JP2000143742A - Cationic starch substrate, its production and liquid starch composition containing the same paste substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cationic starch substrate improved in wash-off property on washing, capable of providing good starchy property to synthetic fibers and comprising cationic polymer particles by subjecting different specific esters to emulsion polymerization in the presence of a cationic monomer, etc., in an aqueous medium. SOLUTION: (C) A lower fatty acid vinyl ester such as vinyl acetate is subjected to emulsion polymerization with (D) an unsaturated carboxylic acid alkyl ester such as ethylacrylate in an amount of 200-300 pts.wt. based on 100 pts.wt. component C in (A) an aqueous medium such as water in the presence of (B) one or more kinds of cationic monomers and/or cationic polymers (e.g. 2-hydroxy-3-methacryloyloxypropyl-trimethylammonium chloride), preferably at 50-90 deg.C and pH 4-8. The component B is preferably contained so as to become 1-10 wt.% in a paste base.

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 that it is not enough to give the desizing property at the time of washing and the good tension property to the synthetic fiber.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to a cationic sizing substrate capable of improving the desizing property during washing and imparting good tenacity to synthetic fibers, and a liquid sizing composition containing the substrate. The purpose is to provide. The present invention also provides
An 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 and an unsaturated carboxylic acid alkyl ester are emulsion-polymerized in an aqueous medium in the presence of a cationic monomer and / or a cationic polymer, followed by aging. Let
It was made based on the finding that the above problem could be solved by further emulsion polymerization of a lower fatty acid vinyl ester. That is, the present invention relates to a cationic polymer obtained by emulsion polymerization of a lower fatty acid vinyl ester and an unsaturated carboxylic acid alkyl ester in an aqueous medium in the presence of one or more cationic monomers and / or cationic polymers. A cationic sizing substrate comprising particles is provided.

The present invention is also characterized in that a lower fatty acid vinyl ester and an unsaturated alkyl carboxylate are emulsion-polymerized in an aqueous medium in the presence of at least one cationic monomer and / or cationic polymer. The present invention provides a method for producing a cationic paste substrate. The present invention also provides
A liquid size composition containing the above cationic size substrate is provided.

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-mentioned monomer, or a copolymer of the above-mentioned monomer with at least one of lower fatty acid vinyl ester and unsaturated carboxylic acid alkyl ester, or a copolymer of these with another monomer. 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%). Such a cationic monomer is preferably contained in the paste base so as to be 1 to 10%. It is preferable that the homopolymer of the above monomer is 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.

[0010] The copolymer of the cationic monomer with a lower fatty acid vinyl ester and an unsaturated carboxylic acid alkyl ester may be used in the polymerization of the lower fatty acid vinyl ester, the unsaturated carboxylic acid and the unsaturated carboxylic acid alkyl ester. It can be easily carried out by coexisting a hydrophilic monomer. The lower fatty acid vinyl ester used in the present invention preferably has 4 to 6 carbon atoms, and examples thereof include vinyl acetate, vinyl butyrate and vinyl propionate. These can be used alone or in combination of two or more. Examples of the unsaturated carboxylic acid alkyl ester used in the present invention include (a) an alkyl ester of an unsaturated monocarboxylic acid having 3 to 6 carbon atoms (1 to 4 carbon atoms of an alkyl group), for example, methyl acrylate, ethyl acrylate Acrylic acid, such as propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc., alkyl esters of methacrylic acid,
(b) diesters of α, β-ethylenically unsaturated dicarboxylic acids having 4 to 7 carbon atoms (1 to 4 carbon atoms in the alkyl group) such as dibutyl maleate, diethyl maleate, fumarate, itaconate and citracone; In addition to the lower fatty acid vinyl ester, the unsaturated carboxylic acid and the unsaturated carboxylic acid alkyl ester, a polymer using a monomer copolymerizable therewith can also be used. Examples of such copolymerizable monomers include (A) alkenes and styrenes such as ethylene, (B) vinyl halides such as vinyl chloride and vinylidene chloride, (C) acrylamide and N-methylolamide. Α, β-ethylenically unsaturated carboxylic acid amide and its N-alkylol derivative, (D) acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid, sorbic acid, cinnamic acid And unsaturated monocarboxylic acids having 3 to 10 carbon atoms and unsaturated polycarboxylic acids such as α-chlorosorbic acid, citraconic acid and p-vinylbenzoic acid. Of these, the monomers mentioned in (A) are preferred.

