JPS6020501B2 - Sizing agent for textile products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates generally to laundry starches and other sizing agents for textile products, and more particularly to sizing agents having a cationic group content of 0.01 to 10.
Polyvinyl alcohol (hereinafter referred to as PVA) modified with cationic groups and having a degree of saponification of 60 to 100 mol% in terms of mol%.

This invention relates to a sizing agent for textile products that has a cationic emulsion formed by emulsion polymerization of ethylenically unsaturated monomers in the presence of ) as a main ingredient, and has excellent adhesion efficiency and a high sizing effect. Conventionally,
Although starch-based sizing agents have been used for a long time, recently carboxymethyl cellulose or PVA has come into use. The performance required of a sizing agent is that it should give textile products sufficient hardness and appropriate texture during washing, be effective in ironing, and not be colored during washing.

It has also become necessary to make requests from this perspective in connection with wastewater regulations. In contrast to these required performances, conventional starch, carboxymethyl cellulose, and the like have disadvantages in that the size solution deteriorates and the viscosity changes significantly due to temperature and time, causing the texture of the textile product to constantly change after being pasted.

In addition, PVA has poor pacing during dewatering after pasting, and furthermore, when pasted textile products are washed again, most of the pasting falls off from the fibers, making it uneconomical. This is not desirable from the standpoint of wastewater regulations as it increases the amount of organic matter. On the other hand, a recently developed sizing agent based on a vinyl acetate emulsion with PVA as a protective colloid has been considerably improved in these respects, but it has the disadvantage of poor stiffness in winter, which needs to be improved. Therefore, there is a drawback that if a film-forming agent is added, sufficient hardness cannot be obtained.

In addition, there is concern about coloring due to heat treatment, and at the same time, stains do not come off easily when washed, and the hardness is not sufficient. As a result of research to solve the above problems, the present inventors found that PVA modified with cationic groups has a cationic group content of 0.01 to 10 mol% and a saponification degree of 60 to 100 mol%. The target laundry paste could be obtained by emulsion polymerization of ethylenically unsaturated monomers as a protective colloid.

The cationic emulsion laundry starch of the present invention has hydrophobic fibers,
Because it is well adsorbed to fibers regardless of whether they are hydrophilic fibers, there is little elution during dehydration operations, a high sizing effect, and less likely to pollute wastewater.

Furthermore, since it has a good texture, the concentration of paste liquid can be lowered and it is also economical. In addition, since 0.01 to 10 mol% of cationic groups are introduced, it has excellent film-forming properties and is slightly hygroscopic, so it has a suitable texture and does not feel sticky and does not cause powder blowing in winter. Also, no discoloration, rot, etc. will occur. The above description has focused mainly on laundry starch among sizing agents, but the sizing agent for textile products of the present invention can also be used for other finishing agents such as non-woven fabrics, hard finishing, resin processing (in combination with thermosetting resin), etc. included in the use as.

The content of cationic groups used in the production of the cationic emulsion used in the novel sizing agent of the present invention is 0.01
PVA modified with cationic groups with a saponification degree of 60 to 100 mol% and a saponification degree of 60 to 100 mol% is modified PVA containing 0.01 to 10 mol% of cationic groups in the main chain or side head. The cationic groups mentioned here include -class amines, secondary amines, tertiary amines, quaternary ammonium salts, pyridine, pyridinium, imidazole, imidazolinium, sulfonium, phosphonium, etc. It means a chemical structural unit that is electrically charged.

Previously reported methods for producing cationically modified PVA include copolymerizing vinyl pyridine and vinyl acetate and then saponifying it, and copolymerizing N-pinylphthalimide or N-vinylsuccimide with vinyl acetate and saponifying it. and further decompose the imide group with alkali or hydrazine, P
A method of aminoacetalizing VA or aminobenzacetalizing VA under an acid catalyst, a method of reacting PVA with alkoxydimethylamine, glycidyltrimethylammonium hydrochloride or 3-chloro-2-hydroxypropyltrimethylammonium hydrochloride, a method of reacting PVA with A method is known in which an amino group is introduced by Hofmann decomposition after addition of acrylamide into a molecule, or a method in which PVA containing a lactone ring is hydrazidized with hydrazine. Cation-modified PVA synthesized by these methods and having a cationic group content of 0.01 to 10 mol% and a saponification degree of 60 to 100 mol% may also be used in the production of the cationic emulsion used in the sizing agent of the present invention. However, in order to industrially produce the above-mentioned cation-modified PVA, there are various difficulties in the cationization process itself, and in addition, in order to obtain a partially saponified product for the purpose of imparting good emulsion stability. Complicated steps such as re-saponification after re-acetylation are required, which poses problems in industrial applications. In contrast, the present inventors first applied for patent application No. 54-1890.
According to the method for producing PVA modified with cationic groups disclosed in No. 78, both the introduction of cationic groups and the method of obtaining a degree of saponification according to the purpose can be carried out stably and easily, and the modified PVA produced in this way can be carried out stably and easily. PVA, that is, the following general formula (1) (where RI is a hydrogen atom or a lower alkyl group,
B is or R3, R4 is a lower alkyl group (may contain a substituent)
, X represents a negative group that forms a salt with ammonium nitrogen, and A represents a group that connects the nitrogen atom in B with the nitrogen atom of the amide group.

