KR20010035366A - Resin composition for slow flavor emission - Google Patents

Abstract

PURPOSE: A sustained release aromatic resin composition comprising perfume powder in which an aromatic component is contained in a separate carrier, and aromatic microcapsule powder is provided, which can continuously deliver perfume or fragrance by reducing loss of an aromatic component having strong volatility at high temperature during processing of polymeric material. CONSTITUTION: This sustained release aromatic resin composition comprises 0.1 to 10 parts by weight of perfume powder prepared by adsorbing an aromatic component in a carrier and adding a binder based on 100 parts by weight of base resin and 0.1 to 10 parts by weight of aromatic microcapsule powder prepared by encapsulating an aromatic component with an additive such as resin and a surfactant and drying.

Description

Sustained release aromatic resin composition {Resin composition for slow flavor emission}

The present invention relates to a sustained-release aromatic resin composition by impregnating and micro-encapsulation the aromatic component in the resin, and more particularly, to control the degree of odor while at the same time giving heat resistance to the aromatic component. The present invention relates to a sustained-release aromatic resin composition having excellent sustained release property by impregnating a resin and a micro-encapsulated powder in parallel.

In the present invention, the molding process temperature of the polymer material including the polyolefin is usually processed at a high temperature of 200 ° C., and the result of applying the fragrance component directly to the fragrance plastic is applied to the fragrance plastic, resulting in the problem that most of the volatilization during processing is low. there was.

Therefore, in order to solve this problem, the application of aromatic components to inorganic materials such as silica gel, natural products such as dextrin, or synthetic resins such as vinyl acetate resin has been developed, but this also improved some of the volatility problems during processing due to improved heat resistance. Further improvement is required, and since the problem of deterioration of the initial fragrance intensity suddenly decreases with time, the conventional fragrance resin was not applicable to various applications.

In order to solve this problem, Korean Laid-Open Patent Publication No. 98-34312 discloses compositions of ethylene vinyl acetate resin, low density polyethylene resin, and high density polyethylene resin impregnated with 20-30% by weight of liquid fragrance. There is a problem that does not.

Meanwhile, a method of microencapsulating the fragrance or essence to impregnate the fiber to impregnate the fragrance or essence in the garment, such as woven fiber knits, is disclosed in Korean Patent Publication No. 89-13239, but in the case of the fiber impregnated with such microcapsules Although it lasts for a long time, it is difficult to apply to resin due to a slight emission of fragrance.

The technical problem to be solved by the present invention is to solve the above problems, while maintaining excellent steering properties by minimizing the loss of highly volatile fragrance components at high temperatures during processing of polymer materials, while the initial fragrance strength is impregnated in the carrier. It is to provide a sustained-release fragrance resin composition invented to maintain the desired strength by utilizing the fragrance of the fragrance component and using the sustained release of the microcapsules for a long time use.

In addition, depending on the use of the natural fragrance with excellent antibacterial and anti-impact, it can exhibit the antimicrobial power without the use of a separate antimicrobial agent or toxic synthetic compound is environmentally friendly and can also exhibit functionality in terms of hygiene.

Figure 1 is a graph showing the degree of flavor dispersion over time at 80 ℃ in Examples and Comparative Examples of the present invention.

Figure 2 is a graph showing the results of aroma sensory test over time at 80 ℃ in Examples and Comparative Examples of the present invention.

Accordingly, an object of the present invention is to use 0.1 to 10 parts by weight of the anti-fragrance powder prepared by adsorbing the fragrance components to the carrier and adding a fixing agent to 100 parts by weight of the base resin, and using the additives such as the wall material resin and the surfactant. To encapsulate and dry it to provide a sustained-release aromatic resin composition consisting of 0.1 to 10 parts by weight of the aromatic microcapsule powder.

At this time, the content of the impregnated fragrance powder is 0.5 to 3.0 parts by weight of impregnated fragrance powder based on 100 parts by weight of the base resin, and the content of the preferred aroma microcapsule powder contains 0.5 to 3.0 parts by weight based on 100 parts by weight of the base resin. will be.

In addition, the base resin of the present invention may include all conventional resins, wherein preferred resins include polyolefin resins such as polypropylene, polyethylene, or copolymers thereof; It is characterized in that at least one resin selected from polyvinyl chloride resin, polyurethane resin, ethylene vinyl acetate resin, aliphatic polyester resin and ionomer resin.

On the other hand, when the ionomer resin is used in the base resin, the divergence of the fragrance is properly adjusted. Particularly, the trade name Surlyn resin (manufactured by DuPont USA) is preferable.

