² O [CH ₂ CH (CH ₃ ) O] _g- (C ₂ H ₄ O) _s H Formula 2

R ^{2 in} Formula 2 may have either a straight-chain structure or a branched structure. s is preferably an integer of 10 to 30, and g is preferably an integer of 0 to 10. When s is 4 or less, or g is 21 or more, it becomes hardly soluble in water and becomes difficult to be uniformly dissolved in the aqueous medium (E), so that the effect of improving permeability may be reduced. When s is 51 or more, hydrophilicity is increased, and there is a possibility that water repellency is reduced.

Specific examples of the nonionic surfactant represented by Formula 2 include the following compounds. However, in the following formula, s and g have the same meaning as described above, and the preferred embodiments are also the same. Further, the oxyethylene group and the oxypropylene group are connected in a block shape.

[0054]

Embedded image C ₁₈ H ₃₇ O [CH ₂ CH (CH ₃ ) O] _g −
_{(CH 2 CH 2 O) s} H, C 18 H 35 O [CH 2 CH (CH 3) O] g - (CH 2 C
_{H 2 O) s H, C} 16 H 33 O [CH 2 CH (CH 3) O] g - (CH 2 C
_{H 2 O) s H, C} 12 H 25 O [CH 2 CH (CH 3) O] g - (CH 2 C
_{H 2 O) s H, (} C 8 H 17) (C 6 H 13) CHO [CH 2 CH (CH
_{3) O] g - (CH} 2 CH 2 O) s H, C 10 H 21 O [CH 2 CH (CH 3) O] g - (CH 2 C
H ₂ O) _s H.

[Surfactant (d ² )] Surfactant (d ² )
² ) is a nonionic surfactant comprising a compound having one or more carbon-carbon triple bonds and one or more hydroxyl groups in the molecule and exhibiting surface activity.

The surfactant (d ² ) is preferably a nonionic surfactant comprising a compound having one carbon-carbon triple bond and one or two hydroxyl groups in the molecule. Further, the nonionic surfactant may have a polyoxyalkylene moiety as a partial structure. As the polyoxyalkylene portion, a polyoxyethylene portion, a polyoxypropylene portion, a portion in which oxyethylene groups and oxypropylene groups are connected in a random shape, or a portion in which polyoxyethylene and polyoxypropylene are connected in a block shape, Is mentioned. Surfactant (d
^As a specific example of ² ), a compound represented by the following formula 3, 4, 5, or 6 is preferable.

[0057]

Embedded image HO—CR ³ R ⁴ —C≡C—CR ⁵ R ⁶ —OH Formula 3 HO— (A ¹ O) _m —CR ³ R ⁴ —C≡C—CR ⁵ R ⁶ — ( OA ² ) _n -OH Formula 4 HO-CR ⁷ R ⁸ -C≡CH Formula 5 HO- (A ³ O) _k -CR ⁷ R ⁸ -C≡CH Equation 6

However, A ¹ , A ² and A ³ in the formulas 3 to 6 may be the same or different and each represents an alkylene group, and m and n each represent an integer of 0 or more. (M + n) is an integer of 1 or more. k is 1
The following integers are shown. When m, n, or k is 2 or more, each of A ¹ , A ² , and A ³ is composed of two or more alkylene groups even if each is composed of only one alkylene group. Is also good.

R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R
⁸ may be the same or different and each represents a hydrogen atom or an alkyl group. The alkyl group has 1 carbon atom
To 12 alkyl groups are preferable, and an alkyl group having 6 to 12 carbon atoms is particularly preferable. Specific examples of these groups include
Examples include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group.

The oxyalkylene portion preferably comprises an oxyethylene portion, an oxypropylene portion, or both an oxyethylene portion and an oxypropylene portion. The number of oxyalkylene groups in the surfactant (d ² ) is preferably from 1 to 50. Further, as the surfactant (d ² ), a nonionic surfactant represented by the following formula 7 is preferable. Here, x and y in Formula 7 each represent an integer of 0 or more. One or more compounds represented by the formula 7 can be used.

