JP2001003270A - Sizing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber-sizing agent excellent in dispersion, when it is charged (dispersed) in a bath and can be applied to the clothing uniformly with reduced unevenness. SOLUTION: This sizing agent is an emulsion type that includes the structure originating from vinyl acetate as a part of the constructive skeleton, has a viscosity of 150-350 mPa.s at 30 deg.C at 12 r/min and 100-250 mPa.s at 30 r/min by using Brookfield type single cylinder rotary viscometer, and has a concentration of the polymer of 25-35 wt.% in the sizing agent where in the case that the sizing agent includes cationized starch, cationized cellulose, modified starch, polyvinyl alcohol, polyvinyl pyrrolidone and/or water-soluble cellulose derivative, their concentrations are also included.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sizing agent for textile products which has excellent dispersibility when poured into a bath and has less unevenness on clothes.

[0002]

2. Description of the Related Art
Water-soluble polymer compounds such as carboxymethylcellulose, starch, and polyvinyl alcohol have been used as the main components of the sizing agent, but the texture of such hard paper is not suitable as a sizing agent for clothing. In addition, aqueous solutions of these high molecular compounds have high viscosities even at low concentrations, are difficult to disperse when added to a washing tub, and have disadvantages such as unevenness. In recent years, emulsion-type pastes based on vinyl acetate-based polymers have been used.
Methods for improving the adsorptivity to fibers and the like have been proposed (for example, Japanese Patent Application Laid-Open Nos. 7-157977 and 7-22906).
7, JP-A-10-195772). However,
Still, the dispersibility when thrown into the bath was insufficient.

[0003]

The present invention relates to a polymer having a structure derived from vinyl acetate as a part of a constituent skeleton (hereinafter referred to as a polymer having a structure derived from vinyl acetate).
A vinyl acetate polymer), and using a Brookfield type single cylinder rotary viscometer to determine the rotor number. 2
The viscosity at 30 ° C. of the sizing agent measured at 12 r / min
At 150 to 350 mPa · s at 30 r / min, and the concentration of the polymer in the paste (provided that cationized starch, cationized cellulose, processed starch, polyvinyl alcohol, polyvinylpyrrolidone and / or Or, when a water-soluble cellulose derivative is contained, the concentration including these is 25 to 35% by weight.
The present invention solves the problem by using an emulsion type paste. The viscosity referred to here is the rotor No. Using JIS K7, the conditions other than keeping the sample at 30 ° C. for 1 hour and keeping the sample at a constant rotation temperature of 1 minute using JIS K7
117.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION The paste of the present invention is 30 r / min.
Is 70% of the viscosity at 12 r / min.
It is preferable to show the above. The above viscosity specification indicates the degree of thixotropic property (thixotropic) of the present paste. The greater the difference between the viscosity at 12 r / min and the viscosity at 30 r / min, the greater the thixotropic properties of the solution. When the thixotropic property is large, the liquid drainage property with a measuring cap or the like is poor, and the dispersibility when thrown into a bath is also poor. These problems are alleviated if the present invention is within the range.

[0005] The vinyl acetate polymer may be a copolymer of vinyl acetate and a monomer other than vinyl acetate. Such monomers include cationic monomers,
Unsaturated carboxylic acids, lower alcohol esters of unsaturated carboxylic acids and unsaturated carboxylic acid amides. As the cationic monomer, the following general formulas (1) to (7)
And the like, and among these, those of the general formulas (3) to (5) are particularly preferable.

