JPS61690A - Dyeing of synthetic resin molded product - 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 Field of Application] The present invention relates to a method for dyeing a synthetic resin molded article with excellent color development.

[Conventional technology]

Conventionally, when dyeing synthetic resin molded articles, it has been customary to select dyes depending on the substance that constitutes the molded article. Especially for molded products made of hydrophobic polymers such as polyester,
Compared to natural fibers, only a limited number of dyes can be used to achieve favorable results. That is, unmodified polyester cannot be colored with ionic dyes and cannot be dyed with disperse dyes or oil-soluble dyes.

[Problem that the invention seeks to solve]

The present invention relates to the dyeing of such synthetic resin molded articles and provides a dyeing method that can produce good color even with dyes that have hitherto been inapplicable at all.

[Means for solving the problem] (1) When dyeing a synthetic resin molded article with a dye liquor containing a solid particulate compound having swelling ability, it is recommended to add a sulfur-containing compound to the dye liquor. Characteristic dyeing method for synthetic resin molded products.

(2) A method for dyeing a synthetic resin molded article according to claim (1), wherein the dye solution is alkaline.

The dye liquor of the present invention is composed of a liquid mixture consisting of a solid particulate compound having swelling ability for a synthetic resin, a sulfur compound, and a dye. Of course, if necessary, thickeners, viscosity modifiers, penetrants, and other additives may be added to the extent that they do not impede the effects of the present invention.

The synthetic resin referred to in the present invention may be a normal synthetic resin, a semi-synthetic resin, or a mixture thereof, regardless of whether it is a homopolymer or a copolymer, as long as it has fiber or film-forming properties.

Examples of such synthetic resins include polyamide, polyester, polyacryloni-1-lyl, polyolefin, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyurethane, polyvinyl acetate, cellulose acetate, polystyrene, polyfluoroethylene, melamine resin, silicon resin, and the like. I can list the following.

Among such synthetic resins, the present invention is particularly effective for those that are hydrophobic and difficult to dye, such as polynisder and polyolefin.

Molded articles made of such synthetic resins are usually 17a films, but the effects of the present invention are not dependent on such forms and can be applied to any form.

In particular, the present invention exhibits an extremely remarkable effect on dyeing polyester resin molded articles.

Such polyester resins include, for example, polyethylene terephthalate, polybutylene terephthalate-1-, and copolyesters obtained by copolymerizing these with other copolymer components, but are not limited to these. This includes polyester made of a compound having a nucleus, unsaturated polyester resin, and the like. It also includes those obtained by mixing such polyester with other synthetic resins, such as polymer blends, mixed fibers, blended yarns, mixed knitting and weaving.

The solid particulate compound used in the present invention is a compound that has the ability to swell the polymer constituting the synthetic resin molded article to be treated and is solid particulate in the paste, and of course is solid at least at room temperature. It is something.

Such compounds include (1) aromatic compounds, particularly compounds having a benzene nucleus or a naphthalene nucleus;

(2) Compounds that are solid below the secondary transition point of the polymer constituting the molded article to be treated, especially those with a melting point of 100 to 300°C
A compound that is

(3) Compounds with a molecular weight of 1000 or less, particularly 500 or less.

It is a compound having the following characteristics, and the above (1) to (3)
The more the properties are satisfied, the better the action and effect will be.

The swelling ability as used in the present invention is a property that causes the normal body WIjr1 addition phenomenon, and is determined by the following method.

That is, a test solution consisting of 28 parts of a 5% aqueous solution of sodium alginate, 27 parts of a sample compound, and 45 parts of water was applied to a molded product that had been dry-heated at 180°C for 60 seconds, and heated at 100°C for 4 minutes. After drying, when treated with superheated steam at 170° C. for 7 minutes, a molded article that causes a shrinkage phenomenon in the portion of the surface of the molded article to which the compound is attached is determined to have swelling ability. In this case, the greater the degree of shrinkage, the greater the a-wetting ability, but the effects of the present invention are not controlled by the magnitude of this swelling ability.

Types of such compounds include, for example, rest'i￥f
Examples include acid derivatives, santylic acid derivatives, phenol derivatives, diphenyl derivatives, naphthalene derivatives, halcoglycated benzene derivatives, phenylmethane derivatives, and terephthalic acid derivatives.

Specific examples include benzoic acid, methyl benzoate, phenyl rutylate, A-paraphenylphenol,
Compounds having various aromatic nuclei and naphthalene nuclei such as paraphenylphenol, trichlorophenol, diaminodiphenyl, bromonaphthalene, dichlorobenzene, triphenylchloromethane, and methyl terephthalate can be exemplified, but are limited to these examples only. However, any compound that satisfies the above requirements can be applied. Such compounds can be applied alone or in combination of two or more.

