JPH05222674A - Sizing composition - Google Patents

Abstract

PURPOSE:To provide a sizing agent composition composed of an emulsion produced by the copolymerization a lower fatty acid vinyl ester in the presence of a specific vinyl alcohol and effective in finishing clothes having stiffness and excellent feeling to the skin. CONSTITUTION:A sizing agent base is synthesized by polymerizing a lower fatty acid vinyl ester (e.g. vinyl acetate) or copolymerizing the ester and a monomer copolymerizable with the ester [e.g. methyl (meth)acrylate] in the presence of an acetylacetonized polyvinyl alcohol of formula ((p) is 30-4,000; (m) is 0-1,000; (n) is 3-3,000; m/p is 0-1.0; n/p is 0.2-3.0). A sizing agent produced by adding a cationic polymer, etc., (e.g. cationic cellulose and cationic starch) to the emulsion of the sizing agent base can finish clothes having stiffness and good feeling to the skin and the applied sizing agent has high durability on the clothes.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a paste composition, and more specifically, it can make clothes to be much more crisp and harder than conventional polyvinyl acetate emulsion-based pastes, and has excellent desmearability during washing. Also relates to an excellent paste composition.

[0002]

2. Description of the Related Art Starch has been used as a pasting agent in the past, but various improvements have been made to make it easier to use. At present, it is easy to dilute in cold water, and it is easy and stable to use. A liquid paste has been developed as a paste, and a 2-15% solution of carboxymethyl cellulose, starch, polyvinyl alcohol, etc. mixed with an antifoaming agent, an antiseptic agent, a brightening agent, a fragrance, etc. is used. .. However, these carboxymethyl cellulose, starch, polyvinyl alcohol, etc. are hard polymers with a glass transition temperature of 80 ° C. or higher,
It is cheap as a sizing agent, but when it is glued to clothes, the clothes become too hard, giving a paper-like texture and no thickness feeling.
Not suitable as a sizing agent for high-quality clothing. Furthermore, the aqueous solution of these polymers has a high viscosity even if the concentration is low, and has the drawback of being difficult to handle.

In order to eliminate these drawbacks, a polyvinyl acetate emulsion (emulsion) is used, which improves the adsorption property to the fiber from a high bath ratio so that it can be treated in a washing machine at home. In addition, a novel paste composition for maintaining a cationic charge in a paste base has been proposed (for example, JP-A-53-53).
70191, 53-94688, 52-53086, 59-88
978, 58-4875, 58-65073, etc.). Also, conventionally, in the case of an emulsion containing vinyl acetate, which is insoluble in water, as a main monomer, the adhesiveness in the washing cycle is poor,
Although it has been a cause of hardening of clothes, also in this respect, a paste composition in which an unsaturated carboxylic acid is copolymerized so that the polymer is swollen and dissolved by an alkali at the time of washing and the glue is removed easily. Is also proposed.

However, in the case of these sizing agents mainly composed of polyvinyl acetate, the adhesiveness of the vinyl acetate portion itself to the fibers (mainly cotton fibers) is low, and the above-mentioned starch is mentioned in terms of imparting tension to the fibers. , Carboxymethyl cellulose,
It has been pointed out that a sufficient hardness and a crisp texture cannot be obtained as compared with the case where a sizing agent such as polyvinyl alcohol is used in a low bath ratio. Therefore, an object of the present invention is to provide a paste composition which is excellent in the adsorptivity to fibers, the tenacity, and the exfoliation property during washing.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to improve the drawbacks of the conventional vinyl acetate type paste compositions, and as a result, at the time of polymerization of the lower fatty acid vinyl ester or with the lower fatty acid vinyl ester, By using an emulsion obtained by coexisting acetylacetonated polyvinyl alcohol at the time of copolymerization or graft polymerization of the monomer or polymer or the mixture of the monomer and polymer copolymerizable with the lower fatty acid vinyl ester, clothes much more than before. The present inventors have found that it is possible to obtain a sizing composition which can be finished hard, has a good texture, and is excellent in desalting property, and has reached the present invention.

[0006] That is, the present invention is, during the polymerization of a lower fatty acid vinyl ester or during the copolymerization of a lower fatty acid vinyl ester and a monomer or polymer copolymerizable with the lower fatty acid vinyl ester or a mixture of monomers and a polymer, or during the graft polymerization. The present invention provides a paste composition comprising an emulsion obtained by coexisting acetylacetonated polyvinyl alcohol.

