JPS599672B2 - Artificial leather surface coating modifier - Google Patents

Description

[Detailed description of the invention] The present invention relates to an artificial leather surface coating modifier.

There has been remarkable progress in artificial leather. However, current technology cannot satisfy some unique and excellent properties of natural products. Although it has some advantages, it is still desired to improve its moisture permeability, processability, and the unique and excellent appearance and feel found in natural products. Although the properties of artificial leather are influenced in part by the composition and structure of the substrate, they are largely influenced by the surface coating.

In particular, factors such as softness, feel, texture, etc. that are sensually evaluated by humans are greatly influenced by the surface coating. Modification of the surface coating of artificial leather has been investigated from various angles, and although significant progress has been made, satisfactory effects have not yet been achieved.

Surface coverings such as artificial leather are made by attaching or coating solutions of various synthetic polymers and paints, or by laminating these films together. The properties of the film can be improved by variously modifying the structure of these polymer materials, such as improving toughness,
Urethane elastic materials have excellent stretchability, amino acid materials are highly flexible, and polyamide materials are strong and have a dry feel.

In particular, polyamino acid-based leathers are expected to have properties similar to natural leather in that they have a polypeptide structure, but satisfactorily results have not been achieved. Also, φ tends to be inferior in terms of elongation and adhesion. Plasticizers are generally added to improve resin defects. These plasticizers include dioctyl phthalate,
Dioctyl adipate, tricresyl phosphate, etc., as well as N-ethyltoluene, sulfonamide, etc. are used. In addition, it has been proposed that similar substances such as fatty alcohols, fatty aldehydes, fatty carboxylic acids, and other esters and ethers be added to modify the compositional structure of the film in the preparation of the film (Japanese Patent Publication No. 48
14939, Special Publication No. 43-4665, etc.). Furthermore, sorbitan stearate, cetyl alcohol, etc. are generally used as film softeners, and in addition, phosphoric acid esters (Japanese Patent Publication No. 47-31002), epoxy or chlorinated fatty acid esters (Japanese Patent Publication No. 48-19922), etc. are used. There is.

However, the effects of conventionally proposed softening agents such as general plasticizers and film structure modifiers are unsatisfactory, and even if they are relatively flexible, they only produce artificial, fiber-like catalysts. First, I am not satisfied with the tactile feel unique to natural leather, especially its "slimy feel." As a result of studying the modification and improvement of the surface coatings of these artificial leathers, the present invention has found that it is possible to create a coating that has a texture extremely similar to that of natural products, which could not be obtained by conventional methods, leading to the present invention. The present invention is an artificial leather surface coating modifier comprising lanolin, lanolin alcohol, lanolin fatty acid or derivatives thereof.

According to the present invention, while maintaining the excellent surface film strength and properties of the synthetic polymer constituting the artificial leather surface coating,
It is possible to obtain the excellent moisture permeability and weather resistance found in natural leather and the like, as well as surface film properties that give a soft, slimy feel with a natural texture.

Generally, the strength of a synthetic polymer is significantly reduced by the addition of a modifier, but in the case of the modifier of the present invention, the decrease in strength is small.

The leather surface coating to which the present invention is directed refers to the surface coating of a single material or a composite material in artificial leather such as leather synthetic leather or artificial leather.

These surface coatings are composed of single or copolymers of polyurethane, polyamide, polyamino acid, polyacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, cellulose acetate, and the like.

A surface coating is formed by adhering, coating, film laminating, etc. a solution of these polymers or a paint onto a substrate made of fibers, resins, fibers, resins, etc. The modifier of the present invention is lanolin and a series of substances derived therefrom, namely lanolin-related substances consisting of lanolin obtained from wool fat, lanolin alcohol which is a hydrolyzate thereof, lanolin fatty acid and various derivatives thereof. Lanolin includes reduced lanolin and liquid lanolin, and lanolin derivatives include ethylene oxide adducts, propylene oxide adducts, acetylated products, sulfated products, and salts thereof.

Lanolin alcohol also includes lanolin alcohol low melting point substances, and lanolin alcohol derivatives include lanolin alcohol adducts with ethylene oxide, propylene oxide adducts, mixed adducts of both oxides, fatty acid esters, sulfuric esters and their salts, phosphoric esters and Refers to its salts, acetylated products, sulfuric esters of ethylene oxide adducts, and salts thereof. Lanolin fatty acid derivatives are soaps of lanolin fatty acids, ethylene oxide adducts, propylene oxide adducts, diethanolamides, glycerade (mono, di, tri and mixed glycerade), esters with polyglycerols, esters with aliphatic mono- and diols. , esters of sorbitan, sorbite, and sorbitol, esters of pentaerythritol, and esters with sucrose.

