JP2767279B2 - Aromatic resin composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an aromatic resin composition, and is used as an interior article, packaging, or packing as a molding material, a powder material, a filling material, a film material, etc. having an aroma. They are important as materials, containers, toys, daily necessities or industrial materials, and their industrial applications are extremely wide.

2. Description of the Related Art Attempts to attach aroma to plastics have been made for some time, and the following are known, for example.

That is, plastics containing a vinyl-based thermoplastic resin, a chlorine-containing plasticizer, and a fragrance (Nippon Tokkai Tokuho., Showa 48-19862)
No.), chlorinated polyethylene or a resin containing the same plus a fragrance (Nippon Tokkai Koho, No. 48-10242, No. 50-29015)
No. 53-8333), a fragrance supported on a hydrophilic poly (meth) acrylate (Nippon Tokkai Koho, No. 49-4946),
Solid fragrance in which volatile fragrance components are confined in a polymer (Japanese Patent Publication No. 53-99252, 56-67356), and a polyolefin to which a fragrance is added (Japanese Patent Publication No. 54-37974). issue),
Silicone rubber with spices
No. 0558, No. 59-135240, No. 60-60153), ethylene
Perfume added to a mixture of vinyl acetate copolymer and aromatic acid ester (Japanese Patent Publication No. 58-141225), perfume added to ethylene, vinyl acetate copolymer or ethylene acrylate copolymer Mono (Japanese special publication, No. 53-98352,
No. 56-121560), a compound obtained by adding an inclusion compound of a fragrance and cyclodextrin to a polymer material (Nippon Special Publication, Showa 55-500)
No. 58, No. 57-185372, No. 58-196257), resin blended with perfume to polycaprolactone (Nippon Tokkai Koho, 57-137351)
No. 1), polycarbonate with fragrance (Japanese Patent Publication No. 59-155451), solid fragrance containing 1 to 20% by weight of an aromatic component in polyoxyethylene polyoxyalkylene (meth) acrylate (Nippon Special Co., Ltd.) Public. No. 60-6610).

[Problems to be Solved by the Invention] The present inventors have conducted a number of additional tests on the above-mentioned known methods, and as a result, some of the following drawbacks appear depending on the case, and an excellent product is obtained. It was found difficult to produce for the purpose.

B) The type of fragrance is limited because the fragrance changes during operation.

B. Perfume causes excessive bleeding and adheres to clothes and objects.

(C) The addition operation and the heating and mixing operation are troublesome, and easily cause pollution in the vicinity.

D. Although it depends on the environment, the fragrance changes considerably during the storage of the product, and the quality deteriorates.

(E) It is difficult to form a precision molded product because the molded product loses its shape and cracks.

F. It is not easy to mix fillers, coloring agents, etc., and the molded product becomes non-uniform, resulting in aging due to an undesirable reaction in some cases.

Here, the present inventors have carried out a number of studies to eliminate these drawbacks, and have finally completed the present invention which should be noted.

[Means for Solving the Problems] That is, the inventors of the present invention have a flexural modulus of 15,000 to 30,000 kg / c.
100 parts of a synthetic resin having an ester bond having a softening temperature of 50 to 200 ° C. at m ² , and a general formula RCOXR ¹ where R and R ¹ are each a hydrocarbon group having 10 to 30 carbon atoms, and R,
R ¹ may be the same or different, and X is an oxygen atom (0), an imino group (NH) or an alkylenebisaminocarbonyl group [NHCnH ₂ nNHCO] (where n is an integer of 1 to 3) When hot-kneading 5 to 50 parts of a lubricant and 5 to 50 parts of a fragrance represented by｝, a large amount of a high-quality aromatic resin composition can be easily produced, and a high-quality product can be obtained. It acknowledges that it can be provided to the market.

