JPH02185256A - Aromatic sheet-like material having silver surface layer - Google Patents

Abstract

PURPOSE:To provide the above material which has a long preservation period and obviates the desorption of the adsorbed matter of a perfume from a resin by washing by incorporating an org. solvent soln. of polyurethane elastomer contg. microcapsules in which an arom. material is included into the silver surface or base body. CONSTITUTION:The prepn. of the polyurethane elastomer soln. is executed by polymerizing polyol, org. diisocyanate and low-molecular chain extender in an org. solvent having miscibility with water. The microcapsules are, for example, the microcapsules, the wall material of which is a urea-formalin resin and which have preferably 5 to 20mu particle size and about 0. 5 to 4mu wall thickness. The ratio at which the perfume microcapsules are compounded with the polyurethane elastomer soln. is preferably 1 to 25wt.% by the solid content of the polyurethane elastomer. Natural fibers, regenerated fibers, synthetic fibers or base bodies used for production of artificial leather are usable as the sheet-like base body to be coated with the polyurethane elastomer soln.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to an aromatic sheet-like material having a porous grain layer,
More specifically, the present invention relates to a sheet-like material containing microcapsules containing aromatic substances.

[Conventional technology]

Generally, organic solvents for polymers such as polyamide and polyurethane i+8? When & is solidified by treating it with a liquid that is a non-solvent for the polymer and is miscible with the solvent of the solution, the inside of the molded product is becomes a porous structure.

This polymer coagulation method is called the wet coagulation method, and compared to other coagulation methods, such as the dry coagulation method, in which the polymer is coagulated by evaporating the solvent, the molded product is generally flexible and has good moisture permeability. have. Taking advantage of this feature, we have conventionally applied 1 volume of a n't8 agent of a polymer such as polyurethane to a nonwoven fabric.
A sheet material having a porous grain layer (hereinafter sometimes referred to as a grain sheet material) is obtained by coating a woven or knitted fabric or a base material filled with a polymer in these fibrous structures and wet coagulating it. It is used as a leather substitute. On the other hand, various methods have been conventionally used for imparting aromatic microcapsules to fiber structures.

For example, a method of applying microcapsules containing an odorant and a sizing agent to a textile product (Japanese Unexamined Patent Publication No. 4919197), a method of applying a mixture of microcapsules containing a fragrance and an acrylic resin to obtain an fragrant towel fabric ( Japanese Patent Publication No. 58-4
886); A method for obtaining a printed article that emits a fragrance by printing a printing paste consisting of a microcapsule of a fragrance coated with a paste wall film, a thermoplastic substance, and a thickener (
A method for obtaining an aromatic printed material that emits an aroma by heat-transferring a special binder layer onto an object to be transferred (Japanese Patent Application Laid-Open No. 1986-1999)
106885).

[Problem to be solved by the invention]

However, such conventional methods have various drawbacks. For example, in the method of applying perfume microcapsules using a glue, the microcapsules fall off when the glue falls off during washing, resulting in poor washing durability and a hard texture. Furthermore, in the method of applying perfume microcapsules together with a resin binder, drying or low-temperature heating alone results in poor adhesion of the resin binder and poor washing durability. In addition, if heat fixation is performed at high temperature after drying, the adhesion will improve, but the high temperature will change the quality of the fragrance, destroy the microcapsules due to vaporization of the fragrance, and cause the resin to penetrate, resulting in a hard texture. There is a drawback. Methods in which fragrance is adsorbed to porous powder or resin and applied using a glue or resin binder provide sustained release, but the initial release of fragrance is low and the effect is inferior, and the fragrance does not release during storage. However, the storage space is short, and the adsorbed fragrance material is easily removed from the resin during washing, resulting in poor washing durability.

Furthermore, the method of directly applying a fragrance together with an adhesive, a-material, and a resin binder has the disadvantage that the preservation of the fragrance is extremely poor and the washing durability is also poor.

In addition, although the method of melt-spinning a fragrance into a synthetic fiber polymer is durable, it may impair the basic physical properties of the thread (strength, elongation, etc.), the compatibility of some fragrances may be poor, or the fragrance may have a low boiling point. They cannot be used, have limited scents, and those that undergo post-processing (dying, finishing) have the drawbacks of being limited in processing and not being able to process a wide variety of scents.