In addition, in the anti-fragrance powder, the carrier content is 20 to 500 parts by weight based on 100 parts by weight of the fragrance stock solution, and 10 to 40 parts by weight of a fixing agent may be used, and the carrier used may be an inorganic compound such as silica, silica gel, zeolite, At least one carrier selected from the group consisting of porous polypropylene resins, synthetic resins such as ethylene vinyl acetate resins, and natural products such as dextrin and gum.

In addition, the aromatic microcapsule powder is one or more resins selected from urethane resin, urea-formin resin, melamine-urea-forminline resin and melamine-forminine resin as wall resin for microcapsules, and as a surfactant, polyethylene glycol, polyethylene One or more surfactants selected from glycol-distearate, styrene copolymer-based and polyvinyl alcohol and the like are used.

In addition, the aromatic component used in the present invention is not particularly limited to synthetic or natural flavors, but fruit flavors such as apples, grapes, lemons, oranges, limonene, pineapples, strawberries, quince, guava; Floral scents such as rose, lilac, lily, lavender, jasmine and the like; At least one of vegetable flavors such as natural vanilla and hazelnuts can be used.

When using the natural lemon, natural orange, natural limonene, natural vanilla flavor and the like among the aromatic components can be added to the aromatic resin composition due to the antimicrobial activity of the natural flavor.

In addition, the present invention is a fragrance packaging products such as sweets bags, shopping bags, poly bags, candy cans, cosmetic cases prepared using the sustained-release resin composition; Scented synthetic leathers applied to furniture floorboards and wallpaper; Provides fragrant golf equipment such as golf balls, golf bags and golf gloves.

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

The impregnated fragrance powder is prepared by adsorbing the fragrance after pretreatment of the carrier and adding a fixing agent, and the microcapsule powder is prepared by interfacial polymerization method, in-si polymerization method, etc. using resin and other additives after the fragrance is emulsified. It is encapsulated and dried immediately using a spray dryer to produce a powder.

The sustained-release aromatic polymer composition of the present invention is prepared by mixing the impregnating fragrance and the microcapsule powder in a synthetic resin and undergoing a process of melt molding. The base resin may be polyolefin resin such as polypropylene, polyethylene, polyvinyl chloride resin, polyurethane resin, ethylene vinyl acetate resin, aliphatic polyester resin, ionomer resin and the like.

As a carrier of the impregnated fragrance powder used in the present invention, synthetic resins such as porous polypropylene resin, ethylene vinyl acetate resin, and porous inorganic materials such as silica, silica gel, zeolite, or natural products such as dextrin and gum are used, and high viscosity adhesives are used. By adding it, the volatilization loss of the fragrance is minimized even during high temperature processing at 200 ° C., thereby providing excellent steering properties. The amount of carrier added during preparation of the impregnated fragrance powder varies depending on the type of perfume, but 20 to 500 parts by weight relative to 100 parts by weight of the fragrance stock solution is appropriate, but preferably 50 to 200 parts by weight, more preferably 80 to 150 parts The parts by weight are most suitable for the fragrance and initial fragrance strength, with the binder preferably 10 to 40 parts by weight.

Urethane resin, urea-forminine resin, melamine-urea-formalin resin and melamine-formalin resin are used as the wall material of the microcapsule powder used in the present invention, and urethane resin and melamine-formalin resin are more preferable, and the surfactant is polyethylene glycol. , Polyethylene glycol-distearate, styrene copolymer or polyvinyl alcohol, etc. may be used. Depending on the type of selective application of a part of the resin or surfactant, an additive of weak base should be used in addition polymerization of the initial precursor. It is preferable to use a weakly acidic additive in the condensation polymerization of the prepared precursor to smooth the reaction.

In the preparation of the microcapsule powder, the surfactant is 1 to 30 parts by weight based on 100 parts by weight of the wall resin, and preferably 5 to 20 parts by weight is most preferred for emulsification. As the weakly basic additive, an organic acid chloride having an alkali metal ion such as sodium or potassium is mainly used, and 0.1 to 5 parts by weight is appropriate. In addition, as the weakly acidic additive, organic compounds such as acetic acid, formic acid, and oleic acid are used, but it is preferable to add 0.01 to 3 parts by weight for smooth encapsulation of the resin. The microcapsules used in the present invention may damage the wall material due to the processing pressure inevitably generated during the processing of the polymer, and at this time, since the internal core substance is released, the sustained release role of the capsule may be greatly impaired. While the thickness should be adjusted to withstand such pressure, on the one hand, if the overdesign is excessive, the sustained release of the fragrance may be excessively interfered, and thus the optimum wall thickness may be solved at the same time. Should be.