Here, synthetic resins having an ester bond having a flexural modulus of 15,000 to 30,000 kg / cm ² and a softening temperature of 50 to 200 ° C. include vinyl acetate copolymer, (meth) acrylate / butadiene copolymer, and cellulose ester Plastics,
It is at least one polymer material selected from the group consisting of oxybenzoyl polyester, polyalkylene terephthalate, and unsaturated polyester resin. Also the general formula RC
OXR ¹ ｛where, R and R ¹ are each a hydrocarbon group having 10 to 30 carbon atoms, R and R ¹ may be the same or different, and X is an oxygen atom ( 0), imino group (N
H) or an alkylenebisaminocarbonyl group [NHCnH ₂ n
NHCO] (where n is an integer of 1 to 3) The lubricant represented by｝ is a higher resin acid ester of a higher alcohol,
At least one compound selected from the group consisting of bis (higher acyl) amide, methylene bis (higher acyl amide), ethylene bis (higher acyl amide), propylene bis (higher acyl amide) and wax; It is at least one scented substance selected from the group consisting of fragrances and powdered fragrances.

The flexural modulus is a method of expressing a flexural characteristic, which is one of the physical properties for evaluating a plastics material for molding, and is also referred to as a flexural modulus. Flexural modulus while changing the value of the load, the deflection of the bending test piece was measured, the load - calculated from computed using deflection curve, those represented in units of kg / cm ^2, this measurement method
It described in JIS K7203 _-1,982 and JIS K6911 _{-1 979.}

The softening temperature is intended to be used to evaluate the thermal properties of the plastics (especially heat distortion resistance), the test method In the JIS standard, Lee deflection temperature under load (so-called heat distortion temperature, JIS K7202 _- is displayed as ₁₉₇₇₎ Toka Vicat softening point (JIS K7206 _-1,982) or crash Berg flexible temperature (JIS K6745 _-1976). The most frequently used of these are the heat distortion temperature (° C) and the Vicat softening point (° C), which show similar values, but the latter often shows a slightly higher temperature than the former. Both are collectively referred to as softening temperature in the present invention. Although the softening temperature is different from the glass transition point, the melting point, or the continuous heat resistance temperature, plastics showing a temperature range that is almost the same in terms of numerical values are quite well known.

However, the bending softening temperature elastic modulus at 15,000~30,000kg / cm ² because the synthetic resins suitable for the present invention is an organic polymer material having an ester bond is 50 to 200 ° C., lubricants of the present invention, a perfume Many of the inventors of the present invention have found that synthetic resins deviating from the above conditions in terms of the formulation of the composition and the properties of the product cannot be used as aromatic resin compositions of excellent quality and practical interest. Experiment revealed. The synthetic resins awarded in the present invention include vinyl acetate copolymers, (meth) acrylate / butadiene copolymers, cellulose ester plastics, oxybenzoyl polyester, polyalkylene terephthalate, and unsaturated polyester resins. Or a mixture of two or more thereof, or a polymer alloy containing these as a main component. Specific polymers of these synthetic resins include ethylene-vinyl acetate copolymer, modified ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-vinyl chloride copolymer (graft polymer), polybutylene terephthalate, and (meth) Acrylic-modified polyvinyl chloride, (meth) acryl-modified ethylene-vinyl acetate copolymer, cellulose acetate, cellulose acetate butyrate, cellulose butyrate, (meth)
Acrylate / butadiene copolymer, (meth) acrylate / ethylene / propylene copolymer, polyester using p-hydroxybenzoic acid as a structural component, maleic ester polymer, fumaric ester polymer, unsaturated polyester prepolymer, modified unmodified And a saturated polyester prepolymer.

