JP3453549B2 - the film - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a film made of a thermoplastic resin having an aroma.

[0002]

2. Description of the Related Art A one-pack detergent in which a detergent for one wash is separately packaged in a water-soluble film or the like in consideration of consumer convenience is known (Japanese Patent Laid-Open No. 63-12467).

As a packaging material for a one-pack detergent, a polyvinyl alcohol-based packaging material is preferably used.
The polyvinyl alcohol-based packaging material has a characteristic that the permeation of the perfume in the contained detergent composition is prevented from being emitted due to its extremely low gas permeability, and the perfume has a long shelf life.
On the other hand, since the fragrance of the detergent composition encapsulated after passing through the polyvinyl alcohol-based packaging material is less likely to smell, the commercialized divided-pack detergent has no scent and becomes a tasteless dry product for consumers. The endless polyvinyl alcohol-based packaging material has a peculiar acetic acid odor, and there is a problem that it may give discomfort during use.

In order to solve the above, the inclusion of a fragrance in the film has the following problems. (I) Generally, a water-soluble film is formed by casting on a drum or an endless belt, but when the water-soluble film contains a mixed flavor, the mixed flavor will be volatilized by heating. When the content of the mixed fragrance is increased to compensate for this, the bleeding and the strength of the water-soluble film decrease. (II) Since the volatilization by heating differs depending on the fragrance material,
When it was made into a film, the scent was sometimes different from the original scent setting. To make up for this, if a mixed fragrance is created only with a group of fragrances with low volatilization, it will give a very heavy scent, and it is difficult to create a scent that is refreshing and clean for consumers.

For example, Japanese Patent Laid-Open No. 168437/1988 discloses a polyvinyl alcohol film for packaging an alkaline substance, and it is described that a fragrance may be blended if necessary. It has not reached the concrete suggestion of a solution to such a problem.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a film made of a thermoplastic resin having a refreshing fragrance that is pleasant to the consumer and masking the odor of acetic acid.

[0007]

The present invention relates to a film made of a thermoplastic resin, which contains 0.05 to 5% by weight of a compounded fragrance containing the following fragrance components (a) and (b):
The total amount of the fragrance components (a) and (b) in the prepared fragrance is 60 to 100% by weight, and the fragrance component (a) / the fragrance component (b) in the prepared fragrance is 7/3 to 3 /. 7 (weight ratio). (A) Fragrance component having a retention time of 60 minutes or more determined by the following gas chromatography measurement conditions (b) Perfume component having a retention time of 40 minutes or more and less than 60 minutes determined by the following gas chromatography measurement conditions (gas chromatography (Graphic measurement condition) Temperature rising condition: 300 at an initial temperature of 60 ° C. and a temperature rising rate of 2 ° C./min.
Temperature rising column: Capillary column Liquid phase: Dimethyl polysiloxane Film thickness: 0.25 μm Carrier gas: He 1.5 ml / min Injection port temperature: 300 ° C. Detector (hydrogen flame ionization detector) temperature: 300 ° C.

The present invention also relates to a thermoplastic resin containing 0.05 to 5% by weight of the mixed fragrance containing the above fragrance components (a) and (b) of the present invention. The total amount of components (a) and (b) is 60 to 100% by weight.
And the thermoplastic resin of the perfume component (a) / perfume component (b) = 7/3 to 3/7 (weight ratio) in the prepared perfume is cast into a film to form a film. It relates to a method of manufacturing a film. Further, the present invention relates to an article in which the contents of the above-mentioned film of the present invention, for example, a detergent is packaged.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION A film made of a thermoplastic resin of the present invention contains 0.05 to 5% by weight of a prepared perfume containing the perfume ingredients (a) and (b). Preferably 0.05-
It is 3% by weight, more preferably 0.1 to 1% by weight. The residual aroma in the film forming step is 0.05% by weight or more, and the film strength is 5% by weight or less.

A solubilizer such as dipropylene glycol, benzyl benzoate, isopropyl myristate, or abietic acid derivative may be added to the prepared fragrance.

The total amount of the fragrance components (a) and (b) in the prepared fragrance is 60 to 100% by weight, preferably 70 to 100% by weight, more preferably 80 to 100% by weight.
% By weight. Furthermore, the flavor component (a) in the blended flavor.
/ Fragrance component (b) = 7/3 to 3/7 (weight ratio),
Preferably (a) / (b) = 6/4 to 3/4.