[0006]

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[0007]

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[0008] The cationic monomer is preferably present in the total monomer mixture used in the polymerization of the vinyl acetate polymer in an amount of 0.1%.
To 2% by weight, more preferably 0.3 to 1.5% by weight. As the unsaturated carboxylic acid, acrylic acid, methacrylic acid and crotonic acid are particularly preferred. Also,
As lower alcohol esters of unsaturated carboxylic acids,
Methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate are preferred. Such unsaturated carboxylic acids or lower alcohol esters of unsaturated carboxylic acids are preferably present in a proportion of 1 to 30% by weight, more preferably 2 to 20% by weight, in the total monomer mixture used for the polymerization of the vinyl acetate polymer. Compounded and polymerized. Examples of unsaturated carboxylic amides include N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-
Preferred are diethylacrylamide, N, N-diethylmethacrylamide, N-propylacrylamide, N-hydroxyethylmethacrylamide, and diacetone isoacrylamide. The unsaturated carboxylic acid amide is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight in the total monomer mixture used for the polymerization of the vinyl acetate polymer.
And polymerized.

[0009] The vinyl acetate polymer of the present invention is a polymer obtained by reacting the vinyl acetate monomer in the largest amount, and the ratio of the vinyl acetate monomer is 75 to 99 per the weight of the total monomer subjected to the polymerization. 0.8% by weight, preferably 82 to 99% by weight.

In the present invention, cationized starch and / or cationized cellulose (hereinafter abbreviated as a cationic high molecular compound) are added to acetic acid for the purpose of promoting adsorption to fibers at a high bath ratio and improving storage stability. It is preferably added during or after the polymerization of the vinyl polymer. These are preferably incorporated in the final paste at 0.5 to 6.0% by weight.

In the present invention, in order to further improve the storage stability of the emulsion, at least one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, modified starch, and a water-soluble cellulose derivative (hereinafter abbreviated as a nonionic polymer compound). Is preferably used in combination. The nonionic polymer compound has a weight average molecular weight of 10,000 to 200,000 when polyethylene glycol is used as a standard substance.
Is preferred. The nonionic polymer compound is preferably contained in the paste at 0.1 to 10% by weight,
More preferably, the content is 1 to 4% by weight.

[0012] The concentration of the vinyl acetate polymer in the paste of the present invention (however, when the composition contains cationized starch, cationized cellulose, modified starch, polyvinyl alcohol, polyvinylpyrrolidone and / or a water-soluble cellulose derivative, these may be used). (Concentration included) is 25-35% by weight. By satisfying this concentration range and a specific viscosity, it is possible to obtain a paste which is excellent in dispersibility in water, can suppress unevenness on clothing, and is excellent in usability.

In the polymerization reaction for obtaining a vinyl acetate polymer, a surfactant is used as an emulsifier. The surfactant used in the present invention includes a nonionic surfactant, an anionic surfactant, and a cationic surfactant. Specifically, those described in JP-A-10-195772, column 7, line 43 to column 8, line 40 can be used. In particular, as the nonionic surfactant, an ethylene oxide adduct of a saturated or unsaturated alcohol having 7 to 22 carbon atoms (addition number of ethylene oxide of 9)
To 100), higher fatty acid alcohol sulfates as anionic surfactants, and alkyltrimethylammonium salts and dialkyldimethylammonium salts as cationic surfactants.

A preferred means for obtaining the sizing agent of the present invention is a preparation method satisfying all of the following conditions (I) to (III). Condition (I) The amount of the surfactant to be added during the polymerization reaction of the vinyl acetate polymer is changed to the amount of the vinyl acetate polymer (however, when the above-mentioned cationic polymer compound and / or nonionic polymer compound are blended, 0.1) with respect to 100 parts by weight.
To 1.5 parts by weight.

Condition (II) The content of the cationic monomer used in the synthesis of the vinyl acetate polymer is 0.1 to 2% by weight, preferably 0.3 to 1.5% by weight in the total monomer mixture. Polymerize or use a cationic polymer compound having a cation substitution degree of 0.02 to 1.0, and adjust the content to 2 to 2 in the paste base.
17% by weight. Here, the degree of cation substitution is the degree of cationization per glucose unit, and the number of hydroxyl groups constituting starch or cellulose is three per glucose unit. This is the value when it is set to 0.

The final sizing agent of the present invention can be obtained by adding other optional components to the emulsion after polymerization. In the present invention, the emulsion solution after polymerization is described separately from the sizing agent. Is used as a paste base.