General formula RCOXR ¹ where R and R ¹ each have a number of carbon atoms
A hydrocarbon group of 10 to 30; R and R ¹ may be the same or different; X is an oxygen atom (0), an imino group (NH), or an alkylenebisaminocarbonyl group [ NH
CnH ₂ nNHCO] (where n is an integer of 1 to 3) represents a compound contained in a fatty acid ester lubricant and a fatty acid amide lubricant. At present, the mechanism of action of the lubricant on plastics has not been completely elucidated, but it is usually used to adjust the frictional force during molding of plastics.
The external lubricant and the internal lubricant are distinguished according to the method of reducing the frictional force. The properties of the lubricant according to the present invention are presumed to be structurally mainly internal lubrication and also have some external lubricity. However, the usual amount of lubricant used is 100 parts of synthetic resin per 1 part of lubricant. Part or less particularly preferably 0.3 to 0.5
It can be used only in the range of the part, and beyond that, it can not be slipped and molded. However, the lubricant used in the present invention uses a large amount, which cannot be considered by common sense, of 5 to 50 parts with respect to 100 parts of the resin, and it is said that kneading or molding is impossible in such a mixing example. It was.
On the other hand, in the present invention, 5 to 50 parts of the lubricant is
It has been found that a significant portion of the lubricant acts as a perfume retention agent, a plasticizer, a solving agent, or a gelling agent, and advantageously acts as a synthetic resin lubricant, since up to 50 parts are combined. This makes it possible to perform molding and other processing of the resin composition even if it is strange, and the composition of the lubricant and the fragrance does not cause excessive bleeding of the fragrance from the synthetic resin, and in some cases, the shape stability of the aromatic resin composition It has been found to act as an agent. As a result, the use of an unprecedentedly large amount of lubricant as shown in the present invention resulted in an aromatic resin composition having practically interesting properties.

What is important for achieving the present invention is that the composition and amount of the lubricant should be limited as described above, and if the conditions of the present invention are not met, undesired results are often obtained. Found in the experiment. Here, first, regarding the composition of the lubricant, it must be selected from esters, amides or bisamides having a long-chain alkyl group as described above. Representative examples thereof include, for example, decyl stearate, dodecyl stearate, myristyl stearate, cetyl stearate, stearyl stearate, palmityl stearate, decyl palmitate, dodecyl palmitate, myristyl palmitate, cetyl palmitate, Stearyl palmitate, palmityl palmitate, methyl hexacosyl methyl hexaconate, higher alkyl esters of montanic acid, waxes (Hoechst wax E), jojoba oil, hydrogenated jojoba oil, higher alkyl esters of hardened oil fatty acids, Ibota wax, carnauba wax , Candelilla wax, Mokuro, Sugarcane wax, Shellac wax, Beeswax,
Montan wax, wool wax, marine animal wax, hydrogenated marine animal wax, rice bran wax, stearic acid higher alkyl amide, palmitic acid higher alkyl amide, methylene bis-stearamide, ethylene bis-stearamide, propylene bis-stearamide, dioleyl Amide, higher fatty acid tallow amide, ethylene diamide oxystearate, N
-A single or a mixture of two or more higher alkyl higher fatty acid amides, many of which have a melting point of 35 to
It is in the range of 150 ° C, most of which have a melting point of 50-130.
The temperature is in the range of ° C. and is selected so as not to change the flavor of the fragrance due to impurities contained therein. The amount used was in the range of 5 to 50 parts, particularly preferably 7 to 40 parts, per 100 parts of the synthetic resin.

The fragrance referred to in the present invention is at least one fragrant substance selected from the group consisting of liquid fragrance, semi-solid fragrance and powder fragrance. Naturally, the fragrance component is as large as possible (for example, 70%). ~ 100%) included is awarded.

For this reason, it is better not to include general low-boiling organic solvents or powdering aids for the purpose of dilution (except for a small amount of adsorbent powder and clathrate powder) in the fragrance. And when blending the above-mentioned lubricant and fragrance, kneading under heating when kneading is to be performed, and in some cases kneading under an inert gas atmosphere or under pressure, the kneaded material is often cooled. It is convenient to powder, flake, or pelletize. The amount of this fragrance is 100 synthetic resin
It has been found that an excellent product is obtained when the amount is 5 to 50 parts per part, particularly preferably 6 to 35 parts per part. When the fragrance is used in this range for synthetic resins and lubricants, the fragrance of the product of the present invention continues to be emitted at room temperature for a long period of time, and since the shape can be kept constant, it can be used as a fragrance material for various uses. is there.

