JPH0791782B2 - Textile / clothing finish composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to an emulsion composition used as a finishing agent for fibers, clothes and the like.

2. Description of the Related Art Conventionally, a polyvinyl acetate emulsion-based sizing agent has been widely used because it has a good finish and is easy to use. More recently, by imparting a cationic property to the surface of the polyvinyl acetate emulsion particles to enhance adsorption to the negatively charged fibers, conditions such as an electric washing machine with a high bath ratio (hereinafter, rinse treatment and However, it has been improved so that it can be glued.

However, such a cationic polyvinyl acetate emulsion-based synthetic sizing agent is sufficiently water-insoluble because the polyvinyl acetate adhered by sizing is water-insoluble, even though the surface of the emulsion particles is cationic. However, there was a drawback that most of the sizing agent was accumulated in the fiber because it could not be completely removed.

As a method for improving this drawback, it has been proposed to copolymerize a vinyl monomer such as vinyl acetate with an unsaturated carboxylic acid such as crotonic acid as a comonomer, and further to impart a cationic property to the surface thereof (Japanese Patent Laid-Open No. 2000-242242). 56-88
414, JP-A-56-91075, JP-A-56-110709
Japanese Patent Laid-Open No. 58-4875). The sizing agent thus obtained can be glued by a rinsing treatment, and at the time of washing the glued fiber, the carboxylic acid becomes a base in an alkaline atmosphere due to the detergent component, so that the hydrophilicity is remarkably increased. It is said that the agent peels from the fibers and exhibits non-accumulation properties.

However, such a sizing agent has a problem that a large amount of aggregates are likely to be generated during the production of a vinyl acetate / unsaturated carboxylic acid copolymer emulsion, and the obtained emulsion has a high viscosity and lacks stability. It was Further, there is a drawback that the texture (texture) of the fibers and clothes pasted by the rinse treatment is not sufficient.

OBJECT OF THE INVENTION The present invention is a cationic emulsion-based finishing agent which is excellent in the stability of emulsion and satisfies the performance required as a sizing agent, and can impart a good texture to fibers, clothes and the like. A composition is provided.

Composition of the Invention The fiber / clothing finish composition of the first invention of the present application is characterized by containing the following components (a) and (b).

(A) When obtaining a copolymer of a lower fatty acid vinyl ester and an unsaturated carboxylic acid,
Emulsion polymerization of 50 to 95% by weight alone, followed by emulsion copolymerization of 5 to 50% by weight of lower fatty acid vinyl ester and unsaturated carboxylic acid, obtained by weight ratio of lower fatty acid vinyl ester / unsaturated carboxylic acid Copolymer emulsion with acid = 99.5 / 0.5-9 / 1.

(B) Cationizing agent In the fiber / clothing finishing composition of the second invention of the present application, the following (a ') copolymer emulsion was used in place of the above (a) component. It is characterized by This finishing composition has the same excellent performance as a conventional sizing agent as the composition of the first aspect of the invention, and can impart an even more excellent texture to fibers and clothes.

(A ') In obtaining a copolymer of a lower fatty acid vinyl ester, an ethylenically unsaturated carboxylic acid ester and an unsaturated carboxylic acid, 50 to 95% by weight of the lower fatty acid vinyl ester is emulsion polymerized alone, and then the lower fatty acid Obtained by emulsion copolymerizing 5 to 50% by weight of vinyl ester, an ethylenically unsaturated carboxylic acid ester and an unsaturated carboxylic acid, in a weight ratio, lower fatty acid vinyl ester / ethylenically unsaturated carboxylic acid ester / unsaturated carboxylic acid Acid = 99.4 / 0.1
/0.5 to 4/5/1 copolymer emulsion.

Hereinafter, the present invention will be described in more detail.

The (a) copolymer emulsion serves as a base for the fiber / clothing finish composition of the present invention, which is a cationic emulsion. This copolymer emulsion has a weight ratio of lower fatty acid vinyl ester / unsaturated carboxylic acid =
99.5 / 0.5-9 / 1, preferably 99 / 1-93 / 7 monomer
It is obtained by copolymerizing in stages. First, 50-95% by weight of lower fatty acid vinyl ester is emulsion polymerized alone,
Then, the remaining amount of lower fatty acid vinyl ester is 5 to 50% by weight.
And an unsaturated carboxylic acid are obtained by emulsion copolymerization. Preferably, 55-90% by weight of the lower fatty acid vinyl ester is homopolymerized first, and then the residual amount and unsaturated carboxylic acid are copolymerized. When the ratio of the lower fatty acid vinyl ester to the unsaturated carboxylic acid is larger than 99.5 / 0.5, it tends to be accumulated in the fiber. On the other hand, when it is less than 9/1, the emulsion polymerization property is insufficient and the amount of the necessary cationizing agent is increased, which is not preferable.