These compounds are usually used in an amount of 0.1% by weight or more, preferably 1% by weight or more.

A dye solution prepared by blending such a compound with a dye is 1
By using it, for example, acidic dyes that have not been dyed into synthetic polyesters and polyesters can be applied.

(According to the present invention, 83 □ addition, sulfur-containing., 4 configuration 1) are combined, and by doing so, a richly colored product can be obtained.

The sulfur-containing compound used in the present invention may be any inorganic or organic compound as long as it contains sulfur.

Specific examples of such compounds include mechabutanes, sulfides, disulfides, polysulfides, sulfoxides, sulfones, sulfocarbamides and their m1 forms, as well as sulfonyls such as sulfonyl hydrazide, etc. sulfur, sulfur dioxide,
Sodium sulfate, sodium sulfide, 1M sodium thio, sodium sulfite, sulfur dichloride, -chloride@yellow, thionyl chloride, sulfuryl chloride, ammonium persulfate, [
l! Examples include ntaat sodium, fiAM human O-xylamine, phosphoric acid, and sulfamic acid.

Among the sulfur-containing compounds mentioned above, sulfocarbamide, particularly thiourea, provides a preferable deep dyeing effect in the present invention.

Such thiourea is usually produced by adding hydrogen sulfide from lime nitrogen in a cyanamide aqueous solution or by adding hydrogen sulfide in lime nitrogen mud, or by heating and melting ammonium thiocyanate, cooling, pulverizing the ingot, and then producing thiourea. It is produced by a method such as extraction with a concentrated ammonium acid solution and crystallization from the extract. Examples of tautomers and derivatives of thiourea include isothiourea, tetramethylthiourea, thiourea formaldehyde dimethylolthiourea, and these are also effective.

Although the mechanism of action of such sulfur-containing compounds is not clear,
Probably the shadow r, l of the solid particulate compound used in the present invention
l! It is presumed that it has the effect of promoting i- in a sweet manner.

A good effect on scales and moths can be obtained by blending the sulfur-containing compound in the dye liquor in an amount of 0.3 to 20.0% by weight, preferably 15 to 10.0% by weight.

If it is used in an amount exceeding 20!1 ffi%, the hardening of the hand becomes dull and results in poor tE.

In the dye liquor of the present invention, the deep color effect can be further promoted by making it more alkaline. More preferably, alkalinity with a pl-18 or higher is more effective. If necessary, add an alkaline agent to the W R'(T).

Such alkaline agents include metals such as alkali metals such as sodium, potassium, and lithium, alkaline metals such as calcium, magnesium, and barium;
! Light and salt combination; power, existence F! In addition to salt compounds, examples include quaternary ammonium hydroxide vyJ and amine compounds.

Particularly preferred alkali agents include alkali metal compounds such as sodium chloride, phosphorus-resistant butryum, notrium carbonate, etc., and alkali metal salts of sulfur-containing compounds such as sodium sulfide, sodium iiiate, potassium sulfate, and the like.

Such an alkaline agent is sufficient as long as the dye liquor becomes alkaline, but it is usually added in an amount of 0.1 to 30% by weight, preferably 13 to 20% by weight, for wave removal.

A smoothing agent can be added to the present invention, if necessary. Smoothing agents have the characteristics of improving flexibility and sharpness. In particular, when used for R&fiber fabrics, the drape properties of the fabrics are greatly improved, and it has the effect of more effectively expressing the vividness and overnight dyeing properties of dyed products.

Such a smoothing agent is used in the dye liquor by blending it in an amount of 0.1 to 10 Qffi%, preferably 0.5 to 7 Qffi%. The blending amount is 10!
r! If it exceeds ffi%, the deep dyeing property will be reduced, and furthermore, the fastness will be reduced.

Examples of such smoothing agents include silicon compounds, fluorinated compounds, waxes, paraffins, lanolin, and the like, as well as surfactants that improve smoothness and flexibility.

Examples of the above-mentioned smoothing agents include methylhydrodienepolysiloxane, dimethylpolysiloxane, perfluoromonocarboxylic acid salts, acrylic and fluorinated alkyl esters, fluoroethoxymethylurea, aluminum stearate, zirconium oxychloride, and vinegar. By using zirconium or stearol, for example, acid dyes that have not conventionally been dyed on synthetic resins or polyesters can be dyed with spring color.

According to the present invention, a sulfur-containing compound is further added to the dye liquor, thereby making it possible to obtain a colored product with a wide thickness.

The sulfur-containing compound used in the present invention may be any inorganic or organic compound as long as it contains sulfur.