Fragrances can be applied to the present invention as cosmetic flavors or food flavors, and most of them are well-balanced with top notes, middle notes (also called body notes), base notes, last notes, and modifiers. Will be awarded. Typical fragrances are citrus notes, fruity notes, aldehyde notes, floral notes, spicy notes, woody notes, animal notes, minty notes, honey notes, vanillic notes, anise notes, green notes, lavender notes, mossy notes. Balsamic note, coniferous note, amber note, fusere note, modern note, bouquet note, oriental note, powdery note, flavor note, etc., which are well compatible with the lubricant of the present invention when heated.

The procedure for blending and kneading the synthetic resin, the lubricant and the fragrance is not particularly limited, but it is preferable to knead the mixture with heating in order to finally homogenize the aromatic resin composition. During the kneading, a colorant, a filler, an antioxidant, an antioxidant, an epoxy stabilizer, a metal soap or an organotin compound, an antistatic agent, a rust inhibitor, a flame retardant, etc. are added if necessary. However, what should be noted in this addition is that a small amount should be used so as not to change the incense tone of the aromatic resin composition. The compounding or kneading is carried out by a mixer, a kneader, a pelletizer, an extruder, an injection machine or the like, and a mixer type or a pelletizer type is generally and conveniently used. Hot kneading means that the kneading is carried out at 60 to 160 ° C., particularly preferably at 60 to 120 ° C., and the operation within a short time causes little fragrance emission. At this time, if a fragrance which is easily oxidized by air is contained, it is preferable that the mixture is kneaded in a sealed state in the presence of an inert gas (nitrogen gas, carbon dioxide gas, argon gas, freon, etc.). In the case of continuous kneading using an ordinary pelletizer, pelletization can be performed so that subsequent molding can be easily performed, and this is widely used as a raw material for molding ordinary plastics.

[Examples] The present inventors have clarified the superiority of the present invention through a number of experiments. However, in order to further explain the technical contents of the present invention, several representative experimental examples were extracted and implemented below. It will be shown as an example.

Example 1 20 parts by weight of an ester wax (Hoechst wax E, a lubricant manufactured by Hoechst) as a lubricant was melted in a nitrogen gas at 86 ° C. or less, and 10 parts by weight of jasmine flower essential oil was added thereto and quickly stirred to obtain a uniform mixture. After the solution was formed, it was rapidly cooled to a solid, which was then pulverized to obtain 25 parts by weight of a powder mixture.

Next, EVA-modified resin (flexural modulus 20,000 kg / cm ² softening point 90
℃) 100 parts by weight of hot melt resin and the above powder mixture 2
The mixture was mixed with 5 parts by weight and subjected to a pelletizer to obtain 120 parts by weight of an aromatic resin composition pellet having a light yellow jasmine scent. The pellet was calendered into a sheet by an extrusion machine, cooled to 10 ° C, punched into a flower pattern with a small hole in the center, and formed into a 3 mm thick aromatic resin composition flower-forming product. It continued to emit the scent of jasmine for about 6 months at room temperature and was inserted into the flower core of an art flower (artificial flower) to obtain an aromatic resin art flower of great commercial value.