Examples of the lower fatty acid vinyl ester used in the present invention include vinyl acetate, vinyl butyrate, vinyl propionate and the like.

Further, examples of the monomer copolymerizable with the lower fatty acid vinyl ester include the monomers shown in the following (1) to (9), and a polymer thereof or a mixture of the monomer and the polymer may be used. . (1) Acrylic acid such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc., alkyl esters of methacrylic acid (2) α, β -Unsaturated carboxylic acids such as 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, etc. In addition to the acid, itaconic acid, maleic acid, alkyl half ester of unsaturated carboxylic acid such as fumaric acid, partial ester or partial amide (3) C _{1 to} C ₃ hydroxyalkyl acrylic acid ester,
Methacrylic acid ester (4) C ₁ -C ₃ alkoxy (C ₁ -C ₁₈₎ alkyl acrylate esters, methacrylic acid esters (5) styrene, ethylene (6) vinyl chloride, vinyl halides such as vinylidene chloride (7 ) α, β-unsaturated carboxylic acid amide and its N-alkylol derivative, for example, acrylamide and N-methylolamide (8) lower fatty acid vinyl ester different from the lower fatty acid vinyl ester used above (9) (1)- A mixture of two or more kinds selected from the group (8).

As the acetylacetonated polyvinyl alcohol used in the present invention, those having a structure represented by the following general formula (1) are preferable.

[0010]

[Chemical 2]

(In the formula, p: 30 to 4000 m: 0 to 1000 n: 3 to 3000, m / p = 0 to 1.0, n / p = 0.1 to 3.0).

In the emulsion used in the paste composition of the present invention, various cationic polymers are allowed to coexist for polymerization for the purpose of improving the adsorptivity to fibers from a high bath ratio, or these cations are used. The polymerizable polymer may be added after the polymerization is completed. In that case, examples of the cationic polymer used include cationic cellulose, cationic starch, cationic vinyl polymer and the like.

As the cationic cellulose and the cationic starch, those represented by the following formula (2) are preferable.

[0014]

[Chemical 3]

(Wherein A: cellulose or starch residue R: alkylene group or hydroxyalkylene group R ₁ , R ₂ , R ₃ : the same or different, alkyl group, aryl group, aralkyl group or . including the nitrogen atom may form a heterocyclic ring X ^-:. anionic group (chlorine, bromine, iodine, sulfate, sulfonate, methylsulfate, phosphate, nitrate, etc.) a: means a positive integer) cation The degree of cation substitution of soluble cellulose and cationic starch is 0.01 to 1, that is, 0.01 to 1 per anhydrous glucose unit.
It is preferable that one, preferably 0.02 to 0.5, cationic groups have been introduced. If the degree of substitution is 0.01 or less, the effect is not sufficient, and the degree of substitution may be 1 or more, but 1 or less is preferable from the viewpoint of reaction yield. Such cationic cellulose can be obtained, for example, by reacting, for example, hydroxyethyl cellulose with glycidyl trimethyl ammonium chloride or 3-chloro-2-hydroxypropyl trimethyl ammonium chloride under alkaline conditions. It can also be obtained by reacting hydroxyethyl cellulose with 4-chlorobutenetrimethylammonium chloride.

The cationic starch can also be obtained, for example, by reacting the starch with glycidyltrimethylammonium chloride or 3-chloro-2-hydroxypropyltrimethylammonium chloride under alkaline conditions. It can also be obtained by quaternizing dimethylaminoethylated starch. It can also be obtained by reacting starch with 4-chlorobutenetrimethylammonium chloride.

Examples of the cationic vinyl polymer include those represented by the following formula (3).

[0018]

[Chemical 4]

(Wherein R _{4 is a} hydrogen atom or a methyl group R ₅ , R ₆ and R ₇ are the same or different and are a hydrogen atom and a carbon number of 1 to 1).
4 represents an alkyl group or a substituted alkyl group Y: an oxygen atom or an NH group in an amide bond X ⁻ : the same as in formula (2), b: an integer of 1 to 10, and c: a number of 5 to 5000. ).