To the aromatic resin composition of the present invention, by adding organic inorganic materials such as antioxidants, catalyst residue neutralizers, antistatic agents, UV stabilizers, internal and external lubricants, dispersants, antiblocking agents, slip agents, etc., which have conventionally been used as synthetic resin additives in general, There is no problem in use, and there is no limitation in addition of dyes such as dyes, organic pigments and inorganic pigments to have a desired color.

The above compositions are physically mixed using a low speed mixer such as a ribbon blender, and then pellets are prepared by using a conventional single or twin screw extruder, or used as pellets, or by using injection, extrusion, compression, and blow molding machines. It can be molded and used. At this time, in order to obtain the maximum efficiency, it is desirable to suppress the temperature and pressure during processing as much as possible.

In addition, aroma components used in the present invention may be used both natural or synthetic aroma components, but when using the natural lemon, natural orange, natural limonene, natural vanilla flavor, etc. of the aroma components of the aromatic resin due to the antibacterial activity of the natural flavor Antimicrobial activity can be added to the composition.

Hereinafter, the antibacterial effect of the natural flavor will be described.

In order to determine the antimicrobial effect of natural fragrance, the antibacterial test of the pressure-adhesive method using natural orange and natural lemon fragrance was performed, and the results are shown in Table 1.

In the test method, E. coli and Staphylococcus were cultured for 1 hour at 25 ° C, and the number of bacteria was measured, and a certain amount of the fragrance solution was contacted with each bacterium. Was calculated.

% Reduction rate = {(number of bacteria after 24 hours of blank-number of bacteria 24 hours after contact)

/ Number of bacteria after 24 hours of blank} × 100

The results showed that the natural orange and lemon flavors had an excellent antimicrobial effect with a reduction of more than 97% after 1 hour.

Antimicrobial test results by pressure bonding method division Escherichia coli (> Escherichia coli) Staphylococcus (> Staphylococcus aureus) Immediately after contact (bacterial ml) After 1 hour (bacterial ml) % Reduction Immediately after contact (bacterial ml) After 1 hour (bacterial ml) % Reduction No addition 6.5 × 10 ³ 6.7 × 10 ³ - 6.1 × 10 ³ 6.2 × 10 ³ - Orange 6.5 × 10 ³ 〈120 98.0 6.1 × 10 ³ 〈80 98.5 lemon 6.5 × 10 ³ 〈80 98.5 6.1 × 10 ³ 〈120 98.0

Hereinafter, the present invention will be described in detail by way of Examples and Comparative Examples. However, the scope of the present invention is not limited by the following examples and comparative examples.

(Example 1)

100 g of silica gel was introduced into the impregnator using a rotary vacuum impregnator, and then water and foreign substances on the surface of the silica gel were removed for 1 hour at a rotation speed of 60 rpm, an internal temperature of 80 ° C., and a vacuum pressure of 60 cm Hg. After lowering to room temperature, a lilac impregnated flavor powder was prepared by impregnating 30 g of palmitate as a spraying agent and fixing agent for 30 minutes at a rotational speed of 150 rpm three times for 30 minutes at the same time.

200 g of lilac flavor and 300 g of styrene maleic hydride were added to the homomixer with an emulsifier and stirred at 300 rpm for 1 hour to make an emulsified state. After 30 minutes of reaction and caustic soda 1g was added to adjust the pH to neutral, the emulsifier was transferred to a homomixer with stirring, the reaction was further added for 200 minutes while adding 1 g of formic acid to adjust the pH to weak acid to complete the reaction. Let's do it. After cooling to room temperature, 20 g of ammonia was added to remove residual formalin and spray-dried at 180 ° C. to prepare lilac microcapsule powder.

15 g of each of the lilac impregnated fragrance powder and the microcapsule powder prepared as described above was mixed well with 970 g of polypropylene, and the screw speed was 300 rpm, the torque was 60 kg / cm 2, the extruder barrel temperature was 63 ° C./130° C./140° C./140° C. in a twin screw stirring extruder. A fragrant resin pellet was prepared by kneading extrusion under the conditions of / 140 ° C / 150 ° C / 150 ° C / 150 ° C / 160 ° C. The pellets thus prepared were evaluated for fragrance persistence through weight reduction due to fragrance and 10-point sensory test by 5 panelists for 10 days at a constant temperature of 80 ℃ in an aging tester. 1 and 2.