The (a ') copolymer emulsion similarly functions as a base for the finishing composition, and uses an ethylenically unsaturated carboxylic acid ester as a monomer during the second stage copolymerization. Can be obtained in the same manner as in the case of the above component (a).

The copolymer emulsion (a ') has a weight ratio of lower fatty acid vinyl ester / ethylenically unsaturated carboxylic acid ester / unsaturated carboxylic acid = 99.4 / 0.1 / 0.5 to 4/5/1, preferably 98.5 / 0.5 / 1.0. It is obtained by copolymerizing monomers of ˜48 / 45/7 in two steps. First, 50 to 95% by weight of lower fatty acid vinyl ester is emulsion polymerized alone, and then the remaining amount of lower fatty acid vinyl ester is 5 to 50% by weight, ethylenically unsaturated carboxylic acid ester and unsaturated carboxylic acid. Emulsion copolymerization. Preferably, 50 to 95% by weight of the lower fatty acid vinyl ester is alone emulsion-polymerized, and then the rest and other monomers are emulsion-copolymerized.

When the amount of the ethylenically unsaturated carboxylic acid ester is less than the above-mentioned copolymerization ratio, the effect of imparting a texture to the fibers / clothes is not sufficiently exerted, and when the amount of the unsaturated carboxylic acid is too small, the fibers are likely to accumulate. On the other hand, when the amount of unsaturated carboxylic acid is too large, the emulsion polymerization property is insufficient, the necessary cationizing agent is increased, and the stability of the emulsion is poor, which is not preferable. On the other hand, if the amount of the ethylenically unsaturated carboxylic acid ester is too large, the effect of imparting a texture is rather deteriorated, and it becomes impossible to impart an appropriate shape retention (flexibility) to the fiber / clothing.

When emulsion-copolymerizing a lower fatty acid vinyl ester and an unsaturated carboxylic acid, or further an ethylenically unsaturated carboxylic acid ester, the monomer of the present invention can be continuously added dropwise to obtain the effects of the present invention. Can not. This is because the copolymerization rate of ethylenically unsaturated carboxylic acid ester and unsaturated carboxylic acid is greatly different from that of lower fatty acid vinyl ester, so that the emulsion produced is not uniform, and as a result, a large amount of aggregates are generated during emulsion polymerization. It is thought that this is due to the occurrence of the emulsion, the viscosity of the obtained emulsion is high, and the stability is lacking.

In the present invention, emulsion polymerization of a lower fatty acid vinyl ester is carried out, and this is used as a core to further form the outer shell.
By copolymerizing a lower fatty acid vinyl ester with an unsaturated carboxylic acid, or further copolymerizing with an ethylenically unsaturated carboxylic acid ester, there is no formation of aggregates during polymerization, and the core layer is hard and the shell layer is A soft different layer emulsion is obtained. This emulsion has a low viscosity and excellent stability. Further, by cationizing the different-layer emulsion, not only the adsorption to the fiber / clothing is good and the non-accumulation property is excellent, but also the texture (texture) of the treated fiber or clothing can be improved.

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

Examples of the unsaturated carboxylic acid include ethylenically unsaturated monobasic acids such as acrylic acid, methacrylic acid and crotonic acid; ethylenically unsaturated dibasic acids such as maleic acid, fumaric acid and itaconic acid; Mention may be made of half esters and half amides. Specific examples of the half ester and half amide include lower alkyl half-esters having 1 to 6 carbon atoms such as monobutyl maleate, monomethyl itaconate, and monobutyl itaconic acid, half amides such as maleic acid monoamide, fumaric acid monoamide, and itaconic acid monoamide. Is mentioned. Among the unsaturated carboxylic acids, acrylic acid, methacrylic acid, maleic acid and itaconic acid are particularly preferable.

Examples of the ethylenically unsaturated carboxylic acid ester include those represented by the following general formula (I).

(The symbols in the formula are as follows.

R ₁ , R ₂ : hydrogen or methyl group, R ₃ : alkyl group having 1 to 18 carbon atoms) Specific examples of such compounds include acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid butyl ester, acrylic acid Acrylic esters such as isooctyl ester, acrylic acid lauryl ester, acrylic acid stearyl ester; methacrylic acid ethyl ester, methacrylic acid isopropyl ester, methacrylic acid butyl ester, methacrylic acid octyl ester, methacrylic acid lauryl ester, methacrylic acid stearyl ester, etc. Methacrylic acid esters of: crotonic acid ethyl ester, crotonic acid isopropyl ester, crotonic acid butyl ester, crotonic acid octyl ester, crotonic acid cetyl ester, crotonic acid stearyl ester, etc. Such as phosphate esters are exemplified.

