KR20020035969A - Repositionable perfume sheet - Google Patents

Abstract

PURPOSE: Provided is an adhesive sheet emitting fragrance continuously or temporarily during storing and using, which dose not generate the transference of an adhesive and has excellent adhesive ability and can be used for memo paper, handouts, invitation cards, and interior supplies. CONSTITUTION: The adhesive sheet emitting fragrance comprises a primer layer(3) and a repositionable adhesive layer spread on one side of a substrate(2) and a release layer(1) spread on the other side of the substrate(2), wherein the adhesive layer contains 100pts.wt. of a repositionable adhesive(4) having a particle size of 20-40 micrometer and 3-20pts.wt. of fragrance capsules(5) having a particle size of 1-10 micrometer. The adhesive(4) is selected from C4-C12 acryl, N-vinyl-2-pyrrolidone, N-vinyl caprolactam, acrylonitrile, and styrene sulfonate. And the fragrance capsules(5) contain at least two selected from the group consisting of rosemary, eucalyptus, basil, pine fragrance, lavender, lemons, peppermint, jasmine, roses, oranges, and etc.

Description

Fragrance-free adhesive sheet {Repositionable perfume sheet}

The present invention relates to a fragrant acid adhesive sheet, and more particularly, by adding a flavor capsule of a specific size to the adhesive layer of the repositionable adhesive sheet which can be repeatedly attached and removed without damaging the original. The present invention relates to a pressure-sensitive adhesive sheet that can emit a scent continuously or temporarily during use, and does not generate a pressure-sensitive adhesive transition and has excellent adhesive force, and thus can be used as a note paper, a flyer, an invitation, an interior article, and the like.

The repositionable pressure sensitive adhesive having a microsphere structure has been widely used in various fields as an adhesive that can be repeatedly attached to and removed from the adhesive without changing the adhesive force. In particular, as a manufacturing technique of adhesive memo papers made using a microsphere adhesive, a method of manufacturing a flexible film containing a repositionable adhesive and a plasticizer [US Patent No. 5,229,207] and wedges or beads having a microstructure Is used in the pressure-sensitive adhesive layer [US Pat. Nos. 5,296,277, 5,795,636]. In addition, the microsphere pressure-sensitive adhesive production and application technology for producing a micro-sphere pressure-sensitive adhesive by a suspension polymerization method using an anionic surfactant in the copolymer of the alkyl acrylate monomer and the ionic monomer, and using benzoyl peroxide as an initiator. Method [US Pat. No. 3,691,140] and a method of polymerization by simultaneously using an anionic stabilizer with a slightly higher molecular weight in addition to the anionic surfactant to prevent agglomeration of particles generated during suspension polymerization [US Pat. No. 4,166,152] ] Was reported. In addition, a hollow microsphere was prepared using ammonium lauryl sulfate or sodium lauryl sulfate as a polymerization stabilizer to obtain an effect of improving adhesion and pressure-sensitive adhesive transition compared to the microsphere adhesive [US Patent No. 5,045,569]. There is [ho].

On the other hand, conventional fragrance-acid products include heat (body temperature, heat of equipment, etc.), water (human sweat, breathing and air vapor, etc.), pressure (microcapsules for pressure reduction, etc.), light (using photosensitive polymers), and time (micro Only a method in which the fragrance is continuously or temporarily dissipated (by diffusion in capsules and polymer binders) or the like was used. If the description of the existing technology to give off the fragrance in detail, the method comprising the encapsulation material contained in the adhesive layer in the label composed of a composite layer, the capsule is broken when the cohesive fracture destroys the fragrance [US Patent No. 4,606,956], multilayer structure [4,874,129] or a method of producing a patch by impregnating a polyurethane membrane with a fragrance [US Patent No. 4,880,690], a label made by protecting a polymer gel impregnated with a fragrance with a protective film [US Patent No. 5,391,420], a method of coating a fragrance-polymer mixture by mixing polyvinylpyrrolidone, acrylic polymer, hydrogel, etc. [US Patent No. 5,399,404], using a protective film after screen printing the fragrance To protect the aromatic acid until use [US Pat. No. 5,566,693]. A technique using microcapsules for paper coating is an example of producing a flavoring paper using simultaneously a 5 micron-sized flavor capsule and a capsule that has an impact buffering effect (US Pat. No. 4,746,567). In addition, techniques for preparing such microcapsules include techniques using various anionic surfactants in urea and formaldehyde or melamine and formaldehyde [US Patent Nos. 3,516,846, 3,516,941, 3,778,383, 4,087,376, 4,089,802 No. 4,100,103, 4,251,386].