Example 2 10 parts by weight of amorphous silica fine powder (Aerosil # 380, manufactured by Nippon Aerosil Co., Ltd.) was mixed with 20 parts by weight of coffee flavor oil and sufficiently impregnated, and then this was semi-cured jojoba as a lubricant. The mixture was dispersed in 20 parts by weight of oil at a warm temperature to obtain 50 parts by weight of a semi-solid composition. Next, 100 parts by weight of a polyvinyl acetate synthetic resin (Evaflex 45X, manufactured by Mitsui DuPont Polychemicals Co., Ltd.) was blended with 30 parts by weight of the above composition, and heated until melted under an argon atmosphere. The resultant was put on a drum / flaker to obtain 130 parts by weight of a flaky aromatic resin composition flake. If this flake is put in a small paper bag made of Japanese paper that can be heat-set in the mouth and sealed, it becomes a scented scented bag. During this time, no oozing of flavor oil was observed. This scent bag is used to advertise coffee beans and instadt coffee.

Example 3 15 parts by weight of montan wax (Hoechst Wax U, manufactured by Hoechst) as a lubricant was melted at 89 ° C. or less, and 20 parts by weight of a leather-like compounded fragrance was added thereto as a fragrance, followed by stirring to obtain a mixed solution. Make it. On the other hand, 15 parts by weight of the above mixed solution was added to 100 parts by weight of a powder of polybutyne terephthalate (flexural modulus 26,000 kg / cm ² ) having a low softening point (85 ° C.), and the mixture was vigorously stirred. Then, 100 ml of the dimethylformamide solution was added, and the mixture was vigorously stirred again to obtain an aromatic resin composition solution having a skin scent. This aromatic resin composition solution was applied to the surface of synthetic leather, dried, and dimethylformamide was evaporated to form a synthetic leather sheet having a leather smell. The product continued to emit the scent of skin at room temperature for a long time and was used as an exterior material for chairs, sofas or trunks.

Examples 4 to 11 Ethylene / vinyl acetate copolymer resin (Soarite / ME-
2, Nippon Synthetic Chemical Industry) After melting and mixing 100 parts by weight and 20 parts by weight of purified Ibotarou as a lubricant at 90 ° C or less,
10 parts by weight of the mixed flavor of red plum are added thereto, and the mixture is stirred in a stream of nitrogen gas to form a uniform solution. The mixture is rapidly cooled to form a solid, which is pulverized into a powder mixture. This powder is 2
When sandwiched between two pieces of cellophane paper and press cut in the shape of a 10-yen coin, a tablet of an aromatic resin composition having a fragrance of light yellow plum was obtained. When this tablet was sealed in a conventional twill weave scent bag and used as a handbag fragrance interpolated pouch, the fragrance was kept for about 12 months under normal use conditions, and the scent tone did not change much during this time Was. When using the natural flower essential oil and the compounded fragrance shown in the following table instead of the red plum in this method,
It was recognized that there was a difference in the fragrance retention period depending on the nature and fragrance of each fragrance, but all were suitable for scented sachets. The results are shown in the following table.

Example Fragrance Perfume period (Mon) 5 Rose flower essential oil Excellent 16 6 Jasmine flower essential oil Excellent 14 7 Prepared jasmine oil Good 10 8 Lavender oil Good 39 9 Hinoki oil Normal 3 10 Character extraction oil Excellent 24 or more 11 Rose floral bouquet Blend oil Excellent 6 Examples 12 to 20 The lubricants shown in the following table (the amount used is also shown) were melted at as low a temperature as possible, and 10 parts by weight of narcissus flower essential oil was added and stirred in a nitrogen stream to homogenize. Then, the mixture is rapidly cooled to form a solid, which is pulverized to obtain a powder mixture. This powder mixture and 100 parts by weight of EVA resin (Evatate, manufactured by Sumitomo Chemical Co., Ltd.) were mixed and pelletized to obtain pellets of an aromatic resin composition having a daffodils scent.

The pellets were cast in an injection molding machine to form a daffodil flower with a thickness of 2 mm, an artificial flower was assembled, stored at room temperature, and the retention period of the fragrance due to the magnitude of the affinity between the lubricant and the narcissus flower essential oil, the magnitude of the change in the incense tone and The results of testing the appearance of the molded product are as shown in the following table. Reference Examples 1 to 5 for comparison are also shown.

