KR20020085414A - Fragnance Slow-Releasing Artificial Leather and Preparing Method Thereof - Google Patents

Abstract

PURPOSE: An artificial leather which is characterized by having slow aromatic character because aromatic decompression fine capsule is contained in a color/pattern printed layer and/or a surface coated layer, not having an unpleasant smell of solvent and being useful for an expensive seat for a car, an outer cover for a sofa, leather clothes, a foam wall-paper, artificial leather for shoemaking, a belt, a handbag, an outer cover for a chair and an interior material of furniture, and a manufacturing method thereof are provided. CONSTITUTION: The artificial leather is obtained by a process containing the steps of: mixing 30-70wt.% of printing ink containing 10-40wt.% of solids, 30-70wt.% of surface treating agent containing 5-40wt.% of solids and 0.1-10wt.% of aromatic emitting agent to manufacture an ink-aromatic agent composition; supplying and foaming a base plate; and then printing color or a pattern on the base plate with the composition.

Description

Fragnance Slow-Releasing Artificial Leather and Preparing Method Thereof}

The present invention relates to a sustained-release artificial leather and a method for manufacturing the same, and more particularly, to an aromatic sustained-release synthetic leather and a method for producing the fragrance release agent contained in the color printing layer and / or surface coating layer. will be.

In general, artificial leather is made of pyloxine leather using nitrocellulose, vinyl leather using polyvinyl chloride paste resin and polyvinyl chloride straight resin, nylon coating leather using nylon resin, and polyurethane resin. It can be classified into polyurethane synthetic leather and the like.

In general, a method of manufacturing artificial leather as described above generally comprises a resin substrate comprising pre-gelling the resin mixture at a temperature of about 190 ° C. and plywooding a backing cloth. Providing step, foaming the substrate at a temperature of about 260 ° C. for about 3 to 5 minutes, printing step of giving color / pattern to the foamed substrate surface, treating with a surface treatment agent to protect the printed layer In addition, it consists of a surface coating step of controlling the surface glossiness. Optionally, before the surface coating step described above, a pretreatment surface coating may be performed, followed by an embossing step of forming an embossed pattern using an embosser.

Conventionally, the artificial leather as described above has a problem in that an unpleasant organic solvent odor remains for a considerable period of time, even months, after the artificial leather is manufactured due to the organic solvent inevitably mixed in the manufacturing process. In addition, even in the case of natural leather, the use of chemicals for the removal and preservation of fats and oils during the process of tanning and processing animal skins causes the characteristic unpleasant leather processing odor to remain for a considerable period of time. have.

On the other hand, various attempts have been made to suppress or use bad odors or to continually disperse good scents, and conventional representative articles include sanitary napkins, tissue paper, textiles, or clothing. Since such articles are porous, a relatively large amount of fragrance releaser is simply and easily adsorbed by instantaneous immersion of the porous pulp layer or fibrous layer in a fragrance releaser such as directional pressure sensitive microcapsule emulsions by the continuous method. I can do it. In recent years, there has been a growing interest in aromatherapy, and the interest in such fragrance products is also increasing.

However, in the case of artificial leather, since the pre-gelling temperature and the foaming temperature of the resin are high temperature of about 190 ° C and about 260 ° C, there is a problem that all of the volatile aromatic components evaporate during manufacturing. Moreover, these artificial leathers do not have a large amount of large space therein, such as pulp or fiber. Therefore, conventional directional artificial leather and its production have been recognized as not possible.

Therefore, the first object of the present invention is to provide a directional, in particular a oriented artificial leather.

A second object of the present invention is to provide a method for producing a slow-release artificial leather according to the first object of the present invention described above.

According to one preferred aspect of the present invention for achieving the first object of the present invention, by the slow-release artificial leather incorporating the fragrance release agent in the printing layer imparts a color / pattern to the surface of the artificial leather Can be achieved.

According to another preferred aspect of the present invention for achieving the first object of the present invention, it can be achieved by a pressure-sensitive directional artificial leather incorporating an aromatic release agent in the surface coating layer for surface protection and glossiness control of artificial leather Can be.

According to a preferred aspect of the present invention for achieving the second object of the present invention, in the manufacturing method of artificial leather consisting of a resin substrate providing step, foaming step, printing step, surface treatment step, the above printing step It can be achieved by a method for producing a slow-release artificial leather, characterized in that the fragrance release agent is incorporated into the printing ink to print.

According to another preferred aspect of the present invention for achieving the second object of the present invention, in the manufacturing method of artificial leather comprising a resin substrate providing step, foaming step, printing step, surface treatment step, the surface described above It can be achieved by a process for producing a slow-release artificial leather, characterized in that the fragrance release agent is incorporated into the surface treatment agent and coated in the treatment step.

Hereinafter, the present invention will be described in more detail.

There is no particular limitation on the artificial leather to which the present invention can be applied, but representative examples thereof include high-grade sheets for automobiles, outer skins for leather, leather garments, foam wallpaper, artificial leather for shoemaking, shoe-changing insoles, belts and handbags. It can be applied to leather for various purposes such as chair shell, furniture interior materials.