However, there is no known technique for applying a flavor capsule to a repositionable pressure-sensitive adhesive sheet, and even if a capsule is broken even if the flavor capsule is used, the problem that the adhesive force is lowered due to the flavor component or the transfer of the adhesive remains a problem to be solved. have.

Accordingly, the present inventors apply the flavor capsule to the repositionable adhesive sheet, but even if the adhesive is repeatedly carried out, the adhesive sheet may continuously emanate the fragrance without degrading its adhesive force or may emit a large amount at a time. Efforts have been made to develop it. As a result, when the sheet is prepared by coating a primer on the other side of the release-coated substrate and then mixing and coating a repositionable pressure-sensitive adhesive having a microsphere structure or a pore microsphere structure and a flavor capsule of a specific particle size, the capsule By controlling the release rate of the fragrance, the fragrance that volatilizes within a short time can be sustained for a long time, and when the capsule is broken due to intentional physical impact, it can emit a large amount of fragrance at once. It was found that the transition of the pressure-sensitive adhesive with and did not complete the present invention. Accordingly, the present invention provides a fragrance-flavored adhesive sheet that provides a functional smell that continually emits fragrance during storage and use, and also provides a sense of smell by applying physical force to the capsule at a desired time and place. There is a purpose.

Figure 1 shows a cross-sectional view of the adhesive sheet produced according to the present invention.

Figure 2 is an enlarged photograph of the repositionable pressure-sensitive adhesive having a microsphere shape prepared according to the present invention.

Figure 3 is an enlarged photograph of the flavor capsules prepared according to the present invention.

Figure 4 is an enlarged photograph of the adhesive sheet coated with a homogeneous mixture of the flavor capsule and the microsphere adhesive prepared according to the present invention.

[Description of Symbols for Main Parts of Drawing]

1: release layer 2: base material

3: primer layer 4: adhesive

5: flavor capsule

The present invention provides a pressure-sensitive adhesive sheet in which a primer layer 3 and a repositionable adhesive layer are coated on one side of the base material 2, and a release layer 1 is applied on the other side of the base material.

The adhesive layer is characterized by an anti-balancing adhesive sheet containing 3 to 20 parts by weight of the flavor capsule 5 having a particle size of 1 to 10 μm with respect to 100 parts by weight of the repositionable pressure sensitive adhesive having a particle size of 20 to 40 μm.

The present invention will be described in more detail as follows.

The present invention is easy to attach and remove without damage to the original without using nails, clips, thumbtacks, and imparts functionality that can continually emanate fragrance during storage and use, and may also shed a large amount of fragrance temporarily. In addition, the present invention relates to an anti-balancing adhesive sheet having excellent releasing force and thus no adhesive transition occurs.

As shown in FIG. 1, the release coating adhesive sheet according to the present invention has a release layer applied to one side of the substrate based on the substrate 2, and a primer layer (on the opposite side of the substrate 2). 3) is applied, and the adhesive composition of the microsphere or the pore microsphere adhesive 4 and the flavor capsule 5 is applied on the primer layer, which will be described in detail with reference to the drawings.

The microsphere adhesive and the pore microsphere adhesive 4 used for the adhesive layer have a particle size of 20 to 40 μm, and when the particle size is less than 20 μm, the microsphere adhesive and the pore microsphere adhesive cannot perform buffering against external impact or pressure. There is a problem that the capsule is easily broken, and when the thickness exceeds 40 μm, the adhesive area decreases, resulting in a drop in adhesive force.