From Reference Examples 1 to 5 in this table, it can be seen that when using a lubricant, it is necessary to select the chemical structure and the amount to be used so as to achieve the object of the present invention.

Examples 21 to 25 100 parts by weight of a synthetic resin having a softening temperature of 60 to 200 ° C. shown in the following table,
30 parts by weight of decolorized and refined rice bran wax and 10 parts by weight of jasmine-based floral bouquet blended oil are placed in a closed container under nitrogen gas, stirred vigorously at 100-200 ° C for a short time, and then a stainless steel belt is taken out from the lower outlet of the container. The resin composition is discharged onto a breaker, quenched, solidified, scraped, and pulverized, and pressed into a business card having a thickness of 1 mm. The results of testing the molded product stored at room temperature are as shown in the following table. The test evaluation method is the same as in Examples 13 and 14 in the preceding table. For comparison, Reference Examples 6 to 12 using various synthetic resins having large flexural modulus deviating from the conditions of the present invention are also shown.

It can be seen from this table that the choice of the chemical structure of the synthetic resin is very important and has been related to the value of the flexural modulus. And a synthetic resin having an ester structure (curing temperature 50
〜200 ° C.) was found to be necessary for the present invention. Reference Examples 6 to 12 show the results of tests on synthetic resins not meeting these conditions, but none of the evaluations could satisfy the object of the present invention.

[Effects of the Invention] The present invention relates to an aromatic resin composition, which provides a new aromatic material that could not be produced by conventional techniques by a novel combination of a specific synthetic resin, a lubricant and a fragrance. It can be said that the effect of the present invention is enormous.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 31/04 C08L 31/04 A 33/06 33/06 47/00 47/00 67/00 67/00 101/12 101 / 12 (58) Field surveyed (Int.Cl. ⁶ , DB name) C08L 1/00-101/14 C08K 5/00-13/08 A61K 7/46

Claims (4)

(57) [Claims] 1. A synthetic resin having an ester bond having a flexural modulus of 15,000 to 30,000 kg / cm ² and a softening temperature of 50 to 200 ° C.
00 parts of the general formula RCOXR ¹ {However, R, R ¹ are each a hydrocarbon group with a carbon number between 10 to 30, also R, R ¹ may be a different, even the same, X is an oxygen atom (0), an imino group (NH) or alkylene bis aminocarbonyl group [NHCnH ₂ nNHCO] (where n is an integer of 1 to 3) lubricants 5-50 parts of perfume represented by} indicates one of 5-50
An aromatic resin composition obtained by kneading a part under heat. 2. A synthetic resin having an ester bond having a flexural modulus of 15,000 to 30,000 kg / cm ² and a softening temperature of 50 to 200 ° C. is a vinyl acetate copolymer or a (meth) acrylate / butadiene copolymer. The aromatic resin composition according to claim 1, which is at least one polymer material selected from the group consisting of cellulose ester plastics, oxybenzoyl polyester, polyalkylene terephthalate, and unsaturated polyester resin. 3. General formula RCOXR ^{1 wherein} R and R ¹ are each a hydrocarbon group having 10 to 30 carbon atoms, and R and R ¹ may be the same or different. well, X is an oxygen atom (0), an imino group (NH) or alkylene bis aminocarbonyl group [NHCnH ₂ nNHCO] (where n is an integer of 1 to 3) lubricant higher fatty acid esters of higher alcohols represented by showing a} Claims (1) or (1) wherein the lubricant is at least one lubricant selected from the group consisting of, bis (higher acyl amide), methylene bis (higher acyl amide), ethylene bis (higher acyl amide), propylene bis (higher acyl amide) and wax. The aromatic resin composition according to 2). 4. The aromatic resin according to claim 1, wherein the fragrance is at least one odorant selected from the group consisting of a liquid fragrance, a semi-solid fragrance and a powder fragrance. Composition.