JP2000144575A - Base substance of cationic fabric size, its production and liquid fabric size composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cationic fabric size base substance high in adhesive property to a blended fiber e.g. polyester-blended fiber and capable of providing its good finishing property. SOLUTION: This cationic fabric size base substance is obtained by polymerizing 100 pts.wt. of a lower fatty acid vinyl ester, 20 to 40 pts.wt. of an unsaturated carboxylic acid and 130 to 300 pts.wt. of an unsaturated carboxylic acid alkyl ester in an aqueous solvent, in the coexistence of one or more cationic monomers and/or cationic polymer and in the presence of cationic polymer emulsion particles obtained by emulsion-polymerizing a lower fatty acid vinyl ester, thus obtaining the base substance where a cationic polymer emulsion is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cationic sizing substrate which can be blended with a liquid sizing composition suitable for being applied to clothing and the like, especially at home for washing, a method for producing the same, and a method for producing the same. To a liquid paste composition.

[0002]

2. Description of the Related Art At present, as a liquid paste used for clothing, a synthetic polymer emulsion mainly comprising polyvinyl acetate as a paste base is mainly used. This polyvinyl acetate is preferable because it can impart moderate hardness and tactile sensation to clothing, but since polyvinyl acetate is insoluble in water, the adhesive adhering to the clothing hardly falls off by washing, and when repeatedly used, the clothing is Had the disadvantage of becoming too hard. Therefore, it has been proposed to improve the desizing property at the time of washing by using a copolymer obtained by copolymerizing an unsaturated carboxylic acid with vinyl acetate as a glue base (Japanese Patent Publication No. 57-3).
No. 3398, No. 57-29483, No. 57-
36284, 58-12959, 60
Japanese Patent Publication No. -7070 and Japanese Patent Publication No. Hei 1-15625). However, there is still a problem in imparting a high finish to the blended fiber such as tet cotton in order to impart a good finish.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a cationic sizing substrate which has a high adsorptivity to blended fibers such as tet cotton and can impart a good finish, and a liquid sizing composition containing the substrate. The purpose is to: Another object of the present invention is to provide a method for efficiently producing the cationic paste substrate.

[0004]

According to the present invention, a lower fatty acid vinyl ester is emulsion-polymerized in an aqueous medium in the presence of a cationic monomer and / or a cationic polymer, and after the reaction is completed, the lower fatty acid vinyl ester is further added thereto. This is based on the finding that the above problems can be solved by emulsion polymerization of a fatty acid vinyl ester, an unsaturated carboxylic acid and an unsaturated carboxylic acid alkyl ester at a specific ratio. That is, the present invention provides a method for preparing a lower fatty acid on the surface of a cationic polymer particle obtained by emulsion polymerization of a lower fatty acid vinyl ester in the presence of at least one cationic monomer and / or a cationic polymer in an aqueous medium. Polymerization of vinyl ester, unsaturated carboxylic acid and unsaturated carboxylic acid alkyl ester using 20 to 40 parts by weight of unsaturated carboxylic acid and 130 to 300 parts by weight of unsaturated carboxylic acid alkyl ester per 100 parts by weight of lower fatty acid vinyl ester. And a cationic paste substrate characterized in that a cationic polymer emulsion is formed.

[0005] The present invention also provides a method of emulsion-polymerizing a lower fatty acid vinyl ester in an aqueous medium in the presence of at least one cationic monomer and / or a cationic polymer. Emulsion polymerization of vinyl ester, unsaturated carboxylic acid and unsaturated carboxylic acid alkyl ester, 20 to 40 parts by weight of unsaturated carboxylic acid and 130 to 300 parts by weight of unsaturated carboxylic acid alkyl ester per 100 parts by weight of lower fatty acid vinyl ester. The present invention provides a method for producing a cationic sizing substrate, which comprises: The present invention also provides a liquid size composition containing the above cationic size substrate.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, use of a cationic monomer or a cationic polymer alone or use of a combination of a cationic monomer and a cationic polymer may be mentioned, but use of a cationic monomer alone is preferred. Examples of the cationic monomer used in the present invention include the following.