In the artificial leather composed of a resin sheet having a color / pattern printed layer and a surface coating layer, the sustained-oriented artificial leather according to the present invention comprises 0.1 to 25% by weight of the printed layer based on the weight of the printed layer. And / or 0.1 to 40% by weight of the fragrance release agent is included in the surface coating layer based on the weight of the coating layer.

Examples of the main raw material resin that can be used for the sustained-release artificial leather according to the present invention include polyvinyl chloride paste resins and / or polyvinyl chloride straight resins, polyurethane resins, nitro cellulose resins, and these resins. The substrate may also be nylon coated. The content of the main raw material resin may vary depending on the type of resin and the intended use. However, when the content of the resin is less than 25% by weight, the toughness and strength of the base substrate are inferior, which is undesirable. When it exceeds%, there is a possibility that the strength of the base substrate becomes so large that it becomes unsuitable as an artificial leather. In particular, when polyvinyl chloride resin is used, 20 to 35% by weight of PVC high polymerization resin and 5 to 20% by weight of PVC low polymerization resin can be mixed, and the above PVC high polymerization resin and the above PVC low polymerization degree can be used. The weight ratio of the resin is preferably 1: 1-5: 1 in terms of wettability, softness, strength and toughness of the final product.

In the production method of the present invention, PVC high polymerization resin refers to a PVC resin having a polymerization degree of about 1500 to 1900, and PVC low polymerization resin refers to a PVC resin having a polymerization degree of about 800 to 1200, but in the present invention, this is limited. Is not

As used herein, the term 'fragrance' means a volatile fragrance component, an essence such as essences, including any known components that can give a good feeling to the person, optionally, the thick water may be optionally mixed with a deodorant. have. The term 'deodorant' refers to known odor absorbing and / or masking agents such as zeolites, activated carbon, cyclodextrins, or mixtures thereof. In addition, the term 'aromatic release agent' as used herein refers to any means known in the art for sealing and releasing aroma as described herein. The term 'microcapsule' or 'composite' also refers to a release agent for retaining the fragrance and then releasing it either temporarily or continuously. As used herein, the term 'fragrance filling' refers to microcapsules at least partially filled with fragrance as defined herein. As used herein, the term 'fragrance divergence' means immediate release of fragrance from fragrance filled microcapsules containing fragrance. The term 'westward fragrance' means a fragrance fragrance characteristic by which the fragrance releaser can be maintained for at least three months or more, typically between six months and one and a half years, and preferably between one and two years.

Examples of the fragrance which can be used for the color / pattern printed layer and / or the surface coating layer in the present invention include rose, pine needle, geranium, cypress, orange, vanilla, lavender, spearmint, lemon, jasmine, ridge Gland scent, sandalwood scent, juniper scent, rosemary scent, rosewood scent, eucalyptus scent, belgamot scent, lemongrass scent, tea tree scent, neroli scent, and the like, but the present invention is not limited thereto. Is arbitrary. The above fragrance may be any of artificial or natural flavors, but is more preferable since the natural fragrance is soft but not intense.

In addition, examples of the deodorant which may be used in the present invention include about 0.01-5% by weight, preferably 0.1-2% by weight of carbon fine particles, silica gel, activated alumina, diatomaceous earth, cyclodextrin, ceramic powder, or mixtures thereof. It can also be included. Activated carbon and zeolite is an effective odor control agent having an average internal surface area of about 1000m ² / g and 400~800m ² / g, respectively. Such deodorant is preferably mainly included in the resin substrate, but may be used for color / pattern printed layers and / or surface coating layers. Commercially, Union Carbide's odor inhibitor ABESCENTS can also be used at such doses, as described in detail in US Pat. Nos. 4,795,482 and 4,826,497.

The term 'cyclodextrin' described above means any known cyclodextrin, such as an unsubstituted cyclodextrin comprising 6-12 glucose units, in particular alpha-, beta and gamma-cyclodextrins, and / or derivatives thereof, And / or mixtures thereof. Alpha-dextrin is 6, beta-dextrin is 7, and gamma-dextrin is composed of glucose units arranged in eight donut rings. The specific coupling structure of the glucose units allows the cyclodextrin to have a conical molecular structure with a constant volume of hollow interiors. The 'lining' of the internal voids is formed by oxygen atoms that are glycosidically bonded to hydrogen atoms, and the surface is hydrophobic. These pores can be filled with organic molecules having a size appropriate to their size to form a 'composite complex'. Alpha-, beta- and gamma-cyclodextrins are commercially available from the American Maize-Products Company, Hammond, Indiana under the trade name Amaizo.