Further, in the homopolymerization of lower fatty acid vinyl ester,
Alternatively, when copolymerizing a lower fatty acid vinyl ester with an unsaturated carboxylic acid, or further copolymerizing these with an ethylenically unsaturated carboxylic acid ester, another monomer copolymerizable with these monomers may be used in combination. it can. As described above, the polymerization of the lower fatty acid vinyl ester alone in the present invention means that the unsaturated carboxylic acid finally contained is polymerized without substantially using it, and the presence of other optional components is excluded. Not something to do.

Examples of the other copolymerizable monomer include the following (1) to (5).

(1) Diesters of α, β ethylenically unsaturated dicarboxylic acids such as diethyl maleate, dibutyl maleate, dimethyl itaconate, dibutyl itaconate, diethyl fumarate, and dibutyl fumarate (2) Ethylene, styrene (3) Chlorination Vinyl halides such as vinyl (4) Vinylidene halides such as vinylidene chloride (5) α, β ethylenically unsaturated carboxylic acid amides such as acrylamide and N-methylolamide and N-alkylol derivatives thereof (b) Cationizing agent Is added during the copolymerization of the lower fatty acid vinyl ester and the unsaturated fatty acid, or during the copolymerization with the ethylenically unsaturated carboxylic acid ester, or after the copolymerization, and is added to the fiber / clothing finish composition. be able to. As the cationizing agent, for example,
The following (i) to (vi) can be exemplified.

(I) Cation-modified hydroxyethyl cellulose, cation-modified starch, cation-modified guar gum, cation-modified chitosan, which is made cationic by introducing a cation group. Among these, those introduced with a quaternary ammonium group represented by the following general formula (II) are preferable.

(Each symbol in the formula is as follows.

_{R 4, R 5, R 6} : an alkyl group or a substituted alkyl group having 1 to 4 carbon atoms, n: 0 or the integer 1, X: 1 monovalent anion) the substituent, for example, hydroxyethyl cellulose, starch, guar gum Alternatively, it can be introduced by the reaction of chitosan with glycidyltrialkylammonium chloride or 3-halogeno-2-hydroxypropyltrialkylammonium chloride.

(Ii) a cationic acrylic ester represented by the following general formula (III), a cationic methacrylic ester,
Polymers of substituted acrylamide or substituted methacrylamide and copolymers of these with acrylamide (The symbols in the formula are as follows.

R ₇ : hydrogen atom or methyl group, R ₈ , R ₉ , R ₁₀ : hydrogen atom or alkyl group or substituted alkyl group having 1 to 4 carbon atoms, Z: oxygen atom or NH, m: integer of 1 to 10, X A monovalent anion) (iii) A polymer of diallyldimethylammonium chloride or a copolymer thereof with acrylamide, methacrylamide or N-methylolacrylamide.

(Iv) Fourth represented by the following general formulas (IV) to (VIII)
Grade ammonium salt (In the formula, each symbol is as follows.

R ₁₁ : an alkyl group having 8 to 22 carbon atoms or an alkenyl group R ₁₂ , R ₁₃ , R ₁₄ : an alkyl group having 1 to 4 carbon atoms or 8 carbon atoms
To 22 alkyl or alkenyl group R _15: alkyl group or alkenyl group R ₁₆ 9 to 21 carbon atoms: hydrogen, an alkyl group having 1 to 4 carbon atoms y: integer of 0 to 7 X: 1 monovalent anion) ( v) Amidoamines or salts represented by the following general formulas (IX) to (XI) (The symbols in the formula are as follows.

R ₁₇ : an alkyl group or an alkenyl group having 9 to 21 carbon atoms R ₁₈ : hydrogen or an alkyl group having 1 to 4 carbon atoms y: an integer of 0 to 7 X: a monovalent anion) (vi) the following general formula (XII) Quaternary ammonium salt of polyoxyalkylene derivative represented by (The symbols in the formula are as follows.

R ₁₉ : an alkyl group having 8 to 22 carbon atoms or an alkenyl group R ₂₀ : an alkyl group having 1 to 4 carbon atoms or an alkyl group or an alkenyl group having 8 to 22 carbon atoms R ₂₁ : an alkylene group having 2 to 4 carbon atoms l, m: 1 to 50 real number X: 1 valent anion) In the fiber / clothing finish composition of the present invention, a copolymer of a lower fatty acid vinyl ester and an unsaturated carboxylic acid or a lower fatty acid vinyl ester is used. A copolymer of ethylenically unsaturated carboxylic acid ester and unsaturated carboxylic acid
It is suitable to contain 20 to 60% by weight. The cationizing agent is added in an amount of 0.1 to 5% by weight, preferably 0.2 to 3% by weight.