In order to prevent a change in the scent and give a refreshing cleanliness, the ratio of the fragrance component (a) in the mixed fragrance is 3%.
0% by weight to 70% by weight, preferably 40% by weight
It is 60% by weight. That is, it is preferably 30% by weight or more from the viewpoint of fragrance stability and 70% by weight or less from the viewpoint of creating a refreshing scent.

Further, in order to realize a refreshing and clean scent, the ratio of the fragrance component (b) in the mixed fragrance is 30% by weight or more, preferably 40% by weight or more. If these conditions are satisfied here, a moderately comfortable and refreshing fragrance tone can be realized, and the change in the fragrance tone due to volatilization of the fragrance component in the film-forming step is small, which is preferable for masking the acetic acid odor.

The fragrance component having a holding time of less than 40 minutes is
Affects smoothness during film formation, resulting in deterioration of film quality,
Since it causes a decrease in production efficiency, it is preferably 40% by weight or less, more preferably 30% by weight or less, still more preferably 20% by weight or less in the mixed fragrance.

The embodiment of the gas chromatography measurement conditions in the present invention is, for example, as follows. (Gas chromatography measurement conditions) Equipment used: Hewlett-Packard Company 5890 series
2 Temperature rising conditions: initial temperature 60 ° C, temperature rising rate 2 ° C / min 300
Temperature rising column: 60 m x 0.25 mm (inner diameter) Capillary column (J & B wide pore capillary column DB-1) Liquid phase: dimethylpolysiloxane (non-polar) Film thickness: 0.25 μm Carrier gas: He 1.5 ml / Minute Sample inlet temperature: 300 ° C Detector (hydrogen flame ionization detector) temperature: 300 ° C.

The retention time referred to in the present invention means the time from the time of sample injection to the time when the peak of the chromatograph of the relevant component appears in the detector. In addition, the fragrance component is, for example, a compound for a compounded fragrance described in "Chemistry of fragrance" (published on September 16, 1983, author: Ryoichi Akahoshi, publisher: Yuzo Sakuma, publisher: Dainippon Tosho Co., Ltd.). is there.

As the fragrance component (a) having a retention time of 60 minutes or longer by gas chromatography, methyl dihydrojasmonate, ceryl methyl ether, hexyl salicylate, 4,6,6,7,8,8-hexamethyl-1,
3,4,6,7,8-hexahydrocyclopentabenzopyran, hexylcinnamic aldehyde, 3α-6
6,9α-Tetramethyldodecahydronaphtho [2,1
b] Furan, cyclopentadecanolide, benzyl salicylate, acetylcedrene, benzyl benzoate, ethylene brassylate, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde) and the like. .

Among these, 4, 6, 6, 7, 8, 8
-Hexamethyl-1,3,4,6,7,8-hexahydrocyclopentabenzopyran, 4- (4-hydroxy-
4-methylpentyl) -3-cyclohexene-1-carboxaldehyde, hexylcinnamic aldehyde,
It is particularly desirable to contain one or more perfume ingredients selected from the group consisting of cyclopentadecanolide.

As a perfume component (b) having a retention time of 40 minutes or more and less than 60 minutes by gas chromatography, pt
-Butyl cyclohexyl acetate, α-damascon,
7-methyl-3,4, -dihydro- (2H) -1,5-
Benzodioxepin-3-one, dimethyl anthranilate, coumarin, tricyclodecenyl propionate,
Aldehyde C-12 (linear), ethyl vanillin, heptyl cyclopentanone, cyclamen aldehyde, ethyl tricyclo [5.2.1.0 ^2,6 ] decane-2-ylcarboxylate, dynascon, tetrahydroindene-
m-dioxin, 2-methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -butane-1
-Ol, methylionone, β-naphthylethyl ether, lilial, raspberry ketone, helional, methyl b-naphthyl ketone, 1- (2-t-butylcyclohexyloxy) -2-butanol and the like.

Among these, pt-butylcyclohexyl acetate, ethyl vanillin, lilial, 1- (2
-T-butylcyclohexyloxy) -2-butanol,
Contain one or more perfume ingredients selected from the group consisting of 2-methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -butan-1-ol, coumarin, α-damascon. Is especially desirable.