(Example 2)

Scented resin pellets were blow-up ratio = 5, Take-up speed = 15m / min, Screw speed = 50rpm, barrel temperature 130 ℃ / 160 ℃ / 185 ℃ / 195 using Haake's Rheocord 90 blown film processing equipment. A film having a thickness of 40 µm was prepared at a temperature of 0 ° C. Perfume persistence evaluation is the same as in Example 1 and the results are shown in Table 2, Figure 1 and 2.

(Example 3)

Except for using maltodextrin instead of palmitate as a fixing agent in Example 1 and the same as in Example 1 and the results of the perfume persistence evaluation is shown in Table 2.

(Example 4)

Except for using 10g impregnated fragrance powder in Example 1, 20g microcapsule powder is the same as in Example 1 and the results of the evaluation of perfume persistence are shown in Table 2.

(Example 5)

Except for using 20g impregnated fragrance powder in Example 1, 10g microcapsule powder is the same as in Example 1 and the results of the fragrance persistence evaluation is shown in Table 2.

(Example 6)

Except for using polyethylene instead of polypropylene in Example 1 and the same as in Example 1 and the results of the perfume persistence evaluation is shown in Table 2.

(Example 7)

Except for using the polyurethane in place of polypropylene in Example 1 and the same as in Example 1 and the results of the perfume persistence evaluation is shown in Table 2.

(Example 8)

Except for using the ionomer resin (Ionomer) resin in place of the polypropylene in Example 1 and the results of the fragrance persistence evaluation is shown in Table 2, Figure 1 and 2.

(Example 9)

61 parts by weight of PVC, 24 parts by weight of DOP as a plasticizer, 5 parts by weight of additives, 5 parts by weight of lilac-impregnated powder and microcapsule powder were mixed well, and made into a film at a temperature of 180 ° C. or higher in a PVC double sheet manufacturing machine. Is the same as in Example 1 and the results are shown in Table 2.

(Example 10)

In Example 1, the same as in Example 1 except for using the natural flavor of the orange flavor impregnated incense powder and microcapsule powder instead of the lilac flavor as a fragrance source and the results of the fragrance persistence evaluation are shown in Table 2, Figure 1 and 2.

(Example 11)

In Example 1, except for using a lemon flavor of natural flavor instead of a lilac flavor in the impregnated flavor powder and microcapsule powder is the same as in Example 1 and the results of aroma persistence evaluation is shown in Table 2.

(Example 12)

In Example 1, the same as in Example 1 except that the lavender (Lavender) flavor instead of the lilac flavor in the impregnated fragrance powder and microcapsule powder as a fragrance source, the results of the fragrance persistence evaluation are shown in Table 2.

(Example 13)

In Example 1, the same as in Example 1 except that the vanilla-nut (Vanilla-nut) flavor in the impregnated flavor powder and microcapsule powder instead of the lilac flavor as a fragrance source, the results of the fragrance persistence evaluation are shown in Table 2.

(Comparative Example 1)

Except for using the impregnated fragrance powder and microcapsule powder in Example 1 and using 30g of lilac flavored undiluted stock solution (liquid phase) is the same as in Example 1 and the results of the fragrance persistence evaluation are shown in Table 2, FIG.

(Comparative Example 2)

Except for using only 30g of impregnating fragrance powder without using the microcapsule powder in Example 1 and the fragrance persistence evaluation results are shown in Table 2, Figure 1 and 2.

(Comparative Example 3)

Except for using the microcapsule powder 30g without using the impregnating fragrance powder in Example 1, the same as in Example 1 and the results of the fragrance persistence evaluation is shown in Table 2, Figure 1 and 2.

Persistence Test Results Percent acidity (%) at 80 ° C Sensory test Remarks Early 3 days 5 days 7 days 10 days Early 3 days 5 days 7 days 10 days Example 1 100 60 47 35 28 10 8.2 6.4 5.9 4.0 Great Example 2 100 51 40 29 19 10 8.2 5.1 4.5 3.2 Great Example 3 100 56 42 31 24 10 5.8 4.1 2.9 2.6 Good Example 4 100 71 57 40 31 10 7.3 4.9 4.3 3.9 Great Example 5 100 50 32 27 18 10 8.9 5.3 3.5 2.9 Good Example 6 100 58 43 33 25 10 8.1 7.0 6.2 3.7 Great Example 7 100 56 43 34 22 10 8.4 6.9 5.5 3.4 Great Example 8 100 53 47 36 21 10 8.0 5.7 5.1 3.1 Great Example 9 100 65 58 48 30 10 7.8 5.4 3.8 2.7 Good Example 10 100 57 48 36 26 10 7.9 6.5 4.6 3.8 Great Example 11 100 53 44 33 23 10 7.5 5.9 5.3 2.5 Good Example 12 100 52 42 33 21 10 8.0 6.8 4.6 3.1 Great Example 13 100 54 43 32 27 10 7.2 6.3 4.1 2.8 Good Comparative Example 1 100 13 7 3 One 10 3.4 2.1 1.1 0.5 Very bad Comparative Example 2 100 50 36 25 18 10 6.8 5.3 3.6 1.6 Bad Comparative Example 3 100 69 53 41 32 10 5.3 4.0 3.0 1.1 Bad