[0006]

Embedded image

[0007]

Embedded image

Wherein R ¹ is a hydrogen atom or a methyl group;
² , R ³ and R ⁴ are each independently a hydrogen atom or a C ₁ -C ₄ alkyl group; R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a C ₁ -C ₂ alkyl group; Represents a monovalent anion. Examples of the cationic polymer used in the present invention include a polymer of the above monomer or a copolymer of the above monomer and a lower fatty acid vinyl ester. Such a cationic monomer and / or cationic polymer is preferably contained in the paste base in an amount of 1 to 10% by weight (hereinafter abbreviated as%). The homopolymer of the above monomer is preferably obtained as an emulsion by, for example, appropriately polymerizing using a commonly used nonionic, anionic or cationic emulsifier.

The nonionic emulsifier used is C ₁
Saturated or unsaturated alcohols of ethylene oxide adduct of -C ₁₁ (additional number of moles 9~100), C ₁ ~C ₁₁ alkyl group and from 9 to 30 or more alkylphenol ethoxylates having an ethylene oxide unit, for example polyoxy Examples include ethylene heptyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene methyl octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and polyoxyethylene dodecyl phenyl ether. In particular, HLB is 12
~ 20, more preferably HLB15 ~
Eighteen. Examples of the anionic emulsifier include sulfuric acid ester salts of C ₈ -C ₁₈ alcohols such as sodium and potassium lauryl sulfate, and C ₈ -C ₁₈ fatty acid salts (eg, sodium salt, potassium salt, ethanolamine salt such as triethanolamine ( Specific examples include triethanolamine oleate, triethanolamine stearate, etc.) and sulfonated alkylaryl compounds, and cationic emulsifiers include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylethylammonium salts, alkyl Dimethylbenzylammonium salt, alkylpyridinium salt, alkylquinolium salt, alkylisoquinolium salt, stearylamidomethylpyridinium salt, acylaminoethylmethyldiethylammonium salt, acyl Aminoethyl pyridinium salt, alkoxymethyl pyridinium salt, 1-methyl-1-acyl aminoethyl-2-alkyl imidazoline, diacyl aminopropyl dimethyl ammonium salts,
Examples thereof include diacylaminoethyldimethylammonium salt, dialkyldi (polyoxyethylene) ammonium salt, and dialkylmethylpolyoxyethyleneammonium salt.

The copolymer of the above-mentioned cationic monomer and lower fatty acid vinyl ester can be easily prepared by coexisting the above-mentioned cationic monomer during the polymerization of the lower fatty acid vinyl ester. The lower fatty acid vinyl ester used in the present invention has 4 carbon atoms.
To 6 are preferable, and examples thereof include vinyl acetate, vinyl butyrate, and vinyl propionate. These are 1
Species or a mixture of two or more can be used. The unsaturated carboxylic acid used in the present invention has 3 carbon atoms.
And 10 to 10 unsaturated monocarboxylic acids and unsaturated polycarboxylic acids. Specifically, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid,
Aconitic acid, sorbic acid, cinnamic acid, α-chlorosorbic acid, citraconic acid, p-vinylbenzoic acid and the like. Also, alkyl half esters, partial esters or partial amides of unsaturated carboxylic acids such as itaconic acid, maleic acid and fumaric acid can be used. In particular,
Lower alkyl half-esters having 1 to 6 carbon atoms, such as monomethyl itaconate, monobutyl itaconate, monomethyl fumarate, monobutyl fumarate and monobutyl maleate, may be mentioned. Among these unsaturated carboxylic acids, acrylic acid,
Methacrylic acid and crotonic acid are preferred. As the unsaturated carboxylic acid, one kind or a mixture of two or more kinds can be used.

The unsaturated carboxylic acid alkyl ester used in the present invention includes (a) an alkyl ester of an unsaturated monocarboxylic acid having 3 to 6 carbon atoms (1 to 3 carbon atoms of an alkyl group).
4) For example, methyl acrylate, ethyl acrylate,
Propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Acrylic acid such as butyl methacrylate, alkyl ester of methacrylic acid, (b) diester of α, β-ethylenically unsaturated dicarboxylic acid having 4 to 7 carbon atoms (1 to 4 carbon atoms of alkyl group), for example, In addition to the lower fatty acid vinyl ester and the unsaturated carboxylic acid and the unsaturated carboxylic acid alkyl ester, such as dibutyl maleate, diethyl maleate, fumarate, itaconate, and citraconate, it is also possible to use a polymer using a monomer copolymerizable therewith. it can. Such copolymerizable monomers include (A) alkenes such as ethylene and styrene,
(B) vinyl halides such as vinyl chloride; vinylidene halides such as vinylidene chloride; (C) α, β-ethylenically unsaturated carboxylic acid amides such as acrylamide and N-methylolamide; and N-alkylol derivatives thereof. can give. Of these, the monomers mentioned in (A) are preferred.