Specific examples of cyclodextrin derivatives are described in US Pat. Nos. 3,426,011 to Palmerter; Farmer's US Patent Nos. 3,453,257, 3,453,258, 3,453,259 and 3,453,260; Gramera, US Pat. No. 3,459,731; Farmer's US Patent No. 3,553,191; Farmer's US Patent No. 3,565,887; US Patent No. 4,535,152 to Szejtli; US Patent No. 4,616,008 to Hirai; Brandt, US Pat. No. 4,638,058; US Patent No. 4,746,734 to Tsuchiyama; And US Patent No. 4,678,598 to Ogino. Examples of cyclodextrin derivatives suitable for use in the present invention include methyl-beta-cyclodextrin, Wacker Chemicals Inc. (USA), having different degrees of substitution (DS) sold by Amazo. Hydroxyethyl-beta-cyclodextrins having different degrees of substitution commercially available and hydroxypropyl-beta-cyclodextrins having different degrees of substitution commercially available from Aldrich Chemical Company. Derivatives are preferred.

In the present invention, a variety of deodorants may be included in addition to the cyclodextrin having a fine particle size. The addition of such additional deodorants can synergistically improve the deodorizing ability of the cyclodextrins that effectively alleviate the unpleasant organic solvent odor. Examples of such deodorants include zeolites, activated carbons, diatomaceous earth and water-soluble antibacterial compounds such as cetyl pyridinium chloride, zinc chloride, copper salts, copper ions, chlorhexadine, quaternary ammonium compounds, chelating agents, parabens, chitin, and the like. Can be mentioned. Especially preferred are zeolites of silicates / aluminates.

Suitable zeolites for use in the present invention include, but are not limited to, foamed CP301-68, foamed CP300-63, foamed CP300-35 and foamed CP300-56 and Conteka from PQ Corporation. CBV100 series.

In the present invention, when using activated carbon, it is preferable to coat the activated carbon with zeolite using a binder for aesthetic reasons.

In the production method of the present invention, a step of providing a resin substrate is first performed, and the composition for preparing a substrate is prepared from a mixture composed of 30 to 80 wt% of the main raw material resin and 20 to 70 wt% of other additives including a solvent. Optionally, it may also comprise 0.01-5% by weight of the deodorant described above.

The size of the deodorant described above is not limited and may be selected and used according to the purpose, but in the case of ceramic or zeolite, it may be about 200 to 500 mesh, and if less than 200 mesh, the particle size is too large, artificial leather It is not preferable because there is a fear of roughening the surface of the surface, and if it exceeds 500 mesh, the cost and effort for the pulverization is increased, which is not preferable because the problem of cost up becomes relatively larger.

Other additives include plasticizers, stabilizers, fillers, foaming agents, pigments, and the like. In addition, other additives known in the art may be appropriately and selectively added as necessary.

The plasticizer that can be used in the present invention is not particularly limited as long as it is compatible with the main raw material resin and is nonvolatile, oil resistant, water resistant, insulating, and nontoxic, and typical examples thereof include tricresyl phosphate, dibutyl phthalate and dioctyl phthalate (di -(2-ethylhexyl) phthalate: DOP), dioctyl dioctyl (dioctyl adipate: DOA), diisodecyl phthalate (DIDP), diisononyl phthalate (DINP), and the like. Dioctyl phthalate is preferred in terms of harmonics. The addition amount is 25 to 45 weight%, Preferably it is 30 to 40 weight%, Especially preferably, it is 35 weight%. On the other hand, if less than 25% by weight, there is a fear that the plasticity of the substrate is inferior, while if it exceeds 45% by weight, the softening point is too low to be inferior in workability, and the strength of the substrate is not preferable.

Ba-based, Zn-based, or K-based stearates may be used as stabilizers that may be used in the present invention. However, Ba-based stearate is experimentally preferable when polyvinyl chloride is used as the main raw material. The addition amount of the stabilizer is usually 0.5 to 3.0% by weight, if less than 0.5% by weight there is a fear that the stabilizing effect is inferior, even if it exceeds 3.0% by weight it is not preferable because it is difficult to expect a synergistic effect accordingly.

As the filler usable in the present invention, various kinds of conventional ones used in the art may be used, but preferred examples thereof include calcium carbonate, potassium carbonate, sodium carbonate, calcium bicarbonate, potassium bicarbonate, sodium bicarbonate, talc, clay, and the like. And most preferably calcium carbonate. The amount of the filler added is not limited but is preferably about 5 to 20% by weight, more preferably 7 to 15% by weight.

Blowing agents that can be used in the present invention include, for example, propane, petroleum ether, carbon dioxide, pentane, hexane, heptane, cyclohexane, benzene, toluene, dichloromethane, trichloromethane, methanol, ethanol, propanol, ethyl ether, and the like. Volatile foaming agent which volatilizes and decomposable foaming agent which generate gas by decomposing gas such as ammonium bicarbonate, sodium bicarbonate, sodium borohydride, azo dicarboxylic acid amide or ammonium carbonate can be used. It is preferable to use a decomposable blowing agent rather than a volatile blowing agent, more preferably an azo compound such as azo dicarboxylic acid amide. The addition amount is about 0.5 to 2.5 weight%, Preferably it is 1.0 to 2.0 weight%. If the amount is less than 0.5% by weight, the degree of foaming is lowered, so that the substrate is high hardness, which is not preferable. If the amount is more than 2.5% by weight, the hardness is too low, so durability is not preferable.