[0061]

Embedded image

The nonionic surfactant represented by the formula 7 includes a nonionic surfactant having an average of the sum of x and y being 10, and a nonionic surfactant having x = 0 and y = 0. A nonionic surfactant having an average of the sum of x and y in Formula 7 is 1.3 is preferable.

[Surfactant (d ³ )] Surfactant (d ³ )
³ ) is that a polyoxyethylene portion in which two or more oxyethylenes are continuously connected and a portion in which two or more oxyalkylenes having 3 or more carbons are continuously connected are connected, and both ends are hydroxyl groups. It is a nonionic surfactant composed of a certain compound. Carbon number 3 in surfactant (d ³ )
As the above oxyalkylene, oxytetramethylene and / or oxypropylene are preferable.

As the surfactant (d ³ ), a nonionic surfactant comprising a compound represented by the following formula 8 or 9 is preferable. Note that h in Equations 8 and 9 is 0 to 200.
And r is an integer of 2 to 100, t is an integer of 0 to 200, and when h is 0, t is an integer of 2 or more, and when t is 0, h is an integer of 2 or more. It is. However, the polyoxyalkylene moiety in the following formula is linked in a block shape.

[0065]

Embedded image HO— (CH ₂ CH ₂ O) _h — [CH ₂ CH (CH ₃ ) O] _r —— (CH ₂ CH ₂ O) _t H Formula 8 HO— (CH ₂ CH ₂ O) ) _H − (CH ₂ CH ₂ CH ₂ CH ₂ O) _r − − (CH ₂ CH ₂ O) _t H Formula 9

Further, as the surfactant (d ³ ), a nonionic surfactant comprising any of the following compounds is preferable.

[0067]

Embedded image _{HO- (CH 2 CH 2 O)} 15 - [CH 2 CH
_{(CH 3) O] 35 -} (CH 2 CH 2 O) 15 H, HO- (CH 2 CH 2 O) 8 - [CH 2 CH (CH 3)
O] _35- (CH ₂ CH ₂ O) ₈ H, HO— (CH ₂ CH ₂ O) ₄₅ — [CH ₂ CH (CH ₃ )
_{O] 17 - (CH 2 CH} 2 O) 45 H, HO- (CH 2 CH 2 O) 34 - (CH 2 CH 2 CH 2 C
_{H 2 O) 28 - (CH} 2 CH 2 O) 34 H.

[Surfactant (d ⁴ )] Surfactant (d ⁴ )
⁴ ) is a nonionic surfactant comprising a compound having an amine oxide moiety in the molecule. Surfactant (d
^{As 4} ), a known or well-known nonionic surfactant having an amine oxide moiety in the molecule can be employed, and a compound represented by the following formula 10 is preferable. Where R ⁹ ,
R ¹⁰ and R ¹¹ may be the same or different and each represents a monovalent hydrocarbon group. The surfactant having an amine oxide moiety (N → O) in the molecule is:
Although it may be classified as a cationic surfactant, it is treated as a nonionic surfactant in the present invention. The surfactant (d ⁴ ) may be one type or two or more types.

As the surfactant (d ⁴ ) in the present invention, in particular, a nonionic surfactant represented by the following formula 11 is used:
It is preferable from the viewpoint of improving the dispersion stability of the polymer. However, in the formula 11, R ¹² is an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, a phenyl group to which an alkyl group (6 to 22 carbon atoms) is bonded, or an alkenyl group (having 6 to 22 carbon atoms). 22) represents a phenyl group bonded thereto,
An alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms is preferable.

[0070]

(R ⁹ ) (R ¹⁰ ) (R ¹¹ ) N (→ O) Formula 10 (R ¹² ) (CH ₃ ) ₂ N (→ O) Formula 11

Specific examples of the surfactant (d ⁴ ) include the following compounds.

[0072]

Embedded image [CH ₃ (CH ₂ ) ₁₁ ] (CH ₃ ) ₂ N (→ O), [CH ₃ (CH ₂ ) ₁₃ ] (CH ₃ ) ₂ N (→ O), [CH ₃ (CH ₂₎ ) ₁₅ ] (CH ₃ ) ₂ N (→ O), [CH ₃ (CH ₂ ) ₁₇ ] (CH ₃ ) ₂ N (→ O).