) Modified PVA containing 0.01 to 10 mol % of copolymerized units and having a degree of saponification of 60 to 100 mol % is most effective for the purpose of producing the cationic emulsion used in the present invention. Content is 0.01-10 mol%
A cationic emulsion can be produced by emulsion polymerizing a pinyl monomer in the presence of modified PVA having a saponification degree of 60 to 100 mol%.

Modified PV containing the copolymerized unit represented by the above single-pronged formula (1)
The details of the manufacturing method for A are as shown in the specification of Tokugan Sho 54-89078. , R4 is a lower alkyl group (which may contain a substituent)
, × represents a negative group that forms a salt with ammonium nitrogen, and A represents a group that connects the nitrogen atom in B with the nitrogen atom of the amide group.

) is copolymerized with a polymerizable monomer represented by B in the presence of a radical polymerization initiator, and then, when B is 60 to 100 mol% of the vinyl ester units in the copolymer are saponified to vinyl alcohol units by reacting an alkali or acid catalyst to the alcohol solution of If not carried out, it is most effectively and simply produced by quaternizing or not quaternizing with a quaternizing agent after the saponification reaction.

Specific monomers represented by the above general formula (0) include the following.

N-(3-dimethylaminopropyl)acrylamide,
Trimethyl-3-(1-methacrylamidopropyl) ammonium chloride, N-(3-dimethylaminopropyl) methacrylamide, trimethyl-3-(1-methacrylamidopropyl) ammonium chloride, N-(
2-dimethylaminoethyl)acrylamide, trimethyl-2-(1-methacrylamidoethyl)ammonium chloride, N-(3-diethylaminopropyl)methacrylamide, trimethyl-3-(1-methacrylamidopropyl)ammonium methosulfate, N-(1
・1-dimethyl-3-dimethylaminopropyl)-acrylamide, trimethyl-3-(1-acrylamide 1,1-dimethylpropyl)ammonium chloride, N
-(1,1-dimethyl-3-dimethylaminobutyl)acrylamide, trimethyl-3-(1-acrylamide-
1,1-dimethylbutyl)ammonium chloride, N-(1-methyl-1,3-diphenyl-3-diethylaminopropyl)methacrylamide, dimethylacrylamidebropyl-4-trimethylammoniumbutenyl-2
monoammonium chloride, 2-(acrylamidomethoxy)ethyltrimethylammonium chloride. Among these, the following four types of monomers, N-(1,1-dimethyl-3-dimethylaminopropyl)acrylamidetrimethyl-3-(1-acrylamido11-dimethylpropyl)ammonium chloride N
1-(3-dimethylaminopropyl)methacrylamidotrimethyl-3-(1-methacrylamidopropyl)ammonium chloride has a cationic group content of 0 for the purpose of producing the cationic emulsion used in the sizing agent of the present invention. .01~10 mol%, saponification degree is 60~
In producing 100 mol % cation-modified PVA, it is the most excellent in terms of polymerization rate, stability of amide groups, and economical efficiency during monomer production.

Regarding the amount of cationic groups, degree of saponification, or degree of polymerization in the cationically modified PVA used as an emulsion stabilizer for producing the cationic emulsion for the sizing agent of the present invention, in producing a highly stable emulsion, The amount of cationic groups is 0.01 to 10 mol%, and the degree of saponification is 60 to 100 mol%.
is essential, and the degree of polymerization is usually 300, although there is no particular restriction.
~3000.