The viscosity of an aqueous solution of these cationic polymers is 5 to 1000 cps (centipoise) (20% for a 1% aqueous solution).
C), preferably 10 to 500 cps.

The relative content of each of these components in the present invention is 0 to 10 parts by weight of the cationic polymer, preferably 100 parts by weight of the lower fatty acid vinyl ester monomer.
0.2 to 6 parts by weight, acetylacetonated polyvinyl alcohol is 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the lower fatty acid vinyl ester monomer, and copolymerizable with the lower fatty acid vinyl ester. The amount of the monomer is 0 to 100 parts by weight, preferably 0 to 30 parts by weight.

In the polymerization for obtaining the emulsion used in the paste composition of the present invention, generally used nonionic, anionic and cationic emulsifiers can be appropriately used. Examples of nonionic emulsifiers include C ₇
To C ₂₂ ethylene oxide adducts of saturated or unsaturated alcohols (addition mole number 9 to 100), alkylphenoxypolyethoxyethanols having C _{7 to} C ₁₈ alkyl groups and 9 to 30 or more ethylene oxide units, for example Heptylphenoxypolyethoxyethanol, octylphenoxypolyethoxyethanol, methyloctylphenoxypolyethoxyethanol, nonylphenoxypolyethoxyethanol, dodecylphenoxypolyethoxyethanol, etc., or polyethoxyethanol derivatives of alkylphenols linked by methylene bonds, nonyl, dodecyl, tetradecyl Such as mercaptan or C _{6 to} C
₁₅ Sulfur-containing emulsifiers by condensation of alkylthiophenol and necessary amount of ethylene oxide, ethylene oxide derivatives of long chain carboxylic acids such as lauric acid, myristic acid, palmitic acid, oleic acid, tall oil mixed acid, hydrophobic carbonization Examples thereof include ethylene oxide derivatives of etherified or esterified polyhydroxy compounds having a hydrogen chain. Nonionic emulsifiers have an HLB of 12-20,
The thing of 15-18 is preferably used. Examples of anionic emulsifiers, C ₈ -C ₁₈ sodium salt of alcohol sulfuric acid esters of higher aliphatic alcohols sulfates typified by potassium, sodium salts of fatty acids of C ₈ -C _18, potassium as lauryl alcohol Salts or ethanolamine salts such as triethanolamine (eg triethanolamine oleate, triethanolamine stearate), funnel oil, sulfone compounds such as sulfated ricinoleic acid, sodium-t-octylbenzenesulfonate, sodium- Exemplified are sulfonated alkylaryl compounds such as t-octylphenol sulfonate. Examples of the cationic emulsifier include alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl dimethyl ethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, alkyl pyridinium salt, alkyl quinolium salt, alkyl isoquinolium salt, stearyl amide methyl pyridinium salt, Acylaminoethylmethyldiethylammonium salt, acylaminoethylpyridinium salt, alkoxymethylpyridinium salt, 1-methyl-1-acylaminoethyl-2-alkylimidazoline, diacylaminopropyldimethylammonium salt, diacylaminoethyldimethylammonium salt, dialkyldi ( Examples thereof include polyoxyethylene) ammonium salt and dialkylmethyl polyoxyethylene ammonium salt.

When preparing an emulsion constituting the paste composition of the present invention, a nonionic water-soluble polymer may be further used in combination in order to obtain a stable polymer for a long period of time. Examples of the nonionic water-soluble polymer include polyvinyl alcohol, polyvinylpyrrolidone, modified starch and cellulose derivatives other than those of the present invention. The modified starch that can be used in the present invention is a water-soluble modified starch, and examples thereof include hydroxyethylated starch, hydroxypropylated starch and pregelatinized starch. The polyvinyl alcohol that can be used in the present invention is a complete or incomplete saponified product of a vinyl acetate homopolymer or a copolymer of vinyl acetate and another monomer other than the acetylacetonated polyvinyl alcohol according to the present invention, or these are modified with, for example, an aldehyde. An example is a polyvinyl alcohol derivative having a 5% aqueous solution having a viscosity of 5 to 10,000 cps at 30 ° C. The nonionic cellulose derivative that can be used in the present invention is water-soluble hydroxyalkylated cellulose or alkylcellulose, and its 5% aqueous solution has a viscosity of 5 to 10000 cps at 30 ° C., such as hydroxyethyl cellulose and hydroxypropyl. Examples thereof include cellulose and methyl cellulose. The amount of these nonionic water-soluble polymers added is 0 to 10% by weight, preferably 1 to 4% by weight, based on the emulsion system.