In the emulsion polymerization in the present invention, conventionally known emulsification conditions can be adopted, and if necessary, an emulsifier, a protective colloid and the like can be appropriately used.

As the emulsifier, any of nonionic, cationic and anionic surfactants can be used, and preferably nonionic and cationic surfactants. Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether type, polyoxyethylene alkylphenyl ether type, polyoxypropylene-polyoxyethylene glycol (pluronic) type, polyoxyethylene fatty acid ester type, polyoxyethylene alkylamine. Type, polyoxyethylene polyoxypropylene polyamine type (including Tetronic type) and the like.

Specific examples of the cationic surfactant include polyoxyethylene monoalkyldimethylammonium salt type, polyoxyethylenedialkylmonomethylammonium salt type, polyoxyethylenealkyltrimethylene diammonium salt type, alkyldimethylamine oxide type, alkyldimethylbenzylammonium salt. Examples thereof include salt type, alkylpyridinium salt type, diacylaminopropyldimethylammonium salt type, diacylaminoethyldimethylammonium salt type, glycine betaine alkyl ester type and the like.

Specific examples of using an anionic surfactant include:
Higher alcohols, higher alcohol ethylene oxide adducts and alkylphenol ethylene oxide adducts of each sulfuric acid ester salt type, alkylbenzene sulfonate type, polyoxyethylene alkylphenol, higher fatty acid salt type, etc. are exemplified, and salts include sodium and potassium, Examples include ethanolamine salts such as triethanolamine. It is appropriate to use these surfactants so that the final emulsion composition is 0.1 to 5% by weight, preferably 0.2 to 3% by weight.

The polymerization initiator used in the emulsion polymerization, a water-soluble redox initiator, for example hydrogen peroxide alone or hydrogen peroxide and tartaric acid, citric acid, oxycarboxylic acids such as ascorbic acid, oxalic acid, sulfinic acid and salts thereof,
Combination with oxyaldehydes, water-soluble iron salts, 2,
Examples thereof include 2'-azobis (amidinopropane) salt, and in addition, persulfate, percarbonate, perborates, peracetate, perbenzoate and the like can be used. The polymerization initiator is 0.01 to 5% by weight with respect to the unsaturated monomer, preferably 0.1.
02-2% by weight is added.

In the fiber / clothing finish composition of the present invention, a nonionic water-soluble polymer compound can be used as a protective colloid agent in order to improve storage stability. Specific examples of the protective colloid agent include polyvinyl alcohol, hydroxymethyl cellulose, hydroxyethyl starch, hydroxypropyl starch, hydroxyethyl chitosan,
Hydroxypropyl chitosan can be exemplified. The addition amount of the protective colloid agent is 0 to 10% by weight, preferably 1 to 5% by weight in the final emulsion composition.

In emulsion polymerization of the unsaturated monomer, conventional emulsion polymerization conditions can be adopted. For example, the reaction temperature is 40 ~
100 ° C, preferably 60 to 80 ° C, pH during polymerization is 3 to
9, preferably 4-8. At this time, a buffering agent such as sodium carbonate, sodium bicarbonate, sodium orthophosphate, dibasic sodium phosphate, monobasic sodium phosphate is used in an amount of 0 to 2% by weight, preferably 0.1 to 1% by weight, based on the final emulsion composition. be able to.

Effects of the Invention The fiber / clothing finish composition of the present invention is obtained by homoemulsifying a part of a lower fatty acid vinyl ester, and then emulsion-copolymerizing the remaining lower fatty acid vinyl ester and an unsaturated carboxylic acid. By using the above copolymer emulsion as a base and mixing it with a cationizing agent to form a cationic emulsion, the generation of aggregates is suppressed during the production, and the obtained cationic emulsion has a low viscosity. It is excellent in stability and, in addition, is excellent in sizing properties such as gluing properties for fibers and clothes and non-accumulating ability as a sizing agent, and can also impart good texture to fibers and clothes.

Further, a part of the lower fatty acid vinyl ester is subjected to homoemulsion polymerization, and then the remaining lower fatty acid vinyl ester, ethylenically unsaturated carboxylic acid ester, and unsaturated carboxylic acid are emulsion-polymerized to obtain a copolymer emulsion. By using the base material, it is possible to achieve the above-mentioned various performances and to further impart a better texture to the fibers / clothes. This texture imparting effect is extremely excellent, and the same effect as when the fiber / clothing is finished with a softening agent can be exhibited.

Hereinafter, the present invention will be described in more detail with reference to specific examples.

The evaluation methods in the examples are as follows.

Polymerization stability The cationic emulsion after the completion of polymerization and aging was separated by filtration with an 80-mesh wire net and evaluated from the ratio of aggregates to the charged amount of unsaturated monomer.

