JPS61167087A - Softener composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field] The present invention provides rebound resilience to fibers.

Improves elasticity, volume, and fluffiness.

This invention relates to a fabric softener composition containing aqueous polycretan and a fabric softener, which can be finished with good texture and firm softness.

[Conventional technology]

Clothing finishing agents used in the home include fabric softeners and glues that maintain and restore the functionality or texture of textile products.

Antistatic agents, water and oil repellents, etc. are used. Especially when looking at fabric softeners, the penetration rate is extremely high, indicating that finishing agent treatments are well-established in laundry habits.On the other hand, antistatic agents, water and oil repellents, etc. are often sold as aerosol products. Reeds are becoming popular depending on the intended use. Fabric softeners are widely used in everything from underwear to towels,
Diapers, shirts, blouses, sheets.

Very widely used in covers.

[Problem that the invention seeks to solve]

However, looking at the apparel industry in recent years, the multi-use of clothing has been strongly promoted.

Underwear is divided into lingerie and foundation, and bras are included in foundation, but they come in a variety of fabrics, ranging from those with strong shaping ability to those with weak shaping ability.On the other hand, from a functional standpoint, there are sports types and shape-up types. It is subdivided into. Of course, outerwear is also differentiated into a wide variety of styles, including casual, formal, and sports wear, based on differences in functionality, fashion, texture, etc. This trend is the result of manufacturers developing products that better match the tastes of wearers, and the background to this is advances in sewing technology such as 3D cutting, There are technological innovations in the textile industry, such as advances in textile processing technology and advances in textile material processing technology. For example, in textile material processing technology,
As is well known, due to this remarkable progress, the materials themselves have been differentiated by various functions, textures, etc., and are now appearing in textile products. For example, many differentiated materials have been put into practical use, such as irregular cross-section yarns, hollow fibers, ultrafine yarns, conjugate yarns, and conductive fibers. The aim of these materials is to provide one function and improve the texture.

Particularly in terms of texture, this product is differentiated by having physical properties that did not exist in the past, such as rebound resilience and compression recovery. In this direction, conventional fabric softeners [9] are of little use. In other words, conventional fabric softeners give a soft finish with no stiffness, and for woven and knitted fabrics made of new materials such as those mentioned above, this treatment tends to destroy the unique characteristics of the clothing.

Under these circumstances, in order to take advantage of the characteristics of clothing, the textile processing industry is conducting a type of resin processing for the purpose of giving clothing rebound elasticity and compression recovery properties. For example, interfacial polymerization method in which low molecular weight diamine and diisocyanate are polymerized on wool fibers, isocyanate monomer method in which fibers are cross-linked with incyanates, and polyisocyanate is added to oligomers having several thousand active hydrogen atoms. A prepolymer method in which a pre-cured polyurethane precursor is processed into fibers and cured on the fibers by means such as baking, a high molecular weight polyurethane resin is forcibly emulsified with a large amount of emulsifier, or A method of processing a urethane prepolymer with an aqueous polyurethane resin obtained by polymerizing it in water in the presence of a chain extender and an emulsifier, and adding cationic, anionic, amphoteric, or nonionic hydrophilic polyurethane resins to the polyurethane resin. Examples include a method of processing with a self-emulsifying water-based poly-9 urethane resin that is made into a self-emulsifying type by bonding groups. However, these methods require chemical reactions with the fiber itself or baking,
Requires post-processing such as heat setting, and cannot be washed at home.
#1 It is almost impossible to incorporate it into a cycle of finishing, drying, and wearing once. For example, even if these difficulties were overcome and the textile processing agents were processed at home, it is difficult to say that conventional textile processing agents are effective for all types of multi-use or segmented clothing.

Therefore, conventional fabric softeners are considered to be superior in that they do not cause any major inconvenience when treated with any kind of clothing. In other words, conventional resin finishing agents such as those mentioned above only have specific effects in terms of elasticity and anti-wrinkle functions, and on the contrary, they are not effective in creating a harmonious texture for all clothing. Inferior to conventional fabric softeners. Therefore, even if these conventional resin processing techniques are simply used, it is impossible to expect sufficient effects as a household clothing finishing agent, similar to conventional fabric softeners.

The purpose of the present invention is to provide clothing with a harmonious texture and at the same time provide functions such as rebound elasticity and compression recovery, thereby meeting the above-mentioned trends in clothing and making the most of its characteristics. The purpose of the present invention is to provide a softener composition suitable for household use.

[Means for solving problems]

As a result of intensive research, the present inventors succeeded in organically and synergistically combining conventional fabric softener technology and resin processing technology, and created a fabric softener composition with completely new functions and effects. I ended up inventing things.

That is, the softener composition of the present invention consists of (1) a textile softener base and (B) an aqueous polyurethane. When clothing is softened with the softener composition, the effects of the fabric softener and water-based polyurethane are organically and synergistically exhibited,
It is possible to finish a wide variety of clothing in a way that further enhances their characteristics. In other words, if a sweater is made of synthetic fibers, it will be fluffy and soft, and its volume and elasticity will be further improved, giving it a warmer feel. Cotton underwear not only has a soft finish, but also dramatically improves its texture. For thin clothing such as grouse, it gives a soft and elastic finish, and for pants, skirts, etc., it not only improves drapability, but also provides functions such as anti-wrinkle and anti-shape properties. In addition, for clothing sewn with materials having new functions and textures as described above, it is possible to further enhance rebound resilience and compression recovery properties. These effects are based on the elastic properties of water-based polyurethane, especially water-based cationic polyurethane, that is, the elastic recovery power such as rebound resilience and compression recovery property, but according to the present invention,
``It is of great significance that this ability is demonstrated in a harmonious environment.

In the practice of this invention, the treated garment exhibits a particularly favorable harmonious hand when the weight fraction of the textile softener is greater than the weight fraction of the aqueous polyurethane. A harmonious texture can be achieved even more effectively through the organic combination of fabric softener technology and resin processing technology, as detailed below.

Textile softeners as used in the present invention refer to all known chemical substances that have been used for a long time by housewives for washing clothes and in the textile industry for softening textiles (finishing). Polyurethane refers to a polyurethane that can be dispersed or dissolved in water by means described below, among polyurethanes produced mainly by the reaction of a compound having an incyanate group and a compound having a hydroxyl group.

It is desirable that the softener composition of the present invention is substantially liquid or solid. The liquid state refers to a water or organic solvent solution or a water or organic solvent dispersion, and can be provided as it is or as a spray (aerosol). Moreover, solid state refers to powder, tablet, granule, sheet, and film.

The method for obtaining the softener composition of the present invention is as follows: (1) A dispersion or solubilization of a textile softener in water and a dispersion or solubilization of aqueous polyurethane in water are separately prepared and mixed.

(2) When producing an aqueous dispersion or an aqueous solubilizer of a textile softener, an aqueous polyurethane or an aqueous polyurethane aqueous dispersion or an aqueous solubilizer is allowed to coexist or is added.