The polymerization initiator used in the polymerization reaction to obtain the emulsion used in the present invention is 2,2′azobis
In addition to (2-amidinopropane), hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, peracetic acid, perbenzoic acid, potassium persulfate, etc. Can be used. The amount of the polymerization initiator added is preferably 0.01 to 5.0% by weight based on the lower fatty acid vinyl ester monomer.

The temperature of the polymerization reaction for obtaining the emulsion according to the present invention is 40 to 120 ° C., preferably 50 to 90 ° C., and the pH during polymerization is 3 to 9, preferably 4 to 8. At this time, as a buffering agent, an inorganic salt such as sodium carbonate, sodium bicarbonate, sodium orthophosphate, dibasic sodium phosphate, monobasic sodium phosphate, sodium chloride or sodium sulfate is used in an amount of 0 to 2% by weight, preferably 0.1% by weight.
It is recommended to use ~ 1% by weight. Further, the method of adding each component at the time of polymerization for obtaining the emulsion according to the present invention may be such that all components are added at the same time and reacted.
More preferably, a method of gradually adding the lower fatty acid vinyl ester monomer to a reaction vessel charged with components other than the lower fatty acid vinyl ester monomer is desirable. Also,
The acetylacetonated polyvinyl alcohol according to the present invention may be allowed to coexist at any time during the polymerization.

The paste composition of the present invention does not need to contain a nonionic water-soluble polymer such as polyvinyl alcohol, nonionic modified starch or nonionic cellulose derivative,
It can give the clothes a crisper texture than the conventional sizing agent, but it is further mixed with polyvinyl alcohol, nonionic modified starch, nonionic cellulose derivative, or conventional vinyl acetate emulsion sizing agent. Even if it is used as it is, it can give a preferable texture to the cloth as in the case of using it alone. That is, the texture has a crisp feel, and is particularly preferred for sheets and the like.

In the pasting composition of the present invention, if necessary, additives for general polymer emulsions, for example, plasticizers such as dibutyl phthalate, dibutyl adipate, dioctyl adipate, triacetin, etc., ethylene glycol, propylene. Antifreeze agents such as glycol and ethanol, and other fragrances, germicides, preservatives, fluorescent dyes, pigments and the like can be added.

In using the paste composition of the present invention, the conventional method of using the paste composition, that is, the amount of water for diluting the paste composition with respect to clothes, that is, the so-called bath ratio, is 1: 1 to 1: 4.
It can also be used by the method of adjusting the degree, and when the above-mentioned cationic polymer is used, it is 1 to 10 to 1
It is also possible to use it against about 40. In particular, such an increase in the bath ratio enables uniform sizing, and when used at home, it can be treated with an electric washing machine.

When the sizing composition of the present invention is used for sizing, the ratio of the sizing composition to the cloth weight is 0.2 to 6% by weight of the sizing composition effective content (solid content) relative to the weight of the clothing. ,
It is preferably 0.5 to 4% by weight.

When the sizing composition of the present invention is used for sizing, clothes can be markedly harder than conventional vinyl acetate sizing agents and can have a crisp texture, especially for sheets and the like. It is possible to give a preferable finish feeling.

[0031]

EXAMPLES Hereinafter, specific examples of the present invention will be described in detail, but the present invention is not limited to these examples. The parts in the examples are parts by weight.

Example 1 A paste base was synthesized using various polymers and monomers, and their basic performances were compared and examined.