In view of the drawbacks of the prior art, the present inventors have conducted intensive studies on a silver-faced sheet-like product that has an aroma without having any problems in terms of quality or production. By incorporating an organic solvent solution of a polyurethane elastomer into the root surface or the substrate, this requirement can be satisfied.
Having learned that it is possible to provide a silver-faced sheet-like product with a fragrance useful as a leather substitute, particularly for shoes, clothing materials, interior materials such as car seats and chair upholstery, and materials for bags, we have completed the present invention. It's arrived.

[Means for solving problems]

That is, the present invention provides a sheet-like article having a silver layer formed by coating a water-miscible organic solvent solution of a polyurethane elastomer on a sheet-like substrate and wet-coagulating the same, in which microcapsules encapsulating an aromatic substance in the polyurethane elastomer solution are provided. and an aromatic sheet-like article having a silver layer, characterized in that the sheet-like substrate contains microcapsules encapsulating an aromatic substance. be.

The polyurethane elastomer used to form the porous grain layer in the present invention may be any wet-type polyurethane elastomer normally used for porous sheet-like substrates such as artificial leather, and is not particularly limited. An elastomer is composed of a polyol having hydroxyl groups at both ends, an organic diisocyanate, and a low molecular chain extender.Specifically, the polyol includes polyethylene ether glycol, polypropylene ether glycol, Polyalkylene ether glycol with hydroxyl groups at both ends such as polytetramethylene ether glycol, polyhexamethylene ether glycol, or polyethylene adipate glycol, polypropylene adipate glycol, polyethylene propylene adipate glycol, polybutylene adipate glycol, polyethylene butylene adipate glycol , polypentamethylene adipate glycol, polyethylene sebacate glycol, and polyester glycols having hydroxyl groups at both ends, such as polycaprolactone obtained by ring-opening polymerization of lactone. Examples of the organic diisocyanate include diphenylmethane-4,4'-diincyanate.

Examples include tolylene-2,4-diisocyanate, xylylene diisocyanate, dicyclohexylmethane-4°4'-diisocyanate, hexamethylene diisocyanate, and the like.

In addition, as a low molecular chain extender, ethylene glycol
Propylene glycol, butylene glycol 5 pentamethylene glycol, diethylene glycol, tetraethylene glycol, N-methyljetanolamine, p,
p'-diphenyloalkane, hydrazine, 1.2
-propylene diamine hexamethylene diamine, p,
Examples include p'-diaminodiphenylmethane.

In the present invention, other molding polymers, such as polyamide, polyacrylonitrile, polyvinyl chloride, etc., may be used in combination with the polyurethane elastomer, as long as they do not impede the quality of the product or the manufacturing process. The mixing ratio varies depending on the polymer and cannot be generalized, but it is generally recommended to be 30% by weight or less based on the polyurethane elastomer.

Dimethylformamide is suitable as the organic solvent for preparing a water-miscible ta'lB agent solution of polyurethane elastomer (hereinafter referred to as polyurethane elastomer solution), and dimethylacetamide, dimethylsulfoxide, etc. can also be used. The concentration of the polyurethane elastomer should not be too low from the viewpoint of the fullness (strength of elasticity) and strength of the resulting sheet-like product;
A range of % by weight is suitable.

Such a polyurethane elastomer solution can be prepared by polymerizing a polyol, an organic diisocyanate, and a small chain extender in a water-miscible organic solvent as described above, or by polymerizing these components in the absence of a solvent. This can be accomplished by well-known methods such as dissolving the polymer in the water-miscible organic solvents mentioned above.

On the other hand, the microcapsules referred to in the present invention are, for example, a wall material made of urea-formalin resin, a particle size of 2 to 50 μm, preferably 5 to 20 μm, and a wall thickness of 0.1 to 20 μm, preferably 0.5 μm.
5-4μ or the wall material is melamine-formalin resin, the particle size is 5-50μ, preferably 5-20μ, the wall thickness is 0
．． The thickness is about 2 to 30μ, preferably about 0.5 to 6μ.