[Surfactant (d ⁵ )] Surfactant (d ⁵ )
⁵ ) is a condensate of polyoxyethylene mono (substituted phenyl) ether or a nonionic surfactant composed of polyoxyethylene mono (substituted phenyl) ether. As the substituted phenyl group, a phenyl group substituted with a monovalent hydrocarbon group is preferable, and a phenyl group substituted with an alkyl group, an alkenyl group, or a styryl group is preferable.

As the surfactant (d ⁵ ), a condensate of polyoxyethylene mono (alkylphenyl) ether,
A condensate of polyoxyethylene mono (alkenylphenyl) ether, polyoxyethylene mono (alkylphenyl) ether, polyoxyethylene mono (alkenylphenyl) ether, or polyoxyethylene mono [(alkyl) (styryl) phenyl] ether is preferable. .

Specific examples of the surfactant (d ⁵ ) include formaldehyde condensates of polyoxyethylene mono (nonylphenyl) ether, polyoxyethylene mono (nonylphenyl) ether, polyoxyethylene mono (octylphenyl) ether, Examples thereof include polyoxyethylene mono (oleylphenyl) ether, polyoxyethylene mono [(nonyl) (styryl) phenyl] ether, and polyoxyethylene mono [(oleyl) (styryl) phenyl] ether.

[Surfactant (d ⁶ )] Surfactant (d ⁶ )
⁶ ) is a fatty acid ester of a polyol. Examples of the polyol include polyethylene glycol, decaglycerin, and ethers of polyethylene glycol and a polyol (other than polyethylene glycol). Specific examples of the surfactant (d ⁶ ) include the following compounds.

1: 1 (molar ratio) ester of stearic acid and polyethylene glycol, 1: 4 of ether of sorbitol and polyethylene glycol and oleic acid
(Molar ratio) 1: 1 of ester, ether of polyoxyethylene glycol and sorbitan and stearic acid
(Molar ratio) 1: 1 (molar ratio) of ester, ether of polyethylene glycol and sorbitan and oleic acid
Ester, 1: 1 (molar ratio) ester of lauric acid and sorbitan, (1 or 2): 1 (molar ratio) ester of oleic acid and decaglycerin, (1 or 2) of stearic acid and decaglycerin: 1 (molar ratio) ester.

[Surfactant (d ⁷ )] Surfactant (d ⁷ )
⁷ ) is a cationic surfactant comprising a substituted ammonium salt, which is obtained by converting a compound in which at least one hydrogen atom bonded to a nitrogen atom of an ammonium salt is substituted with an alkyl group, an alkenyl group, or a polyoxyalkylene group. Are preferred, and in particular, a cationic surfactant comprising a compound represented by the following formula 12 is preferred. _{^{[(R 13) 4 N +}} ] · X - ··· formula 12

However, the symbols in the expression 12 have the following meanings. R ¹³ : The four R ^{13 s} may be the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms,
It is an alkenyl group or a polyoxyalkylene group.
However, four R ¹³ are not simultaneously hydrogen atoms. X ^-: 1 monovalent anion.

Examples of the cationic surfactant represented by Formula 12 include mono (long-chain alkyl) amine hydrochloride, mono (long-chain alkyl) dimethylamine hydrochloride, mono (long-chain alkyl) dimethylamine acetate, mono (long-chain alkyl) dimethylamine acetate and mono (long-chain alkyl) dimethylamine acetate. (Long-chain alkenyl) dimethylamine hydrochloride, mono (long-chain alkyl) dimethylamine / ethyl sulfate, mono (long-chain alkyl) trimethylammonium chloride, di (long-chain alkyl) monomethylamine hydrochloride, di (long-chain alkyl) Examples include dimethyl ammonium chloride, mono (long-chain alkyl) monomethyldi (polyoxyethylene) ammonium chloride, and di (long-chain alkyl) monomethylmono (polyoxyethylene) ammonium chloride.