The film made of the thermoplastic resin of the present invention is a film which is convenient for the user, when the contents are individually packaged and used in applications such as foods, pharmaceuticals, agricultural chemicals and household sundries. A water-soluble film that can function by being dissolved and allowing the contents to be taken out is preferable.

In particular, agricultural chemicals, laundry products (detergents, softeners,
It is effective to use it as a packaging material such as bleaching agent and sizing agent. For the convenience of the consumer, it is preferable to provide the product packaged in a usage amount unit.

Water-soluble film means 1 L of water at 40 ° C. or lower
And is more preferably dissolved in water at 10 ° C. or lower. Here, "melting" means an inner diameter of 105 m.
1L distilled water at a given temperature in a cylindrical 1L beaker of m
A stirrer with a total length of 35 mm and a maximum diameter of 7.5 mm (Kagyo Kyoei Co., Ltd., model SA-35, etc. is a suitable example) is stirred at 550 rpm to give a film (3 cm × 3 c).
m, 4 sheets) and continued stirring for 8 minutes, and the residue after passing through a sieve with an opening of 125 μm is 5% by weight or less of the charged film.
The following is more preferable.

From the viewpoint of stabilizing the prepared fragrance, it is preferable to incorporate a surfactant into the film made of a thermoplastic resin. Examples of the surfactant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, and the like, and a nonionic surfactant is more preferable.

In particular, a film made of a thermoplastic resin is
It is preferable to contain the nonionic surfactant in an amount of 0.01 to 5% by weight. It is more preferably 0.05 to 3% by weight, still more preferably 0.1 to 2% by weight. The peelability is 0.01% by weight or more, and the film strength is 5
It is less than or equal to wt.

The nonionic surfactant is, for example, an aliphatic alcohol having an aliphatic hydrocarbon group having 8 to 20 carbon atoms, a fatty acid residue having 9 to 21 carbon atoms and a fatty acid alkyl ester, or an aliphatic hydrocarbon group. Ethylene oxide (hereinafter referred to as EO) and propylene oxide (hereinafter referred to as PO) are added to a compound having at least one atom having an unshared electron pair, such as an aliphatic amine having 8 to 20 carbon atoms, by a conventional method. In general, the above-mentioned products, those containing a sugar-derived polyol as a hydrophilic group, and those containing fatty acid amides are common.

As the nonionic surfactant, an alkylene oxide adduct of a higher alcohol is preferable, and an alkylene oxide adduct of a higher alcohol represented by the following general formula (1) and / or (2) is more preferable. Particularly, the EO adduct of higher alcohol represented by the general formula (1) is preferable. R ₁ O (EO) _m H (1) [wherein, R ₁ has an average carbon number of 8 to 20, preferably 10
18 primary branched chain alkyl groups and / or secondary alkyl groups. EO is an ethyleneoxy group, m is preferably 1 to 40, more preferably 3 to 30, and further preferably 5 to 25 as the average number of moles added. ] _{R 2 O (EO) k /} (PO) l H (2) wherein, R ₂ is an average carbon number from 8 to 20, preferably 10 to
18 primary alkyl groups. EO is an ethyleneoxy group and PO is a propyleneoxy group. k and l are average addition mole numbers, k is preferably 3 to 30, and 5 to 25
Is more preferable, 1 is preferably 1-10, and more preferably 1-5. EO and PO may be random addition or PO may be added after EO is added, and vice versa. ].

As the nonionic surfactant, in addition to the above-mentioned ones, the following general formula (3) R _3- (OR ₄ ) _x G _y (3) [wherein R ₃ is a straight chain or a branched chain] An alkyl group having 8 to 18 carbon atoms, an alkenyl group, or an alkylphenyl group, R ₄
Is an alkenyl group having 2 to 4 carbon atoms, G is a residue derived from a reducing sugar having 5 or 6 carbon atoms, x is a number having an average value of 0 to 6, and y is a number having an average value of 1 to 10. ] Alkyl polysaccharide surfactants represented by the following formula, fatty acid alkanolamides, polyhydroxy fatty acid amides and the like can be added.

The water-soluble film preferably contains a plasticizer in order to improve processability, flexibility, hydrophilicity when dissolved in water, prevention of blocking during storage of the material, prevention of blocking during storage, and the like. . As the plasticizer, polyhydric alcohol plasticizers such as ethylene glycol, propylene glycol, glycerin, diglycerin, polyglycerin, polyethylene glycol (molecular weight: 600 or less) and trimethylolpropane are preferable, and glycerin is more preferable. Further, a coloring agent, a release agent and the like can be compounded or applied within a range that does not impair the gist of the present invention.