Here, the microsphere adhesive is prepared by the suspension polymerization method, the pore microsphere adhesive is prepared by the seed suspension polymerization method using the seed polymer particles as a raw material. Examples of the preparation component of the microsphere adhesive or the seed polymer particles include a main monomer, an ionic auxiliary monomer, a suspension stabilizer and an initiator. Main monomers include styrene, methyl methacrylate (MMA), n-butyl acrylate (BA), hexyl acrylate, 2-ethylhexyl acrylate (2-EHA) isooctyl acrylate, isononyl acrylate, and decyl acyl. Relate, dodecyl acrylate, and the like. In addition, as the ionic auxiliary monomer, acrylic acid (AA), maleic acid (MA), acrylamide itaconic acid, hydroxyalkyl acrylate, N-vinyl-2-pyrrolidone, N-vinyl caprolactam, acryl Ronitrile and the like are useful. Suspension stabilizers include sodium dodecylbenzenesulfonate (SDBS), ammonium lauryl sulfate (ALS), sodium lauryl sulfate (SLS), triethanolamine lauryl sulfate (TEALS), and sodium salts of alkaline aryl ether sulfate (Triton). X-200) can be used. As the initiator, 2,2'-azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO) and the like are useful.

In this case, since the produced seed polymer particles influence the final particle size after the seed suspension polymerization reaction, it is very important to form initial particles having a desired particle size by maintaining an appropriate stirring speed in the initial particle formation process. In addition, it is advantageous to use AIBN in consideration of the degree of crosslinking as an initiator. Seed polymer particles for preparing pore microspheres are composed of 90 to 99.8% of alkyl acrylate, 2-ethylhexyl acrylate (2-EHA), isooctyl, a monomer having an alkyl group having 4 to 14 carbon atoms. It is preferable to use acrylate, butyl acrylate, isononyl acrylate (INA), etc., and ionic co-monomers for copolymerization are acrylic monomers (AA), itaconic acid (IA) and male, which have polar polarities. It is preferable to use Ixide (MA) or the like.

In addition to the adhesive, the microencapsulated flavor is added to the adhesive layer in an amount of 20 parts by weight (solid content) or less with respect to 100 parts by weight of the adhesive. The size of the flavor capsule is 1 to 10 μm, and preferably the size of the flavor capsule is 1 to 1. Adjust to 5 μm. At this time, when the size of the flavor capsule exceeds 10 ㎛, the flavor capsule acts as a spacer between the pressure-sensitive adhesive to reduce the adhesive area, resulting in a decrease in adhesive strength, if less than 1 ㎛ it is difficult to control the fragrance Becomes difficult. In other words, if the size of the flavor capsule is appropriately adjusted according to the size of the pressure-sensitive adhesive does not affect the adhesive force. At this time, as a wall material of the flavor capsule, that is, a material that can be used when encapsulating the flavor may be used such as melamine resin, formaldehyde resin, urea resin. In addition, the fragrance used in the fragrance capsule can be made by combining aroma having aromatherapy function. That is, rosemary, yukarizesu, basil, etc., which are known to be good for memory promotion, mental concentration, meditation, relaxation, stress relief, scent with air purifying function, lavender, etc., relaxation, refreshing lemon, peppermint, etc. 2 or more kinds selected from jasmine, rose, ylang-ylang, orange, bergamot, beige, grapefruit, mandarin, musk, civet, castoreum, ambergris Mixtures can be used.

The substrate (2) is a material capable of printing aptitude using paper or coated cellulose such as rayon, acetate, or selected from synthetic films such as flexible vinyl chloride, polyester, acrylic, polyethylene, polypropylene, etc. do.

Hereinafter, the present invention will be described in detail based on production examples and examples, but the present invention is not limited by the examples.

