The invention relates to a non-aqueous shade enhancing agent composition for a soft goods, in ^' particular which serves to improve the chromophoric property of.a dyed material as well as the depth and sharpness of a color. It may be calle as a non-aqueous shade improver or a non-aqueous color-enric agent.

( statement of Prior Arts )

Heretofore, as a serious problem of a synthetic fiber, parti larly a polyester type fiber, as compared with a natural fiber such as wool, silk, etc., there has been mentioned a point that it is inferior to them in depth and sharpness of color of a dyed material. Accordingly, research has been

continued to improve sharpness and depth of a dyed material and some reports have been effected.

For example, in "Dyes and Chemicals", Vol. 15, No. 1, p. 3 to 8 (1970), there has been explained experimentally and theore¬ tically, from the fact when a dye cloth is wetted with water (a refractive index: 1.33), it looks like dark and sharp, so tht if a dyed cloth is treated with a resin processing agent having a low refractive index, the same color-enriching effect as in wetting with water can be obtained, and further explained that the reason is that it decreases a surface reflectance. Also, in "Textile Engineering", Vol. 26, No. 3, p. 188 (1973), in the summary of discussion entitled "Textile surface and color developability", color development of a polyester fiber due to a disperse dye decreases reflectance of a surface layer, and in order to increase a light volume incident in the fiber and heighten a color development effi¬ ciency, it is effective to form a layer having a suitable refractive index on a surface of the fiber, and it is disclos¬ ed that by coating a low polymerized material of trifluoro- chloroethylene (refractive index: 1.4) to a dyed PET fila¬ ment, it becomes dark color.

Various proposals have been effected based on these facts. In Japanese Provisional Patent Publication No. 111192/1978, there has been discloses a fiber structural material having a thin film formed by a polymer having a refractive index of 1.50 or less, and as a method for preparation, there has been proposed a method in which a monomer having a refractive index of 1.5 or less when prepared a polymer is charged in a closed apparatus with a fiber and plasma polymerization or discharge graft polymerization to form a thin film. Also, in Japanese Provisional Patent Publication No. 26232/1980, there is disclosed a method in which a compound having a low refrac¬ tive inex of 1.45 or less is adsorbed onto a surface of a fiber structural material with an amount of 0.3 % to 10 % in

the form of thin film, and then dry heating or wet heating processing is carried out. Further, as a starting material for formation of the thin film, there has been described that a fluorine resin, an acrylate resin, a vinyl polymer or a silicone resin having a refractive index of the polymer of 1.45 or less can be used, and as a concrete example, there has been disclosed a method in which by using an emulsified material or a solvent solution of a fluorine-containing compound or acrylate, fiber is dipped therein and adsorbed at a high temperature or after spray coating, dry heating or wet heating processing is carried out to form a thin film on fiber.

However, the method disclosed in Japanese provisional Patent Publication No. 111192/1978 has many disadvantages that since it is batch producing system, efficiency is bad, and it requres specific facilities, and when polymerization of monomers, loss of the polymer is remarkable since the polyme¬ rized polymer attaches to a wall of an apparatus and washing thereof is troublesome whereby the method is not suitable for industrial production. Also, in the method disclosed in Japanese provisional Patent Publication No. 26232/1980, a large amount of a solution should be made a high temperature since uniform adsorption is impossible only at a high tempera¬ ture in a dipping method with a large bath ratio, so that it has a defect of high cost from the view point of saving energy. On the other hand, in the spray coating method, dangerous and complicated operations are necessary and there¬ fore it has a fatal defect that the finish becomes dappled . since the coating amount becomes ununiform.

Also, in Japanese provisional Patent Publication No. 176275/- 1982, there has been disclosed a color-enriching processing agent comprising a polymer in which a superstrate segment having a blocked polyfluoroalkyl group is bonded to a back¬ bone segment. However, the polymer and a solvent are special

ones and its utilizable value in industry is small

( Summary of the Invention )

In order to found a non-aqueous type color-enriching agent which can use a cheap non-aqueous solvent such as tetra- chloroethylene, trichloroethan, etc. as a solvent and has great utilizable value in industry, the present inventors have intensively studied concerning a necessary function to develop a color-enriching effect and as a result, the follow¬ ing finding has been obtained.