Generally speaking, partially saponified products with a moderate degree of saponification have better emulsion stability than completely saponified products, and have the great advantage that surfactants do not need to be used in the polymerization of vinyl acetate emulsions. Completely saponified products or highly saponified products generally have poor emulsion stability, so in many cases, partially saponified products of thione-modified PVA or ordinary PVA are used.
A method of emulsion polymerization can be adopted by using a partially saponified product of VA or a surfactant. The above-mentioned P modified with cationic groups has a content of cationic groups of 0.01 to 10 mol% and a degree of saponification of 60 to 100 mol%, which is used when producing a cationic emulsion.
The amount of VA used is preferably 0.01 to 2 parts by weight per 100 parts by weight of the ethylenically unsaturated monomer.

PVA modified with cationic groups and normal completely saponified PV
A. It is also possible to use partially saponified PVA in combination, and the amount of total PVA used is usually 1 to 20 parts by weight per 100 parts by weight of the ethylenically unsaturated monomer. The addition method is that it can be added all at once before the start of polymerization as an aqueous solution, or it can be added dividedly or continuously during one part polymerization. Also, when obtaining a cationic emulsion, a nonionic surfactant or a cationic surfactant may be added as necessary. There is no problem in adding an agent.

In particular, in the case of ethylenically unsaturated monomers other than vinyl acetate, it is used in a maximum of 5 parts by weight per 100 parts by weight of the ethylenically unsaturated monomer in order to improve the mechanical stability of the emulsion. It's good to do that. However, if a large amount of surfactant is used, disadvantages such as a decrease in water resistance and a decrease in adhesive strength occur when an emulsion is used, so care must be taken depending on the purpose. In addition, it is necessary to consider the toxicity of cationic surfactants. Examples of nonionic surfactants used in combination include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, and ethylene oxide propylene oxide protox copolymer. Additionally, anionic surfactants are generally not recommended due to charge mismatch. Next, examples of ethylenically unsaturated monomers that can be used in producing the emulsion used in the sizing agent of the present invention include vinyl esters such as vinyl acetate, vinyl propionate, vinyl versatate which is a higher fatty acid vinyl ester, and acrylic acid. Acrylic esters such as methyl, ethyl acrylate, butyl acrylate and octyl acrylate, methacrylic esters such as methyl methacrylate and ethyl methacrylate, or vinyl chloride,
Vinylidene chloride, acrylonitrile, ethylene, styrene, vinyltoluene, chlorstyrene, Q-methylstyrene, acrylamide, N-methylolacrylamide, methacrylamide, maleate ester, fumarate gester, itaconate gester, butadiene, isoprene or aminoalkyl (meth)acrylic Examples include acid esters, cationic monomers such as aminoalkyl (meth)acrylamide or its quaternized products, etc.
Both are carried out by homopolymerization or copolymerization.

Among these, emulsions obtained by emulsion polymerization from monomers containing vinyl acetate, that is, vinyl acetate homopolymer, vinyl acetate-ethylene copolymer, or vinyl acetate-acrylic acid ester or methacrylic acid ester copolymer emulsion are the present invention. It is particularly preferred as a sizing agent in terms of physical properties. The cationic emulsion used in the present invention has a cationic group content of 0.01 to 10 mol% and a saponification degree of 60 to 100 mol%, in the presence of cationic group-modified PVA. The above-mentioned ethylenically unsaturated monomers are combined with commonly used polymerization initiators such as hydrogen peroxide, potassium persulfate, ammonium persulfate, and
2-azobis(-2-methylpropamidinium) dihydrochloride, which is a grade hydroperoxide or kyumene hydroperoxide or a cationic polymerization initiator;
It is produced by polymerizing 2-azobis-(2'-isopropylimidazolinium) dihydrochloride or the like under a frame loss condition.

As the polymerization initiator, the above may be used alone, but a known redox system in which the above initiator is combined with a reducing agent such as sodium bisulfite, sodium pyrosulfite, or a sodium metasulfite formaldehyde adduct is employed. It's okay. The amount of these polymerization initiators used is 0.01 to 5 parts by weight per 10 parts by weight of the ethylenically unsaturated monomer.
It is best to use within the range of parts by weight. The temperature when producing the emulsion of the present invention is 30 to 120°C, preferably 40°C.
-9020, and the pH during polymerization is 3-8. Examples of pH buffering agents include salts such as sodium carbonate, sodium bicarbonate, sodium orthophosphate, monobasic sodium phosphate, dibasic sodium phosphate, and sodium acetate in an amount of 0.0% by weight per 10 parts by weight of the ethylenically unsaturated monomer. It is recommended to use it in a range of 0.05 to 2 parts by weight. In addition, PV modified with cationic groups
If the cation group in A is a chemical structural unit such as primary amine, secondary amine, tertiary amine, pyridine or imidazole, add acetic acid, formic acid, phosphoric acid, hydrochloric acid or sulfuric acid to adjust the pH to a range of 3 to 8. It is preferable to adjust. The fact that the particles of the emulsion of the present invention are cationic can be determined by observing tortoise migration measured using a zetameter, etc., and observing that the particles move toward the cathode, and further by measuring the electrophoretic velocity (mobility). By doing so, the streaming potential (zeta-potential) can be calculated.