Further, as the cationic surfactant represented by the formula 12, monooctadecyltrimethylammonium chloride, monooctadecyldimethylmonoethylammoniumethyl sulfate, mono (long-chain alkyl) monomethyldi (polyethylene glycol) ammonium chloride, di ( Tallowalkyl) dimethylammonium chloride, dimethylmonococonutamine acetate and the like are preferred.

[Surfactant (d ⁸ )] Surfactant (d ⁸ )
⁸ ) is an amphoteric surfactant composed of alanines, imidazolinium betaines, amidobetaines, or betaine acetate. Specific examples of the surfactant (d ⁸ ) include:
Dodecyl betaine, octadecyl betaine, dodecyl carboxymethyl hydroxyethyl imidazolinium betaine, dodecyl dimethyl amino acetate betaine, fatty acid amidopropyl dimethyl amino acetate betaine, and the like.

The surfactant (D) in the present invention is selected from surfactant (d ¹ ), surfactant (d ³ ), surfactant (d ⁵ ), and surfactant (d ⁷ ). It is preferable that one or more surfactants (hereinafter, also referred to as specific surfactants) are essential. If necessary, a surfactant other than the specific surfactant may be used. When the specific surfactant is used, the mechanical stability, permeability and adsorbability to paper of the paper processing composition are improved, and the occurrence of processing unevenness can be prevented.

[Aqueous Medium (E)] The aqueous medium (E) is preferably water alone or a mixed medium of water and a water-soluble organic solvent. As the water-soluble organic solvent, glycol-based, ester-based, ketone-based, and ether-based organic solvents are preferable. The ratio between water and the organic solvent is not particularly limited. The following are mentioned as an organic solvent.

Acetone, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether , Propylene glycol dibutyl ether, 3
-Ethyl ethoxypropionate, 1-methoxymethylethanol, 2-t-butoxyethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, ethanol, ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like.

[Paper Processing Composition] Next, the paper processing composition of the present invention will be described. The composition for paper treatment of the present invention essentially comprises a polymer (B) and / or a polymer (C), a polymer (A), a surfactant (D), and an aqueous medium (E). When the polymer in the composition is a combination of the polymer (A), the polymer (B), and the polymer (C), and when the polymer is a combination of the polymer (A) and the polymer (B), And a combination of the polymer (A) and the polymer (C), and a combination of the polymer (A), the polymer (B), and the polymer (C) is preferable.

The respective amounts in the composition correspond to the polymer (A)
And the total amount of the polymer (B) and the polymer (C) is 4% in the composition.
0% by weight or less, preferably 1 to 30% by weight
It is preferred that The polymer (A) in the total amount of the polymer
Is preferably 30 to 90% by weight, the ratio of the polymer (B) is preferably 0.01 to 50% by weight, and the ratio of the polymer (C) is 0.01 to 50% by weight. It is preferred that Further, the total amount of the polymer (B) and the polymer (C) is preferably 0.1 to 3 times the weight of the polymer (A).

The amount of the surfactant (D) is 0.5 to 1 based on the total amount of the polymer (A), the polymer (B) and the polymer (C).
It is preferably 0% by weight. The amount of the aqueous medium (E)
It is preferably at least 60% by weight in the composition. The composition of the present invention is diluted to an appropriate concentration depending on the type of paper, the processing method, the intended performance, and the like.
Dilute to an appropriate concentration with water. The composition of the present invention may contain other water and oil repellents, insect repellents, flame retardants, antistatic agents, sizing agents, and the like.

The paper treating composition of the present invention comprises a polymer (A)
And the aqueous medium (E) dispersion of the polymer (B), the aqueous medium (E) dispersion of the polymer (B) and / or the aqueous medium (E) dispersion of the polymer (C). Here, it is preferable to produce by a method of adding other components. Other components include other water and oil repellents, insect repellents, flame retardants, antistatic agents, sizing agents, and the like.

Further, each of the polymers that can be contained in the paper processing composition of the present invention may be obtained by adding a polymerizable monomer, which is a basis of a polymerized unit of each polymer, to a surfactant (D) and an aqueous medium ( It is preferably a polymer obtained by a polymerization reaction in the presence of E). The polymerization reaction is preferably carried out under the action of a polymerization initiator. As the polymerization initiator, a water-soluble or oil-soluble polymerization initiator is preferable, and an azo compound,
It is preferable to employ an initiator composed of a peroxide compound or a redox compound according to the polymerization temperature. The polymerization initiator is particularly preferably a water-soluble initiator, and particularly preferably a salt of an azo compound. The polymerization temperature is not particularly limited.
~ 150 ° C is preferred.