(2) A textile softener or a dispersion or solubilization solution of a textile softener in water is preliminarily added to the water used when dispersing or solubilizing the aqueous polyurethane in water. The preferred method is 0. Such a softener composition may be used as it is as an emulsion or a solubilized solution in water for softening treatment by washing clothes in a washing machine or in a washing machine.

Alternatively, it may be used for softening treatment by filling an aerosol can, a pressure accumulating sprayer, or the like, and spraying an appropriate amount onto clothing.

In this case, the content of the fabric softener in the softener composition is 1
~20% by weight, the content of aqueous polyurethane is ~0.05
It is preferable to adjust the concentration to 10% by weight. If the concentration is below this level, it may not be possible to give the desired texture to the clothing, or the amount required for one treatment of fabric softener may be too large, making it difficult to process, and above this concentration, it may not be possible to give the clothing a harmonious texture. or have poor mechanical or thermal stability as softener compositions.

Another preferred method is to replace part or all of the water to be used in producing the aqueous dispersion or aqueous solubilization solution in the above method with a solvent capable of dissolving the textile softener and the aqueous polyurethane. There is a way to replace it. In this case as well, the emulsion or solubilized liquid may be subjected to the softening treatment as it is, or it may be filled into an aerosol can or pressure accumulating sprayer and subjected to the softening treatment. In this case, the weight fraction and content of the fiber softener and the aqueous polyurethane are preferably in the same range as above.

Another preferred method is to prepare the textile softener in powder form, and use a dispersion or solubilized solution of aqueous polyurethane in water, or a dispersion or solubilized solution in which part or all of the water is replaced with a solvent, to form the textile softener in powder form. There is a method of after-spraying and drying to obtain a powdered softener composition of the present invention.

Such softener compositions can be provided as tablets in powder form as they are or under appropriate pressure, or if necessary, mixed with a suitable drug and then compressed with a tablet machine. Alternatively, the softener composition required for one-time softening treatment can be packaged in water-soluble or water-insoluble film paper or the like, or packaged in a bag, and subjected to softening treatment in a washing machine or washing rack. .

In this case, the fabric softener is 1 to 9 for the softener composition.
It is preferable to use 9% by weight, and 0.05 to 50% by weight of aqueous polyurethane.

If it is less than this range, it will not be possible to give the desired texture to the clothes, or the amount of fabric softener required for one treatment will be too large and the treatment will not be easy. It is impossible to give it a smooth texture.

Another preferred method is to melt the textile softener, impregnate a suitable substrate such as cloth, nonwoven fabric, or paper towel with the softener, and then prepare a dispersion or solubilization of the aqueous polyurethane in water.

Alternatively, there is a method of spraying an emulsion or solubilized liquid in which part or all of the water in the dispersion is replaced with a solvent to form a sheet-like softener composition. Other methods for obtaining a sheet-like softener composition of the present invention include dispersion or solubilization of a textile softener in water, or emulsion or softener in which part or all of the water in the dispersion is replaced with a solvent. Drying after impregnating the substrate with a mixture of a solubilizing solution and an aqueous polysurethane dispersion or solubilizing solution in water, or an emulsion or solubilizing solution in which part or all of the water in the dispersion is replaced with a solvent. There is a way to do it.

In these cases, it depends on whether the sheet-like softener composition is put into the washing tub during softening treatment in a washing machine or into the dryer when drying clothes in a clothes dryer. It can impart flexibility and antistatic properties to clothing.

In such a case, 1 to 10% of the fabric softener is added to the total weight of the sheet-like softener composition of the present invention excluding the base material.
99% by weight, 0.05-50% by weight of water-based polyurethane
It is preferable to use

If it is below this range, it will not be possible to give the desired texture to the clothes, or the amount used as a fabric softener at one time will be too large to be convenient, and if it is above this range, i! la
i It is not possible to give a harmonious texture.

The softener composition of the present invention has a dispersion emulsion,
It can take various forms such as transparent solubilized liquid, sprays, tablets or powders, and sheet forms, but in addition to the two essential ingredients, mechanical and thermal stability improvers, propellants, and powders may be added depending on the form. Various additives such as a tabletting or tabletting accelerator and a melting point regulator can be added.

In addition, in the form of softener compositions, dispersed emulsions, transparent solubilized liquids, tablets, and powders are suitable for softening treatment in a washing machine or in the washing machine, sprays are suitable for use when wearing clothes, and sheets are suitable for use when wearing clothes. These types are suitable for softening in a clothes dryer, but in any case, they can also be softened in a washing machine or in a washing rack. This possibility is based on (1) the softener composition having good dispersibility in water; (2) The softener composition should have good adsorption to clothing, which generally exhibits a negative charge in water. This can only be achieved if these two conditions are satisfied.

The textile softener used in the present invention is conventionally known and generally has good dispersibility in water, but preferably has one or more long-chain aliphatic groups and one or more quaternary nitrogen atoms. Textile softener with cationic surfactant 50-100
A textile softener consisting of 0 to 50% by weight of other textile softeners is preferred. Such woven fabrics have the advantage that they have good dispersibility in water and can be treated with any type of clothing without any major inconvenience.Furthermore, when dispersed or solubilized in water, Dispersed particles, solubilized micelles, or solubilized molecules exhibit a cationic positive charge, and have excellent adsorption to negatively charged clothing in water during softening treatment in a washing machine or wash basin. Furthermore, when the fabric softener composition of the present invention produced by the above-mentioned method is used in the above-mentioned washing machine or washing machine, the water-based polyurethane particles dispersed in water or the solubilized molecules are Whether the ionicity is cationic, nonionic, or anionic, the dispersed particles or solubilized micelles and molecules of the textile softener coalesce with the aqueous polycrethane dispersed particles or solubilized molecules, or surrounding the
This has the effect of forming new particles dispersed in water of the softener composition, and thus exhibiting cationic properties, and dramatically improving adsorption to clothing.
Examples of fabric softeners that can be used in the present invention are shown below, including the compound Mu! The group is an example of a cationic surfactant having one or more long-chain aliphatic groups and one or more quaternary nitrogen atoms, and the compounds A-II group to A-■ group are examples of other textile softeners. (A) Textile Softener (Z) Quaternary ammonium compound R0: At least one of them is a C6 to C22 saturated or unsaturated linear or branched alkyl group or a C3 to C22 secondary alkanol group R. R: C! 1~0. alkyl group or hydroxyalkyl group or +0H20H204H with n = 1 ~
10 CnH2n+10P05 with n=8~18° halogen.