○: Less than 0.1% △: 0.1 to less than 1% ×: 1% or more Storage stability 50 g of emulsion with solid content adjusted to 40% by weight is placed in a container with a lid and left standing in a thermostat at 25 ° C for 3 months. Was observed.

◯: No change Δ: Phase separation occurs and does not restore even when stirred.

X: There are aggregates when filtered with a 80 mesh wire mesh.

Rigidity Mini-mini washing machine (manufactured by Matsushita Electric Industrial Co., Ltd.)
Add the emulsion to a solids concentration of 0.05% by weight to prepare the finishing liquid, and add 150 g of cotton broad (60)
Was put in and the washing machine was operated for 3 minutes for finishing. Next, use a dehydrator (using the dehydrator of a washing machine manufactured by Matsushita Electric Industrial Co., Ltd.)
After dehydration for 2 seconds, air dry, ironing, JIS-L-1079-1
Tensile hardness (flexibility) of the finished cloth was measured by the cantilever method according to 976. (The higher the value, the harder it is and the higher the ability to adsorb to the fiber.) Non-accumulative property In a mini-mini washing machine, an equivalent test cloth used for the measurement of bending resistance, a commercially available synthetic detergent, and water at 25 ° C were used for detergent concentration. 0.133
% And the bath ratio was 30 and the washing machine was operated for 10 minutes. Then, put the test cloth in the dehydrator for 1 minute, then put it in the mini-mini washing machine again, put water at 25 ° C. so that the bath ratio was 30 and rinse for 3 minutes, then dehydrate in the dehydrator for 1 minute and air dry,
Ironing was performed, and the tensile hardness (rigidity / softness) of the test cloth was measured by the cantilever method according to JIS-L-1079-1976, and the specific storage property was determined by the following formula.

A: Bending flexibility of the finished fabric B: Bending flexibility of the finished fabric C: Bending flexibility of the untreated fabric The texture of the finished fabric was evaluated by a pair of comparisons with a tactile test by 10 females.

＋2: Good texture ＋1: Fair texture 0: Same as the texture of untreated cloth −1: Slightly poor texture −2: Remarkably poor texture (feels stiff) Furthermore, from the total score of 10 people, Was evaluated according to the standard.

⊚: +20 to +15 ○: +14 to +10 △: 0 to +9 x: -1 to -20 Example 1 A glass reactor equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen introducing pipe and a dropping funnel, 2.5 parts by weight of polyoxyethylene nonyl phenyl ether (= 50) and 1.5 parts by weight of polyvinyl alcohol (polymerization degree 1400, saponification degree 85%) and 8.75 parts by weight of the cationizing agent shown in Table 1 and water 110
Part by weight was charged, and while the system was sufficiently replaced with nitrogen gas, the system was melted at 80 ° C. for 1 hour.

After complete dissolution, the mixture was cooled to 40 ° C, 5.5 parts by weight of a 9.1% aqueous solution of sodium carbonate, 6.3 parts by weight of a 4.76% aqueous solution of potassium persulfate, and 10.45 parts by weight of vinyl acetate were added to the reaction vessel, and emulsified at 40 ° C for 30 minutes. went.

Then, the temperature was raised to 75 ° C., and 62.7 parts by weight of vinyl acetate was dropped into the reaction vessel to carry out homopolymerization of vinyl acetate. Vinyl acetate was continuously dripped over 2.6 hours, on the way,
Two hours after the start of polymerization, a 4.76% aqueous solution of potassium persulfate 6.3
Parts by weight were added. After 2.66 hours from the initiation of polymerization, the homopolymerization of vinyl acetate was completed, and then an unsaturated monomer mixture consisting of 31.35 parts by weight of vinyl acetate and 5.5 parts by weight of the unsaturated carboxylic acid shown in Table 1 was continuously added dropwise over 1.34 hours. did.
After the addition of the unsaturated monomer was completed, the mixture was aged at 80 ° C. for 1 hour to obtain a cationic emulsion, which was used as a fiber / clothing finish composition. The performance is shown in Table 1.

Sample Nos. 1 to 7 are examples of the present invention, and sample Nos. 8 to 11 are comparative examples. However, the preparation of the finishing composition in Comparative Example is almost the same as the above-mentioned polymerization method, but in the Examples, the polymerization of the unsaturated monomer is carried out by homopolymerization of vinyl acetate, vinyl acetate and unsaturated carboxylic acid. In contrast to the second stage of copolymerization,
In the comparative example, vinyl acetate and unsaturated carboxylic acid were copolymerized in one step.