In the present invention, first, a lower fatty acid vinyl ester is emulsion-polymerized in an aqueous medium in the presence of one or more cationic monomers and / or cationic polymers. Emulsion polymerization can be carried out by any method. Initial polymerization is carried out by adding a lower fatty acid vinyl ester and a polymerization catalyst to a reactor in which one or more cationic monomers and / or cationic polymers have been added in advance. It is preferable to continue the emulsion polymerization by dropping a mixture containing the lower fatty acid vinyl ester and the polymerization catalyst. Various polymerization initiators can be used in the polymerization performed in the present invention. For example, 2,2'-azobis (2-amidinopropane), hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxide,
Examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, peracetic acid, perbenzoic acid, potassium persulfate, and the like. The polymerization is carried out at 40 to 120 ° C., preferably 50 to 90 ° C., and the pH at the time of polymerization is preferably in the range of 3 to 9, preferably 4 to 8.

In the first stage polymerization, it is preferable that the monomers have been reacted before proceeding to the next polymerization step. Therefore, it is preferable to continue the polymerization for 15 minutes to 24 hours, preferably 30 minutes to 3 hours after the completion of the dropping of the monomer.
This is because, when the process proceeds to the next polymerization step, the lower fatty acid vinyl ester, unsaturated carboxylic acid and unsaturated carboxylic acid alkyl ester supplied in the second stage are added to the polymer in the first stage, and the polymerization proceeds. However, no so-called core / shell type particles are formed, and the unit of the unsaturated carboxylic acid alkyl ester which should originally be present in the shell is uniformly present in the particles, and the lipophilicity of the particles is reduced to the core / shell type particles. This is because the chemical fiber becomes weaker and the adsorption to the chemical fiber is weakened. In the present invention, as the second stage, further lower fatty acid vinyl ester,
The unsaturated carboxylic acid and the unsaturated carboxylic acid alkyl ester are emulsion-polymerized. Specifically, the lower fatty acid vinyl ester, the unsaturated carboxylic acid and the unsaturated carboxylic acid alkyl ester, and the polymerization catalyst (the above polymerization catalyst can be used) are added to the cationic polymer emulsion polymerized in the first stage. It is preferable to carry out the polymerization by dropping the mixed solution. The polymerization is carried out at 40 to 120 ° C (preferably 50 to 90 ° C).
C), and the pH is 3 to 9, preferably 4 to 8.

Here, the lower fatty acid vinyl ester 100
20 to 40 parts by weight (preferably 25 to 40 parts by weight) of unsaturated carboxylic acid and 130 to 300 parts by weight (preferably 2 to 40 parts by weight) of the unsaturated carboxylic acid alkyl ester per part by weight.
(00 to 300 parts by weight). By such multi-stage polymerization, the cationic sizing substrate of the present invention can be obtained. In the present invention, the unsaturated carboxylic acid is used in an amount of 1 to 10 parts by weight (preferably 2 to 8 parts by weight) based on 100 parts by weight of the lower fatty acid vinyl ester in the final emulsion as the cationic paste base obtained. 10 to 50 parts by weight of alkyl ester (more preferably 30 to 5 parts by weight)
0 parts by weight). The liquid sizing composition of the present invention can be formed from the cationic sizing substrate itself, but is preferably contained at 20 to 60%, more preferably 35 to 55%, and other components are used in combination. Is good. Other components, for example, bisulfite. Various salts can be used as the bisulfite, but a sodium salt and a potassium salt are preferable. The amount of the bisulfite can be arbitrary, but is not more than 0.0 in the liquid paste composition.
The content is preferably 001 to 0.2%, more preferably 0.2%.
001 to 0.05%. In particular, it is preferable to use 0.002 to 0.1 part by weight per 100 parts by weight of the glue base. Further, a water-soluble polymer can be contained for the purpose of enhancing the dispersion stability of the paste composition. As such a water-soluble polymer,
Cationic polymers such as cationic cellulose and cationic starch cationic vinyl polymer; processed starch such as PVA, hydroxyethyl starch and hydroxypropylated starch; and nonionic polymers such as hydroxyethyl cellulose. These are preferably contained in the liquid paste composition in an amount of 0.1 to 5%.