That is, color-enriching'effect of a synthetic fiber, particu larly a polyester type fiber is insufficient by forming a film of a low refractive index and remarkable color-enriching effect can be obtained by roughing a polymer on a surface of the fiber. Thus, in order to adsorb a polymer on a synthetic fiber, particularly a polyester type fiber and roughing the surface, it is necessary that the polymer is insoluble to a solvent and disperses therein stably, i.e., it becomes non- aqueous emulsion. For this purpose, a graft copolymerized material which is obtained by graft polymerization of a backbond polymer insoluble to, a solvent with a superstrate polymer soluble to a solvent is suitable.

Further, in natural fibers such as wool, silk, etc., by adsorbing a polymer on a surface of the fiber and roughing the surface, as in the synthetic fiber such as the polyester, etc. , depth of a color and sharpness become good whereby color-enriching effect can be obtained. However, even if the natural fibers such as wool and silk are treated only by a graft polymerized material, adhesion is not good and suffi¬ cient color-enriching effect cannot be obtained. For height- ening the color-enriching effect to the natural fibers such as wool and silk, it is necessary that adherability of the graft polymerized material should be improved. The present

inventors have intensively studied concerning a color-enrich¬ ing agent capable of obtaining a color-enriching effect in both of the synthetic fiber such as a polyester and the natural fiber such as wool and silk, and as a result, accom¬ plished the present invention.

The invention provides a non-aqueous shade enhancing agent composition which comprises:

(a) a copolymer obtained by graf -polymerizing a main chain polymer being substantially insoluble in a non-aqueous solvent having a solubiity parameter in the range of 6.5 to 10.0 with a branch polymer being soluble in said solvent at a weight ratio of the main chain polymer to the branch polymer in the range between 90/10 and 10/90 and

(b) a quaternary ammonium salt having the formula (1) :

in which R1 is an alkyl having 8 to 22 carbon atoms, R2 is an alkyl having 1 to 22 alky., hydroxyethyl or hydroxypropyl, R3 and R4 are each an alkyl having 1 to 3 alkyl., hydroxyethyl or hydroxypropyl, at least one of R3 and R4 being hydroxyethyl or hydroxypropyl, Y is a group of ethylene or propylene, m is ^" zero or 1 , n is a number of zero to 5 and X- is ^' an anion of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid, paratoluenesulfonic acid or a hydroxyalkanecarboxyliσ acid having 2 to 6 carbon atoms, at a weight ratio ^' of (a) to (b) in the range of 95/5 to 20/80.

The copolymer to use in the invention consists essentially of the main chain polymer portion, or the backbone polymer, and the branch chain polymer portion, or the superstrate polymer.

It is preferred that the main chain ^' polymer is ^' polybutadie or a copolymer of butadiene and the branch polymer is a vinyl polymer or a vinyl copolymer.

It is ^" preferred that the anion is an anion of paratoluenes acid ^' or hydroxyalkanecarbox lic acid ^' having 2 to 6 carbon atoms.

The composition may comprises 1 to 20 percent by weight of the copoymer (a) and 0.5 to 30 percent by weight of the quaternary ammonium salt -(b) . It may further comprise a solvent from the practical point of view. That is, it may comprise 0.05 to 5 percent by weight of a mixture of the copolymer (a) and the quaternary ammonium salt (b) and the balance of a non-aqueous solvent having a solubility parameter of 6.5 to 10.0.

The backbone polymer in the copolymerized material of the present invention may be those which are substantially insolu¬ ble to sai solvent, and there may be mentioned, for example, polybutadiene or a copolymer of at least one or more monomer capable of copoly erizing with butadiene and butadiene.

The superstrate polymer may be those which are soluble to said solvent, and there may be mentioned, for example, a copolymer of at least one of vinyl monomers. More specifi-

cally, as a monomer which is capable of copoly erizing with butadiene, there may be mentioned acrylonitrile, acrylate, methacrylate, aromatic vinyl, etc. Also, as the vinyl mono¬ mer which is to polymerize with the backbone polymer, there may be mentioned styrene, i-methyl styrene, c-ethyl styrene; or nucleus-substituted derivatives thereof of aromatic vinyl monomers such as vinyl toluene, isopropenyl toluene, chloro- styrene, styrene, etc.; methacrylate monomers such as methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, normal butyl methacrylate, etc.; acrylate monomers such as methyl acrylate, ethyl acrylate, normal butyl methacrylate, etc.