That is, when the same amount of vinyl acetate 104.5 parts by weight and unsaturated carboxylic acid 5.5 parts by weight as in the example were polymerized, the amount of vinyl acetate added in the emulsification step was 10.45 parts by weight, which was the same as that in the polymerization. Saturated monomer dropping method is vinyl acetate 9
A mixture of 4.05 parts by weight and 5.5 parts by weight of the unsaturated carboxylic acid shown in Table 1 was continuously added dropwise over 4 hours.

For the resulting finishing composition, emulsion stability,
The gluing characteristics and texture were evaluated and are shown in Table 1.

From Table 1, it is obtained by emulsion-polymerizing an unsaturated monomer by first homopolymerizing a part of the lower fatty acid vinyl ester and then copolymerizing the remaining lower fatty acid vinyl ester and the unsaturated carboxylic acid. It can be seen that the different-layer emulsion has excellent finishing performance.

Example 2 In the same manner as in Example 1, in carrying out emulsion polymerization of 110 parts by weight of all unsaturated monomers, vinyl acetate and itaconic acid monoethyl ester were mixed at various weight ratios shown in Table 2. First, homopolymerization of 70% by weight of vinyl acetate, and then copolymerization of 30% by weight of the remaining amount of vinyl acetate and itaconic acid monoethyl ester are carried out in a two-step polymerization to form a cationic different layer emulsion and a finishing agent. A composition was obtained. This finish composition was evaluated and the results are shown in Table 2.

Sample Nos. 13 to 15 are examples of the present invention, and sample Nos. 12 and 16 are comparative examples. According to Table 2, the polymerization ratio of lower fatty acid vinyl ester and unsaturated carboxylic acid is 99.5 / 0.5-9 /
It can be seen that when 1 is set, excellent emulsion stability, sizing property and texture are obtained.

Example 3 In a reaction vessel equipped with the same device as in Example 1, 2.5 parts by weight of polyoxyethylene nonylphenyl ether (= 30), polyvinyl alcohol (polymerization degree 1800, saponification degree 85
%) 1.5 parts by weight and 110 parts by weight of pure water were charged, and while the inside of the reaction vessel was sufficiently replaced with nitrogen gas, the temperature was raised to 80 ° C.
Stir for hours.

After complete dissolution, cool to 40 ° C and add 10% sodium carbonate aqueous solution 5.5
Parts by weight, 5 parts by weight of a 5% aqueous solution of 2,2'-azobis (amidinopropane) hydrochloride, and 10.45 parts by weight of vinyl acetate were added to the above reaction vessel and emulsified at 40 ° C for 30 minutes.

Then, the temperature was raised to 75 ° C., and a predetermined amount of vinyl acetate shown in Table 3 was continuously dropped for a predetermined time to carry out homopolymerization of vinyl acetate. On the way, 2 hours after the initiation of polymerization, 5.5 parts by weight of a 5% aqueous solution of 2,2'-azobis (amidinopropane) hydrochloride was added. After completing the dropping of vinyl acetate at the predetermined time shown in Table 3, the remaining amount of vinyl acetate and 3.3 parts by weight of itaconic acid are continuously dropped at the predetermined time shown in Table 3, and as shown in Table 3, The amount of vinyl acetate used for homopolymerization and the amount of vinyl acetate used for copolymerization with itaconic acid were changed. Here, the time required from the start of the dropping of vinyl acetate to the end of the final dropping was 4 hours for all the samples, and the unsaturated monomers used were vinyl acetate / itaconic acid = Adjusted to be 97/3. After the dropping, the temperature was raised to 80 ° C, aging was performed for 1 hour, and then the cationized chitosan (nitrogen content of 4.8
%) 5% aqueous solution was added, and the mixture was stirred at 60 ° C. for 30 minutes. As the cationized chitosan, a reaction product of chitosan and 3-chloro-2-hydroxypropyltrimethylammonium chloride was used.

Next, the concentration of the copolymer emulsion of vinyl acetate and itaconic acid was adjusted to 40% by weight to obtain a cationic emulsion. The performance of the obtained emulsion is shown in Table 3.

Sample Nos. 18 to 20 are examples of the present invention, and sample Nos. 17 and 21 are comparative examples. From Table 3, it is possible to obtain a good finishing composition by homopolymerizing 50 to 95% by weight of the lower fatty acid vinyl ester and then copolymerizing the remaining 5 to 50% by weight with the unsaturated carboxylic acid. It can be seen that a cationic emulsion is obtained.

Example 4 Using the various lower fatty acid vinyl esters and unsaturated carboxylic acids shown in Table 4, various cationic emulsions were obtained in the same manner as in Example 1 to obtain the finishing composition of the present invention. The performance is shown in Table 4.

Sample Nos. 22 to 26 are all examples of the present invention.