In the polymerization reaction, a chain transfer agent may be included for the purpose of controlling the molecular weight. As the chain transfer agent, an aromatic compound or a mercaptan compound is preferable, and an alkyl mercaptan is particularly preferable. Specific examples include n-octyl mercaptan, dodecyl (n-dodecyl or t-dodecyl) mercaptan, and octadecyl mercaptan. Further, α-methylstyrene dimer is also preferable.

At the time of polymerization, a composition containing a polymerizable monomer, water, and a surfactant (D) may be pre-dispersed in advance using a homomixer, a high-pressure emulsifier, or the like. By sufficiently stirring the composition before the start of polymerization, there is an effect of improving the yield of the finally obtained polymer.

When the paper treating composition of the present invention is treated on paper, it is preferred to carry out the treatment by a method such as dipping or coating. The amount of paper processing is 0.1 to
It is preferably 3.0% by weight. The paper obtained by the treatment can be preferably used as a food container as it is or by processing it into another shape.

[0094]

The mechanism by which the paper-treating composition of the present invention exhibits high mechanical stability and high water repellency and water and oil resistance is not always clear. It is considered that the effect of these polymers acts synergistically to exhibit excellent effects. Further, the polymer according to the present invention has an R ^f group having high film forming properties and water repellency (meth).
It is presumed that the performance of each polymerized unit is balanced by making the polymerized unit of acrylate essential and adding a specific polymerized unit to this. In particular, when a specific surfactant is used, stability and permeability are remarkably improved.

[0095]

EXAMPLES Next, the present invention will be described specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

[Synthesis Example 1] Synthesis Example of Polymer (A) A perfluoroalkylethyl acrylate [F (CF ₂ ) _n CH ₂ C] was placed in a glass autoclave having an internal volume of 1 L.
H ₂ OCOCH ＝ CH ₂ , where n is 6 to 16 and the average value of n is 8. Hereinafter, it is referred to as FA. (60 g), vinylidene chloride (38 g), N-methylolacrylamide (NMAA, 2 g), ion-exchanged water (250 g), diethylene glycol monomethyl ether (50 g), polyoxyethylene mono [(alkyl) (styryl) phenyl] ether ( 8 g) and azobisisobutylamidine hydrochloride (0.2 g, manufactured by Wako Pure Chemical Industries, Ltd.), sealed, and purged with nitrogen gas. The temperature inside the reactor was 55 ° C,
The polymerization reaction was carried out for 15 hours. A translucent aqueous dispersion was obtained with a yield of 97%. This aqueous dispersion is diluted with water to obtain a solid content of 1%.
What was 0% is referred to as a stock solution A ^1.

[Synthesis Example 2] Synthesis Example of Polymer (B) FA (168.2 g), dioctyl maleate (15.
6 g), NMAA (6.0 g), 0.5 g of dodecyl mercaptan, polyoxyethylene mono (1-methylundecyl) ether (PEOLE, 12.0 g) and mono (long-chain alkyl) trimethylammonium chloride [(R ¹⁷ ) (CH ₃ ) ₃ N ⁺ .Cl ⁻ (where R ¹⁷ is a mixture of alkyl groups having 16, 17, and 18 carbon atoms; 2.4 g), water (480.5 g), dipropylene glycol (12.0 g) ) At 40 ° C. for 30 minutes,
After pre-dispersion, the mixture was treated at 200 kg / cm ² using a high-pressure emulsifier (manton gourin) to obtain an emulsion.

