JPH1112939A - Liquid paste composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid paste composition good in dischargeability from containers in winter, not generating aggregates, good in usability and used for pasting clothes, by making the composition include a paste base agent obtained by polymerizing a lower fatty acid vinyl ester and a specific compound. SOLUTION: This composition comprises (A) a paste base agent obtained by polymerizing a lower fatty acid vinyl ester such as vinyl acetate, and (B) a compound of the formula (R<1> -R<6> are each a 1-6C alkyl; X<-> is an anion), preferably 2-hydroxy-3-methacryloxypropyltrimethylammonium salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid paste composition suitably used for pasting clothes and the like at the time of washing at home.

2. Description of the Related Art Conventionally, starch has been used for household laundry paste for a long time. However, in recent years, those based on vinyl acetate-based synthetic resin emulsions have become popular in terms of ease of use. I have. However, since gluing to clothing such as cloth is performed at a low concentration by diluting the synthetic resin emulsion, which is a sizing agent, with water, the sizing agent is not sufficiently adsorbed to the cloth, etc., and the treated cloth has a sufficient hardness. In addition, not only does not come out, but also the resin that has not been adsorbed flows as waste liquid, which is inefficient.

In order to solve this problem, various methods have been proposed in which a sufficient adhesive efficiency of the sizing agent can be obtained even when used at a low concentration. In these methods, a resin emulsion is charged to cations and electrically adsorbed on cellulose fibers such as cotton which are negatively charged in water. These methods include a method of polymerizing a cationic surfactant as an emulsifier (JP-A-52-53086) and a method of blending a nonionic emulsion with a cationic polymer (JP-A-55-142772). And emulsion polymerization using a cationic polymer as a protective colloid agent (JP-A-56-9)
No. 1074). However, according to these methods, at the time of the emulsion, the cationic substance is adsorbed on the resin surface as the paste base, and the resin particles take on a cationic property. There is a problem that the fibers are desorbed and only the cationic substance is adsorbed on the fiber, and the adsorbability of the resin particles as a sizing agent is not improved.

Investigations have been made to solve the above problems, and it has been found that the above problems can be solved by using a cationic copolymer obtained by copolymerizing a cationic vinyl monomer with vinyl acetate as a cationic glue base. However, when this cationic glue base is used, especially in winter, the viscosity of the liquid glue composition becomes high, and when it is measured and charged, the dischargeability from the container is poor, and a part of the liquid glue is generated. There was a problem with sex.

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid paste composition having good usability.

[0004]

Means for Solving the Problems The present invention has been made based on the finding that the above problems can be efficiently solved by adding a specific compound to a polymer of a lower fatty acid vinyl ester. That is, the present invention provides a liquid glue composition comprising a glue base obtained by polymerizing a lower fatty acid vinyl ester and a compound represented by the following general formula (I).

[0005]

Embedded image

(In the formula, R ^{1 to} R ⁶ may be the same or different, an alkyl group having 1 to 6 carbon atoms, and X ⁻ represents an anion.)

BEST MODE FOR CARRYING OUT THE INVENTION The lower fatty acid vinyl ester (A) used for forming the paste base used in the present invention includes:
Examples thereof include vinyl acetate, vinyl butyrate, and vinyl propionate having 4 to 8 carbon atoms. These can be used as one kind or as a mixture of two or more kinds. As the glue base used in the present invention, in addition to the above-mentioned monomer (A), those obtained by copolymerizing a monomer copolymerizable therewith can be used. Examples of such a copolymerizable monomer (B) include alkyl (meth) acrylates having 1 to 6 carbon atoms in the alkyl group, ethylene, vinyl chloride, styrene,
C3-C12 ethylenically unsaturated carboxylic acids such as acrylonitrile, acrylic acid, methacrylic acid, crotonic acid, maleic acid, acrylamide, methacrylamide, N
-Methylol acrylamide, divinylbenzene, ethylene glycol dimethacrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, acetoacetoxyethyl methacrylate, cationized vinyl monomers and the like. Examples of the cationic vinyl monomer include those represented by the following general formulas (II) to (VIII).