Example 5 In the same glass reactor as used in Example 1, 8.68 parts by weight of polyoxyethylene nonylphenyl ether (= 50) and polyvinyl alcohol (polymerization degree 1700, saponification degree 98%) 21.24 were used.
Then, 398.64 parts by weight of water and 398.64 parts by weight of water were charged, and the inside of the system was sufficiently replaced with nitrogen gas, and dissolved at 80 ° C. for 1 hour.

After complete dissolution, cool to 40 ° C and prepare a 10 wt% aqueous solution of sodium carbonate 1
7.48 parts by weight, 84.7 parts by weight of a 3.0% by weight aqueous solution of potassium persulfate, and 17.6 parts by weight of vinyl acetate were added to the reaction vessel.
Emulsification was performed at 30 ° C. for 30 minutes.

Then, the temperature was raised to 75 ° C., and 233.78 parts by weight of vinyl acetate was dropped into the reaction vessel to carry out homopolymerization of vinyl acetate. Vinyl acetate was continuously added dropwise over 2.8 hours, and 8 hours by weight of 3.0% by weight aqueous solution of potassium persulfate was added 2.0 hours after the initiation of polymerization. The homopolymerization of vinyl acetate was completed 2.8 hours after the initiation of polymerization, and subsequently 10.8 parts by weight of vinyl acetate and the ethylenically unsaturated carboxylic acid ester shown in Table 5 were used.
An unsaturated monomer mixture consisting of 96.96 parts by weight and 11.1 parts by weight of unsaturated carboxylic acid was continuously added dropwise over 1.2 hours. Thirty minutes after the completion of the dropwise addition of the unsaturated monomer, 25.0 parts by weight of a 75% by weight isopropyl alcohol solution of distearyldimethylammonium chloride previously dissolved at 80 ° C. was added to the reaction vessel. Further, it was aged at 80 ° C. for 1 hour to obtain a cationic emulsion, which was used as a fiber / clothing finish composition. The performance is shown in Table 5.

Sample Nos. 31 to 38 are examples of the present invention, and Sample Nos. 39 to 42 are
Is a comparative example. However, the preparation of the finishing agent composition in the comparative example is almost the same as the above-mentioned polymerization method, but in the examples, the polymerization of the unsaturated monomer is carried out by homopolymerization of vinyl acetate, vinyl acetate and ethylenically unsaturated carboxylic acid. In the comparative example, the total amount of vinyl acetate, the ethylenically unsaturated carboxylic acid ester and the unsaturated carboxylic acid were copolymerized in one step, while the acid ester and the unsaturated carboxylic acid were copolymerized in two steps. .

That is, when polymerizing 262.16 parts by weight of vinyl acetate in the same amount as in the example, 96.96 parts by weight of ethylenically unsaturated carboxylic acid ester and 11.1 parts by weight of unsaturated carboxylic acid, the amount of vinyl acetate added in the emulsification step is 17.6 parts by weight. The same applies to the other parts, but the method of dropping the unsaturated monomer during polymerization is as follows:
4.58 parts by weight, 96.96 parts by weight of the ethylenically unsaturated carboxylic acid ester shown in Table 5 and 11.1 parts by weight of the unsaturated carboxylic acid were continuously added dropwise as a mixture for 4 hours. However, when these respective monomers lack compatibility, the respective monomers were separately and continuously added dropwise for 4 hours.

The resulting finish composition was evaluated for emulsion stability, sizing characteristics, and texture and is shown in Table 5.

From Table 5, when emulsion-polymerizing an unsaturated monomer, first, a part of the lower fatty acid vinyl ester is homopolymerized, and then the remaining lower fatty acid vinyl ester, ethylenically unsaturated carboxylic acid ester and unsaturated carboxylic acid. It can be seen that when the different layer emulsion obtained by copolymerizing and is used as a base, not only the performance as a sizing agent but also the texture is remarkably excellent.

Example 6 In the same manner as in Example 1, when emulsion-polymerizing an unsaturated monomer in a total amount of 110 parts by weight, vinyl acetate (A), ethyl acrylate (B) and acrylic acid (C) were added in an amount of The various ratios shown in Table 6 were used. First, 70% by weight of vinyl acetate was homopolymerized, and then the remaining amount of vinyl acetate was 30% by weight,
A two-step polymerization in which ethyl acrylate and acrylic acid were copolymerized to give a cationic different layer emulsion to obtain a finishing composition. This finish composition was evaluated and the results are shown in Table 6.

Samples 43, 44, 46 to 49 and 51 are examples of the present invention, and sample Nos. 45, 50 and 52 are comparative examples.

From Table 6, excellent emulsion stability and sizing can be achieved by setting the weight ratio of lower fatty acid vinyl ester, ethylenically unsaturated carboxylic acid ester and unsaturated carboxylic acid to 99.4 / 0.1 / 0.5 to 4/5/1. It can be seen that the characteristics are obtained and the texture is remarkably improved.