The pigments usable in the present invention are optional without particular limitation, and inorganic or organic pigments can be appropriately selected and used depending on the desired color. The addition amount of the pigment is also not limited in the present invention, but usually about 0.3 to 5% by weight is generally used.

After preparing a mixture of the components and the composition ratio as described above, and then uniaxially or biaxially stretched to a constant thickness, and performing a foaming step of maintaining the foam for 1 to 5 minutes at a temperature of about 180 ~ 230 ℃. The maintenance at the above temperature is carried out using a suitable heating means such as a heating oven or chamber, or a furnace. The backing cloth is then pressed to plywood and cooled to provide a substrate comprising the same. It is preferable to wind up the board | substrate manufactured in this way in consideration of the efficiency in a manufacturing process.

Except for adding a deodorant, the above-described resin substrate providing step and the foaming step are conventionally known.

Subsequently, a printing step for imparting color and / or pattern in the present invention is carried out, and in the printing step, 30 to 70 weight of an acrylic ink or an aqueous ink (solid content of 10 to 40% by weight) known in the art is conventional. 30% to 70% by weight of acrylic treatment agent, polyurethane treatment agent, or aqueous treatment agent (solid content of 5 to 40% by weight) and 0.1 to 10% by weight of fragrance release agent are homogeneously mixed under mild conditions to form an ink-fragrance composition. On the substrate provided in the substrate providing step, color or pattern is printed using a suitable printing method known in the art, such as gravure printing or silk printing. In general, when the content of the fragrance release agent is less than 0.1% by weight, it is not preferable because the fragrance effect may be insufficient, and when it exceeds 10% by weight, there is an increase in the possibility of poor printing characteristics is also preferable. Can not do it.

As the printing ink described above, it can be appropriately selected and used according to various needs such as desired color, but for example, various series of inks commercially available from Younglim Chemical Co., Ltd.

The acrylic treatment agent, polyurethane treatment agent, or aqueous treatment agent described above is the same as the conventional surface treatment agent known in the art used in the subsequent surface coating step, which will be described in the surface coating step described below.

These treatment agents mixed in the above printing step are for protecting the printed layer and for embossing when the optional embossing step is carried out, but in the present invention, in addition, it is an important function as an aromatic component carrying layer. Can be done.

Optionally, an embossing step may be performed to form an embossed pattern, but this is optional.

The surface coating step performed subsequent to the printing step is for the protection reinforcement and surface glossiness control of the printing layer, and the aforementioned acrylic treatment agent, polyurethane treatment agent, or aqueous treatment agent may be used. Their solid content is usually 5 to 40% by weight. Generally, acrylic treatments have high gloss and high surface strength, so they are not easily scratched. However, acrylic treatments have a strong smell of residual organic solvents and have a rough surface texture. This soft but weak surface strength tends to cause scratches, while the polyurethane treatment has a soft surface feel and high gloss, but has a strong smell of residual organic solvents and a weak surface strength, so it is easily scratched. It is appropriately selected according to use.

Such treatments may use those known in the art that are commercially available. As the acrylic treatment agent, trade names DIBG, DI14M, etc., manufactured by the same industry can be used, and as aqueous treatment agents, trade names SWF9034, 9031 matt, etc., manufactured by Dae-A Chemical Co., Ltd., can be used. 930M, DI952GL and the like can be used.

These treatment agents mixed in the surface coating step are performed for protective reinforcement and glossiness control of the printing layer, but in addition to the present invention, they may also perform an important function as a carrying component layer.

In the above-described surface treatment (coating) step in the present invention, 65 to 90% by weight of the aforementioned treatment agent (5 to 40% by weight of solid content), 10 to 25% by weight of an organic solvent such as methyl ethyl ketone, and an aromatic release agent 0.1-10 weight% is used after mixing uniformly under mild conditions.

In the present invention, the fragrance release agent may be added in any one or both of the above-described printing step and surface coating step. However, when the fragrance release agent is added only in the surface coating step described above, it may be desirable to increase the addition amount of the fragrance release agent since the initial fragrance property may be good but the fragrance effect may be remarkably lowered over time. On the other hand, in the case where the fragrance release agent is added only in the above printing step, there is an advantage that there is little change in the fragrance effect over time, but it may be desirable to increase the addition amount of the fragrance release agent because there is a possibility that the fragrance amount is reduced. Most preferably, the fragrance release agent is added in both of the above steps, but the present invention is not limited thereto.

This surface coating step may be used in a variety of methods known in the art, 20 to 300 mesh rolls, preferably 60 to 150 mesh rolls that are partially dipped in the vessel containing the surface coating liquid composition as described above is rotated It may be desirable to coat with. The coating amount may be about 10 to 80g per m ² , preferably about 20 to 40g, but this may be arbitrarily controlled within a relatively wide range depending on various parameters such as the type of resin, the use of artificial leather, and the type of coating solution. Do.

The artificial leather surface-treated in the surface coating step described above is shipped as a final product by drying for 1 to 3 minutes at a temperature of 50 to 120 ° C.

The fragrances used in the present invention are known ones. The selection of a specific fragrance component or its addition amount is based on functionality, a customer's preference, etc. Perfume components useful in the present invention are volatile low boiling components.