In addition, the aromatic substances include natural fragrances, synthetic fragrances, and compounds that generate fragrances, either in liquid form or in powder form, either singly or as a mixture. Natural fragrances include animal fragrances such as musk 1, castorium 1, ambergris, etc., and vegetable fragrances 14 include lemon oil, rose oil, citronellan, white 112 mountain,
Peppermint mountain, cinnamon oil, etc. Further, as synthetic fragrances, there are mixed fragrances made of α-pinene, limonene, geraniol, linalool, lavangerol, nerolidol, and the like.

The amount of the fragrance microcapsules added to the polyurethane elastomer solution is usually 0.2% by weight or more, more preferably 1 to 1% by weight based on the solid content of the polyurethane elastomer.
25 double stars%. Aromatic microphone + 1 power psel combination value is 0
．． In the case of double ring% Miura, the aromaticity of the silver-faced sheet material obtained is small, and the improvement effect is insufficient, as is not much different from the case where it is not blended. Although there is no particular limit on the upper limit of the blending amount from the viewpoint of aromatic properties, if the blending amount is too large, the mechanical properties of the porous grain layer formed after wet solidification will deteriorate, so it is generally limited to about 25% by weight. It is desirable to do so.

In the present invention, the sheet-like substrate to which the above aromatic microcapsule-containing polyurethane elastomer melt is applied is as follows:
Natural fibers, recycled fibers, synthetic fibers, or their lR@
Fabrics made of fibers, knitted fabrics, non-woven rubber, or substrates obtained by filling polyurethane elastomers, etc., which are normally used in the production of synthetic leather and artificial leather, can be used. An appropriate one is selected depending on the required performance, usage, etc. of the surfaced sheet material.

For example, if an internal structure and texture similar to natural leather is desired, it is preferable to use a base material obtained by impregnating and filling a three-dimensional nonwoven fabric with synthetic rubber or polyurethane elastomer.

The process of producing a sheet-shaped article with a granite surface using the above-mentioned aromatic microcapsule-containing polyurethane elastomer solution and a sheet-shaped substrate can be carried out according to a conventional method.

For example, a polyurethane elastomer melt containing aromatic microcapsules, optionally pigments.

The above-mentioned sheet form is prepared by adding coloring agents such as dyes, heat/light stabilizers, anti-aging agents such as antibacterial agents, anti-mold agents, etc., and adjusting the solution concentration (solid content) within the specified range. Generally, 100 to 1500 g/m, preferably 200 to 1000 g/m, is applied to the body using a reverse roll coater, knife coater, etc.
m'' coating amount, immersed in an aqueous medium, i.e. water, or a mixed system of water and a solvent for polyurethane elastomer for wet coagulation, followed by washing with water (removal of solvent).
By drying, a silver-faced seal is obtained.

The silver-faced sheet material of the present invention obtained in this way can be used as is, or if necessary, a colored finishing layer can be further formed on the surface thereof so as not to reduce the aromatic property as much as possible.

Further, in the present invention, the sheet-like substrate may contain microcapsules containing an aromatic substance. In that case, the aroma microcapsule content of the sheet-like substrate is 0.2
~20% by weight is preferred.

A method for applying aromatic microcapsules to the substrate side of a sheet with a granite surface is, for example, a method of mixing aromatic microcapsules into polyurethane elastomer, synthetic rubber, etc. and filling the mixture, or a method of adding an aqueous treatment liquid containing aromatic microcapsules. There are methods of applying it to a substrate by a coating method, a gravure method, a spray method, and the like.

According to the present invention, it is possible to produce the above-mentioned silver-plated sheet material with excellent aromatic properties using the simple scraping method described above without requiring any special measures in each step such as the coagulation step. Furthermore, the resulting notebook exhibits mechanical properties, such as bending resistance, which are as high as those without aromatic microcapsules.

〔Example〕

The method of the present invention will be explained in more detail with reference to Examples below.

It should be noted that all parts and percentages in the examples refer to weight unless otherwise specified. In addition, as shown in the examples,
The methods for measuring tensile strength, elongation at break, tear strength, and bending resistance are as follows.

(1) Tensile strength, elongation at break, and tear strength JIS
The method for K-6550 was followed.

(2) Bending resistance According to the method of JIS K-6545.

(3) Fragrance It is shown as the average value of the score of the silver-faced sheet material itself and when bent according to the method of JIsK-6545, evaluated by 10 testers based on the criteria shown below.