In order to increase the strength of the water-soluble film and improve the water solubility, the average particle size is 0.1 to 10 μm, more preferably 0.1 to 5 μm, and further preferably 0.2 to 3 μm.
The water-insoluble or poorly water-soluble powder of 0.
It is preferable that the content is 05 to 5% by weight, more preferably 0.1 to 4% by weight, and further preferably 1 to 3% by weight.
This makes it possible to reduce the amount of the thermoplastic resin used as the film raw material.

Examples of the water-insoluble or sparingly water-soluble powder include titanium dioxide, calcium carbonate, talc, insoluble silica, clay mineral, aluminosilicate, aluminum hydroxide, barium sulfate, silicate, pulp, and cellulose.
These may be used alone or in combination of two or more as required. Among these, titanium dioxide, calcium carbonate, talc, insoluble silica, and clay minerals are preferable in terms of storage stability and good appearance, and it is more preferable to use titanium dioxide and titanium dioxide in combination.

The water-soluble film is preferably a polyvinyl alcohol material having an unsaponifiable portion of 5 mol% or less, more preferably 3 mol% or less, in order to prevent deterioration of solubility in water due to the influence of the composition to be encapsulated. preferable. From the viewpoint of cold water solubility and alkali resistance, cation-modified, anion-modified and non-ion-modified polyvinyl alcohol are preferable. From the viewpoint of productivity, anion-modified polyvinyl alcohol such as carboxylic acid-modified or sulfonic acid-modified is more preferable, and maleic acid-modified polyvinyl alcohol is still more preferable. Further, from the viewpoint of flexibility at low temperature, nonionic modification is more preferred, and alkylene oxide modification (polyoxyalkylene modification is more preferred, polyoxyethylene modification is more preferred).

The modified amount of the modified polyvinyl alcohol is preferably such that the modified unit content is 0.1 to 20 mol%,
0.5 to 15 mol% is more preferable, and 1 to 10 mol% is further preferable. It is preferably 0.1 mol% or more from the viewpoint of solubility in water, and 20 mol% or less is preferable from the viewpoint of preventing the solubility from being lowered by forming a gel-like substance when added to water.

In terms of solubility, modified polyvinyl alcohol has an average molecular weight of polyethylene glycol as a standard,
When measured by gel permeation chromatography, it is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000.

As the method for producing the water-soluble film of the present invention, for example, an aqueous solution of a thermoplastic resin is mixed with a hydrolyzable ester compound and, if necessary, a surfactant, a plasticizer, a fragrance, etc. The method of casting and drying may be mentioned.

The thickness of the film of the present invention can be arbitrarily set according to the purpose of use, but is preferably 10 to 100 μm from the viewpoint of mechanical strength and water fast solubility, and 15 to 50 μm.
Is more preferable.

In addition, processability, touch when touched, solubility,
In order to improve blocking prevention during storage of the material, blocking prevention during storage of the laundry composition, and the like, it is preferable that the water-soluble film be provided with grid-like or hexagonal irregularities by embossing or the like.

[0038]

Examples Formulated perfume A used in the following examples and comparative examples
D is shown in Table 1.

[0039]

[Table 1]

Example 1 Polyvinyl alcohol modified with maleic acid (modification rate: 2 mol%) (saponification degree: 99 mol%): 100 parts by weight, water: 550
Parts by weight, glycerin: 10 parts by weight, Emulgen 120
(Nonionic surfactant obtained by adding 12 mol of EO to an alcohol having an average carbon number of alkyl group of 12; manufactured by Kao):
0.2 parts by weight, 0.5 parts by weight of the mixed fragrance A are dispersed,
After defoaming, while casting on a 120 ° C. drum, it was dried with 140 ° C. hot air (dry residence time 2 minutes) to obtain a long film having a water content of 7% by weight and a film thickness of 30 μm. The following evaluations were performed on this film.
The results are shown in Table 2.