Highly volatile low boiling fragrances typically have boiling points up to about 250 ° C. Highly volatile fragrances disappear relatively quickly and quickly disappear when released. The medium volatile fragrance components have a boiling point of about 250 ° C to about 300 ° C. The low volatility fragrance components have a boiling point of about 300 ° C to about 430 ° C. Its kind and aromatic properties and physicochemical properties, such as boiling points and molecular weights, are described in detail in 1969 publication 'Perfume and flavor Chemicals (Aroma Chemicals)' by SteffenArctander et al.

Examples of volatile low-boiling fragrances are anetol, benzaldehyde, benzyl acetate, benzyl alcohol, benzyl formate, iso-bonyl acetate, camphor, cis-citral (neral), citronellal, citronellol, citronellol acetate , Para-cymene, decanal, dihydrolinalul, dihydromylenol, dimethyl phenyl carbinol, eucalyptol, geralnial, geraniol, geranyl acetate, geranyl nitrile, cis-3-hexenyl acetate, Hydroxycitronellal, d-limonene, linalul, linalul oxide, linalyl acetate, linalyl propionate, methyl anthranilate, alpha-methyl ionene, methyl nonyl acetaldehyde, methyl phenyl carvinyl acetate, la Ebomentyl acetate, menton, iso-mentone, myrsen, myrsenyl acetate, myrsenol, nerol, neryl acetate, nonyl acetate, phenyl ethyl alcohol, alpha-pinene, Ta-pinene, gamma-terpinene, alpha-terpineol, beta-terpineol, terpineyl acetate and vertenex (para-tert-butyl cyclohexyl acetate), amyl cinnamic aldehyde, iso-amyl salicylate , Beta-cariophyllene, cedrene, cinamic alcohol, coumarin, dimethyl benzyl carvinyl acetate, ethyl vanillin, eugenol, iso-eugenol, flor acetate, heliotropin, 3-cis-hexenyl salicylate, hexyl Salicylate, Lilial (Para-tert-Butyl-alpha-Methyl Hydrosinic Aldehyde), Gamma-Methyl Ionene, Nerolidol, Patchouli Alcohol, Phenyl Hexanol, Beta-Seleline, Trichloromethyl Phenyl Carvinyl Acetates, triethyl citrate, vanillin, veratraldehyde and the like. Natural oils also contain volatile aromatic ingredients. Lavadine, for example, comprises linalul as the main component; Linalyl acetate; Geraniol; And citronellol. Lemon oil and orange terpenes are known to contain about 95% of d-limonene. Cedarwood terpenes are mainly composed of alpha-sedrene, beta-sedrene and other C15H24 sesquiterpenes.

An example of an aromatic release agent that can be used in the present invention is an aromatic / cyclodextrin containing complex that can be formed by any method known in the art. Such complexes can be formed by adding fragrance and cyclodextrin together in a suitable solvent, such as water, or by kneading / slurrying the components together using a minimum amount of solvent in the presence of water. The kneading / slurrying method is preferred in that it produces small particles that do not need to reduce particle size. For the formation of such complexes, see Artwood, J.L.Davies and J.E.D.Davis and D.D.MacNichol, Inc. Compounds, Vol. III, Academic Press (1984), in particular Chapter 11 and Proceedings of the Second International Symposium of cyclodextrins Tokyo, Japan (July 1984) and Zeze This is described in detail in Clyclodextrin Technology, Kluwer Academic Publishers (1988).

Particularly preferred examples of fragrance releasers that can be used in the present invention include fragrance filled microcapsules that can be formed by any method known in the art. Among these perfume-filled microcapsules, pressure-sensitive microcapsules are particularly preferred in which the microcapsules are broken by pressure and the perfume is divergent or diffused.

Controlling the number of microcapsules and the amount of fragrance released by pressure is associated with the burst strength of the microcapsules, the number and distribution of the microcapsules, the amount of perfume in each microcapsule and the burst strength of the microcapsules. It can be controlled by one skilled in the art by adjusting the relative capture strength of the capsule capture layer.

The microcapsules may be designed to burst and release fragrance as a result of the frictional forces created by the pressure and movement generated when a person sits, moves on or rises on the artificial leather sofa of the present invention. The pressure produced when moving or sitting is generally in the range of 0.05 to 1.5 Kgf / cm ² . Changes in body position (i.e. posture changes, such as sitting with legs crossed) can exert several times the normal pressure on the West-facing artificial leather, which can rupture the microcapsules as fragrance release agents.

The structure of the microcapsules should be manufactured to withstand certain conditions, e.g., stored at 120 DEG C and 1% relative humidity for 72 hours without any external physical forces or impacts, and the burst strength of at least 4.0 g / cm ² (measured with an Instron Force Gauge measuring device marketed by Instron Corporation, Canton, Mass.), particularly preferably externally at 200-430 ° C. and under 1% relative humidity. After 72 hours of storage without any physical force or impact, the burst strength is at least 0.05 Kg / cm ² . These measurements are performed by transferring under a neutral environment (eg, a sealed pack, etc.) from standing in the oven to room temperature and then measuring the burst strength. Rupture strength 0.1~1.5Kg / cm ² are preferred, and about, 0.5~1.2 Kg / cm ² and most preferably is about. The product should exhibit a burst strength of 0.1-1.2 Kg / cm ² at 20 ° C. and 50% relative humidity, preferably using microcapsules that do not decompose upon contact with moisture.