In the present invention, first, a lower fatty acid vinyl ester and an unsaturated carboxylic acid alkyl ester are emulsion-polymerized in an aqueous medium in the presence of at least one cationic monomer and / or cationic polymer. Emulsion polymerization can be carried out by any method, but a lower fatty acid vinyl ester and an unsaturated carboxylic acid alkyl ester, and a polymerization catalyst are added to a reactor previously added with one or more cationic monomers and / or cationic polymers. In addition, it is preferable to carry out initial polymerization, and then to drop a mixed solution containing a lower fatty acid vinyl ester unsaturated carboxylic acid alkyl ester and a polymerization catalyst, and to continue emulsion polymerization. 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, methyl ethyl ketone peroxide, cyclohexanone peroxide, peracetic acid, perbenzoic acid Acids, potassium persulfate and the like. The polymerization is carried out at 40 to 120 ° C.
It is preferably 50 to 90 ° C., and the pH at the time of polymerization is 3 to 9,
Preferably, the range is 4 to 8. Here, in the present invention, it is preferable to carry out emulsion polymerization using 130 to 300 parts by weight (preferably 200 to 300 parts by weight) of the unsaturated carboxylic acid alkyl ester per 100 parts by weight of the lower fatty acid vinyl ester.

In the present invention, 10 to 50 parts by weight (more preferably 30 to 50 parts by weight) of the unsaturated carboxylic acid alkyl ester is used with respect to 100 parts by weight of the lower fatty acid vinyl ester in the final emulsion as the cationic paste base obtained. Part). The liquid sizing composition of the present invention can be formed from the cationic sizing substrate itself, but contains other components such as a water-soluble polymer for the purpose of enhancing the dispersion stability of the sizing composition. be able to.
Examples of such water-soluble polymers include cationic polymers such as cationic cellulose and cationic starch / cationic vinyl polymer, PVA, hydroxyethyl starch, processed starch such as hydroxypropylated starch, and nonionic polymers such as hydroxyethyl cellulose. Molecules. These are present in the liquid glue composition in amounts of 0.1-5.
%. The liquid paste composition of the present invention may further contain, if necessary, additives for general polymer emulsions, for example, dibutyl phthalate, plasticizers such as dibutyl adipate, ethylene glycol, antifreezing agents such as propylene glycol, Other fragrances, 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 80.
It is preferably about 0 cp (25 ° C.) and the pH is preferably about 3 to 6.

[0013]

According to the present invention, there is provided a cationic sizing substrate capable of improving the desizing property during washing and imparting good tenacity to synthetic fibers, and an efficient production method thereof. . 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 with reference to examples.

[0014]

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
Charge 5.0 parts by weight and heat to 70 ° C. To this were added 1.4 parts by weight of vinyl acetate, 0.6 parts by weight of ethyl acrylate, and 0.08 parts by weight of methacrylic acid.
An initial polymerization was initiated by adding 8.0 parts by weight of a 5% aqueous solution of 2′-azobis (2-amidinocyclopropane) hydrochloride. 68.6 hours after the start of the initial polymerization for 6 hours
Parts by weight, 29.4 parts by weight of ethyl acrylate, 3.92 parts by weight of methacrylic acid, and 8.0 parts by weight of a 5% aqueous solution of 2,2′-azobis (2-amidinocyclopropane) hydrochloride were added, and the dropwise addition was completed. Thereafter, the mixture was aged for 1 hour to complete the reaction.
After the reaction, the additives and water were blended to adjust the nonvolatile content to 50% by weight. The obtained composition was a uniform milky white liquid having a viscosity of 400 mPa · s and an average particle diameter of 0.5 μm (manufactured by 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).
An aqueous solution (7.0 parts by weight) is 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, 1.4 parts by weight of vinyl acetate, 0.6 parts by weight of ethyl acrylate, and 0.08 parts by weight of methacrylic acid. 5.0 parts by weight, 5% aqueous solution of 2,2′-azobis (2-amidinocyclopropane) hydrochloride as a polymerization initiator 8.
0 parts by weight was added to initiate the initial polymerization. 6 after the start of initial polymerization
68.6 parts by weight of vinyl acetate, 29.4 parts by weight of ethyl acrylate, 3.92 parts by weight of methacrylic acid, and a 5% aqueous solution of 2,2′-azobis (2-amidinocyclopropane) hydrochloride over 0 minutes to 6 hours 8.0 parts by weight were continuously added dropwise, 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 blended to adjust the nonvolatile content to 50%. The resulting composition is a homogeneous milky white liquid with a viscosity of 500 mP
a · s, average particle diameter 0.6 μm.

Example 3 55 parts by weight of water charged in a separable flask was changed to 50 parts by weight, and 7.0 parts by weight of a 3% aqueous solution of cationic cellulose (Leogard G, manufactured by Lion Corporation) was replaced with 5 parts by weight of cationic starch. The reaction was completed in the same manner as in Example 2 except that the amount of the aqueous solution was changed to 14 parts by weight. After the reaction, an additive and water were blended to adjust the nonvolatile content to 50%. The resulting composition is a homogeneous milky white liquid with a viscosity of 300 mPa · s,
The average particle size was 0.6 μm. Example 4 1.4 parts by weight of prepolymerized vinyl acetate, ethyl acrylate
0.6 parts by weight of methacrylic acid and 0.08 parts by weight of vinyl acetate.
0 parts by weight, 1.0 part by weight of ethyl acrylate, 0.08 parts by weight of methacrylic acid (change of vinyl acetate / EA ratio), 68.6 parts by weight of vinyl acetate to be dropped, and 2 parts by weight of ethyl acrylate
9.4 parts by weight and 3.92 parts by weight of methacrylic acid
The reaction was completed in the same manner as in Example 1 except that 9 parts by weight, 49 parts by weight of ethyl acrylate, and 3.92 parts by weight of methacrylic acid were changed (the ratio of vinyl acetate / EA was changed). The resulting composition was a uniform milky white liquid having a viscosity of 400 mPa · s and an average particle size of 0.5 μm.