The liquid glue composition of the present invention may further contain, if necessary, additives for general polymer emulsions, for example, plasticizers such as dibutyl phthalate and dibutyl adipate, and freezing agents such as ethylene glycol and propylene glycol. Inhibitors, other perfumes, fluorescent agents, antibacterial agents, pigments, dyes, and the like can also be added. Although the viscosity of the liquid paste composition of the present invention is not limited, it is 400 to 800 cp (25 ° C.).
The degree is good, and the pH is preferably about 3 to 6.

According to the present invention, there is provided a cationic sizing base which has a high adsorptivity to mixed fibers such as tet cotton and can impart a good finish, and a method for efficiently producing the same. . Therefore, the liquid sizing composition containing the cationic sizing substrate can be suitably used as a home sizing composition.

Next, the present invention will be described by way of examples.

Example 1 A separable flask equipped with a stirrer, a dropping funnel, a thermometer and a reflux condenser was charged with 60 parts by weight of water and 14 parts by weight of a 50% aqueous solution of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride. And ethanol
5.0 parts by weight were charged and heated to 70 ° C. 2.0 parts by weight of vinyl acetate was added thereto, and 8.0 parts by weight of a 5% aqueous solution of 2,2'-azobis (2-amidinocyclopropane) hydrochloride was added as a polymerization initiator to initiate initial polymerization. 58 parts by weight of vinyl acetate and 6.0 parts by weight of a 5% aqueous solution of 2,2'-azobis (2-amidinocyclopropane) hydrochloride were continuously added from 60 minutes to 4 hours after the initiation of the initial polymerization. After dropping, the mixture was aged for 30 minutes. Then, 15 parts by weight of vinyl acetate, 25 parts by weight of ethyl acrylate, 4 parts by weight of methacrylic acid and 2.0 parts by weight of a 5% aqueous solution of 2.2′-azobis (2-amidinocyclopropane) hydrochloride were continuously applied over 2 hours. After dripping, the mixture was aged for 1 hour after completion of the dropping to complete the reaction. After the reaction and by adding water, the nonvolatile content was adjusted to 50% by weight. The resulting composition is a homogeneous milky white liquid with a viscosity of 300 mP
a · s, average particle size 0.5 μm (Shimadzu Corporation, centrifugal sedimentation system: SA-CP3 type).

Example 2 A separable flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser was charged with 55 parts by weight of water and 3% of cationic cellulose (Leogard G, manufactured by Lion Corporation).
7.0 parts by weight of the aqueous solution was charged and heated to 70 ° C. To this were added 14 parts by weight of a 50% aqueous solution of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride and 2.0 parts by weight of vinyl acetate, 5.0 parts by weight of ethanol, and 2,2'-azobis ( 8.0 parts by weight of a 5% aqueous solution of 2-amidinocyclopropane) hydrochloride was added to initiate initial polymerization. 58 parts by weight of vinyl acetate and a 5% aqueous solution of 2,2′-azobis (2-amidinocyclopropane) hydrochloride over a period of 60 minutes to 4 hours after the initiation of the initial polymerization 6.
0 parts by weight was continuously dropped. After dropping, the mixture was aged for 30 minutes. Next, 15 parts by weight of vinyl acetate and ethyl acrylate 2
5 parts by weight, 4 parts by weight of methacrylic acid and 5% aqueous solution of 2,2′-azobis (2-amidinocyclopropane) hydrochloride
2.0 parts by weight was continuously added dropwise over 2 hours, and after completion of the addition, the mixture was aged for 1 hour to complete the reaction. After the reaction, an additive and water were added to adjust the nonvolatile content to 50% by weight. The resulting composition was a uniform milky white liquid having a viscosity of 400 mPa · s and an average particle size of 0.4 μm.