5: Optimal scent 4; Slightly less 3: About half 2; Slightly present; Almost none 0: No Example 1. Comparative example 1. 2 Using a 6-nylon stable with a fineness of I, 0 denier, and a fiber length of 51 mm, a web was created using a card and a cross wrapper, and the web was passed through a double-needle lono car loom, and needles of 1000 wood/cm" were inserted from above and below. Punching was performed, and the weight was 150 g/m'' and the thickness was 1. A three-dimensional nonwoven fabric with an apparent density of 0.15 g/cm' was obtained.

A polyurethane obtained by reacting a cough nonwoven fabric with polyethylene butylene (l: 1 mole) having a molecular weight of 11,500, adipate glycol diphenylmethane-4,4'-diisocyanate, and ethylene glycol as a chain extender at a molar ratio of t:S:4 in dimethylformamide. After impregnating the elastomer with a 16% dimethylformamide solution so that the impregnation rate is approximately 500% per weight of the nonwoven fabric,
It was immersed in a coagulation bath (water; dimethylformamide = 8 (120 (weight ratio)) to coagulate.Next, it was immersed in warm water at 60°C for 2 hours to remove the solvent, and then
Hot air drying was performed at °C to obtain a base material filled with polyurethane elastomer.

The thus obtained base material had a weight of 1280 g/m, a thickness of 1.0 mm, and an apparent density of 0.28 g/Cm.

Next, on the surface of this base material, a particle system of 5 to 10 µm (average 8 µm) containing 80% by weight of fragrance BA7985 (jasmine-based synthetic fragrance manufactured by Takasago Fragrance Industry 01) is added to a 25% dimethylformamide solution of the same polyurethane elastomer as above. microcapsules with urea-formalin resin as wall material at 6% solid content of polyurethane elastomer
The mixed solution was doctor-coated at 400 g/m2, then immersed in a coagulation bath at 40°C [water dimethylformamide - 80:20 (weight ratio)] for 30 minutes, and then heated at 60°C.
The sample was immersed in hot water for 2 hours, thoroughly rinsed with water, and then dried with hot air at 100°C to obtain a sheet with a silver surface (Example 1).

For comparison, a dimethyl formamide solution of a polyurethane elastomer without the addition of aromatic microcapsules (Comparative Example I) and a polyurekne elastomer dimethyl prepared by adding and mixing Mi or Fragrance 2S [3A7985 in an amount of 4.8% based on the solid content of the polyurethane elastomer. Formamide?
8? & (Comparative Example 2) were applied to the base material, respectively, in the same manner as in Example 1, to obtain a silver-plated sheet.

Table 1 shows the physical properties of the sheet-like material obtained here. In Comparative Example 2, the fragrance was insufficient, but this is thought to have fallen off during the coagulation-drying process of the polyurethane elastomer.

Example 2 Example 1 was applied to the base side of the silver-plated sheet obtained in Comparative Example 1.
3% by weight of aromatic microcapsules and organopolysiloxane prepolymer emulsion (KM-2002) used in
After coating with an aqueous treatment solution consisting of 6% by weight (manufactured by Shin-Etsu Chemical)
weight%), dried and heated at 120 to 130°C for 1 minute.

The physical properties of the sheet-like material obtained here are shown in Table 1. [Effects of the Invention] The aromatic sheet-like material having a silver surface layer according to the present invention can be aromatically processed without impairing its mechanical properties and texture. It is useful for various leather substitutes, especially for shoes, clothing materials, interior applications such as car seats and chair upholstery, and materials for bags and bags.

Claims (2)

[Claims] (1) In a sheet-like article having a silver surface layer formed by coating a water-miscible organic solvent solution of a polyurethane elastomer on a sheet-like substrate and wet-coagulating the same, microcapsules encapsulating an aromatic substance are added to the polyurethane elastomer solution. 1. An aromatic sheet-like material having a silver surface layer. (2) A sheet-like article having a silver layer formed by coating a water-miscible organic solvent solution of polyurethane elastomer on a sheet-like substrate and wet coagulating the sheet-like substrate, wherein the sheet-like substrate contains microcapsules encapsulating an aromatic substance. 1. An aromatic sheet-like material having a silver surface layer.