Condition (III) The obtained paste base is treated with ion-exchanged water and other optional components in a vinyl acetate polymer concentration (provided that the cationic polymer compound and / or the nonionic polymer compound is When blended, the mixture is diluted and prepared into a paste having a concentration of 25 to 35% by weight.

Under the above conditions, it is possible to obtain a sizing agent having the viscosity of the present invention, excellent sizing effect and excellent dispersibility, and excellent in usability.

The average particle size of the emulsion of the emulsion type paste of the present invention is preferably 0.5 to 1.2 μm.
This can be obtained by adjusting the reaction temperature and the stirring speed in addition to the method of dropping the monomer mixture during the polymerization of the vinyl acetate polymer in 3 to 8 hours.

The most preferred production method of the present invention is a method for preparing a polymer having a structure derived from vinyl acetate as a part of its constituent skeleton in the presence of a cationic polymer compound, a nonionic surfactant and a nonionic polymer compound. This is a method of polymerizing the coalescence.

The detailed production conditions, optional components and the method of use may be the same as those described in JP-A-10-195772, page 6, column 9, line 8 to page 10, column 12, line of the present invention. In particular, plasticizers such as dibutyl phthalate, dibutyl adipate, dioctyl adipate or triacetin, antifreeze agents such as ethylene glycol, propylene glycol or ethanol, fungicides, and fungicides such as proxel, etc. It is preferable to add a bactericide, a stable fragrance and the like, and a diluent such as water can be additionally blended for adjusting the concentration in the paste.

[0022]

According to the present invention, the poor dispersibility in a bath, which is a drawback of the conventional paste, is improved, and the unevenness is improved. In addition, the present invention has little problem of remaining in the measuring cap and is excellent in usability.
It is also suitable for refilling in thin plastic film sachets that deal with problems such as resource saving and plastic trash because it can be easily transferred.

[0023]

EXAMPLES <Preparation of sizing agent> Preparation Example 1 50 parts by weight of ion-exchanged water and 60 parts by weight of water-soluble cationized starch (cation substitution degree 0.09) were placed in a polymerization reaction tank (separable flask, hereinafter abbreviated). Parts and polyvinyl alcohol (PVA saponification degree 80%, weight average molecular weight 66,00
0) 425 parts by weight of 15 parts by weight of a mixed aqueous solution, 7.2 parts by weight of a nonionic surfactant (polyoxyethylene lauryl ether, average addition mole number of ethylene oxide 40),
3.0 parts by weight of trisodium phosphate, 16 parts by weight of vinyl acetate, and 1.4 parts by weight of 2,2′-azobis (2-amidinopropane) hydrochloride were charged, and heated to 75 ° C. while blowing nitrogen gas. . This was previously mixed so that the final weight ratio of vinyl acetate to methacrylic acid was 97.5: 2.5 (however, vinyl acetate is the total amount of 16 parts by weight previously added). 500 parts by weight of the mixture was dropped over 6 hours to carry out emulsion polymerization. Further, from 1 hour after the start of the dropping of the monomer to the end of the dropping, 2,2′-azobis (2-
190 parts by weight of 1.0 part by weight of amidinopropane) hydrochloride
A weight part of the aqueous solution was sequentially dropped. After completion of the dropwise addition, the mixture was stirred for 1 hour, cooled to room temperature, and adjusted to pH 5.0 using 10% by weight sodium carbonate solution to obtain the emulsion (paste base). Finally, it was prepared with ion-exchanged water so that the total weight of vinyl acetate, methacrylic acid, cationized starch and polyvinyl alcohol was 31% by weight, to obtain a paste. The viscosity of the paste according to the above measuring method is 250 mPa · s at 12 r / min and 30 r / mi.
n was 188 mPa · s. This is referred to as product 1 of the present invention.