Among these lanolin and related substances, those having particularly excellent effects include lanolin fatty acids, soaps thereof, ethylene oxide adducts, glycerin esters, polyglycerin esters, and ethylene oxide adducts of lanolin alcohol. The lanolin shown here is obtained by extracting the wool grease that adheres to wool and refining it through physical or chemical treatment.The lanolin fatty acid is obtained by separating the acid component from the saponified decomposition product of lanolin. Lanolin alcohol is a collection of alcohol components from the saponified decomposition product of lanolin, and lanolin fatty acids and lanolin alcohol are not single compounds, but alcohol contains a high percentage of styrene, especially cholesterol (approximately 30%). Both alcohol and fatty acids have few straight chains, most are branched at the ω position, and the number of carbon atoms is widely distributed from 9 to 34, including a considerable number of carbon atoms, and a considerable amount (about 30%) of fatty acids. It consists of a complex and unique mixture of oxyacids (EV.Truter.J.S.O.
c. COsm. Chem. 1962) 0 In order to apply the modifier of the present invention to the surface coating of artificial leather, there is a method of adding the modifier to a solution or emulsion of a polymer for forming the surface coating of artificial leather, and a method of adding the modifier to the formed artificial leather surface. Methods include dipping, spraying or brushing the coating in a solution or emulsion of the modifier. Solvents that can be used to prepare solutions of the above polymers and modifiers include dimethylformamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl ethyl ketone, tetrahydrofuran, and water, methanol, isopropanol, ethylene glycol, etc. can.

When the above polymer and modifier are used in an emulsion system, the emulsion is prepared by a conventional method.

In particular, when creating an emulsion of polyurethaneurea, which is said to be extremely difficult to create a stable emulsion, the use of ethylene oxide adducts such as lanolin fatty acids and lanolin alcohol, and their sulfate ester salts exhibits extremely excellent emulsifying properties. , a stable emulsion can be made. Furthermore, films coated with emulsions made with these lanolin-based activators have superior flexibility and sliminess compared to cases where other activators are used. Therefore, it has outstanding characteristics as an emulsifier for stable and excellent urethane urea emulsions. Furthermore, an emulsion can also be prepared by combining these lanolin-based activators with conventional sulfosuccinates, alkyl alkylene oxides, and the like. To make the film durable,
A method of adding the modifier to the polymer solution or emulsion is preferred.

When the modifier is added to the film-forming polymer solution or emulsion, the amount of the modifier of the present invention relative to the coating is 100 to 3% by weight, preferably 40 to 5% by weight (dry amount) of the polymer.
Added. If it is too much, there will be disadvantages such as stickiness of the film, and if it is too little, the effect will be weak. When the coating is immersed in a solution or emulsion of a modifier, the modifier is added in an amount of 20 to 0.2% by weight, preferably 10 to 0.5% by weight, based on the coating.
(Dry amount) It is desirable to adhere.

In these uses, general plasticizers such as dioctyl phthalate and dioctyl adipate can also be used.

Further, as a method for the immersion treatment, the material is dissolved and dispersed in the above-mentioned solvents, especially water, and then heated to room temperature or 40 to 80 DEG C. for treatment.

It is also possible to use a general surfactant for solubilization and dispersion.

The activator may be anionic, cationic, or nonionic, but it is preferable to use an activator derived from lanolin fatty acid and lanolin alcohol. In addition, additives such as carbon black, titanium oxide, pigments,
Dyes, stabilizers, etc. can also be added. The modifier of the present invention does not react with these additives, therefore,
There is no need to worry about the effect on additives. Although the mechanism by which the modifier of the present invention softens the film is not clear, many hydrogen bonds and other weak secondary bonds are formed between the molecules of the substrate and the polymer forming the surface film. It is said to have a tight network structure, and it is thought that the modifier penetrates into these intermolecular structures, weakens these secondary bonds to some extent, and changes the internal structure as a whole into a soft one.

According to the modifier of the present invention, antistatic properties, moisture permeability, moisture absorption, weather resistance,
It also exhibits effects such as anti-mold and anti-bacterial properties, contributes to ease of handling, ease of organization, richness, etc., and there is no fear of toxicity.