This emulsion was placed in a 1 L stainless steel autoclave and purged with nitrogen. In addition, vinyl chloride (V
After adding CL, 50.2 g), 2,2′-azobis (N, N′-dimethyleneisobutylamidine) disulfate (VA-046B, 2.4 g, manufactured by Wako Pure Chemical Industries, Ltd.) was added. After raising the temperature to 50 ° C., polymerization was carried out for 15 hours to obtain 730 g of an aqueous dispersion having a solid content of 32% and an average particle size of the polymer of 0.24 μm. The The aqueous dispersion obtained by the 10% diluted solids concentration in water is referred to as a stock solution B ^1.

Synthesis Example 3 Synthesis Example of Polymer (C) FA (154 g), octadecyl acrylate (St
A, 90 g), cyclohexyl methacrylate (CHM
A, 12.8 g), octadecyl mercaptan (StS
H, 0.77 g), polyoxyethylene monooleyl ether (PEOOE, 15.4 g), trimethyloctadecyl ammonium chloride (StTMAC, 5.1)
g), dipropylene glycol (DPG, 90 g), and ion-exchanged water (320 g) were stirred at 50 ° C. for 30 minutes. Next, the mixture was emulsified at 200 kg / cm ² using a high-pressure emulsifier (manton gourin) while maintaining the temperature at 40 to 50 ° C. The average particle size of the polymer contained in the emulsion is 0.1.
It was 23 μm.

Next, this was transferred to a 1 L glass autoclave, and 2,2′-azobis (N, N′-dimethyleneisobutylamidine) dihydrochloride (VA-044, manufactured by Wako Pure Chemical Industries, Ltd., 0.5 g) ) Was added, and the autoclave was replaced with nitrogen. While stirring, the temperature was raised to 60 ° C., and polymerization was carried out for 6 hours to obtain a milky white aqueous dispersion containing a polymer having an average molecular weight of 98,000. The solid concentration of the aqueous dispersion is 3
7.6% by weight, and the average particle size of the polymer was 0.11 μm. What the aqueous dispersion solids concentration was diluted with water so that 10% by weight referred to as a stock solution C ^1.

Synthesis Example 4 Synthesis Example of Polymer (C) FA (167 g), StA (46.2 g), NMAA
(5.1 g), StSH (0.77 g), PEOOE
(10.3 g), a nonionic surfactant (5.1 g) comprising a compound in which the sum of x and y in Formula 7 is 10,
A mixture consisting of PEOLE (5.1 g), tripropylene glycol (TPG, 90 g), and ion-exchanged water (320 g) was stirred at 50 ° C. for 30 minutes. The mixture is
High-pressure emulsifier while maintaining at ~ 50 ° C (Mantongurin)
And emulsified at 300 kg / cm ² . The average particle size of the polymer contained in the emulsion was 0.17 μm.

Next, this was transferred to a 1-liter glass autoclave, VA-044 (0.5 g) was added, and the autoclave was purged with nitrogen. Then VCL (38.5)
g) was added thereto, and the mixture was heated to 60 ° C. with stirring and polymerized for 15 hours to obtain a milky white aqueous dispersion containing a polymer having an average molecular weight of 80,000. The solid concentration in the aqueous dispersion is 3
8.1% by weight, and the average particle size of the polymer was 0.07 μm. What the aqueous dispersion solids concentration was diluted with water so that 10% by weight referred to as a stock solution C ^2.

[Examples 1 to 5 (Examples) and Examples 6 to 7 (Comparative Examples)] Treatment baths having the compositions shown in Table 3 were prepared, and the mechanical stability was measured using the baths. In addition, non-size paper (basis weight 50 g / m ² ) was immersed in the treatment bath using a size press at a speed such that the drawing ratio became 50%.
Next, it was dried for 15 seconds by a drum dryer heated to 80 ° C. The treated paper was measured for water repellency, oil resistance and size.

[Water repellency] The water repellency is measured according to JIS P8137.
The test was performed according to the following. The evaluation was performed based on the criteria shown in Table 1. Table 3 shows the results.

[0105]

[Table 1]

[Oil resistance] The oil resistance was measured using a 3M kit test (T
APPI-RC-338). The 3M kit test method uses the test oils (kit Nos.
16) was placed on the surface of the evaluation sample, and it was determined whether the test oil permeated or not. The largest kit number among the kit numbers of the permeated test oil was measured. The larger the kit number, the better the oil resistance. Table 3 shows the results.