Preparation Example 2 In the same manner as in Preparation Example 1, 50 parts by weight of ion-exchanged water and cationized cellulose (cation substitution degree 0.0
6) 425 parts by weight of a mixed aqueous solution of 60 parts by weight and 15 parts by weight of polyvinyl alcohol (PVA saponification degree 80%, weight average molecular weight 66,000), nonionic surfactant (polyoxyethylene lauryl ether, average addition mole of ethylene oxide) 40) 6.6 parts by weight, trisodium phosphate 3.0 parts by weight, vinyl acetate 16 parts by weight, and 2,2′-azobis (2-amidinopropane) hydrochloride 1.4 parts by weight were charged, and nitrogen gas was added. While raising the temperature to 75 ° C.
The final weight ratio of vinyl acetate to acrylic acid and ethyl methacrylate was 94.5: 2.5: 3.0 (provided that
500 parts by weight of vinyl acetate which had been previously mixed so as to be 16 parts by weight of vinyl acetate previously added) were added dropwise over 6 hours to carry out emulsion polymerization. After that, Preparation Example 1
And an emulsion (size base) was obtained in the same manner as described above. Finally, vinyl acetate, acrylic acid, ethyl methacrylate,
The mixture was adjusted with ion-exchanged water so that the total weight of the cationized cellulose and polyvinyl alcohol was 31% by weight to obtain a paste. This is designated as Product 2 of the present invention.

Preparation Example 3 In the same manner as in Preparation Example 1, a mixed aqueous solution, a nonionic surfactant, trisodium phosphate, vinyl acetate, and 2,2′-azobis (2-amidinopropane) were placed in a polymerization reactor. The hydrochloride was charged, and the temperature was raised to 75 ° C. while blowing nitrogen gas.
The final weight ratio of vinyl acetate to methacrylic acid and N, N-dimethylacrylamide was 94.5: 2.5:
Emulsion polymerization was performed by dropping 500 parts by weight of a premixed 3.0 parts (provided that the total amount of vinyl acetate was 16 parts by weight previously added) over 6 hours. . Thereafter, it was prepared in the same manner as in Preparation Example 1 to obtain an emulsion (paste base). Finally, vinyl acetate, methacrylic acid,
The mixture was adjusted with ion-exchanged water so that the total weight of N, N-dimethylacrylamide, cationized starch and polyvinyl alcohol was 31% by weight to obtain a paste. This is the product of the present invention 3
And

Preparation Example 4 In the same manner as in Preparation Example 1, a mixed aqueous solution, a nonionic surfactant, trisodium phosphate, vinyl acetate, and 2,2'-azobis (2-amidinopropane) were placed in a polymerization reactor. The hydrochloride was charged, and the temperature was raised to 75 ° C. while blowing nitrogen gas (however, the amount of the nonionic surfactant was 3.6 parts by weight). This includes vinyl acetate and methacrylic acid, and N, N
The final weight ratio of dimethylacrylamide is 94.5:
2.5: 3.0 (However, vinyl acetate is added to the previously added 1
500 parts by weight, which had been mixed in advance so as to obtain a total amount of 6 parts by weight), was added dropwise over 6 hours to carry out emulsion polymerization. Thereafter, it was prepared in the same manner as in Preparation Example 1 to obtain an emulsion (paste base). Finally, the mixture was adjusted with ion-exchanged water so that the total weight of vinyl acetate, methacrylic acid, N, N-dimethylacrylamide, cationized starch and polyvinyl alcohol was 33% by weight to obtain a paste. This is referred to as product 4 of the present invention.

Preparation Example 5 In the same manner as in Preparation Example 1, a mixed aqueous solution, a nonionic surfactant, trisodium phosphate, vinyl acetate, and 2,2′-azobis (2-amidinopropane) were placed in a polymerization reactor. Hydrochloride was charged, and the temperature was raised to 75 ° C. while blowing nitrogen gas (the amount of the nonionic surfactant was 14.4 parts by weight). This was previously mixed so that the final weight ratio of vinyl acetate to methacrylic acid was 97.5: 2.5 (however, vinyl acetate is the total amount of 16 parts by weight previously added). 500 parts by weight of the mixture was dropped over 6 hours to carry out emulsion polymerization. Thereafter, it was prepared in the same manner as in Preparation Example 1 to obtain an emulsion (paste base). Finally, it is adjusted with ion-exchanged water so that the total weight of vinyl acetate, methacrylic acid, cationized starch and polyvinyl alcohol is 31% by weight,
A paste was obtained. This is designated as Comparative Product 1.