The cationic emulsion thus obtained showed strong adsorption to substances that tend to be negatively charged, such as fibers, pulp, glass fibers, sand, etc.

In this sense, this emulsion exhibits excellent performance as a laundry paste. The laundry starch of the present invention may further contain a plasticizer such as dibutyl phthalate, dioctyl phthalate, dibutyl adibate, dioctyl adibate, butyl carbitol acetate, butyl stearate, etc.
Antifreeze agents such as ethylene glycol, propylene glycol, and toluene, other fragrances, luminescent dyes, pigments, preservatives, PVA, starch, carboxymethyl cellulose, and the like may be added.

The amount of sizing agent used for the textile product when pasting is 0.2% by weight to 5% by weight, preferably 0.
．． It is 4% to 3% by weight. When using the sizing agent of the present invention, a sufficient amount of water (for example, bath ratio 1
Even if the paste is diluted with 1/4 or more), uniform gluing can be achieved, and gluing with a crisp and appropriate firmness is possible.

The present invention will be explained in more detail with the above examples. Note that parts and percentages are based on weight unless otherwise specified. Example
1 N-(3-dimethylaminopropyl)methacrylamide unit 0.6 mol% and vinyl acetate unit 99.4 mol%
The containing copolymer was saponified in methanol to form N-(
Contains 0.6 mol% of 3-dimethylaminopropyl) methacrylamide units, and the saponification degree of vinyl acetate units is 80.
．． A white cationically modified PVA powder containing 0 mol % was obtained.

The viscosity at 2 and 0 of this 4% aqueous solution of modified PVA is 9
．． It was P. (The viscosity was measured using a Burckfield viscometer. The same applies hereinafter.) Next, 930 parts of the above modified PVA 56% aqueous solution was added to the reaction atmosphere equipped with a flywheel, a thermometer, a dropping funnel, and a reflux condenser. After adjusting the pH of the system to 4.0 with a 50% acetic acid aqueous solution, 10 pinyl acetate monomers were added.
00 parts was added, the temperature was raised to 60:00, and emulsion polymerization was carried out for 3 hours while adding hydrogen peroxide and an aqueous sodium pyrosulfite solution.

The resin content of this emulsion was 51.6%, which was 25%.
The emulsion particles had a viscosity of 116 ratio P at °C, excellent mechanical stability and dilution stability, and the zeta potential of the emulsion particles measured by a zetameter was 110.5 mV, indicating cationicity. A sizing agent A is prepared by adding 1 part of dibutyl adibate to 100 parts of this emulsion. Example 2 Trimethyl-3-(1-acrylamido-1,1-dimethylpropyl) By saponifying a copolymer of ammonium chloride and vinyl acetate, trimethyl-3-(
Cation-modified PV containing 1.0 mol% of 1-acrylamido-1,1-dimethylpropyl) ammonium chloride units and having a saponification degree of pinyl acetate units of 78.0 mol%
I got an A.

The viscosity of this 4% aqueous solution of modified PVA at 20°C is 1
It was 0.2P. Emulsion polymerization was carried out in the same manner as in Example 1 except that this modified PVA was used, and a cationic polymer of V with a resin content of 52.4%, a viscosity of 139 at 25 qC, and a zeta potential of 114.7 was obtained. A polyacetic acid pinylate emulsion was obtained. Thickening agent B was prepared by adding 1 part of dibutyl adibate to 10 parts of this emulsion. Example 3 93 parts of an 8.6% aqueous solution containing the same cation-modified PVA as used in Example 2 and 95 parts of vinyl acetate monomer were charged into a pressure-resistant reaction vessel, and the system was replaced with nitrogen while being accompanied by flies. Introduce ethylene gas to reduce the pressure of the system due to ethylene to 10
The temperature was raised to 60 qo while adjusting to k9/carp.