[0107]

[Table 2]

[Sizing Test] The size test was conducted according to JIS P
The test was performed according to the 8122 Stequicht method. For the judgment, the time at which one red point occurred in the ferric chloride solution was recorded.
The longer the time, the better the size.
Table 3 shows the results.

[Mechanical stability test] The solid content concentration was 0.5
The processing solution, which was a weight%, was kept at 40 ° C., and was stirred at 5000 rpm for 30 minutes using a homomixer. The generated suspended matter was filtered through a well-washed 200-mesh wire net, dried, and then evaluated for mechanical stability by its weight (mg). Table 3 shows the results.

[0110]

[Table 3]

[0111]

The composition for paper treatment of the present invention is an excellent composition for imparting excellent water resistance, excellent oil resistance and excellent water repellency to paper. In addition, since this property can be imparted by a low-temperature and short-time treatment, it is excellent in versatility. Further, since the composition of the present invention is excellent in mechanical stability, it is advantageous also in workability during processing.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D21H 21/16 D21H 21/16 F term (Reference) 4J002 BD09X BD10W BD13X BD14W BG08W BG08X BG08Y CH02Z ED066 EH036 EN026 EN136 FD31Z FD316 GK04 HA08 4L055 AG34 AG35 AG67 AG68 AG71 AG97 AH23 AH24 AH29 AH50 BE10 EA30 EA32 FA11 FA17 FA19 FA30 GA47 GA48

Claims (8)

[Claims] 1. A paper treatment composition comprising the following polymer (B) and / or the following polymer (C), the following polymer (A), a surfactant (D), and an aqueous medium (E) as essential components. object. Polymer (A): a polymer essentially comprising a polymerized unit of a (meth) acrylate having a polyfluoroalkyl group and a polymerized unit of vinylidene halide. Polymer (B): a polymer that essentially requires a polymer unit of a (meth) acrylate having a polyfluoroalkyl group and a polymer unit of a vinyl halide, and does not include a polymer unit of a vinylidene halide. Polymer (C): a polymer unit of a cycloalkyl (meth) acrylate and / or a polymer unit of an alkyl (meth) acrylate and a polymer unit of a (meth) acrylate having a polyfluoroalkyl group are indispensable. Polymer containing no polymerized units and polymerized units of vinylidene halide. 2. The paper treating composition according to claim 1, wherein the vinylidene halide in the polymer (A) is vinylidene chloride. 3. The paper treating composition according to claim 1, wherein the vinyl halide in the polymer (B) is vinyl chloride. 4. The method according to claim 1, wherein the alkyl (meth) acrylate in the polymer (C) is octadecyl (meth) acrylate or hexadecyl (meth) acrylate.
4. The paper processing composition according to 2 or 3. 5. The paper treating composition according to claim 1, wherein the total amount of the polymer (A), the polymer (B) and the polymer (C) is 1 to 30% by weight. 3. The composition for paper treatment according to item 1. 6. A surfactant (D) comprising the following surfactant (d)
¹ ), the following surfactant (d ³ ), the following surfactant (d
⁵ ) and 1 selected from the following surfactants (d ⁷ )
The paper treating composition according to any one of claims 1 to 5, which is at least a seed. Surfactant (d ¹ ): a nonionic surfactant composed of polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, or polyoxyalkylene monoalkapolyenyl ether. Surfactant (d ³ ): a polyoxyethylene portion in which two or more oxyethylenes are continuously connected and a portion in which two or more oxyalkylenes having 3 or more carbon atoms are continuously connected are connected, and both A nonionic surfactant comprising a compound having a terminal hydroxyl group. Surfactant (d ⁵ ): a condensate of polyoxyethylene mono (substituted phenyl) ether or a nonionic surfactant composed of polyoxyethylene mono (substituted phenyl) ether. Surfactant (d ⁷ ): a cationic surfactant comprising a substituted ammonium salt. 7. The paper treating composition according to claim 1, wherein the aqueous medium (E) is water alone or a mixed medium of water and a water-soluble organic solvent. 8. A treated paper treated with the paper treating composition according to claim 1.