Microcapsules for use in the present invention may be prepared by any of a variety of known encapsulation methods, including chemical encapsulation methods and mechanical encapsulation methods. Methods for producing microcapsules can be prepared by a wide variety of methods. By these various methods, it is possible to include microcapsules of various sizes, the composition of the capsule shell and various functional substances in the shell. Among these methods, examples of typical ones include U.S. Patents 3,516,846, 3,516,941, 3,996,156, 4,409,156 and 5,180,637, and British Patents 1,156,725, 2,041,319 and 2,048,206. have.

As an example of a mechanical encapsulation process, droplets of a substance to be encapsulated (i.e., perfume and / or deodorant in the case of the present invention) on a liquid or semi-solid film of the desired capsule envelope material are collided and impinged. The encapsulated droplets are separated from the film and then the microcapsule envelope material is solidified.

Chemical encapsulation methods generally encapsulate a first reactant and a second reactant by mixing them into droplets in a continuous phase capsule preparation vehicle. The droplets are then dispersed in the preparation vehicle and the reaction between reactants is carried out. Liquid-liquid phase separation of the polymeric capsule shell (wall) material from the vehicle is performed, where the phase-separated polymeric material is wetted and enclosed in the dispersion droplets to be encapsulated.

A wide variety of materials can be used to make microcapsule shells. Typical materials that can be used for the formation of the envelope of the microcapsules include polymerization of polycondensation products of urea and formaldehyde or melanin with formaldehyde, or monomeric or low molecular weight polymers of dimethylolurea or methylolated urea and aldehydes. Reaction products. In addition, various microcapsule forming materials are known and are described, for example, in US Pat. Nos. 3,516,846, 4,087,376 and UK Pat. Nos. 2,006,709 and 2,062,570.

The size of the microcapsules can play an important role in the present invention. In general, the microcapsules should have an average diameter in the range of 0.5 to 100 microns, preferably 1 to 40 microns when the capsule load is 80 to 90% by weight of the total capsule weight. More preferably, the microcapsules have an average diameter of 2 to 20 microns, most preferably the microcapsules have an average diameter of 2 to 15 microns. These dimensions can be particularly useful for controlling the percent rupture of the microcapsules. If the microcapsule envelope has a lower self weight (eg 70 to 80%), the microcapsules must be larger in size to achieve the same burst strength. Under most conditions, the widest range of average microcapsule sizes is about 0.5 to 100 microns, but when using about 2 to 15 microns of microcapsules, 90 to 95 weight percent microcapsule weight is preferred.

Microcapsule shell (wall) materials suitable for use in the present invention include any suitable polymeric film-forming material, for example, microcapsules include natural hydrophilic polymeric materials such as gelatin, gum arabic, starch, cara Ginine and zein; Natural polymerizable materials modified by various known methods such as ethyl cellulose, carboxymethyl cellulose, shellac, resins and nitrocellulose; Other polymerizable materials such as polyvinyl alcohol, polyethylene, polystyrene, polyacrylamide, polyether, polyester, polybutadiene, silicone, epoxy and polyurethane.

The types of fragrances and deodorants and the types of complexed or encapsulated fragrance releasers are all well known, and they do not directly form the present invention, and these can be variously changed by various known methods. Various examples of fragrances that may be used in the present invention are described in detail in Chapter 32, 'Fragrance' of Balsam.

The fragrance material included in the microcapsules described above can be any of a variety of liquids, including solutions, dispersions, and gelled materials. A preferred form of perfume component is an organic solid which is a fragrance-releasing substance that volatilizes upon rupture of the microcapsules. The most preferred forms of components are fragrance substances (eg essences and volatile fragrances) and / or substances which chemically release active vapors or liquids (eg bacterial growth inhibitors or deodorants). The aromatic material should be a material having compatibility which does not cause a special reaction with other components in artificial leather.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Example 1 :

(A) Resin substrate provision step :

Polyvinyl chloride was used as the main raw material resin, and the sol mixture having the components and the composition ratio as described below was kneaded.

Composition Composition ratio (wt%) PVC high polymerization resin 35% PVC low polymerization resin 15% D.O.P. 35% Ba-based stearate 1.5% Calcium carbonate 10% Azo compounds 1.5% Pigment 2%

The thickness of the sheet was adjusted to the desired size by inserting the kneaded sol compound into a calender four roll through a conveyor belt and making the sheet and adjusting the gap between the rolls in three of the four rolls. . The pulled sheet and the backing cloth located underneath were laminated through a press roll.

(B) foaming step :

As described above, the laminated board was held in a chamber maintained at a temperature of 200 ° C. for 2 minutes and foamed. The foamed laminated board was cooled to room temperature through a cooling drum.