[0007]

Embedded image

(Wherein R ⁷ is a hydrogen atom or a group having 1 to 3 carbon atoms)
R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom or carbon atom. number alkyl group having 1 to 3 (preferably 1~2), R ^14, R ¹⁵
And R ¹⁶ independently represent an alkyl group having 1 to 3 carbon atoms (preferably a methyl group), and X ⁻ represents a monovalent anion. Among the above monomers, a monomer of the formula (IX) having a quaternary ammonium group, a hydroxyl group, an oxycarbonyl group and a polymerizable double bond in the molecule, 2-hydroxy-3-methacryloxypropyltrimethylammonium salt preferable.

[0009]

Embedded image

Wherein X ^- represents an anion. The amount of these copolymerizable monomers to be used can be within a range that does not impair the performance of the obtained cationic glue base, and is preferably 0 to 30 parts by weight per 100 parts by weight of the component (A). Is good. Particularly preferred cationic glue bases are 5 to 60 parts by weight of a C _1-3 alkyl ester of acrylic acid or methacrylic acid per 100 parts by weight of vinyl acetate and a polymerizable quaternary ammonium salt of the component (B) 0.1. A cationic paste base obtained by copolymerizing 10 to 10 parts by weight. At this time, it is preferable to coexist the compound (C) represented by the general formula (I). As the compound (C) represented by the general formula (I) used in the present invention, in the formula, R ^{1 to} R ⁶ are preferably independently an alkyl group having 1 to 3 carbon atoms. X ^-
Examples thereof include a halogen ion and an alkyl sulfate group, and a halogen ion is preferable. Of these, R
Compounds of the following formula (X) in which ^{1 to} R ⁶ are a methyl group and X ⁻ is a chloride ion are preferred.

[0011]

Embedded image

The above components may be copolymerized by ordinary emulsion polymerization, and preferably by radical polymerization using an emulsifier and a polymerization initiator. As the emulsifier, a water-soluble polymer can be used as a protective colloid, or a surfactant can be used. In the present invention, it is preferable to use a water-soluble polymer as a protective colloid.

Examples of the water-soluble polymer used as the protective colloid include polyvinyl alcohol and derivatives thereof, cellulose derivatives such as hydroxyethyl cellulose, starch and modified starch, and water-soluble vinyl polymers. Are preferred. Specific examples of the cation modified, cationic cellulose,
Cationic PVA or cationic starch is mentioned. These water-soluble polymers are present in the liquid glue composition in an amount of 0.
It is preferable to contain 1 to 5% by weight (hereinafter abbreviated as%). In the present invention, the above-mentioned size base can be used in an arbitrary amount, but it is preferable that the content is 20 to 60%, more preferably 30 to 50%, in the liquid size composition.
The compound (C) represented by the general formula (I) is preferably contained in the liquid cationic paste composition in an amount of from 0.0005 to 0.5%, more preferably from 0.0005 to 0.02%. It is.

In the present invention, an inorganic electrolyte can be used in combination with the above paste base. Examples of the inorganic electrolyte include an alkali metal salt, an alkaline earth metal salt, and an ammonium salt of an inorganic acid. Specifically, sodium sulfate, sodium chloride, potassium chloride, calcium chloride, magnesium sulfate, zinc sulfate, lithium chloride, One or more selected from the group consisting of barium chloride, magnesium chloride, manganese chloride and ammonium sulfate are exemplified. Among these, sodium sulfate, calcium chloride, magnesium sulfate and sodium chloride are particularly preferred. The amount of the inorganic electrolyte is preferably 0.01 to 7%, more preferably 0.1 to 5%, of the liquid cationic paste composition. In the liquid glue composition of the present invention, dimethyl silicone, methyl phenyl silicone,
Amino-modified silicone, amide-modified silicone, polyether-modified silicone, alkyl-modified silicone, epoxy-modified silicone, fluorine-modified silicone, alcohol-modified silicone and the like can be contained. These silicones are present in the liquid cationic glue composition in an amount of 0.01%.
It is preferably set to ２2%.

In addition, additives for general polymer emulsions, for example, plasticizers such as dibutyl phthalate, dibutyl adipate, dioctyl adipate, triacetin, etc .; antifreeze agents such as ethylene glycol, propylene glycol and ethanol; ,Fungicide,
Preservatives, fluorescent dyes, pigments and the like can be added.
Further, the liquid glue composition of the present invention is preferably in the form of being put in a container with a cap such as a plastic bottle. The liquid cationic paste composition of the present invention has a viscosity of 200 to 6
Those having a pH of 3 to 7 at 00 cp (25 ° C.) are preferred.