Hydrogen peroxide aqueous solution and sodium pyrosulfite aqueous solution were added to the system, and emulsion polymerization was carried out for 3 hours while maintaining the pressure of the system at 10 kg' with ethylene, resulting in a resin content of 52.3%,
Viscosity 180 ratio P at 260, zeta potential 115
．． A cationic vinyl acetate-ethylene copolymer emulsion (ethylene content: 10 mol %) of 8 Kite V was obtained. This is called paste C. Example 4 93 parts of an 8.6% aqueous solution containing the same cation-modified PVA used in Example 2 and 80 parts of vinyl acetate monomer were charged into a pressure-resistant reaction vessel, and ethylene gas was introduced to lower the system pressure. was kept at 50 k9/base and emulsion polymerized by the same method as in Example 3, and a cationic vinyl acetate-ethylene copolymer with a resin content of 50.1%, a viscosity of 12&P at 25°C, and a zeta potential of 119.5 mV was used. A polymer emulsion (ethylene content: 45 mol%) was obtained.

This is called adhesive D. Example 5 Trimethyl-3-(1-acrylamido-1,1-dimethylpropyl) By saponifying a copolymer of ammonium chloride and vinyl acetate, trimethyl-3-(
Cationically modified PV containing 0.4 mol% of 1-acrylamido-1,1-dimethylpropyl) ammonium chloride units and having a saponification degree of vinyl acetate units of 83.0 mol%
I got an A.

A 4% aqueous solution of this modified PVA has a viscosity of 9. The ratio was P. Next, 930 parts of the above modified PVA 5.6% aqueous solution, 900 parts of vinyl acetate monomer and 100 parts of ethyl acrylate monomer were charged into a reaction vessel similar to that in Example 1, heated to 60°C, and heated to 60°C. Hydrogen peroxide and an aqueous sodium pyrosulfite solution were added while stirring, and emulsion polymerization was carried out for 3 hours.

The obtained vinyl acetate-ethyl acrylate copolymer emulsion had a resin content of 50.3% and a viscosity of 1 at 25 qo.
83 ratio P and zeta potential were 117.2 mV. This is called paste E. Example 6 Two anchors of PVA having a degree of polymerization of 1000 were immersed in an 8% caustic soda aqueous solution at room temperature for 1 hour, and then the liquid was filtered through a glass filter.

Put the wet PVA into a flask, add glycidyltrimethylammonium chloride (G-MA manufactured by Shell Chemical Co., Ltd.)
C) 20.3 parts were added and reacted for 8 hours at 5,000 C. with constant monitoring. After cooling to room temperature, it was neutralized with acetic acid, washed with a 70% methanol aqueous solution, and dried to obtain a cation-modified PVA powder with a nitrogen content of 0.68%. In the reaction vessel used in Example 1, 78 parts of a 10% aqueous solution of the modified PVA, 20 parts of polyoxyethylene nonyl phenyl ether, and 100 parts of vinyl acetate were charged and uniformly emulsified.
It rose to 0oo.

A hydrogen peroxide aqueous solution and a sodium pyrosulfite aqueous solution were added and emulsion polymerized for 3 hours to obtain a cationic polyvinyl acetate emulsion with a resin content of 50%, a viscosity ratio of 65 at 2500, and a zeta potential of 11.7 V. Obtained. This is called glue F. Comparative Example 1 Emulsification was carried out in the same manner as in Example 1, except that unmodified PVA (degree of saponification 88 mol%, viscosity of 4% aqueous solution 9.ratio P) was used in place of cationically modified PVA in Example 1. Polymerized, resin content 50%, viscosity at 25qo is 108
A polyvinyl acetate emulsion with a ratio P and a zeta-potential V of -25.0 was obtained.

This is called glue G. Comparative Example 2 A vinyl acetate emulsion commercially available as a laundry glue was used as a glue.

This emulsion has a resin content of 40%, a Bruckfield viscosity at 2500 of 60 P, and a zeta potential of -2.
It was 1.8 mV. Example 7 A gluing test was conducted using the gluing agents A to D of Examples 1 to 6 and Comparative Examples 1 and 2.

The results are shown in Table 1. [Gluing Test] Each sizing agent was diluted with distilled water to prepare an aqueous gluing solution with a solid content concentration of 0.8%.