R6, R7: 01~. alkylene group or + OH2
CH20 sweet n=1~10 (Io 5th class amine @) Nonionic activator HO60H20112 Choyaku0H20H20 Youngyaku0H20
H20(tl)OR.

n + m + J = 2000 (CH2CH
20 tsu ■ n = O ~ 100! = 0~100 m=0~100 0H20Hor 0H20H u1coo(oH2an2o-)τCo-R2(1sn
= 1 ~100 R1000(OR20H20+-H(15)n=1 ~
100 (g) Fatty acid R1000H (16) (V) Anionic surfactant Fat Wl [sodium alkylbenzene sulfonate, alkyl sulfate ester salt, alkylnaphthalene sulfonate, alkyl phosphate, etc. (VD Amphoteric surfactant alkyldimethylaminoacetic acid betaine.

The aqueous polyurethane used in the fabric softener composition of the present invention, such as alkylcarpoxymethylhydroxyethylimidazolinicum petaine, has a salt-forming ability. It can be made water-based by giving it strong hydrophilicity. When a group capable of forming a salt is introduced, it may be introduced during the production of polyurethane or by grafting after production. These methods are detailed below.

■ When obtaining a polyurethane block from a compound having a hydroxyl group, a compound having an incyanate group, and optionally a chain extender having an active hydrogen atom, at least one hydrogen atom or A compound having at least one incyanate group and at least one salt-type or salt-forming group may be used in combination. In the case of a compound having at least two cyanate groups, this compound can completely replace the compound having hydroxyl groups, the compound having incyanate groups, and the chain extender constituting the polyurethane mass), and the resulting polyurethane. The mass is then converted into the salt form and finally the polyurethane mass (which may dissolve in the organic layer depending on its physical properties) is converted into the aqueous form.

■ When polyurethane lumps are obtained from a compound having a hydroxyl group, a compound having an incyanate group, and optionally a chain extender having an active hydrogen atom, a diol having an unsaturated bond is used in combination, resulting in a polyurethane lump obtained. (Depending on the physical properties of the lumps, they may dissolve in the organic layer)
The polyurethane obtained after graft polymerization of a compound having a K-unsaturated bond and a group capable of forming salts is converted into an aqueous polyurethane.

(2) A polyhydroxyl compound such as polyethylene glycol in which the hydroxyl compound forming the polyurethane structure exhibits aqueous properties, and optionally a chain extender having an active hydrogen atom.

After obtaining a polyurethane mass from a compound having incyanate groups, the resulting polyurethane mass (which may be dissolved in the organic layer depending on the physical properties of the mass) is converted into an aqueous solution.

K to be converted into an aqueous form in the above methods ① to ② is a mixture of water, an aqueous solution containing an emulsifier, or an acid aqueous solution.
Alternatively, it may be dispersed in an alkaline aqueous solution, or in a solution in which part or all of the water or aqueous solution is replaced with a water-soluble solvent.

Preferred compounds used in the above production methods (1) to (2) are illustrated below.

(B) Water-based polyurethane (1) Compounds having hydroxyl groups Preferred compounds having hydroxyl groups include polyethers, polyesters, polyester amides, polyacetals and polythioethers.

(2) Polyethers include, for example, polymerization products of tetrahydrofuran, propylene oxide and ethylene oxide, and copolymers or graft polymers of these compounds, such as addition products of alkylene oxide and polystyrene. It is also possible to start from homogeneous or mixed polyethers, such as those obtained by condensation of hexanediol, methylhexanediol, heptanediol, octanediol, optionally with the addition of 10 to 50% of lower glycols. . Furthermore, globoxylated and ethoxylated (or mixed-alkoxylated) glycols and amines come into consideration.

■ Examples of polyesters and polyesteramides include those obtained by known methods from polyhydric alcohols and polyhydric carboxylic acids, and in some cases using kujihumins and amino alcohols. 0■ As polyacetals is, in particular, for example from hexanediol and formaldehyde 11 or from 4,4'-dioxy, r
-) Water-insoluble types consisting of xy-diphenyl-dimethyl-methane and formaldehyde are considered.

■ Examples of polythioethers include thiodiglycol alone or condensation products of thiodiglycol with other glycols, and the glycols include those having a tertiary amino group (for example, dioxyethylaniline). I can do it.

(2) As other preferred hydroxyl compounds, it is also possible to start from polyhydroxyl compounds which already contain urethane or urea groups. Of course, mixtures of various polyhydroxyl compounds can also be used, for example hydrophilic polyethers (polyethylene glycol X polyesters and polyacetals mixed in certain proportions with hydrophobic polyhydroxyl compounds).

Natural polyols such as castor oil, tar oil, and carbohydrates can also be used in combination. If necessary, glycols commonly used together with the above polyols, such as ethylene glycol, di- and triethylene glycol, phthanediol, guapanediol, 1,6-hexanediol, pentyl glycol, bisphenol A, and an ethylene oxide adduct or a globylene oxide adduct of bisphenol A are used in combination.

(1) Compound diisocyanates having an incyanate group include all aliphatic and aromatic diisocyanates such as 1,5-7 tyrene diisocyanate, 4,4'-cyphenylmethane diisocyanate),
4.4'-Diphenyl-dimethylmethane-diisocyanate, di- and tetraalkyl-diphenylmethane-diisocyanate.

4.4'-dibenzyrudiinsinocyanate, 1°5-phenylene-diisocyanate% 1,4-phenylene-
Diisocyanates, xylylene diisocyanates, toluylene diisocyanates, chlorinated and brominated incyanates, phosphorus-containing incyanates, butane-1,4
-diisocyanate, hexane-1,6-diisocyanate, dicyclohexylmethane-diincyanate, cyclohexane-1,4-diisocyanate.

In particular partially or completely with partially masked incyanates which are capable of forming self-reticulating polyurethanes, such as dimeric toluylene diisocyanate and, for example, phenol, tertiary butanol, phthalimide, caprolactam. Mention may be made of reacted polyisocyanates, which, if completely masked, do not initially take part in the reaction and are merely mixed.

((2) Chain extenders having a reactive hydrogen atom that may be used in combination include 1. For example, commonly used glycols 1. Diol-1,2, propanediol-1,3, neopentyl glycol, dioxyethoxyhydroquinone, dioxyethyl-diamine, as well as diamines such as ethylenediamine, hexamethylenediamine, hydrazine, ammonia, benzizine, diaminodiphenylmethane, amine alcohols and water. It is.