According to the present invention, a liquid paste composition having low viscosity and good usability can be provided. Next, the present invention will be described with reference to examples.

[0016]

【Example】

Example 1 Trimethylaminohydroxypropylated starch was added to a five-necked separal flask equipped with a nitrogen inlet tube, a stirrer, a monomer metering device, a thermometer and a reflux condenser so that 0.5% of the final emulsion was ionized. The mixture was added together with exchanged water, dissolved at 80 ° C., cooled to 60 ° C., and 2 parts of vinyl acetate and the compound of the formula (X) were added.
Azobis (2-aminodicyclopropane) hydrochloride 0.07
After adding 5 parts by weight of a 5% aqueous solution, 5 parts by weight of ethanol was added and the temperature was raised to 70 ° C. to initiate polymerization. Twenty minutes after the start, 0.05 parts by weight of 2,2'-azobis (2-aminodicyclopropane) hydrochloride was added as a 5% aqueous solution, and 90 parts by weight of vinyl acetate and 300 parts of another copolymerizable monomer were added.
It was added continuously over a period of minutes. After completion of the dropwise addition, the temperature was raised to 80 ° C. to terminate the reaction. A predetermined amount of an inorganic electrolyte was added to the aqueous emulsion of the paste base prepared by the above method to prepare a liquid paste composition. Further, the liquid paste compositions of Examples 2 to 7 and Comparative Examples 11 to 13 were prepared in the same manner. The raw materials and amounts used here are also shown in Table 1.
In Examples 6 and 7, and Comparative Examples 12 and 13, an inorganic salt was added after the liquid paste composition was prepared, while Examples 4, 6, and 7 were added with ethylene glycol.

The liquid paste composition thus prepared was evaluated for drainability and appearance by the following methods. Drainability Exactly 10 g of the liquid paste composition adjusted to 10 ° C. was placed in a 20 ml glass beaker, and then the beaker was tilted at 90 ° for 3 minutes to release the liquid paste composition from the spout. The amount was quantified, the fractional fraction was calculated according to the following formula, and evaluated based on the following criteria.

[0018]

[Formula 1] Fractionation rate = (residual emulsion amount / added emulsion amount) × 100 ○: fractionation rate is less than 5% △: fractionation rate is 5 to 10% ×: fractionation rate exceeds 10% The appearance after leaving the liquid paste composition at room temperature for one week is visually determined.
Evaluation was made according to the following criteria. ：: No separation observed ×: No separation observed Table 1 summarizes the results.

[0019]

[Table 1] Table-1 Example Comparative Example 1 2 3 4 5 6 7 11 * 12 * 13 * Vinyl acetate * 35 35 35 40 30 35 35 35 35 35 Cationic monomer *--1 1.5 1 2 1--1 Formula (X) Compound 0.005 0.01 0.005 0.0005 0.02 0.003 0.005---Ethyl acrylate * 10 10 5 10-10 10 10 10 10 Trimethylamino 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Hydroxypropylated starch Crotonic acid *--1.0--1.0 ----Methacrylic acid *-------1.0---Sodium chloride---------2-Sodium sulfate ------2--3 Ethylene glycol---3-44 - - - ink ejection cutoff property ○ ○ ○ ○ ○ ○ ○ × ○ × appearance ○ ○ ○ ○ ○ ○ ○ ○ × × value content in the final emulsion (wt%) in Table, 11 ^* to 13 ^* comparative It is an example. In the table, the components marked with * are the monomers used for the polymerization of the glue base. The numerical values in the table are the contents in the liquid glue composition, and the balance is water.
The cationic monomer is a cationic monomer of the formula (IX) wherein X is chlorine.

Claims (1)

[Claims] 1. A liquid glue composition comprising a glue base obtained by polymerizing a lower fatty acid vinyl ester and a compound represented by the following general formula (I). Embedded image (Wherein, R ^{1 to} R ⁶ may be the same or different,
Alkyl group having 1 to 6 carbon atoms, X ^- represents an anion. )