The artificial leather coating modified by the present invention can be applied to furniture, automobiles, bags, shoes, sandals, clothing gloves, stationery cases, etc.
Applicable to products such as book spines, building materials, and belts.

Next, typical examples of the present invention will be shown.

Parts and percentages in the examples are based on weight. Example 1 Molecular weight 1 consisting of 1,6 hexanediol and adipic acid
50 parts of diol 000 and 25 parts MD were reacted at 90°C for 2 hours and dissolved in dimethylformamide (DMF).
% concentration.

Next, DMF in which 9.9 parts of diaminomethane diphenyl was dissolved was gradually added dropwise to the solution to give a final concentration of 25%.

This was reacted at 80'C for 4 hours to obtain a polyurethane composition. For 100 parts of this composition, 5 parts of each modifier listed in Table 1
1 part, and heated to 60°C to uniformly dissolve.

This polyurethane urea solution is applied to a thickness of 1.5 mm on a glass plate, immersed in a 40% DMF aqueous solution coagulation bath at a temperature of 50°C to coagulate, remove the solvent, and dry to obtain a film. Table 1 shows the Young's modulus and tactile quality of this film.

Example 2 120 parts of a polyol of maleic acid and hexamethylene diol with an average molecular weight of 1200, 24 parts of polyethylene glycol with an average molecular weight of 1000, 80% of 2.4-tolylene diisocyanate, 20% of 2.6-tolylene diisocyanate
32 parts of the mixture was reacted in a nitrogen gas stream at 60° C. for 16 hours with stirring to obtain a prepolymer.

To this prepolymer, 5 parts of sodium di-2-ethylhexylsulfosuccinate (purity 70%) and 4 parts of each modifier listed in Table 2.
Add 300 parts of water, stir evenly, and keep at 5°C.

Next, add 4 parts of ethylenediamine to 100 parts of water prepared separately.
A partially dissolved aqueous solution kept at 5° C. is quickly added to the above solution while stirring vigorously to terminate the reaction.

The obtained emulsion was spread on a glass plate to a thickness of 0.1 mm, left at room temperature for 24 hours, and then heated at 100°C for 30 minutes.
Heat for 1 minute to obtain a film.

The physical properties of the obtained emulsion and film were as shown in Table 2.

Example 3 Synthetic leather made of urethane urea was
-1rL and treated under the following treatment conditions.

Processing conditions 1 Concentration: 5% aqueous solution 2 Temperature, time: room temperature, 20 minutes 3 Bath ratio, squeezing: 1:20, 100% squeezing 4 Drying:
The feel of the leather treated under the conditions of 10'C x 3 minutes or more was evaluated by a panel of five people, and the effects were determined by the following method.

◎ 4 or more people recognized the soft and slimy feeling 〃3 people △ 1 person 〃 × No one recognized the effect The judgment results are shown in Table 3.

The tear strength of the treated leather was determined by the JISL-1004 tear strength test, and the results are shown in Table 4.

When the abrasion fastness of the treated leather was tested using the JISL-0849 abrasion fastness test method, it was found that lanolin fatty acid ethylene oxide adduct ('p=3), lanolin alcohol ethylene oxide adduct (lower 15), lanolin fatty acid glycerin diester, In both the wet and dry processes modified with lanolin fatty acid soap (Na), there was no significant difference from additive-free products.

The dry-cleanability of the treated leather was tested by washing with 0.5% commercially available detergent (Genbu Clean PH, manufactured by Gemp Co., Ltd.) and perchlorethylene, drying and tactile evaluation. As a result, lanolin fatty acid ethylene oxide adduct ( J5=3
), same ('p=10), and it was confirmed that the product modified with lanolin fatty acid glycerin monoester was sufficiently flexible and had a slimy feel. Example 4 A mixture of the following composition is applied onto a Tetoron cotton mixture and dried to produce a leather-like material.

When the treated leather-like material was evaluated, the results shown in Table 5 were obtained.

Example 5 To a mixture of 625 parts of nylon, 15 parts of N-methoxymethylated nylon, 70 parts of zinc chloride, and 100 parts of methyl alcohol, 20 parts of each modifier shown in Table 6 was added to prepare a solution.

Each solution was coated on a glass plate and placed in water at 30°C for 3 hours.
After being immersed for 0 minutes to form a film and desalting, it was peeled off from the glass plate and air-dried to form a porous wet film with a thickness of 0.15±0.05 mm.

Claims (1)

[Claims] 1. An artificial leather surface coating modifier consisting of lanolin, lanolin alcohol, lanolin fatty acid or derivatives thereof.