Weight ratio of the backbone polymer/the superstrate polymer is i ^' n the range of 90/10 to 10/90, preferably 80/20 to 20/80. If only the backbone polymer is present, it is insoluble to a solvent and yet a secondary aggregated polymer at polymer purification cannot be uniformly and stably dispersed in a solvent whereby it is not suitable for a color-enriching agent. On the other hand, if only the superstrate polymer is present, it is soluble in a solvent and a smooth film can be formed on ^' a surface of a fiber but roughing surface cannot be obtained so that sufficient color-enriching effect cannot be obtained. To the contrary, when the superstrate polymer which is soluble in a solvent is graft polymerized with the backbone polymer which is insoluble in a solvent according to the present invention, while the copolymerized material is

insoluble to a non-aqueous solvent, it is stable dispersed in a solvent to form a non-aqueous emulsion and the emulsion forms a rough surface due to fine particles of 0.2 μ or less on a surface of the fiber. Therefore, it has excellent color-enriching effect as a non-aqueous color-enriching agent.

When the backbone polymer of the present invention is a copolymer of butadiene and other monomer, a content of buta¬ diene is preferably 30 % by weight or more, particularly 50 % by weight or more is desired. If the content of butadiene is less than 30 % by weight, a color-enriching agent obtained by graft polymerization hardly forms a stable non-aqueous emul¬ sion, and increase in particle size due to secondary aggrega¬ tion is caused so that color-enriching is bad.

In the present invention, the backbone polymer to be graft polymerized should form a latex, and its average particle size is desirably 0.2 μ or less, preferably 0.15 μ or less. If the avarage particle size exceeds 0.2 μ, stability of the resulting non-aqueous emulsion is bad and color-enriching effect is little.

In the color-enriching agent of the present invention, a cross-linking agent may be added at polymerization of the backbone polymer or graft polymerization of the superstrate polymer in order to improve iron resistance (ironability) . As the cross-linking agent, there may be mentioned bifunc- tional monomers such as divinyl benzene, dimethacrylate, e.g., mono-, di, tri- or tetraethylene dimethacrylate, 1,3- butylene glycol dimethacrylate, etc.

The copolymerized material of the present invention is pre- ferably formulated in an amount of 1 to 20 % by weight in the composition.

In the quaternary ammonium salt represented by the formula (1) to be used in the present invention, those having less than 8 or more than 22 carbon atoms are not preferred since lowering in property, particularly in charge preventive effect.

Further, as X ^~ , there may be mentioned acid residue of hydro chloric acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid or para-toluenesulfonic acid, and a hydroxy- alkane carboxylic acid having 2 to β carbon atoms. Above all, an acid residue of para-toluenesulfonic acid and hydrox alkane carboxylic acid (particularly glycollic acid) are preferred. As specific examples of the preferred quaternary ammonium salt, there may be mentioned stearyldimethylhydroxy ethyl ammonium paratoluenesulfonate, palmityldi ethylhydroxy ethyl ammonium paratoluenesulfonate, stearoylaminoethyldi- ethylhydroxyethyl ammonium paratoluenesulfonate, dilauryldi hydroxyethyl ammonium paratoluenesulfonate, distearyldihydr- oxypropyl ammonium paratoluenesulfonate, coconut or "beef tallow alkyldimethylhydroxyethyl ammonium paratoluenesulfon¬ ate, stearyldimethylhydroxyethyl ammonium paratoluenesulfon¬ ate, stearoylaminoethyldi ethylhydroxyethyl ammonium hydroxy propionate, palmityldimethylhydroxyethyl ammonium glycolate, dilauryldihydroxyethyl ammonium glycolate, stearyltrihydroxy ethyl ammonium glycolate, myristyldihydroxyethylhydroxypropy ammonium glycolate, etc. These quaternary ammonium salt is preferably formulated in an amount of 0.5 to 30 % by weight in the composition.