Cotton fabric (Kanakin No. 3) and Estel-cotton blend fabric (Estel 65%, shirt fabric) were used for the gluing test.
For each fabric, the fabric was soaked in 100% of the liquid and kneaded by hand for 1 minute, then dehydrated using a centrifugal dehydrator with 3-top sand, and then air-dried. Then iron at 130oo, 20q○,
65%R. Day. After controlling the humidity with JIS-1005-19
The bending resistance (the larger the value, the harder) was measured by the cantilever method according to No. 59. Table 1 shows that the sizing agent of the present invention has a high adsorption rate and is excellent in sizing effect.

Table 1 Example 8 The emulsion paste B obtained in Example 2 was adjusted to a solid content concentration of 5%, and a polyester web (basis weight 15 mm/elbow) was
20% resin content per fiber weight by layering and soaking mangle
Squeeze it so that
Heat treatment was performed for 0.3 minutes.

The tensile strength under normal conditions was 2.0k9/25 ribs. Comparative Example 3 In Example 8, the emulsion paste B was replaced with the emulsion paste G obtained in Comparative Example 1, and the nonwoven fabric was treated in the same manner as in Example 8. The tensile strength in the normal state was 1.3 kg/25 ribs. Ta.

Example 9 Using emulsion paste B, the following resin processing test was conducted.

Emulsion paste B5 Anchor part: Spray a mixture of 50 parts of a 12% PVA aqueous solution with a degree of polymerization of 1700 and a degree of saponification of 98% and 20 parts of water onto the surface of the polyester web (
Application amount: 20 coats/final). Thereafter, it was air-dried and heat-treated and pressed at 14,000°C for 4 minutes. Thereafter, when water droplets were dropped on the resin-treated surface and the state of bleeding was observed, almost no bleeding was observed. Comparative Example 4 The emulsion paste solution B obtained in Example 9 was replaced with the emulsion paste solution G obtained in Comparative Example 1, and the treatment was carried out in the same manner as in Example 9. When the bleeding state was observed, the results were compared to those in Example 9. Considerable bleeding phenomenon was observed.

This is because cationic emulsions have excellent film-forming properties.
It is thought that a good film was formed. Comparative example
5 Emulsion polymerization of vinyl acetate was attempted under the same conditions as in Example 1, except that the following cationized starch was used instead of the cationic group-modified PVA used in Example 1, but during the polymerization (polymerization (at a rate of about 30%), the polymer coagulated and precipitated, and the desired cationic emulsion could not be obtained.

[Cationized starch]

Trimethylaminohydroxypropylated starch (starch residue) with a degree of cation substitution (average value of the number of cationic groups introduced per unit of anhydroglucose) of 0.10 Comparative Example 6 With the cationic groups used in Example 1 Emulsion polymerization of vinyl acetate was attempted under the same conditions as in Example 1, except that the following cationized urethane was used instead of modified PVA, but the polymer solidified during the polymerization (at a polymerization rate of about 30%). precipitation,
The desired cationic emulsion could not be obtained.

[Cationic urethane]

Polyoxypropylene glycol (OH value 56) 150
Dehydrate the water, add 4,4'-diphenylmethane diisocyanate 563 water at 70°C, and heat for 15 minutes.

Claims (1)

[Claims] 1. Ethylenically unsaturated monomers in the presence of cationic group-modified polyvinyl alcohol having a cationic group content of 0.01 to 10 mol% and a saponification degree of 60 to 100 mol%. A sizing agent for textile products whose main ingredient is a cationic emulsion produced by emulsion polymerization. 2. The sizing agent according to claim 1, wherein the polyvinyl alcohol modified with a cationic group is a modified polyvinyl alcohol containing a copolymerized unit represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R^1 is a hydrogen atom or lower alkyl group, B
▲There are mathematical formulas, chemical formulas, tables, etc.▼ or▲There are mathematical formulas, chemical formulas, tables, etc.▼ R^2, R^3, R^4 are lower alkyl groups, X is a negative group that forms a salt with ammonium nitrogen , A represents a group that connects the nitrogen atom of B and the nitrogen atom of the amide group. )3 The sizing agent according to claim 1 or 2, wherein the ethylenically unsaturated monomer is mainly vinyl acetate. 4. The sizing agent according to claim 1 or 2, wherein the ethylenically unsaturated monomer is mainly a mixture of vinyl acetate and ethylene. 5. The sizing agent according to claim 1 or 2, wherein the ethylenically unsaturated monomer is mainly a mixture of vinyl acetate and acrylic ester or methacrylic ester.