Example 3 The weight of water charged into a separable flask was changed to 55 parts by weight, and 7.0 parts by weight of a 3% aqueous solution of cationic cellulose (Leogard G, manufactured by Lion Corporation) was charged with cationic starch (Neopositparin, manufactured by Matsutani Chemical Co., Ltd.). The reaction was completed in the same manner as in Example 2 except that the aqueous solution was changed to 14 parts by weight of the 5% aqueous solution. The composition obtained is a homogeneous milky white liquid with a viscosity of 400 mPa
S, average particle diameter was 0.6 μm. Example 4 15 parts by weight of vinyl acetate, 25 parts by weight of ethyl acrylate, and 4 parts by weight of methacrylic acid dropped in the latter half were mixed with 1 part of vinyl acetate.
The reaction was completed in the same manner as in Example 1 except that 0 parts by weight, 30 parts by weight of ethyl acrylate, and 4 parts by weight of methacrylic acid were changed (the ratio of vinyl acetate / EA was changed). The resulting composition is
It was a uniform milky white liquid having a viscosity of 300 mPa · s and an average particle size of 0.5 μm.

Example 5 15 parts by weight of vinyl acetate, 25 parts by weight of ethyl acrylate, and 4 parts by weight of methacrylic acid were added dropwise to vinyl acetate 1 part.
The reaction was completed in the same manner as in Example 1 except that 5 parts by weight, 25 parts by weight of ethyl acrylate and 4 parts by weight of crotonic acid were used. The resulting composition is a homogeneous milky white liquid with a viscosity of 3
The particle size was 50 mPa · s and the average particle size was 0.6 μm. Comparative Example 1 A separable flask equipped with a stirrer, a dropping funnel, a thermometer, and a reflux condenser was charged with 5 parts by weight of water and 30 parts by weight of a 3% aqueous solution of cationic cellulose (Leogard G, manufactured by Lion Corporation) at 70 ° C. Until heated. 5 parts by weight of vinyl acetate and 0.5 parts by weight of crotonic acid were added thereto, and 0.2 parts by weight of 2,2′-azobis (2-amidinocyclopropane) hydrochloride as a polymerization initiator was added as a 5% aqueous solution to carry out initial polymerization. Started. After 20 minutes from the start of the polymerization, 40 parts by weight of vinyl acetate, 5 parts by weight of crotonic acid and 2,
2'-azobis (2-amidinocyclopropane) hydrochloride
0.2 parts by weight was continuously dropped as a 5% aqueous solution. After completion of the dropwise addition, the mixture was aged for 1 hour to complete the reaction. After the reaction, additives and water were added to adjust the nonvolatile content to 50% by weight. The resulting composition is a homogeneous milky white liquid with a viscosity of 1000 mP.
a · s, average particle diameter 1.0 μm.

Comparative Example 2 In a separable flask equipped with a stirrer, a dropping funnel, a thermometer and a reflux condenser, 14 parts by weight of a 50% aqueous solution of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, 25 parts by weight of water, Ethanol 5
Parts by weight, 2.2′-azobis (2-
Amidinocyclopropane) hydrochloride (0.2 part by weight) was added as a 5% aqueous solution and polymerized at 70 ° C. to obtain a cationic polymer aqueous solution. 5 parts by weight of vinyl acetate, 0.5 parts of crotonic acid
Parts by weight, and as a polymerization initiator, 0.2 part by weight of 2.2′-azobis (2-amidinocyclopropane) hydrochloride was added to 5 parts by weight.
% Aqueous solution to initiate initial polymerization. 2 after initiation of polymerization
From 0 minutes to 5 hours, 40 parts by weight of vinyl acetate, 5 parts by weight of crotonic acid, and 0.2 parts by weight of 2,2'-azobis (2-amidinocyclopropane) hydrochloride were continuously dropped as a 5% aqueous solution. After completion of the dropwise addition, the mixture was aged for 1 hour to complete the reaction.
After the reaction, the additives and water are added to reduce the nonvolatile content to 50% by weight.
Was adjusted. The composition obtained was a uniform milky white liquid having a viscosity of 500 mPa · s and an average particle diameter of 0.6 μm.