polyethylene polyamine, polypropylene polyamine,
Rice polyalkylene polyamines including polybutylene polyamines and the like are also used. More specifically, nitrogen is
Polyamines which are linked by groups of the formula -CnH2n- which are larger integers, and where there are from 2 to about 8 such groups in the molecule. The nitrogen atom is a group -
〇nH2n- is bonded to adjacent carbon atoms, but not to the same carbon atom. Specifically, the use of polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and dipropylenetriamine, as well as mixtures and various crude polyamine materials, is contemplated. Additionally, hydroxylalkyl-substituted polyamines may also be used in combination. Also, when using these polyamines, you can also use epichlorohydrin (6
)) Compounds containing at least one hydrogen atom capable of reacting with an incyanate group or at least one incyanate group and at least one salt-forming group include primary compounds alone or in mixtures thereof. is taken into account. (However, in the case of a compound having at least two hydrogen atoms capable of reacting with an isocyanate group or having at least two inocyanate groups, this compound is a compound that can react with the hydroxy compound, incyanate, and chain extender constituting the polytalethane mass.) ■ Compounds with basic tertiary amine groups that can be neutralized or quaternized with aqueous acids C&) Alcohols, especially alkoxylated aliphatic, cycloaliphatic, aromatic and Heterocyclic secondary amines 1 such as N, N-dimethylethanolamine, IJ, N-diethylethanolamine, M-1
1-diptylethanolamine, 1-dimethylaminopropanol-(2), N,N-methyl-β-hydroxyethyl-aniline, N,N-methyl-β-hydroxyglobyaniline, N,N-ethyl -β-Hydroxyethyl-aniline% N,N-phthyl-β-hydroxyethylaniline, N-oxyethylpiperidine, N-oxyethylmorpholine, α-hydroxyethylpyridine, γ-hydroxyethylxyline (1)) Diols , triols, especially alkoxylated aliphatic, cycloaliphatic, aromatic and heterogeneous primary amines, such as N-methyl-getanolamine, N-butyl-getanolamine, N-oleyl-getanol. Amine, K-cyclohexyl-jetanolamine, N-methyl-diisopropanolamine, N-cyclohexyl-diisogropanolamine.

H,H-dioxyethylaniline%N,N-dioxyethyl-m-)luidine, N,N-dioxyethyl-Xl-)luidine, N,
M-dioxyglobylnaphthylamine, N,M-
Tetraoxyethyl-α-aminopyridine, dioxyethylpiperazine, polyethoxylated butyl-jetanolamine, polypropoxylated methyljetanolamine (molecular weight 100G), polypropoxylated methyljetanolamine (molecular weight 2000), Polyester having tertiary amine group, tri[2-hydroxypropyl-(1)-3-amine, N-N-di-n-
(2,3-dihydroxyglobil)-aniline, N, N
'-dimethyl-N.

N'-bis-oxyethylhydrazine.

N,N'-dimethyl-N,N'-bis-oxypropyl-ethylenediamine (0) Amino alcohols obtained, for example, by hydrogenation. Addition products of alkylene oxides and acrylonitrile with primary amines 1 For example, N-methyl-N-(3-aminopropyl)-ethanolamine, N-cyclohexyl-N-(3-7minoglobil)-propanol-( 2)-Amine, N, N-bis-(3-7 minoglobir)-ethanolamine, N-3
-Aminopropyl-jetanolamine ((L) Amines such as N,N-dimethylhydrazine.

y, N-dimethyl-ethylenedi7mine.

1-di-ethylamino-4-amino- Pentane, α-aminopyridine, 3- 7 Mino-w-ethylcarbazole, N.

N-dimethyl-propylene-diamine.

N-aminopropyl-piperidi7,N -aminopropyl-morpholine, N -7 Minobrobyl-nithyleneimine.

1.3-Bis-piperidino-2-amino-propane (θ) Obtained by hydrogenation of diamines, triamines, amides, especially addition products of acrylonitrile and primary and di-secondary amines. Compounds such as bis-(3-7minopropyl)-methylamine, bis-(3-7minoprovir)-cyclohexylamine, bis-(3-7minopropyl)-aniline, bis-(3-aminopropyl)-toluidine, diamino Carbazole, bis-(aminopropoxyethyl)-butyl 7mine, tris-(aminopropyl)-amine, H,
H'-bis-carbonamidopropyl-hexamethylene diamine.

and acrylamide and diamines. obtained by addition with diols and diols. Compound.

■ Compounds containing halogen atoms or corresponding esters of strong acids capable of quaternization reaction; 2-chloroethanol, 2-7" rom methanol, 4-
Chlorobutanol, 3-bromopropanol, β-chloroethylamine, 6-/lorohexylamine, Engineering II/
-Lumin-sulfuric acid varnish? #, N,N-bis-hydroxyethyl-N'-m-chloromethylphenyl-urea,
N-hydroxyethyl-N'-chlorohexylurea,
/Lycerin-7minorchloroethyl-urethane, Chloro-acetyl-ethylenediami/, From-acetyl-dipropylenetriamine, Trichloroacetyl-triethylenetetramine, Glycerin-α-bromohydrin,
polyglopoxylated glycerin-α-chlorohydrin,
Polyester with aliphatically bonded halogen, 1
, 3-cycloglobanol-isocyanates include the following; chlorohexyl isocyanate, m-chlorophenyl-isocyate*-sp-chlorophenyl-isocyanate, bis-chloromethyl-diphenylmethane-diisocyanate), 2. 4-Diisocyanate-
Benzyl chloride, 2.6-dicyanatopenzyl chloride % N-(4-methyl-3-incyanate phenyl)-β-bromoethyl urethane■ Compound having a carboxylic acid group or hydroxyl group with salt-forming ability; (a) Hydroxy- and mercagtocarboxylic acid salts; glycolic acid, triglycolic acid, lactic acid, trichlorolactic acid, malic acid, dioxymaleic acid, dioxyheptamaric acid, tartaric acid, dioxytartaric acid, mucilage acid, sugar acid, citric acid acids, glycerin-boric acid, 7-taerythritol-boric acid, mannitoboric acid.

Salicylic acid% 2.6-dioxybenzoic acid.

Glotocatechuic acid, α-resorcylic acid.

β~resorcylic acid, hydroquinone-2゜5-dicarboxylic acid, 4-hydroxyisophthalic acid, 4,6-hydroxyisophthalic acid,
Oxyterephthalic acid, 5,6,7,8-tetra2t°
°−su71″−“ ・ [.

-(2)-Carboxylic acid = (3), 1-hydroxynaphthoic acid - (2)% 2,8-dihydroxynaphthoic acid -
(3) % β-oxypropionic acid, m-oxybenzoic acid, pyrazoline-carboxylic acid, urine s, barbituric acid, resol and other formaldehyde-phenol condensation products (b) Polycarboxylic acids: sulfonic acids, nitrilo- Triacetic acid, ethylenediamine-tetraacetic acid.

Diglycolic acid, thiodiglycolic acid.

Methylene-bisuthiochrycol rM% malonic acid, oxalic acid, cohelic acid, glutaric acid, adipic acid, maleic acid, 7 malic acid, gallic acid, phthalic acid.

Tetrachlorophthalic acid, isophthalic acid, terephthalic acid, naphthalenetetracarboxylic acid-(1,4,5,8)%0-tolylimidodiacetic acid, β-naphthylimidodiacetic acid bipyridine caribonic acid, dithiodipropionic acid (C) Aminocarboxylic acids; oxaluric acid, anilide acetic acid, 2-hydroxy-carbazole-carvone M-(3), glycine, sarcosine, methionine,
α-alanine, β-alanine.

6-aminocarboxylic acid, 6-penzoy Ruamino-2-chloro-carboxylic acid.

4-amino-butyric acid, aspartic acid.

glutamic acid, histidine, anthra nilic acid, 2-ethylaminobenzoic acid.