Preparation Example 1 Preparation of Microsphere Adhesive

A 4-liter reactor with a 1 L capacity was equipped with a thermometer, reflux condenser, stirrer, and vacuum or nitrogen inlet tube. First, 513 g of distilled water and 11.23 g of sodium dodecylbenzenesulfonate (21.6% solids) were added and stirred. . 21.8 g of 2-hydroxyethyl acrylate, 0.1 g of maleic acid, and 0.097 g of 2,2′-azobisisobutyronitrile (AIBN) were added to a separately prepared 0.1 L beaker, and the contents were completely dissolved. The reactor was slowly fed into the reactor while maintaining at 300 rpm. Thereafter, vacuum and vacuum were removed for 1 minute to remove dissolved oxygen and air, and the reactor was filled with nitrogen, followed by stirring the reactor contents at 300 rpm for 1 hour to complete polymerization preparation. The average particle diameter of the monomer particle formed in this way was about 20 micrometers. Subsequently, after carrying out the suspension polymerization for 3 hours at 65 ℃ while continuing nitrogen filling, the reactor temperature was lowered to room temperature. At this time, the resulting microsphere pressure-sensitive adhesive was 4% solids and the average particle diameter was 20 to 40 ㎛.

Preparation Example 2 Preparation of Pore Microsphere Adhesive

The mixture solution prepared by lowering the temperature of the polymer particles obtained in Preparation Example 1 to room temperature (152.4 g of 2-hydroxyethyl acrylate, 0.7 g of maleic acid, and 1.52 g of benzoyl peroxide) was lowered to 70 rpm. Slowly feed from Stirring was continued for 3 hours while nitrogen was continuously charged to allow the mixed solution to sufficiently swell the polymer particles prepared in Example 1. At this time, each particle size was 20 ~ 25 ㎛. Whether the swelling was sufficiently confirmed using an optical analyzer (Image analyzer), and when the swelling was completed to further increase the temperature of the reactor to 65 ℃ was carried out additional suspension polymerization. After the polymerization was completed after 8 hours, the reactor temperature was lowered to room temperature and filtered using a 60 mesh filter. As a result, solid content of the obtained final product was about 25%, and the final average particle of the pore microsphere adhesive particle obtained at this time was about 20-40 micrometers. 35 g of 4% polyvinyl alcohol solution was added to the final adhesive to improve the storage stability of the adhesive.

Production Examples 3 to 6: Preparation of flavor capsule

35 g of melamine and 240 g of distilled water were added to an aqueous 4% NaOH solution, stirred for 5 minutes, homogenized, and then stirred for 60 minutes at a speed of 700 rpm by adding 90 g of 35% formalin to prepare a prepolymer mixture. Next, 80 g of fragrance (mixed oil of peppermint, eucalyptus and rosemary) are added to 600 g of 6% aqueous styrene-maleic anhydride solution and stirred for 30 minutes with a homer mixer to form an emulsion. 680 g of this emulsion oil was added to a prepolymer mixture and polymerized at 60 ° C. for 2 hours. After the polymerization, the pH was adjusted to 8 using ammonia, adjusted to pH 10 using 10% NaOH, and cooled to room temperature to obtain an encapsulated flavor having a size of 1 to 5 μm. In addition, the preparation examples 3 to 5 were carried out in the same manner as above, but the flavoring and stirring speeds were varied, and are specifically shown in Table 1 below.

Examples 1-4 and Comparative Examples 1-4: Preparation of Adhesive Sheet

Prepare a basis weight 80 g / m 2 paper coated with a release coating agent on one side and a primer on the opposite side. 90 g of the pressure-sensitive adhesive obtained in Preparation Example 1 and 10 g of the flavor capsule obtained in Preparation Example 3 were stirred, dried, coated to a thickness of 50 μm on the primer layer of the prepared paper, and dried at 90 ° C. in a drying oven for 2 minutes to prepare an adhesive sheet. Prepared. In addition, Examples 2 to 4 and Comparative Examples 1 to 4 were carried out in the same manner as above, but the flavor capsules were different, and are shown in Table 2 below.

The physical properties of the Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 3 below.

1) Peel Strenth Measurement

The test plate (adhesive; stainless steel (SUS 304), glass, etc.) washed and dried with a solvent is reciprocally attached with a 2 kg roller with the adhesive side of a 25 mm wide test piece (sample) facing down. After 20 minutes of attachment, the peel force is measured by a tensile force tester (Adhesion / Release Tester AR-1000, Chem Instruments). The measurement speed at this time is 300 mm / min. The measurement conditions are 22 ± 2 ℃ and 65 ± 5 RH.