<Evaluation of Unique Odor> Using the film of Example 1 containing the compounded fragrance and the film having the composition of Example 1 not containing the compounded fragrance, a specialized panel of fragrances (experienced developer of compounded fragrance) Sensory evaluation was carried out by a pair of comparisons by 10 people, and the evaluation was performed according to the following criteria. ◯: 8 or more panelists who do not feel the peculiar odor of the film Δ: 5 to 7 panelists who do not feel the peculiar odor of the film X: 4 or less panelists who do not feel the peculiar odor of the film <Evaluation of change in odor> With respect to the fragrance tone of the prepared fragrance itself and the film of Example 1 containing the prepared fragrance, a sensory evaluation was conducted by 10 expert panelists of the fragrance, and the evaluation was made according to the following criteria. ◯: 7 or more panelists who do not feel a change in scent tone Δ: 4 to 6 panelists who do not feel a change in scent tone X: 3 or less panelists who do not feel a change in scent tone

Example 2 A film was obtained in the same manner as in Example 1 except that the blended fragrance B was used. This film was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 1 A film was obtained in the same manner as in Example 1 except that the prepared fragrance C was used. This film was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 2 A film was obtained in the same manner as in Example 1 except that the blended fragrance D was used. This film was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Example 3 After polymerizing vinyl acetate and polyoxyethylene (EO average addition mole number 7) monoallyl ether, saponification reaction was carried out to obtain polyoxyethylene (EO average addition mole number 7) monoallyl ether / acetic acid. A vinyl copolymer was obtained. As for the copolymer, unsaponified vinyl acetate was 0.5 mol%, polyoxyethylene (EO average addition mole number 7) monoallyl ether was 4 mol%, and the average molecular weight was about 20,000.

100 parts by weight of the copolymer, 2 parts by weight of titanium dioxide (average particle size: 0.3 μm), 550 parts by weight of water, 10 parts by weight of glycerin, 0.2 part by weight of the above-mentioned Emulgen 120, 0.5 part by weight of perfume A. Part, and after defoaming, while casting on a 120 ° C drum,
After drying with hot air at ℃ (dry residence time 2 minutes), a long film having a water content of 6% by weight and a film thickness of 30 μm was obtained. This film was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Example 4 Polyvinylpyrrolidone (K-60, manufactured by Wako Pure Chemical Industries, Ltd.) 1
00 parts by weight, 550 parts by weight of water, 10 parts by weight of glycerin,
0.2 parts by weight of the above-mentioned Emulgen 120, a mixed fragrance B0.
After dispersing 5 parts by weight and defoaming, while casting on a 120 ° C. drum, it was dried with hot air at 140 ° C. (dry residence time 2 minutes), the water content was 7% by weight, and the film thickness was 30 μm.
A long film of m was obtained. This film was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0048]

[Table 2]

Example 5 To the film obtained in Example 1, an embossing roller having a deformed square pattern having a compression area ratio of 25% and a side of 2 mm was set at 120 ° C.
And embossed at a linear pressure of 30 kg / cm. Next, a bag of 8 × 8 cm that is heat-sealed on three sides is made, and 20 g of the detergent composition obtained as described below is filled,
The filling port was heat-sealed to obtain a divided packaged article.

(Detergent Composition) 35.7% by weight of water was added to a mixing tank having a stirring blade. After the water temperature reaches 55 ℃,
50% by weight of an aqueous solution of sodium linear alkylbenzene sulfonate (having 12 to 13 carbon atoms) 6.0% by weight, sodium tallow fatty acid 7.5% by weight, 4A type zeolite 22.
5% by weight, No. 1 sodium silicate 1.5% by weight, sodium sulfite 2.3% by weight, 40% by weight acrylic acid-maleic acid copolymer (sodium salt, 70 mol% neutralized, monomer ratio: acrylic acid / Maleic acid = 7/3 mol) aqueous solution 1
8.8% by weight, 0.5% by weight of a fluorescent dye (a 1/1 weight ratio mixture of Chinopearl CBS-X and Chinopearl AMS-GX (both manufactured by Ciba Specialty Chemicals)) and 5.2% by weight of Glauber's salt under stirring Was added. This was stirred for another 30 minutes to obtain a slurry (final temperature 60 ° C). The water content in this slurry was 50% by weight.

This slurry was supplied to a spray-drying tower, and spray-dried from the top of the tower to prepare spray-dried particles. The water content of the obtained spray-dried particles was 4.0% by weight.