However, in case of fragrance acidity, it is data of accelerated aging test at 80 ℃, and 1 day at 80 ℃ corresponds to about 60 days when inferred to 25 ℃ at room temperature through Arrenius equation.

2. In the case of sensory tests, it is the average of three data except the maximum and minimum values.

From the above results, the impregnation and microcapsules of the present invention could be maximized in terms of the stability and sustainability of the fragrance due to the thermal stability during the processing of the polymer and the sustained release effect of the microcapsules. Even when the effect was confirmed to be excellent.

The effect of the present invention is that the present invention is applied at the same time as the sustained-release fragrance resin composition impregnated fragrance powder and microcapsule powder is stable at high temperature during resin processing and in addition to the excellent initial fragrance strength by the impregnated fragrance powder, the fragrance due to the sustained release of microcapsules It is possible to control the durability of the strength, so it can be widely used in various applications. In addition, when using the fragrance of natural substances with antimicrobial power can increase the value of the product because it can exhibit additional functions such as antibacterial.

Claims (8)

0.1 to 10 parts by weight of the anti-fragrance powder prepared by adsorbing the fragrance component to the carrier and adding the fixing agent to 100 parts by weight of the base resin, and encapsulating the fragrance component using additives such as a wall resin and a surfactant. Sustained release fragrance resin composition consisting of 0.1 to 10 parts by weight of the aromatic microcapsule powder prepared by drying According to claim 1, wherein the content of the impregnated fragrance powder is 0.5 to 3.0 parts by weight based on 100 parts by weight of the base resin, the content of the aromatic microcapsule powder is 0.5 to 3.0 parts by weight based on 100 parts by weight of the base resin. Sustained release aromatic resin composition According to claim 1, wherein the base resin is a polyolefin resin such as polypropylene, polyethylene or copolymers thereof; Sustained release aromatic resin composition characterized in that the resin is at least one resin selected from polyvinyl chloride resin, polyurethane resin, ethylene vinyl acetate resin, aliphatic polyester resin and ionomer resin. The sustained-release aromatic resin composition according to claim 3, wherein the base resin is a trade name Surlyn resin (manufactured by DuPont, USA) which is an ionomer resin. According to claim 1, wherein the anti-fragrance powder is used in the carrier content of 20 to 500 parts by weight with respect to 100 parts by weight of the fragrance stock solution, 10 to 40 parts by weight of the fixing agent is used, the carrier is used such as silica, silica gel, zeolite Sustained release fragrance resin composition, characterized in that at least one carrier selected from the group consisting of inorganic compounds, porous polypropylene resins, synthetic resins such as ethylene vinyl acetate resin, and natural products such as dextrin and gum The method of claim 1, wherein the aromatic microcapsule powder is a wall resin for microcapsules, and at least one resin selected from urethane resin, urea-formalin resin, melamine-urea-formalin resin and melamine-formalin resin is used as a surfactant. Is a sustained-release aromatic resin composition characterized in that at least one surfactant selected from polyethylene glycol, polyethylene glycol distearate, styrene copolymer and polyvinyl alcohol is used. The method of claim 1, wherein the aromatic component is a synthetic or natural flavor, such as apple, grape, lemon, orange, limonene, pineapple, strawberry, Chinese quince, guava, fruit flavor; Floral scents such as rose, lilac, lily, lavender, jasmine and the like; Sustained release fragrance resin composition characterized in that at least one of plant flavors such as natural vanilla and hazelnut is used. Aromatic packaging products such as a bag, shopping bag, poly bag, candy box, cosmetic case manufactured using the sustained-release resin composition of claim 1; Scented synthetic leathers applied to furniture floorboards and wallpaper; Scented golf products such as golf balls, golf bags and golf gloves