In the present invention, the copoly erized material/quater¬ nary ammonium salt is used in weight ratio of 95/5 to 20/80, but it is preferred to use in the ratio of 95/5 to 30/70. Out of the above range, if an amount of the quaternary ammo¬ nium salt is little, color-enriching effect in the natural fiber such as wool, etc. cannot sufficiently be obtained. O the other hand, an amount of the quaternary ammonium salt is

too large, it is not preferred since heat resistance (iron resistance) of a clothing is bad.

The non-aqueous color-enriching agent of the present inven¬ tion is prepared as a composition by diluting and dispersing the above both of components (a) and (b) in a solvent, and the solvent to be used is not limited. For example, a sol¬ vent for syhtesis mentioned below, a petroleum solvent, an alcoholic solvent, a ketone solvent, tetrahydrofuran, di- oxane, etc. may be used. Also, water may be added in the range capable of dissolving the polymer.

Contents of the components (a) and (b) in the composition are preferably in sum 5 to 30 % by weight.

In the non-aqueous color-enriching agent of the present invention, if necessary, surfactants such as anion or nonion, or hydrotrop agent for improvement of stability of the sys¬ tem, oily agents such as silicone for improvement of iron slip property, and further perfumes, dyes, pigments, fluores¬ cent dyes, anti-fugus agents, antispetic agents, etc. may be added.

The the non-aqueous color-enriching agent of the present invention can be used by diluting and dispersing in the range of 0.05 to 5 % by weight, preferably 0.3 to 2 % by weight in a non-aqueous solvent. As the solvent for dilution and dispersion, there may be mentioned a non-aqueous solvent having a solubility parameter in the range of 6.5 to 10.0, and for example, synthetic solvents such as tetrachloroethyl- ene, trichloroethylene, trichloroethane, trichlorotrifluoro- ethane, etc.; naphthene, petroleum solvent with high paraffin content, etc. may be used. If necessary, an alcoholic sol- vent such as methanol, ethanol, isobutanol and normal butan- ol; a ketone series solvent such as methyl ethyl ketone and acetone; and tetrahydrofuran, dioxane, etc. may be added.

[Examples]

In the following, the present invention will be described in more detail, but the present invention is not limited by these Examples. In the Example, all parts and % are based on weight otherwise expressly mentioned.

Example-1

A graft polymerized material was synthesized by the following method.

A) Polymerization of a backbone polymer

1,3-Butadiene 75 parts

Styrene 25 Sodium lauryl sulfate 3.0

Potassium persulfate 0.25

Dodecylmercaptane 0 ^' .15

Water 150

The above formulated material was polymerized at 60 °C for 24 hours. A rate of polymerization reached to 92 % or more. An average particle size of a latex was 0.084 μ. This was used as the backbone polymer and isobutyl methacrylate was used as the superstrate polymer, and graft polymerization was carried out with the following formulation.

B) Graft polymerization of a superstrate polymer

Backbone polymer X part

Isobutyl methacrylate Y

Cumenhydroperoxide 0.75

Half-cure beef tallow aliphatic acid potassium salt 1.5

Sodium salt of β-naphthalenesulfonic acid-

formalin condensate 0.15 dl-Glucose 1.0

Ferrous sulfate 0.01

Water 160

Polymerization was carried out at 70 °C for 6 hours and the resulting latex was poured into methanol to aggregate and precipitate the graft polymerized material, and after filtra¬ tion, the residue was washed three times with methanol and dried.

By using the copolymerized material obtained, the composition as shown in Table-1 was prepared and color-enriching effect was investigated by the following.

The sample obtianed was diluted and dispersed in tetrachloro- ethylene with a concentration of 1.0 %, and to the solution were dipped a polyester tuft with a black ground and a wool muslin with a black ground for 1 minute and they were dried with air. The color-enriching effect was measured by light and dark index L ^" value with a colorimetry color difference meter (produced by Nippon Denshoku Kogyo K.K. , ND-1001DP type). Smaller L value indicates dark color. The.results are shown in Table-1.