Preparation Example 6 As in Preparation Example 1, a mixed aqueous solution, a nonionic surfactant, trisodium phosphate, vinyl acetate, and 2,2′-azobis (2-amidinopropane) were placed in a polymerization reactor. The hydrochloride was charged, and the temperature was raised to 75 ° C. while blowing nitrogen gas.
The final weight ratio of vinyl acetate to methacrylic acid and N, N-dimethylacrylamide was 94.5: 2.5:
Emulsion polymerization was performed by dropping 500 parts by weight of a premixed 3.0 parts (provided that the total amount of vinyl acetate was 16 parts by weight previously added) over 6 hours. . Thereafter, it was prepared in the same manner as in Preparation Example 1 to obtain an emulsion (paste base). Finally, vinyl acetate, methacrylic acid,
The mixture was adjusted with ion-exchanged water so that the total weight of N, N-dimethylacrylamide, cationized starch and polyvinyl alcohol was 43% by weight to obtain a paste. This is designated as Comparative Product 2.

Examples 1-4, Comparative Examples 1-2 Pastes prepared above (Products 1-4 of the present invention, Comparative Products 1-2)
Was evaluated as follows. Table 1 shows the results together with the viscosity and the like of each paste. <Evaluation method>-Gluing effect test A tergotometer type washing tester was used. Tap water 50
0 ml and 1.3 g of the paste prepared above were put into a washing tank (1000 ml in internal volume) and dispersed well, and then 20 g of 60 # cotton broad cloth was put into the washing tank and stirred at a rate of 100 r / min.
Glued for minutes. After dehydrating for 1 minute,
It was dried all day and night in a constant temperature and humidity room of 65% relative humidity. A small piece of 5 cm width was prepared from the cotton cloth glued by the above method, and a set of 10 pieces was made using a pure bending tester (manufactured by Kato Tech Co., Ltd.) at a constant temperature and humidity chamber of 20 ° C. and 65% relative humidity. Was measured for bending stiffness. Pass 0.22 or more.・ Dispersibility evaluation test 30m of paste prepared above
1 was put into a washing tub containing 4 liters of tap water, and its dispersibility was visually determined. The results are shown in Table 1. ○ is a pass. Judgment criteria: Quickly disperse ... Sediment at the bottom ........... Almost non-dispersible, sediment at the bottom of the washing tub .. × × Liquid drainage test Polypropylene cylindrical cup (diameter 28 mm, height 4)
(0 mm), 30 g of each prepared paste was then added, and the paste was tilted at 90 degrees, and the drainage was evaluated from the remaining amount of the liquid after the paste was discharged (15 seconds). The results are shown in Table 1. ○ is a pass. Residual rate (%) = (weight after discharge of glue−weight of cup) / 30
× 100 (%) Evaluation criteria: Residual rate is less than 5% ........... Residual rate is 5 to 10% ..... Residual rate exceeds 10% ..・ ・ ×

[0030]

[Table 1]

Claims (1)

[Claims] Claims: 1. Use a Brookfield-type single cylinder rotational viscometer, which contains a polymer having a structure derived from vinyl acetate as a part of its constituent skeleton. The viscosity at 30 ° C. of the paste measured at 2 was 1 at 12 r / min.
10 at 50 to 350 mPa · s and 30 r / min
0 to 250 mPa · s, and the concentration of the polymer in the paste (provided that cationized starch, cationized cellulose,
An emulsion-type paste having a modified starch, polyvinyl alcohol, polyvinylpyrrolidone and / or a water-soluble cellulose derivative, if contained, having a concentration of 25 to 35% by weight.