37.3% by weight of the obtained spray-dried particles, amorphous aluminosilicate (Al ₂ O ₃ = 29.6% by weight, S
iO ₂ = 52.4% by weight, Na ₂ O = 18.0% by weight)
5.0% by weight and 29% by weight of powder SKS-6 (manufactured by Hoechst Tokuyama Co., Ltd., average particle size 50 μm) were put into a Loedige mixer (stirring granulator, manufactured by Matsusaka Giken Co., Ltd.). Stirring was started. 17 wt% of polyoxyethylene alkyl ether (having 12 to 16 carbon atoms and 7.0 moles of average EO added) is added thereto by spraying,
Granulation was performed. Next, 5.0% by weight of amorphous aluminosilicate was added to carry out surface modification. 4. The obtained granulated particles were put into a rotary kiln to obtain amorphous aluminosilicate 5.
0% by weight, enzyme (Cellulase K (JP-A-63-2646)
99) and Lipolase 100T (manufactured by Novo Co.) in a weight ratio of 3: 1) and 1.5% by weight, and 0.2% by weight of a fragrance was sprayed at the same time to obtain a laundry component. The obtained laundry component has a bulk density of 780 g / L and an average particle size of 48.
It was 0 μm.

Continuation of front page (56) Reference JP-A-8-183897 (JP, A) JP-A-6-116598 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1 / 00-101/16

Claims (7)

(57) [Claims] 1. A film made of a thermoplastic resin, containing 0.05 to 5% by weight of a blended fragrance containing the following fragrance components (a) and (b), wherein the fragrance component (a ) And (b) are in a total amount of 60 to 100% by weight, and the perfume component (a) / perfume component (b) in the prepared perfume is 7/3 to 3/7 (weight ratio). (A) Fragrance component having a retention time of 60 minutes or more determined by the following gas chromatography measurement conditions (b) Perfume component having a retention time of 40 minutes or more and less than 60 minutes determined by the following gas chromatography measurement conditions (gas chromatography (Graphic measurement condition) Temperature rising condition: 300 at an initial temperature of 60 ° C. and a temperature rising rate of 2 ° C./min.
Temperature rising column: Capillary column Liquid phase: Dimethylpolysiloxane Film thickness: 0.25 μm Carrier gas: He 1.5 ml / min Inlet temperature: 300 ° C. Detector (hydrogen flame ionization detector) temperature: 300 ° C. 2. The fragrance component (a) is 4, 6, 6, 7,
8,8-Hexamethyl-1,3,4,6,7,8-hexahydrocyclopentabenzopyran, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1
-The film according to claim 1, containing one or more perfume ingredients selected from the group consisting of carboxaldehyde, hexylcinnamic aldehyde, cyclopentadecanolide. 3. The fragrance component (b) is pt-butylcyclohexyl acetate, ethyl vanillin, lilial,
1- (2-t-butylcyclohexyloxy) -2-2
Contains one or more perfume ingredients selected from the group consisting of butanol, 2-methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -butan-1-ol, coumarin, α-damascon. The film according to claim 1 or 2. 4. The film according to claim 1, wherein the thermoplastic resin contains polyvinyl alcohol and / or modified polyvinyl alcohol. 5. A thermoplastic resin containing 0.05 to 5% by weight of a compounded fragrance containing the following fragrance components (a) and (b), wherein the fragrance components (a) and (b) in the compounded fragrance are included. ) Is 60 to 100% by weight, and the perfume component (a) / perfume component (b) in the prepared perfume is 7/3 to 3/7.
A method for producing the film according to any one of claims 1 to 4, wherein the thermoplastic resin having a (weight ratio) is cast into a film. (A) Fragrance component having a retention time of 60 minutes or more determined by the following gas chromatography measurement conditions (b) Perfume component having a retention time of 40 minutes or more and less than 60 minutes determined by the following gas chromatography measurement conditions (gas chromatography (Graphic measurement condition) Temperature rising condition: 300 at an initial temperature of 60 ° C. and a temperature rising rate of 2 ° C./min.
Temperature rising column: Capillary column Liquid phase: Dimethylpolysiloxane Film thickness: 0.25 μm Carrier gas: He 1.5 ml / min Inlet temperature: 300 ° C. Detector (hydrogen flame ionization detector) temperature: 300 ° C. 6. An article in which the contents are packaged with the film according to any one of claims 1 to 4. 7. The article according to claim 6, wherein the content is a detergent.