N-(2-carboxyphenyl)-7minoacetic acid, 2-(3'-amino-benzenesulfonyl-amino)-benzoic acid.

5-7 minobenzoic acid, 4-7 minobenzoic acid, N-phenylamino-acetic acid %3゜4-diaminobenzoic acid, 5-7 minobenzene monodicarvone M, 5-(4'-7minobenzoylamino)- 2-Aminobenzoic acid (d) Hydroxy- and carboxy-sulfonic acids; 2-hydroxyethanesulfonic acid, phenolsulfone Mt -(z) s phenolsulfonic acid-(3), phenolsulfone Ml -(4
) % Phenol disulfonic acid-(214) % Sulfoacetic acid, m-sulfobenzoic acid, p-sulfobenzoic acid, benzoic acid-(1)-disulfonic acid-(5,5) 2-chloro-benzoic acid-(1) -Sulfonic acid- (1).

2-Hydroxy-benzoic acid-(1)-sulfonic acid-(5
), naphthol-(1)-sulfonic acid, naphthol-(
1)-Disulfonic acid.

8-chloronaphthol-(1)-disulfonic acid, naphthol-(1)-)disulfonic acid, naphthol-(2)-
Sulfonic acid-(1), naphthol-(2)-)disulfonic acid, 1°7-hydroxynaphthalenesulfonic acid-(S), 1. S-dihydroxynaphthalene disulfonic acid (2,4), /lomotocofic acid, 2-hydroxynaphthoic acid (5)-sulfonic acid (6), 2-hydroxycarbazole sulfonic acid (7) (e) Aminosulfonic acids ; Amidosulfonic acid, hydroxyamine-monosulfonic acid, hydrazine-disulfonic acid, sulfanilic acid, N-phenylamino-methanesulfonic acid% 416-di/loroaniline-sulfonic acid- (2), phenylenediamine-(1,3 )-disulfonic acid-(4t6) *'-7 cetylna 7f ruamine-(
1)-sulfonic acid-(3), naphthylamine-(1)-
sulfone rn, naphthylamine-(2)-sulfonic acid,
naphthylamine-disulfonic acid, naphthylamine-trisulfonic acid, 4.4'-di(p-aminobenzoyl-amino)-diphenyl R-disulfonic acid-CspS/) S phenylhydrazine-disulfonic acid-(2,5), 2 .3
-dimethyl-4-, iaminoazobenzene-disulfonic acid- (4', 5)% a'-yminostilbenzene-disulfonic acid-(2,2')-<4-azo-4>-anizole, carbasol disulfone acid-(2,7), taurine, methyltafrine, butyltacrine, 3-7 minobenzoic acid-(1)-sulfonic acid-(s), 3-amino-
Toluene-N-methane-sulfonic acid, 6-nitrilo-1,3-dimethylbenzene-4
-Sulfamine Ms4s6-diamitbenzene-disulfonic acid-(L3), 2,4-diamino-toluene-sulfonic acid-(5)% 4,4'-diamino-diphenyl-disulfo:4- (212'), 2 -7 minophenol sulfonic acid- (4), 4,4'-diamino-diphenyl ether sulfonic acid- (2), 2-amino-ayuzole-N-methanesulfonic acid, 2-amino diphenylamine-sulfone θ ( ■ Diols with unsaturated bonds Carbon-carbon unsaturation in the main chain and side chain such as 1.2-polybutadiene diol, 1.4-polybutadiene diol, copolymer diol of propylene oxide and butadiene monoxide, etc. Diols with bonds.

(Compounds with unsaturated bonds and groups capable of forming salts) Vinyl monomers used in the unsaturated carboxylic acid grafting reaction include α, acrylic acid, methacrylic acid, maleic acid, etc.
β-unsaturated carboxylic acids.

Itacone M% may be phosphoric acid, cinnamic acid, or a mixture of these unsaturated carboxylic acids and a vinyl monomer such as acrylic acid ester, methacrylic acid ester, or vinyl acetate.

As the vinyl monomer used for mixing, for example, α,β-unsaturated carboxylic acid esters such as acrylic ester and methacrylic ester are used. Particularly hydrophilic vinyl monomers include ethylene glycol monomethacrylate, ethylene glycol monoacrylate, diethylene glycol monomethacrylate, diethylene glycol monoacrylate, 2
-Hydroxypropyl monoacrylate% 2-Hydroxypropyl monoacrylate, diethylene glycol monoacrylate, diethylene glycol monoacrylate, etc., polyhydric alcohol monoesters of α, β-unsaturated carboxylic acids, and acids such as tartaric acid, pyruvic acid, malic acid, etc. Also included are monovinyl or monoallyl esters of organic oxycarboxylic acids. Furthermore, unsaturated sulfuric acids, unsaturated phosphoric acids, unsaturated sulfonic acids are also considered.

■ Compounds 2-vinylpyridine and 4-vinylpyridine that have an unsaturated bond and at least one nitrogen atom ■ Any one of a halogen atom or a corresponding strong acid ester group that also has an unsaturated bond and has a quaternization reaction Also considered are compounds having .

(4) Aqueous polyhydroxy compounds ■ Polyethylene glycol, ethylene oxide-propylene oxide block copolymer, diols such as ethylene glycol % C and triethylene glycol, butanediol, propanediol, 1,6 hexanediol, neopentyl glycol, bisphenol Ethylene oxide adducts, glycerin, etc.
Ethylene oxide adduct of pentaerythritol, sorbitol, ethylene oxide adduct of mannitol.

Compounds with hydrophilicity imparted by ethyl ether groups, such as ethylene oxide adducts of dicarboxylic acids or tri- or tetra-rubonic acids, terminal hydroxyl groups, or ethylene oxide adducts of polyesters with carboxylic acid groups.■ A compound in which the cypolyhydronacyl compound itself contains a group capable of forming a salt through copolymerization, such as a terminal hydroxyl polyester compound polymerized so that a carboxyl group remains, and (f)-■, ■, ■, It also includes polyhydroxyl compounds obtained by coexisting unsaturated diols of group (V) when producing polyhydroxyl compounds of each group (①), and later graft polymerizing compounds of groups (V) -■, ■, and ■. It will be done.

(To) Salt-forming agent ■ A salt-forming agent that corresponds to the compound of group ■-■ of the compounds containing a group having salt-forming ability used in manufacturing method ■, and an unsaturated bond used in manufacturing method ■. Among the compounds containing a group having salt-forming ability, organic and inorganic acids, compounds having a reactive halogen atom, and corresponding esters of strong acids are considered as salt-forming agents corresponding to the compounds of the W-2 group. Hydrochloric acid, nitric acid, primary hypophosphorous acid, 7 to name a few examples.
Midosulfonic acid, hydroxylamine-monosulfonic acid, formic acid, acetic acid, glycolic acid, lactic acid.

Chloroacetic acid, bromoacetic acid ethyl ester.