Example 7 In a reaction vessel equipped with the same apparatus as in Example 1, 2.5 parts by weight of polyoxyethylene nonylphenyl ether (= 50), polyvinyl alcohol (polymerization degree 1800, saponification degree 88
%) 1.5 parts by weight and 110 parts by weight of pure water were charged, and while the inside of the reaction vessel was sufficiently replaced with nitrogen gas, the temperature was raised to 80 ° C.
Stir for hours.

After complete dissolution, cool to 40 ° C and add 10% sodium carbonate aqueous solution 5.5
Parts by weight, 5 parts by weight of a 5% aqueous solution of 2,2'-azobis (amidinopropane) hydrochloride, and 5.0 parts by weight of vinyl acetate were added to the reaction vessel, and emulsified at 40 ° C for 30 minutes.

Then, the temperature was raised to 75 ° C., and a predetermined amount of vinyl acetate shown in Table 7 was continuously dropped for a predetermined time to carry out homopolymerization of vinyl acetate. On the way, 2 hours after the initiation of polymerization, 5.5 parts by weight of a 5% aqueous solution of 2,2'-azobis (amidinopropane) hydrochloride was added. After the addition of vinyl acetate was completed within the prescribed time shown in Table 7, the remaining amount of vinyl acetate and butyl acrylate 37.5
Parts by weight and 7.5 parts by weight of itaconic acid are continuously added dropwise at a predetermined time shown in Table 7, and as shown in Table 7, the amount of vinyl acetate used for homopolymerization and butyl acrylate and itaconic acid The amount of vinyl acetate used for copolymerization was varied. Here, the time required from the start of the dropping of vinyl acetate to the end of the final dropping was 4 hours for all the samples. The unsaturated monomers used were vinyl acetate / butyl acrylate / itaconic acid = 82/15 /
Adjusted to be 3. After the dropping, raise the temperature to 80 ° C,
After aging for 1 hour, 5 parts by weight of a cationized chitosan (nitrogen content (4.8%) 5% aqueous solution) that had been heated to 60 ° C. was added, and the mixture was stirred at 60 ° C. for 30 minutes. As the reaction product, a reaction product of chitosan and 3-chloro-2-hydroxypropyltrimethylammonium chloride was used.

Next, the concentration was adjusted so that the solid content of the obtained copolymer emulsion was 40% by weight to obtain a finishing composition. The performance of this composition is shown in Table 7.

Sample Nos. 54 to 56 are Examples of the present invention, and Sample Nos. 53 and 57 are Comparative Examples. From Table 7, it is possible to homopolymerize 50 to 95% by weight of the lower fatty acid vinyl ester, and then copolymerize the remaining 5 to 50% by weight with the ethylenically unsaturated carboxylic acid ester and unsaturated carboxylic acid. It is understood that a good cationic different layer emulsion can be obtained as a finishing composition.

Example 8 Using the various lower fatty acid vinyl esters, ethylenically unsaturated carboxylic acid esters and unsaturated carboxylic acids shown in Table 8, various cationic emulsions were obtained in the same manner as in Example 5 to obtain the finishing agent of the present invention. It was a composition. The performance is shown in Table 8.

Sample Nos. 58 to 62 are all examples of the present invention.

Claims (2)

[Claims] 1. When (a) a copolymer of a lower fatty acid vinyl ester and an unsaturated carboxylic acid is obtained, 50 to 95% by weight of the lower fatty acid vinyl ester is emulsion polymerized alone, and then a lower fatty acid vinyl ester of Obtained by emulsion copolymerization of 5 to 50% by weight with unsaturated carboxylic acid, and by weight ratio, lower fatty acid vinyl ester / unsaturated carboxylic acid = 99.5 / 0.5
A textile / clothing finish composition comprising 9/1 copolymer emulsion and (b) a cationizing agent. 2. In obtaining a copolymer of (a ') lower fatty acid vinyl ester, ethylenically unsaturated carboxylic acid ester and unsaturated carboxylic acid, 50 to 95% by weight of lower fatty acid vinyl ester is emulsion polymerized alone. Then, 5 to 50% by weight of the lower fatty acid vinyl ester, the ethylenically unsaturated carboxylic acid ester and the unsaturated carboxylic acid are obtained by emulsion copolymerization, and the weight ratio is lower fatty acid vinyl ester / ethylenically unsaturated carboxylic acid. A textile / clothing finish composition comprising: a copolymer emulsion of ester / unsaturated carboxylic acid = 99.4 / 0.1 / 0.5 to 4/5/1; and (b) a cationizing agent.