The properties of the compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were examined by the following methods. Table-
It is shown in FIG. Gluing method A commercially available Tetron (registered trademark) / cotton broad blended product (50% polyester / 50% cotton) was used, and a commercially available laundry detergent "Super Top (manufactured by Lion Corporation)" was used in a household electric washing machine. 15 minutes washing with 50 ° C warm water -15
The minute rinsing operation was repeated five times, and this was used as a test cloth. Next, using a Rounder meter manufactured by Daiei Kagaku Seiki Co., Ltd., 250 cc of water and 0.1 g of an emulsion solid were added to a stainless steel pot and uniformly dispersed. About 12 g of test cloth was put in this dispersion, treated for 3 minutes, dehydrated for 30 seconds, and air-dried overnight. After that, ironing was performed. At the time of gluing at the adsorption rate , the liquid before and after the treatment is collected and 660 n
The absorbance at m was measured, and the adsorption rate to the cloth was determined based on the following equation.

[Formula 1] Adsorption rate = 100 × [absorbance (abs) before treatment−
Absorbance after treatment (abs)] / [Pretreatment of absorbance (abs) - Tsuyoshi軟based absorbance tap water (abs)] stiffness treated with the gluing method fabric JIS-L-1096 softness Method E The degree was measured.

[0022]

[Table 1] Table-1 Examples Comparative Examples * 1 2 3 4 5 1 * 2 * Adsorption rate (%) 60 65 66 72 66 35 33 Softness (g) 60 61 58 55 53 38 36

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 291/12 C08F 291/12 (72) Inventor Naoichi Murase 353-7 Daihama, Ogasa-gun, Shizuoka Prefecture Inside the Shizuoka Research Laboratories of Heist Synthesis Co., Ltd. (72) Inventor Yoshikazu Fukumoto 1-3-7 Honjo, Sumida-ku, Tokyo Inside Lion Corporation (72) Shuichi Nihei 1-3-3 Honjo, Sumida-ku, Tokyo No. 7 Lion Corporation F term (reference) 4J011 AA05 KA02 KA03 KA04 KA08 KA10 KB13 KB14 KB19 KB29 4J026 AA19 AA31 AA37 AA38 AA47 AA50 AA61 AC26 BA02 BA05 BA10 BA19 BA20 BA25 BA27 BA32 BA04 DA09 DA04 DB12 DB14 DB15 DB31 DB32 FA07 GA08 GA09 4J100 AA02S AB02S AC03S AC04S AG02P AG04P AJ01Q AJ02Q AJ03Q AJ08Q AJ09Q AL03R AL34R AL41Q AL44Q AL44R AM15S AM21S BA03S BB 01Q CA05 CA06 CA29 EA07 FA02 FA20 FA34 FA39 FA43 JA11 4L033 AC12 AC15 BA85 CA03 CA19

Claims (3)

[Claims] 1. An aqueous medium, in the presence of one or more cationic monomers and / or cationic polymers, in the presence of cationic polymer emulsion particles obtained by emulsion polymerization of a lower fatty acid vinyl ester, Lower fatty acid vinyl ester, unsaturated carboxylic acid and unsaturated carboxylic acid alkyl ester, 20 to 40 parts by weight of unsaturated carboxylic acid and 130 to 300 parts by weight of unsaturated carboxylic acid alkyl ester per 100 parts by weight of lower fatty acid vinyl ester A cationic sizing substrate, wherein the cationic sizing substrate is polymerized to form a cationic polymer emulsion. 2. A lower fatty acid vinyl ester is emulsion-polymerized in an aqueous medium in the presence of at least one cationic monomer and / or a cationic polymer. After the reaction is completed, the lower fatty acid vinyl ester and The saturated carboxylic acid and the unsaturated carboxylic acid alkyl ester are used in an amount of 20 to 100 parts by weight of the lower fatty acid vinyl ester to obtain an unsaturated carboxylic acid.
40 parts by weight and 1 part of unsaturated carboxylic acid alkyl ester
A method for producing a cationic paste substrate, comprising subjecting 30 to 300 parts by weight of emulsion polymerization. 3. A liquid paste composition containing the cationic paste substrate according to claim 1.