Sorbit - boric acid; Methyl chloride, butyl bromide.

Dimethyl sulfate, diethyl sulfate, benzyl chloride, p-toluenesulfonic acid-methyl ester, methyl bromide, ethylene chlorohydrin.

Ethylene bromohydrin, glycerin-'α-glychromhydrin. Loroacetic acid ester.

These are chloracetamide, bromoacetamide, dibromoethane, chlorobromobutane, dibromobutane, ethylene oxide, propylene oxide, and 2,3-epoxyprobanol.

■ For compounds of the N-0 group, ■-■ group, organic and inorganic bases 1 such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium bicarbonate,
Ammonia, primary, secondary and tertiary amines are suitable. In addition, inorganic phosphorus compounds are also considered as salt-forming compounds, and basic phosphines (e.g. diethyl-β-hydroxyethyl7-osphine, methyl-bis-β-hydroxyethylphosphine, tris- -β-hydroxymethyl-phosphine)
and, for example, phosphinic acid, phosphinic acid, derivatives of phosphinic acid and esters of phosphorous acid and phosphoric acid, and their thio homologs 1, such as bis-(α-hydroxy-isoglobil β-phosphonic acid, hydroxyalkanephos heptaonic acid, phosphoric acid) -Bis-glycol esters are also considered.

2) The compounds of the 2-2 group are quaternized or tertiaryized with tertiary amines and also with sulfides or phosphines. In this case, quaternary ammonium salts and phosphonium salts or tertiary sulfonicum salts are formed.

For example, the following may be mentioned; trimethylamine, triethylamine, tributylamine, pyridine, triethanolamine and the compounds listed in group 1a and group 1b, as well as dimethyl sulfide, diethyl sulfide, thioglycolthiodicricolic acid, trialkylphosphine, When the polyhydroxyl compound used in the production method (■) for alkylaryl7-osphine and triarylphosphine is selected from the group ■-■, the corresponding group (4)-■, ■, ■, respectively. salt forming agents can be used. Polyhydroxyl compound (2
)-0 group, there is no need to use a salt forming agent.

The production of these polyurethane masses is carried out in a manner known per se in the presence or absence of solvents, in the aqueous phase:
No difficulties will arise during the subsequent conversion. When choosing a solvent, the first aqueous latex formed is at most
It should be noted that only very small amounts of hydrophobic, especially flammable, solvents should be contained, ie generally less than 20% of the polyurethane mass. However, since polyurethane latex preferably does not contain any solvents, solvents added during the manufacturing process to facilitate processability should be easily removed from the water-containing layer by distillation. be. Benzene, acetate, acetone, methyl ethyl ketone are preferred solvents. However, it is also possible to use solvents whose boiling point is not higher than that of water and which do not contain groups that react with incyanate. However, the latter limitation (not having a group that reacts with incyanate)
teeth.

It only applies if the # agent is added during the reaction, ie while free incyanate groups are still present.

In order to dilute the reaction mass after the reaction has been completed, for example, lower alcohols can be added.

On the other hand, it is also possible to carry out the entire reaction in the molten state without solvent and to dissolve the rubbery mass obtained subsequently in a polar or non-polar and water-containing solvent.

The polyurethane mass obtained in this way is now not limited to being hydrophilic and can be easily dispersed in water in the usual manner in the chemistry of elastic and plastic polymers. Naturally, with or without solvent,
It may be used for the purpose of producing the softener composition of the present invention in liquid, powder, solid, or spray sheet form.

However, due to the physical properties, especially the viscosity properties, of polyurethane lumps, if it is difficult to handle, water or some or all of it may be soluble in water so that the polyurethane lumps are 20 to 50% by weight. It is preferable to use it by dispersing or dissolving it in an aqueous solution instead of a solvent.

In this case, in the case of a polycrethane block containing a group having salt-forming ability, it is preferable to simultaneously use a salt-forming agent as described above to convert it into a salt form.

These dispersions or dissolutions are carried out by methods known per se.

For example, it is possible to simply dilute it in water, to perform it under strong stirring force, to inject it into water using a nozzle or in some cases using compressed air, or to apply ultrasonic waves.

In either case, it is possible to disperse or dissolve without adding an emulsifier; however, for example, oleyl alcohol polyglycol ether or oxyethylated phenols may be used to aid dispersion.

Of course, protective colloids, such as casein decomposed with ammonia for anionic latex and casein decomposed with acetic acid or lactic acid for cationic latex, as well as gelatin, gum arabic, gum tragacanth, modified starch, and fish.

It is also possible to use agar, rosin, polyvinyl alcohol.Finally, it is also possible to add, after evaporation of the water, a reticulating agent which acts chemically to reticulate at a room source or at a relatively high temperature.

Examples include sulfur-sols, formaldehyde and substances that give or react with formaldehyde, and masked isocyanates and peroxides. In this case, water-soluble reticulating agents 1 such as formaldehyde, methylol compounds and their ethers are easily added to the latex, while hydrophobic masked incyanates are soluble in non-polar solvents that are immiscible with water. Preferably, it is emulsified in the form of a solution into a latex without the addition of emulsifiers. The hydrophobic latex particles then absorb the hydrophobic solvent along with the reticulating agent while expanding.

The water-based polyurethane obtained in this way is
The fabric softener composition of the present invention can be produced by the method described in detail above.

Among the above-mentioned aqueous polycretanes, particularly preferred ones are:
When the hydroxyl compound of manufacturing method (1) is (b)-(2) or is made into a salt form, which does not contain a group having salt-forming ability and is itself aqueous, the base is It is an aqueous polyurethane containing a group having the ability to form a salt such that the structure is as follows.

Preferred base: In the fabric softener composition of the present invention using such an aqueous polyurethane, the fabric softener and the aqueous polyurethane have very good compatibility, and the desired impact resilience and compression recovery properties can be further improved to clothing. can be given. Furthermore, when softening clothes in a washing machine or washing machine, the fabric IKt is usually 30 °sb for 30 kg of water, and the softener concentration is about 20-50 ppm, which is very low compared to a large bath. When used in concentrations of the softener composition of the present invention, the fabric softener and the water-based polyurethane act synergistically over and above their use alone.

Shows excellent adsorption to Japanese crab.

In addition, when the softener composition of the present invention is used for home use by housewives, it is preferable that the softener composition adhering to clothing can be easily removed by normal washing, and the aqueous polyurethane.

It is particularly preferable that the polymer has a molecular weight of 1,000 to 100,000, is mainly linear without monobranching, and is not later formed into a network. Clothing softened with the fabric softener composition using such a water-based polyurethane exhibits excellent non-accumulation properties even when iron-pressed at home.

Furthermore, in general, water-based polyurethanes with residual unsaturated bonds tend to yellow the urethane itself; therefore, it is preferable to use water-based polyurethanes with a structure in which no unsaturated bonds remain.

However, there are many cases where it is not necessary to satisfy these conditions. For example, in sheet form.