Examples of such compounds include, for example, mecabutanes, sulfides, disulfides, polysulfides, sulfoxides, sulfones, sulfocarbamides and their derivatives, as well as sulfonyls such as sulfonyl hydrazide, etc. sulfur, sulfur dioxide,
Sodium sulfate, sodium sulfide, thio[1 sodium, sodium sulfite, sulfur dichloride, -sulfur chloride, thionyl chloride, sulfuryl chloride, ammonium persulfate, m
Examples include uiw sodium, human O-xylamine sulfate, chlorosulfonic acid, and sulfamic acid.

In the present invention, among the above-mentioned sulfur-containing compounds, thiourea gives a preferable deep dyeing effect to sulfocarbamide and Fl.

Such thioureas are usually prepared from lime nitrogen to cyanamide water.
Hydrogen sulfide is added in BF&, hydrogen sulfide is added in lime-nitrogen mud, or ammonium thiocyanate is heated and melted, and after cooling, the ingot is crushed and then oiled with concentrated ammonium thiocyanate liquid, and the extract is T1 is produced by a method such as obtaining from a crystallization method. Tautomers and derivatives of thiourea include isothiourea, tetramethylthiourea,
Thiourea, formaldehyde, dimethyl 0-ruthiourea, etc. are also effective.

Effects of such sulfur-containing compounds! ! ! Although the mechanism is not clear, it is presumed that it has the effect of significantly promoting the swelling ability of the solid particulate compound used in the present invention.

The sulfur-containing compound is 0.3 to 20.0 ffim% in the dye liquor.
, preferably 0.5 to 10.0% by weight, good effects can be obtained.

OHM, C00I-II, Sos HE4, but metals such as chromium are present during the dyeing process (the ratio of the dye component to the metal is 1 = 1 or 2).
:1) are also effective, and specific examples include leveling type acid dyes, milling type acid dyes, and i-type dyes.

The dye liquor of the present invention can be applied to molded articles by any suitable dyeing method such as puffing, showering, spraying, coating, foaming, dipping, etc. Among them, printing, coating, and foaming methods are preferred from the viewpoint of the concentration of the agent to be treated on the surface to be treated.

After applying the dye liquor, a heat treatment is performed, and the heat treatment may be either dry heat or wet heat, but the temperature condition must be at least higher than the secondary transition point of the polymer constituting the molded article. The effects of the present invention cannot be obtained under such conditions.

This heat treatment is a process in which the solid particulate compound diffuses the dye into the molded article, and conditions are preferably selected to allow the compound to adhere to the molded article. However, this fusion requires a very high temperature (t), but the dry heat method requires a temperature of 130°C or higher, preferably 150 to 25°C.
Achieved culmability in 5 seconds to 20 minutes at 0°C. Even with a dry heat method, if flame treatment or the like is used, it can be achieved in an even shorter vI of 5 seconds or less. Moist heat method For example, when using saturated steam, it is achieved at 95°C or higher, preferably 100 to 165°C, for about 15 seconds to 60 minutes, and with superheated steam, it is achieved at 120°C or higher, preferably 140 to 200°C, for about 60 seconds to 60 minutes. .

Molded articles subjected to such heat treatment are subjected to regular cleaning and reduction cleaning as necessary. This step is essential especially when the dye liquor is used in an alkaline state.

(Example) Example 1 Reduction of ff1tll of Fujigumi (“Tetron” 50D silk made by Toshi Co., Ltd.) made of 100% polyester
The following dye solution was screen applied to one side of the treated product.

[Paste] Fine Gum 1-IT-1062, 0 parts (sizing agent manufactured by Daiichi Kogyo Co., Ltd.) Indal Cuff 40 6.5 (Cesa
Thickening agent manufactured by lpinia) Sodium alginate 0.7 water
90.8
100.0 parts dye liquor composition] Paste 30% by weight paraphenylphenol (granular) 27 Thiourea 3 Silicon 5H-
82405 (dimethylolsiloxane: manufactured by Toray Silicone) Sodium sulfate 5C1, No.
acid red 1143 water
27 Theater After applying 100% by weight of the above dye composition to the treated fabric, it was dried at 120°C for 4 minutes, and then color development treatment was performed using superheated steam at 160°C for 0 minutes. Next, this fabric was treated with Hydrolylnoide Iq/
12. Sodium hydroxide (30' Be = >0.5
g/M, temperature 90℃ including non-ionic detergent 0.5g/σ
Reduction cleaning treatment was carried out in a bath for 15 minutes, followed by washing with hot water and water.

Although the finished product is unmodified polynisal 4JJ, it has a deep red a (+) color due to the milling type acid dye.
- value: 33.1>.