(C) printing step :

48% by weight of acrylic ink (solid content of 27% by weight: Yeonglim Chemical), acrylic treatment agent (solid content of 5-40% by weight: DIBG manufactured by the same industry), 50% by weight of fragrance release agent (J & C Microchem, powder type fine) 2% by weight of a capsule, geranium flavor) was gently mixed to form an ink-flavor composition, and then gravure printed on the substrate provided in the substrate providing step described above.

(D) embossing step :

Embossing the pattern using an embosser was performed as an optional step.

(E) surface coating step :

Subsequently, 82% by weight of the same acrylic treatment agent (18% by weight of solids content), 16% by weight of methyl ethyl ketone organic solvent as organic solvent, and 2% by weight of the same aromatic release agent were used as embossed artificial leather in the printing step. After mixing the surface coating solution was prepared by coating the surface coating agent per m ^{2 in} an amount of 30g (using a 100 mesh roll), and dried at a temperature of 90 ℃ 2 minutes, the final product of the present invention according to the production method of the present invention Westward synthetic leather was obtained.

Example 2 :

In the resin substrate providing step (A), the sol mixture having the same components and composition ratios as in Example 1 was kneaded, and then the kneaded sol compound was applied to a release paper at a thickness of 0.30 mm, and in the foaming step (B), 260 ° C. Was foamed in a chamber of and cooled through a cooling furnace. Subsequently, after applying the adhesive layer, the bubble paper was laminated and dried in an oven at a temperature of 90 ° C. to evaporate the solvent, and then the release paper was peeled off. Then, the printing step (C), the embossing step (D) and , Surface coating step (E) was carried out to obtain a slow-release artificial leather of the present invention.

Example 3 :

Except for not including the fragrance release agent in the surface coating step (E) described above, it was carried out in the same manner as in Example 1 to obtain a slow-release artificial leather of the present invention.

Example 4 :

Except for not including the fragrance release agent in the printing step (C) described above, it was carried out in the same manner as in Example 1 to obtain a slow-release artificial leather of the present invention.

Comparative Example 1 :

In the resin substrate providing step (A), 33% by weight of the PVC high polymerization resin was used, and 2% by weight of the fragrance release agent (JC Microchem, powder type geranium) was added, and the printing step (C) and the surface coating step were performed. In (E), the artificial leather of Comparative Example 1 was obtained in essentially the same manner as in Example 1, except that no aromatic release agent was used.

Comparative Example 2 :

In the resin substrate providing step (A), the printing step (C), and the surface coating step (E), the artificial leather of Comparative Example 2 was obtained by performing a completely conventional method without using any of the above-described aromatic release agents.

Example 5 :

A polyurethane resin was used instead of polyvinyl chloride as the main raw material resin, and a sol mixture was prepared having the following components and composition ratios.

Composition Composition ratio (wt%) Polyurethane resin 48% Methyl ethyl ketone 33% D.M.F. 5% Pigment 14%

The above sol mixture was applied to a release paper at a thickness of 0.02 mm and heated to a temperature of 130 ° C. in a chamber to prepare a soft film. Then, an adhesive was coated on the soft film, and then the bubble paper was laminated and the temperature was 90 ° C. The solvent was volatilized by drying in the chamber of. Subsequently, the release paper and the product were rolled together and aged in a aging room at 70 ° C. for 12 to 24 hours, and then the release paper was peeled from the product to prepare a polyurethane substrate.

In addition, the present invention according to the manufacturing method of the present invention by carrying out essentially the same procedure as in Example 1, except that the polyurethane-based treatment agent (930G of the same industry) was used in the printing step (C) and the surface coating step (E). Sustainable artificial leather was prepared.

Example 6 :

After performing the resin substrate providing step (A) and the foaming step (B) in Example 2 (after peeling off the release paper), a polyurethane sol mixture having the same components and composition ratio as in Example 5 was prepared on the foamed PVC substrate. After applying to a thickness of 0.02 mm and heated to a temperature of 130 ℃ in the chamber to form a soft film layer, the printing step (C), the embossing step (D) and the surface coating step (E) as in Example 1 Was carried out to obtain the slow-release artificial leather of the present invention.

Example 7 :

0.05% by weight of VALFOR CP301-68 zeolite manufactured by PQ Corporation as a deodorant in the resin substrate providing step (A) and the trade name Amaizo (complex dextrin) from American Maize-Products Company Except for the addition of 0.15% by weight, the sustained-release artificial leather of the present invention was prepared by substantially the same procedure as in Example 1.

Test Example 1: Measurement of the direction according to the change over time by the panel test

Twenty female panels (four for each age group) in their twenties to sixties who were non-smokers were panel-tested for the orientation of the artificial leathers of Examples 1-7 and Comparative Examples 1 and 2 described above. The results are shown in Table 1 below. Here, (circle) is a case where 16 people evaluated that aromaticity was favorable, O evaluated 12, (triangle | delta) was 8, and 4 was good. In the blind test, the two sides of the artificial leather (10 × 10 cm) were grasped with both hands and evaluated after 3 seconds of rubbing three times back and forth.