Alternatively, in the case of the softener composition according to the invention in the form of a spray (aerosol), all of the above-mentioned aqueous polyurethanes are preferred.

In addition, the conditions for non-accumulation are that no matter what form the softener composition takes in home softening treatment, the treatment concentration is low, at most about 1f for 1 to 1000 ounces of clothing; therefore, each condition must be met in particular. Even if these conditions are not met, there is almost no problem with polishing in actual use, and it is not a necessary condition.

When the softener composition of the present invention is in liquid form, in order to improve its mechanical or thermal stability, emulsifiers such as polyoxyethylene alkyl ether and polyoxyethylene sorbitan fatty acid ester, ethylene glycol, etc. , solvents such as propylene glycol, inorganic electrolytes such as sodium chloride, calcium chloride, ammonium chloride, and wood structure disrupting agents commonly known as hydrotropic agents, such as urea.

In addition, when it is filled into a spray container and used as an aerosol, it is not necessary, for example, in the case of a pressure accumulation type spray, but in other cases, an appropriate propellant can be used. Examples of preferred propellants include Freon-113, liquefied petroleum gas, carbon dioxide gas, and the like. Although such forms of softeners or antistatic agents have been well known, the softener composition of the present invention not only has an antistatic effect but also has a remarkable hand-improving effect as detailed above. ing.

When the composition is in the form of a powder or solid tablet, a melting point regulator, a moldability improver, etc. may be added for the purpose of improving its thermal stability and moldability. The melting point adjuster may be any compound as long as it is soluble in f&, a material softener, such as paraffins, oils and fats, various surfactants, and waxes. In addition to inorganic electrolytes, examples of moldability improvers include polymers such as cellulose and starch, silicones, and various adhesives.

In addition, when the sheet form is used, the above-mentioned melting point regulator can be used depending on its thermal stability.

Furthermore, silicone may be added to the fabric softener composition of the present invention, which can be formed into a moderate amount of form, for the purpose of improving iron lubricity, or fragrances, dyes, and pigments may be added as desired. Furthermore, various preservatives, antibacterial agents, etc. may be added for the purpose of antibacterial properties.

〔Example〕

Next, the present invention will be further explained with reference to examples.

These examples are not intended to limit the invention. After adding 2 parts of the aqueous polyurethane dispersion synthesized according to the method, the mixture was cooled to obtain a fabric softener composition according to the present invention. Clothes were softened using this liquid softener composition to prepare test garments. Table 1 shows the results of the right-handedness measurement test.

Synthesis of aqueous polyurethane dispersion Polytetramethylene ether glycol (hydroxyl value OH
After adding 27.7 parts of hexamethylene diisocyanate to 200 parts of 7% 56 (molecular weight \2000), the mixture was stirred and reacted at 75°C for 10 hours to obtain a cretane prebomer block having incyanate groups at the ends.

Analysis of isocyanate groups revealed that it was 1.2%. Then, after adding 8.7 parts of N-methyljetanolamine,
The mixture was stirred at 75° C. for 5 hours to carry out a chain extension reaction, and a polyurethane block was obtained.

Next, 750 parts of a 0.74% hydroxyacetic acid aqueous solution was added with stirring, hydroxyacetic acid and water were added, and PR and concentration were adjusted. In this way, a homogeneous and stable aqueous polycrethane dispersion g(()) with a resin content of 25% is obtained.

test clothing The test clothing has the following configuration.

1. 2 cotton towels 130f2 2 cotton knitted underwear 220f3, 1 cotton dress shirt 150v48 Nylon stockings
2 pieces 2or5, 1 piece nylon slip 15
0t & polyester blouse 1 piece 100f (using irregular cross section yarn) 7. Acrylic chassis knit sweater 1 piece 25
A total of 1000 tons of these garments were all used simultaneously in one test.

The clothes were washed three times with a commercially available detergent before being used for trial MK.

Softening treatment test 1 When treating clothes with the liquid softener composition of the present invention in a washing machine, wash it in a commercially available two-tub washing machine at 25°C and 35°DH.
Water for 30! The softener composition is added to the fabric until its effective content is 35%.
ppm, stirred for 1 minute, added 1Kf of test clothing, stirred for 3 minutes, dehydrated in a dehydration tank for 1 minute, air-dried, and placed in a constant temperature and humidity room at 20°C and 65% RH. The fabric was stored for 24 hours and subjected to a sensory test and a fabric property measurement test.

Fabric property measurement tests were conducted on cotton stockinette underwear and acrylic chassis knit sweater.

■Bending test After cutting the clothing to a predetermined size, the bending test was carried out using a pure bending tester manufactured by Kato Iron Works.
m/s) was calculated. The larger the value, the harder and less elastic it is, and the smaller the value, the softer and more elastic it is.

(1) Tensile Test After cutting the garment into a predetermined size, it was used in a tensile tester manufactured by Kato Iron Works to determine the recovery rate (resilience) of the tensile work. The larger this value is, the stronger the rebound elasticity is, and the smaller this value is, the more plastic it is.

In this way, the product of this invention gives all clothing a soft finish,
It is possible to provide the desired rebound resilience.

Example 2 40 parts of G-hardened beef tallow imidazolinium methosulfate was melted in 900 parts of 55°C warm water with stirring.1 Then 20 parts of aqueous polyurethane synthesized by the following method (
5 m of nonylphenol ether (20 moles of ethylene oxide added), 50 parts of ethylene glycol, 1 part of silicone, and fragrance were added to JT.

was added to obtain a fabric softener composition ((1).Using this liquid fabric softener composition, the same fabric softening treatment as in Example 1 was carried out, and the fabric was used as a test garment and a sensory test was conducted.Softening Treatment Method was conducted in accordance with the flexible treatment test run 1 of Example 1.

Synthesis of aqueous polyurethane dispersions Polybutylene adipate with terminal hydroxyl groups (
molecular weight 2000) 200 parts methyl ethyl ketone 2
00 parts, then xylylene diisocyanate 31
．． After adding 0 parts, the mixture was stirred and reacted at 75° C. for 10 hours to obtain a urethane prepolymer solution having incyanate groups at the ends.

Next, 26.1 parts of N-stearyljetanolamine was added and a chain extension reaction was carried out with stirring at 75° C. for 5 hours to obtain a polyurethane solution. Next, 750 parts of 0.74% hydroxyacetic acid was added with stirring, and the temperature was increased to 40-50%.
℃ and topping under reduced pressure to remove the solvent in the system, and then add a small amount of hydroxyacetic acid and water to obtain a uniform and stable aqueous polyurethane dispersion (b) with a resin content of 25%.