EXAMPLE 5 1.4 parts by weight of prepolymerized vinyl acetate, ethyl acrylate
0.6 parts by weight of methacrylic acid and 0.08 parts by weight of methacrylic acid.
4 parts by weight, 0.6 parts by weight of ethyl acrylate, crotonic acid
0.08 parts by weight, 68.6 parts by weight of vinyl acetate to be added dropwise, 29.4 parts by weight of ethyl acrylate, and 3.94 parts by weight of methacrylic acid.
The reaction was completed in the same manner as in Example 1 except that 92 parts by weight was changed to 68.6 parts by weight of vinyl acetate, 29.4 parts by weight of ethyl acrylate, and 3.92 parts by weight of crotonic acid. The resulting composition was a uniform milky white liquid having a viscosity of 300 mPa · s and an average particle diameter of 0.6 μm.

Comparative Example 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). Heat to 70 ° C. 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 60 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
A part by weight was continuously dropped as a 5% aqueous solution. After dripping 1
After aging for a time, the reaction was completed. After the reaction, an additive and water were blended to adjust the nonvolatile content to 50%. The resulting composition is a homogeneous milky white liquid with a viscosity of 1000 mPa · s
And the average particle diameter was 1.0 μm. The properties of the compositions obtained in Examples 1 to 5 and Comparative Example were examined by the following methods. The results are summarized in Table 1.

Gluing method Commercial polyester georgette (PS-JT) and tetron / cotton broad blend (65% polyester / cotton 3)
5%), using a commercially available laundry detergent “Super Top (Lion Co., Ltd.)” using a household electric washing machine,
The operation of washing with 50 ° C warm water for 15 minutes and rinsing for 15 minutes was repeated 5 times, and this was used as a test cloth. Next, using a round meter from Daiei Kagaku Seiki Co., Ltd., 25
0.1 g of 0 cc tap water and 0.1 g of emulsion solids were added 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. Bending resistance The cloth treated by the above gluing method was measured for the bending resistance based on the JIS-L-1096 Rigid-softness E method. Glue removal rate The glued cloth was washed with a commercially available laundry detergent "Super Top (manufactured by Lion Corporation)" using a household electric washing machine at a standard use concentration for 10 minutes, rinsed for 15 minutes, and then used as a washed cloth. . The size removal property was calculated based on the following equation.

[Formula 1] Glue removal rate = 100 × [Bending softness during gluing−Bending softness after washing] / [Bending softness before gluing−Bending softness before gluing]

[0020]

[Table 1] Table-1 Example Comparative Example 1 2 3 4 5 Bending resistance (g) PS-JT * 170 160 165 160 170 130 Tet cotton 70 68 70 65 63 54 Paste removal rate (%) PS-JT * 60 65 60 62 60 45 Tet Cotton 73 75 72 70 68 53 PS-JT *: Polyester Georgette

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // (C08F 265/04 218: 04 220: 10) (C08F 285/00 218: 04 220: 10) ( 72) Inventor Naoichi Murase 353-7 Chihama, Oto-cho, Ogasa-gun, Shizuoka Prefecture Inside the Shizuoka Research Laboratories (72) Inventor Yoshikazu Fukumoto 1-3-7 Honjo, Sumida-ku, Tokyo Lion Corporation (72) Inventor Shuichi Nihei 1-3-7, Honjo, Sumida-ku, Tokyo F-term in Lion Corporation (reference) 4J011 KA15 KA17 4J026 AA47 AA50 AA60 AA61 BA29 BA32 BA39 BA40 4L033 AC12 CA03 CA19 CA28

Claims (3)

[Claims] 1. Cationic polymer particles obtained by emulsion polymerization of a lower fatty acid vinyl ester and an unsaturated carboxylic acid alkyl ester in an aqueous medium in the presence of one or more cationic monomers and / or cationic polymers. A cationic sizing substrate comprising: 2. A cationic method comprising subjecting a lower fatty acid vinyl ester and an unsaturated carboxylic acid alkyl ester to emulsion polymerization in an aqueous medium in the presence of at least one cationic monomer and / or cationic polymer. A method for producing a paste base. 3. A liquid paste composition containing the cationic paste substrate according to claim 1.