<Synthesis of various paste bases> A 5-neck separable flask equipped with a nitrogen introduction tube, a stirrer, a monomer dropping device, a thermometer, and a cooling tube was used as shown in Table 1 or Table 2. 6.0 parts of the cationic polymer and acetylacetonated polyvinyl alcohol in the amounts shown in Table 1 or 2 and 100 parts of ion-exchanged water were added and dissolved at 90 ° C., cooled to 60 ° C., and then the low grade shown in Table 1 or 2 10 parts of fatty acid vinyl ester monomer and 2.0 parts of Emulgen 150 (manufactured by Kao Corporation) were added, and 0.5 part of sodium carbonate, 0.1 part of 2,2'-azobis (2-amidinopropane) hydrochloride and 20 parts of ion-exchanged water were added. In addition, the temperature was raised to 75 ° C to start the polymerization. The lower fatty acid vinyl ester monomer as shown in Table 1 or Table 2 and the monomer copolymerizable with the lower fatty acid vinyl ester monomer are mixed in advance at a ratio shown in Table 1 or Table 2 for 30 to 360 minutes after the initiation of the polymerization. 90 parts of the previously prepared product was continuously added dropwise to the polymerization reaction solution. After the dropping was completed, the temperature was raised to 80 ° C. and the mixture was stirred for 1 hour. Then, the reaction was terminated to obtain a paste base.

(Gluing test) 0.4 g of solid content of the glue base synthesized as described above
Is dispersed in 20 g of water and then forcedly attached to 20 g of Tetoron / cotton (65/35) No. 60 broad cloth (T / C) or No. 60 cotton broad cloth. After air-drying, leave it in a constant temperature and humidity room at 25 ° C and 65% relative humidity for 24 hours, and then use it for the following gluing effect test. Using a tergotometer-type washing tester, ion-exchanged water (500 ml) and the paste base synthesized as described above (0.4 g) as solids were placed in a washing tank (1000 ml internal volume) and dispersed well, and then Tetron / Cotton (65/35) 60th broad cloth (T / C)
Or, add 20g of No. 60 cotton broad cloth and stir and paste at 100 rpm for 3 minutes. Air-dried after dehydration, 25 ℃, 65
After leaving it in a constant temperature and humidity room at a relative humidity of 24% for a whole day and night, it is subjected to the following gluing effect test. (Gluing effect test) (1) Pure bending test method The Tetoron / cotton blended cloth or cotton cloth glued by the above-mentioned gluing test is cut into 2 cm x 2.5 cm, and 10 pieces are set as a set, and a pure bending tester is used. Bending rigidity (g · cm) was measured in a constant temperature and humidity room at 25 ° C. and 65% relative humidity using (manufactured by Kato Iron Works). The results are shown in Tables 1 and 2.

[0035]

[Table 1]

[0036]

[Table 2]

Example 2 A sizing composition having the following composition was produced using the sizing material base synthesized in Example 1, and a texture test was conducted by a paired comparison method with a conventional sizing composition. <Glue composition> Glue base ^* 90 parts Dibutyl phthalate 4 parts Ethylene glycol 3 parts Silicone emulsion 0.5 parts (2000 centistokes 30% emulsion of silicone oil) Fragrance 0.5 parts Ion-exchanged water 2 parts Note) * Glue base The agents shown in Table 3 below were used.

[0038]

[Table 3]

(Gluing test) Using a normal household washing machine, after adding 6 g of each paste composition as an effective component to 20 liters of tap water, disperse well and add 500 g of cotton sheets, Stir for 3 minutes and paste. After dehydrating with a dehydrator for 30 seconds, air-dry. With respect to the tension of the sheets glued by the above-mentioned method, a touch test by 10 persons was performed by paired comparison, and the performance of each glue composition was evaluated. The evaluation criteria at this time are as follows. +2: There is tension +1: There is some tension 0: Same as the control -1: There is no tension -2: There is no tension These results are shown in Table 4.

[0040]

[Table 4]

In all cases, the paste composition C was used as the control paste composition.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C09J 131/02 JCY 6904-4J 151/00 JDH 7142-4J D06M 15/327

Claims (3)

[Claims] 1. Acetylacetonated polyvinyl during the polymerization of a lower fatty acid vinyl ester or during the copolymerization of a lower fatty acid vinyl ester with a monomer or polymer copolymerizable with the lower fatty acid vinyl ester or a mixture of a monomer and a polymer, or during graft polymerization. A paste composition comprising an emulsion obtained by coexisting alcohol. 2. The lower fatty acid vinyl ester is vinyl acetate, vinyl butyrate or vinyl propionate.
The paste composition described. 3. The paste composition according to claim 1, wherein the acetylacetonated polyvinyl alcohol has a structure represented by the following general formula (1). [Chemical 1] (In the formula, p: 30-4000 m: 0-1000 n: 3-3000, m / p = 0-1.0, n / p = 0.1-3.0.)