5 hours after manufacture 1 week after manufacture 1 month after manufacture 2 months after manufacture 6 months after manufacture Example 1 O ◎ ◎ ◎ ◎ Example 2 O ◎ ◎ ◎ ◎ Example 3 O ◎ ◎ ◎ ◎ Example 4 O ◎ ◎ ◎ O Example 5 O ◎ ◎ ◎ ◎ Example 6 O ◎ ◎ ◎ ◎ Example 7 ◎ ◎ ◎ ◎ ◎ Comparative Example 1 △ X X △ △ Comparative Example 2 X X X △ △

In the slow-release artificial leather according to the present invention produced by the production method of the present invention, the fragrance release agent, in particular the aromatic pressure-sensitive microcapsules are contained in the color / pattern printing layer and / or the surface coating layer, the surface coating layer itself is aromatic characteristics In addition to functioning as a millipore membrane to control the fragrance, the fragrance emanates only by friction or pressure on the surface of the artificial leather, so that a good fragrance can be exhibited every time it is used. It can be effectively adapted to consumer's preferences, such as high-grade sheets for automobiles, sofa jackets, leather garments, foamed wallpaper, synthetic leather for shoes, shoe-changing insoles, belts and handbags, chair jackets. It can be applied to various uses such as furniture interior materials.

Claims (14)

In the artificial leather which consists of a resin substrate, a printing layer, and a surface coating layer, A slow-facing artificial leather in which a fragrance-releasing agent is incorporated as a fragrance carrying layer on a printing layer or a surface coating layer or both to give a color / pattern to a surface. The sustained-release artificial leather according to claim 1, wherein the fragrance-releasing agent is a pressure-sensitive microcapsules having an average diameter of 0.1 to 100 microns filled with a fragrance. The sustained-release artificial leather according to claim 1, wherein the aromatic release agent is contained in an amount of 0.1 to 25% by weight based on the weight of the printed layer. The artificial leather of claim 1 or 3, wherein the fragrance release agent is contained in an amount of 0.1 to 40% by weight based on the weight of the surface coating layer. The artificially oriented synthetic leather according to claim 2, wherein the pressure-sensitive microcapsule has a burst strength of 0.1 to 1.5 Kg / cm ² . The method of claim 1, wherein at least one deodorant selected from the group consisting of carbon fine particles, silica gel, activated alumina, diatomaceous earth, cyclodextrin, ceramic powder, and mixtures thereof is about 0.01-5% by weight resin based on the weight of the resin substrate. Sustainable artificial leather embedded in the substrate. In the manufacturing method of artificial leather comprising a resin substrate providing step, foaming step, printing step, surface treatment step, The printing step is a homogeneous mixture of 30 to 70% by weight of the printing ink having a solid content of 10 to 40% by weight, 30 to 70% by weight of the surface treating agent having a solid content of 5 to 40% by weight, and 0.1 to 10% by weight of the fragrance release agent. After preparing the ink-fragrance composition, the manufacture of a West-facing artificial leather, characterized in that the color or pattern is printed by gravure printing or silk printing on the substrate provided through the substrate providing step and the foaming step described above. Way. According to claim 7, wherein the surface treatment step is a mixture of 65 to 90% by weight of the surface treatment agent of 5 to 40% by weight solid content, 10 to 25% by weight of the organic solvent, and 0.1 to 10% by weight of the fragrance release agent uniformly A method of producing a slow-facing artificial leather, wherein the surface treatment liquid-fragrance composition is formed and then surface coated. In the manufacturing method of artificial leather comprising a resin substrate providing step, foaming step, printing step, surface treatment step, The above-mentioned surface treatment step is the surface treatment liquid-fragrance composition which uniformly mixed 65-90 weight% of surface treatment agents, 10-25 weight% of organic solvents, and 0.1-10 weight% of fragrance | release agents with a solid content 5-40 weight%. Method for producing a slow-release artificial leather, characterized in that after the surface coating. 10. The pressure-sensitive fine microparticle according to claim 7 or 9, wherein the fragrance-releasing agent has an average diameter of 0.1 to 100 microns with a fragrance filled therein and a burst strength in the range of 0.1 to 1.5 Kg / cm ² . Sustainable artificial leather, capsule. The weight of the resin substrate according to claim 7, wherein at least one deodorant selected from the group consisting of carbon fine particles, silica gel, activated alumina, diatomaceous earth, cyclodextrin, ceramic powder, and mixtures thereof in the resin substrate providing step. Sustainable artificial leather incorporated in the resin substrate in an amount of about 0.01-5% by weight as a reference. The method according to claim 7 or 9, wherein the coating in the surface treatment step is carried out using 20 to 300 mesh rolls, and the coating amount of the surface treatment liquid is in the range of 10 to 80 g per m ² of the resin substrate. Method for producing directional artificial leather. The method for producing a sustained-release artificial leather according to claim 7 or 9, wherein the printing ink is an acrylic ink or an aqueous ink. The method for producing a slow-release artificial leather according to claim 7 or 9, wherein the surface treating agent is an acrylic surface treating agent, a polyurethane surface treating agent or an aqueous surface treating agent.