Table 1

Compara¬ Comparative tive This invention example example

Copolymer Backbone polymer X 0 10 20 50 80 90 100 composition Isobutyl meth- _γ 100 90 80 50 20

(%) acrylate 10 0

Copolymer 10 10 10 10 10 10 10 Un¬ treat¬

Stearyldimethyl- ed

Formulated hydroxyethyl ammo¬ 5 5 5 5 5 5 5 composition nium paratoluene¬ sulfonate

Tetrachloroethyl¬ ene 85 85 85 85 85 85 85

Dilution and dispersibility Dissol¬ o ^*21 O O O O Insolu¬ in tetrachloroethylene ved ble^)

Polyester L value , 18.1 ^• 17.0 16.8 16.7 17.4 17.5 18.7 tuft *1 ) Δ L ^{l )} 0.6 1.7 1.9 1.4 1.3 1.2 —

L value 11.3 10.4 10.0 10.2 10.3 10.5 — 11.5

Wool mulsin *1 \ Δ L ^1J 0.2 1.1 1.5 1.3 1.2 1.0 —

*1) ΔL = L value of untreated material - L value of treated material *2) Good dispersibility *3) Bad dispersibility

The color-enricing agents of the present invention become non-aqueous emulsions in tetrachloroethylene, respectively, and they are good in dilution dispersibility and have excel¬ lent color enriching effect ^" in both of polyester and wool.

Example-2

By using a copolymerized material in which a ratio of the backbone polymer (X) and isobutyl methacrylate (Y) in the graft copolymerized material was 20/80, and by varying a formulation ratio to a quaternary ammonium salt and also using various quaternary ammonium salts, treatments and mea¬ surements were carried out in the same manner as in Example- 1. The results are shown in Table-2.

Table 2

This invention

Formulation 1 2 3 4 5 6 7 8 9

Copolymer 9.5 9 8 7 6 5 4 3 2

Stearyldimethylhydroxyethyl ammonium paratoluenesulfonate 0.5 1 2 3 4 5 6 7 8

Stearoylaminoethyldi ethylhydr- oxyethyl ammonium paratoluene¬ sulfonate

Stearyldimethylhydroxyethyl ammonium glycolate

Dilaurylhydroxyethyl ammonium glycolate

Myristyldihydroxyethylhydroxy- propyl ammonium glycolate

Tetrachloroethylene 90 90 90 90 90 90 90 90 90

Ratio of copolymer/quaternary ammonium salt 95/5 90/10 80/20 70/30 60/40 50/50 40/60 30/70 20/80 60

Dilution and dispersibility in tetrachloroethylene o ^{*2 )} Ό O O O O O O O

Polyester L value 16.1 17.0 16.9 16.7 16.7 16.9 17.2 17.2 17.3 1 tuft ΔL *1 ^λ ) ⁾ 1.6 1.7 1.8 2.0 2.0 1.8 1.7 1.5 1.4

L value 10.5 10.3 10.1 10.1 10.0 10.0 10.1 10.0 10.0 1

Wool mulsin AL ^{1 }} 1.0 1.2 1.4 1.4 1.5 1.5 1.4 1.5 1.5

Table 2 ( Contd )

This invention Comparative examp] .e

Formulation 11 12 13 14 15 16 ^J 17 ^} 18 ^{i ]}

Copolymer 6 6 6 6 10 1.5 1

Stearyldimethylhydroxyethyl ammonium paratoluenesulfonate 8.5 9 10

Stearoyla inoe hyldimethylhydr- oxyethyl ammonium paratoluene¬ 4 sulfonate Untrea

Stearyldimethylhydroxyethyl ed ammonium glycolate 4

Dilaurylhydroxyethyl ammonium glycolate 4

Myrist ldihydroxyethylhydroxy- propyl ammonium qlycolate 4

Tetrachloroethylene 90 90 90 90 90 90 90 90

Ratio of copolymer/quaternary ammonium salt 60/40 60/40 60/40 60/40 100/0 15/85 10/90 0/100

Dilution and dispersibility in tetrachloroethylene O O O O O O O dis¬ solved .2

Polyester L value 16.7 16.7 16.7 16.7 16 17.7 17.7 17.9 18.7 tuf Δ L ^{l )} 2.0 2.0 2.0 2.0 1.5 1.0 1.0 0.8

L value 10.0 10.0 10.0 10.0 0.8 10.2 10.2 10.2 11.5

Wool mulsin Δ L *1 ^X ) ⁾ 1.5 1.5 1.5 1.5 0.7 1.3 1.3 1.0

-