For comparison, two formulations were processed and finished in the same manner as in this example, one excluding paraphenylphenol and one excluding thiourea and 1-lium sulfate from the above dye composition.
The values were 65.2 and 93.8, respectively, and no color was developed.

Note: For L4fi, a value measured with a Macbeth spectrophotometer model MS-2000 was used. Items with small numbers (indicates that they are dyed very deeply).

Example 2 Same as Example 1. However, the I)H was changed by adding a pl-1 regulator such as sodium sulfate to the dye liquor, and the change in the L value was examined. The results are shown below.

pi-I L value Sodium sulfate O weight% 7.5 38.1
2 N 8.2 36.710〃9.53
4.2 20,, 11.0 34,4 acetic acid
5% by weight 2.3 61.5 In the table: Acetic acid refers to the dye composition of Example 1 in which acetic acid was used in place of sodium sulfate.

From the table above, it can be seen that when the pH is on the alkaline side, deep dyeing occurs, and the degree of dyeing increases as the pH increases, preferably 8 or higher, preferably 9 or higher. In addition, on the acidic side, there was almost no coloration, and the result was only staining.

Example 3 According to Example 2, the relationship between the amount of thiourea added and the L value was investigated.

However, as the fabric to be treated, a strongly twisted fabric with a length of 50D "de 1 to long" and a width of 75D "tetron" was used.
The color development treatment was performed using a 1-IP steamer at 125° C. for 30 minutes.

(Amount of thiourea added) (L value) O small (to) %
47.9 0,”I n 46.60.5n
39.4 1 39, 0 3 37.3! 'i 33.11C133,
5 2 (135,3 3040,3) As a result, if the amount of thiourea added is less than 0.5% by weight, effective deep dyeing cannot be obtained. It was found that the dyeability was rather reduced and the shrinkage of the fibers was increased, which was not preferable.

Example 1 A reduced scouring product of Habutae made of 100% Poly Nisful (using Tetron 70D silk manufactured by Toshi Co., Ltd.) was coated on one side according to Example 1, and heated with superheated steam at 160°C for 6 minutes. Finished with treatment and reduction cleaning.

However, the dyes used were C1, No. and Acid Blue 92.

The evaluation results for tithing items are as follows.

Color fastness JIS l-0844: Washing fastness grade 4, J
IS 1--0849: Rubbing fastness grade 4, J
IS L-, 0842: Light fastness 20 hours or more
Both the 4th grade JIS l-0860:1 to ply-leaning fastness grade and the 5th grade JIS l-0850 near iron sublimation fastness showed excellent color development.

Example 5 One sheet of double digit A and a conventional disperse dye C1 prepared in Example 1,
A solvent (trichlorethylene) was added dropwise to each of the colored products (No. 60 was used) and left on the filter paper at room temperature for an hour. Afterwards, we observed the degree of coloring of the filter paper, and found that the filter paper with the disperse dye colored product was colored red.
No color transfer was observed on the filter paper on which the product of the present invention was placed.

Eggplant Example 6 The same treatment as in Example 1 was carried out. However, the following sulfur-containing compound was used instead of thiourea.

Sulfur-containing compounds L value mercap 1
~Benzothiazole 33.5 Cyclohexylamine salt of 2-mercaptobenzothiazole 39.1 Tetramedyldiuram disulfide 44.4 For comparison, the same treatment except that no sulfur compound was added, but L
The value was 68.5, indicating that there was no coloring at all and the level of staining was high.

Example 8 The treatment was carried out according to Example 1. However, 3% by weight of sulfur powder was used instead of thiourea. The L value was 36.6 and a deep red color was obtained.

Example 9 The treatment was carried out according to Example 1. However, the same treatment was performed except that 3% by weight of sodium sulfide was used instead of thiourea. After reduction washing treatment and finishing, the 1-value was /IO,5, not 1;3, a bright red dyed product was observed.

(Moving Bed of the Invention) The present invention can achieve vivid and mild dyeing properties as well as extremely good color fastness using various dyes.

In particular, according to the present invention, it is possible to add polarity to hydrophobic synthetic resin molded products such as polyester, which was previously thought to be impossible.
The characteristic feature is that dyeing can be achieved stably and with good durability even when dye R31 is used.

Claims (2)

[Claims] (1) A method for dyeing a synthetic resin molded article, which is characterized in that when dyeing a synthetic resin molded article with a dye liquor containing a solid particulate compound having swelling ability, a sulfur-containing compound is blended into the dye liquor. (2) A method for dyeing a synthetic resin molded article according to claim (1), wherein the dye liquid is alkaline.