Sensory test The sensory test was conducted by a panel of 10 women, comparing the comfort, feel, and fit of the wearer, as well as the softness and elasticity (or waist) of the wearer without wearing it. Judgment was made using criteria such as:

+2 = Comparison is very good +1: l Fairly good 0: Same as comparison - 1 = Comparison is slightly better -2: I Very good Comparison product G-cured beef tallow without stirring in 950 parts of warm water at 55°C Added 45 parts of imidazolinium methosulfate, and further added 5 parts of nonylphenol ether (20 moles of ethylene oxide added), 30 parts of ethylene glycol, and 1 part of silicone.
Table 2 shows the results of a sensory test based on paired evaluation of the product of the present invention and a comparative product.As described above, the fabric softener of the present invention has a composition that is harmonious with all clothing. It exhibits a smooth texture and is highly praised for its comfort and texture when actually worn, especially for clothing that requires elasticity such as plastics and sweaters using irregular cross-section yarns, compared to conventional fabric softener treatment. Improves texture.

Example 3 50 parts of dihydroxyethylammonium hydroxyacetate, 16 parts of sodium laurate, and 10 parts of an aqueous polyurethane mass synthesized by the method described below were dissolved in 920 parts of ethyl alcohol. Add 60 parts of this ethanol solution to an aluminum aerosol can, and after adhering the pulp and clinching it with a clincher, fill it with 11,340 parts of Freon to form a spray-type softener composition (
I gained skill.

Synthesis of aqueous polyurethane block After adding 57.5 parts of 1 hexamethylene diisocyanate to 200 parts of polyethylene glycol (molecular weight 600), the mixture was reacted with stirring at 75°C for 10 hours. A polyurethane mass was obtained.

A comparative fabric softener composition was obtained in Example 5 except that the aqueous polyurethane was excluded. Using this as a comparison, the following tests were conducted.

(Test method) Ten female panelists were asked to wear nylon stockings, nylon slips, and polyester skirts in a constant temperature and humidity room at 120°C and 65% RR. After spraying the product and a comparison product for 4 seconds, the wearer's feeling of wearing and the presence or absence of clinginess were compared and judged. The results are shown in Tables 5 and 4.

Table 3 Table 4 Table 59 As shown in Table 4, the product of the present invention has a remarkable effect in terms of wearability and stiffness, although both the clinginess and wrinkles of clothing are eliminated.

Example 4 To 200 parts of polytetramethylene ether glycol (OHV=56°, molecular weight 200) which can be dehydrated at 90°C and 50 n+Hg for 1 hour, 27.7 parts of hexamethylene diisocyanate was added and heated with stirring at 90°C for 2 hours. Do the following. Then, cool to room temperature and add tert-butanol 22
Add 7.7 parts to dilute the solution to obtain a urethane prepolymer solution having incyanate groups at the ends. Analysis of the residual incyanate groups in the obtained Brepolymer solution revealed that 1
．． It was 2%.

In another four-loaf flask, add 300 tert-butanol.
and 3.46 parts of diethylenetriamine, and while stirring while keeping the temperature below 25°C with external cooling, 200 parts of the above greborimer solution was gradually added dropwise over 1 hour.
The reaction was carried out at 50° C. for 30 minutes to obtain a polyurethaneurea polyamine solution. Next, add 4 parts of epichlorohydrin and add 50
Heat and stir at ℃ for 1 hour. Then, after cooling to room temperature, 0.68
% aqueous acetic acid solution was added with stirring.

The temperature was raised to 40 to 50°C, topping was performed under reduced pressure to remove the solvent in the system, and then acetic acid and water were added to adjust the pH and concentration to obtain an aqueous polyurethane with a solid content of 25%.

40 parts of this water-based polyurethane, 30% by weight of mono-tallow dimethylamine, and 7 parts by weight of di-tallow dimethylammonium chloride.
40 parts of a textile softener consisting of 0% by weight was added to 9 parts of water at 55°C.
The mixture was added to 20 parts with stirring to obtain a softener composition (G).

According to Example 1.

A softening treatment was performed, and the sensory evaluation of the clothing was performed according to the method of Example 2. The results are shown in Table 5.

As a comparative product for evaluation of a pair of comparative products, a softener composition was obtained by adding 50 parts of a fabric softener having the same composition as above to 950 parts of water at 55°C.

Table 5 shows that even in the case of a softener composition made of aqueous polyurethane having branches, it has an excellent hand-improving effect.

Example 5 10% by weight of the aqueous polyurethane mass synthesized in Example 3
, monolafuryltrimethylammonium chloride 10
Weight%, di-beef tallow imidazolinium chloride 20% by weight
and 50 parts of a textile softener consisting of 60% by weight of sorbitan monostearate are dissolved in 100 parts by weight of ethanol,
1 m of dry non-woven fabric made of rayon with a basis weight of 2017 m2
2. After impregnating the nonwoven fabric with a fabric softener ethanol solution so that the fabric softener 2Of is supported,
Ethanol was removed with warm air at 40°C to obtain a sheet-like, substantially solid softener composition of the present invention. This sheet-like softener composition was applied to the test garment of Example 1.

Electric clothes dryer for quiet gardens (Toshiba model l! ID-90
0N). A pair of treated garments was evaluated using the sensory evaluation test method shown in Example 2.

A comparative product for paired evaluation was a woven fabric containing 11.11% by weight of monolauryltrimethylammonium chloride, 22.22% by weight of di-tallow imidazolinium chloride, and 66.67% by weight of sorbitan monostearate, and the same method was used. A sheet-like, substantially solid softener composition manufactured by the Company was used. The results are shown in Table 6.

Processing method Test clothing 1~ was washed in a washing machine for 10 minutes.

After 10 minutes of rinsing and 3 minutes of dehydration, the clothes were placed in an electric dryer together with the sheet-like soft composition (217IX2 am) and dried for 5 minutes.
I ran the car for 0 minutes and lost my clothes.

Take out the clothes and put them in a constant temperature and humidity room at 20℃ and 65%RH.
It was stored for 4 hours and then subjected to sensory evaluation.

Table 6

Claims (1)

[Scope of Claims] 1. A softener composition comprising a) a textile softener and b) an aqueous polyurethane. 2. The softener composition according to claim 1, wherein the content of the fabric softener is greater than that of the aqueous polyurethane in terms of weight fraction. 3. The soft material according to claim 1 or 2, wherein the content of the fabric softener is 1 to 20% by weight, the content of the aqueous polyurethane is 0.05 to 10% by weight, and the material is substantially liquid. agent composition. 4. The fabric according to claim 1 or 2, wherein the content of the textile softener is 1 to 99% by weight, the content of the aqueous polyurethane is 0.05 to 50% by weight, and the material is substantially solid. Softener composition. 5. The textile softener comprises 50 to 100% by weight of a compound having one or more long-chain aliphatic groups and one or more quaternary nitrogen atoms, and 0 to 50% by weight of other textile softeners The softener composition according to any one of Item 4. 6. The softener composition according to any one of claims 1 to 5, wherein the aqueous polyurethane is a compound containing a group capable of forming a cationic salt. 7 The aqueous polyurethane does not contain any salt-forming groups,
The softener composition according to any one of claims 1 to 5, which is a compound containing a hydrophilic hydroxyl group exhibiting water properties.