2) Repeat adhesion

The test plate (adhesive; stainless steel (SUS 304), glass, etc.) washed and dried with a solvent is reciprocally attached 10 times with a 2 kg roller with the adhesive side of a 25 mm wide test piece (sample) facing down. . After 20 minutes after 10 round trips, the peel force is measured by a tensile force tester (Adhesion / Release Tester AR-1000, Chem Instruments). The measurement speed at this time is 300 mm / min. The measurement conditions are 22 ± 2 ℃ and 65 ± 5 RH.

3) Adhesive transition and contamination

Washed clean with solvent, and reciprocally attached 20 times with a 2 kg roller so that the 25 mm by 25 mm area of the test piece is in contact with the center of the test plate with the adhesive face of the 25 mm by 55 mm size test piece (sample) down. When the test piece was squeezed vertically from the test plate, whether the adhesive remained in the test piece was determined as follows based on the adhesive residue in an area of 2.5 cm x 2.5 cm using an optical microscope with a ratio of 100 times.

4) Persistence of Hyangbalsan

After the final product was made according to each prescription, the degree to which the fragrant acid was strongly maintained over time was determined as follows before packing in a polypropylene wrapper and a month later.

From the results of the above examples and comparative examples, when the size of the microsphere or the pore microsphere adhesive is 20 to 40 μm and the size of the flavor capsule is 1 to 5 μm, the adhesive force is maintained up to 20 times even when repeatedly attached and removed. And it was confirmed that no adhesive transition occurred. However, when the size of the flavor capsule is 15 to 20 ㎛ as in the comparative example, it can be seen that the fragrance capsule is broken by the external pressure during repeated use, the fragrance is eluted inside the pressure-sensitive adhesive to decrease the adhesive strength. This indicates that the preferred size of the flavor capsule which does not affect the change in the adhesive force is in the range of 1 to 5 μm. In addition, it can be seen that when the size of the flavor capsule is 1 ~ 5 ㎛ and mixed with the pressure-sensitive adhesive, the fragrance persistence is obtained. To prevent them from being destroyed.

As described above, the fragrance-release adhesive sheet of the present invention by applying a microcapsule surrounding the fragrance to the adhesive sheet to adjust the particle size, and also coated with a microsphere or pore microsphere adhesive is also adjusted in size, When you apply the physical force to the capsule at the desired time and place, the effect of smelling the place where the sheet is placed is effected.If you remove the protective layer of Hyangbal when you open letters, postcards, cards, bills, etc. When the fragrance is continuously emitted, there is an effect of aromatherapy for a long time user. In addition, the adhesive force is excellent even when repeated use, and can reduce the economic burden by coating the scent in a smaller area than the existing fragrance products, and color printing on various substrates can be effectively applied to office supplies, fancy supplies, postal supplies, etc. Can be.

Claims (4)

In the pressure-sensitive adhesive sheet formed by coating the primer layer 3 and the repositionable adhesive layer on one side of the base material 2 and the release layer 1 on the other side of the base material, The said adhesive layer contains 3-20 weight part of flavor capsules (5) of 1-10 micrometers of particle diameters with respect to 100 weight part of repositionable adhesives of 20-40 micrometers of particle diameters. The method of claim 1, wherein the adhesive is selected from acryl, N-vinyl-2-pyrrolidone, N-vinyl caprolactam, acrylonitrile, and styrene sulfonate having 4 to 12 carbon atoms. . The fragrance capsule (5) according to claim 1, wherein the rosemary, eucalyptus, basil, pine scent, lavender, lemon, peppermint, jasmine, rose, ylang-ylang, orange, bergamot, beige, grapefruit, mandarin and synthetic fragrance Perfumed adhesive sheet, characterized in that a mixture of two or more selected from among. The volatile adhesive sheet according to claim 1, wherein the substrate (2) is selected from paper, coated rayon, acetate, vinyl chloride, polyester, acrylic, polyethylene, and polypropylene.