KR102394911B1 - gel deodorant - Google Patents

Abstract

(식 중, R¹은 탄소수 1 내지 3의 알콕시기를 나타내고, R²는 수소원자 또는 수산기를 나타냄); 및/또는
(C2) 하기 일반식 (II):

(식 중, R³은 탄소수 10 내지 14의 알킬기를 나타냄)
로 표시되는 화합물의 1종 또는 2종 이상을 함유하는 것을 특징으로 한다.An object of the present invention is to provide a technique for suppressing the growth of bacteria and mold from the start of use to the end of the use without being affected by the adsorbent in a gel-form deodorant. The gel-form deodorant that has solved the problem includes the following components (A) to (D): (A) an adsorbent; (B) a gelling agent; (C) antibacterial and antifungal agents; and (D) a solvent, wherein component (C) comprises:
(C1) the general formula (I):

(Wherein, R ¹ represents an alkoxy group having 1 to 3 carbon atoms, and R ² represents a hydrogen atom or a hydroxyl group); and/or
(C2) the general formula (II):

(wherein R ³ represents an alkyl group having 10 to 14 carbon atoms)
It is characterized in that it contains one or two or more of the compounds represented by

Description

gel deodorant

The present invention relates to a gel-form deodorant, and more particularly, to a gel-form deodorant capable of inhibiting the generation or proliferation of bacteria or fungi.

BACKGROUND ART Conventionally, many deodorants and deodorants for removing odors generated in toilets, rooms, refrigerators, cars, and the like have been proposed. Among these, as the deodorant, a type of deodorizing agent in which a granular material having physical or chemical adsorption performance, such as activated carbon or zeolite, is stored in a bag having air permeability, and the odor is adsorbed to the granular material to remove it is generally known.

However, although such a deodorant is excellent in the deodorizing effect, there is a problem in that it is difficult to determine the replacement time of the deodorant without knowing the life of the deodorant, that is, the end time of the deodorant.

In order to solve this problem, the present applicant first developed and applied for a patent for a deodorant (hereinafter referred to as a "gel-form deodorant") obtained by dispersing an adsorbent in a gel (see Patent Document 1). This gel-type deodorant was very easy to use because it had a high deodorizing effect and easy to understand the termination time, but there was a problem that bacteria and mold grew in the gel-type deodorant itself depending on the environment of use.

On the other hand, although many gel formulations, such as a gel-form air freshener and a deodorant, have been proposed until now, the problem that these also generate|occur|produce and propagate bacteria and mold was known. As a means to solve the problem, it is usually practiced to mix an antibacterial and antifungal agent such as paraben and sodium benzoate in a gel deodorant.

However, even if these antibacterial and antifungal agents, which have been used in conventional gel-type perfumes and deodorants, are mixed with gel-type deodorants, the effect is not recognized at all, or the effect is exhibited unless the amount is significantly increased compared to the formulation amount for general gel formulations. It didn't happen. In addition, although the antibacterial and antifungal effect can be confirmed immediately after the preparation of the gel deodorant, the antibacterial and antifungal effect may decrease in the latter part of the use period of the gel deodorant. It has been estimated that these reasons are because antibacterial and antifungal agents such as parabens and sodium benzoate are adsorbed to the adsorbent dispersed in the gel deodorant.

Also, in recent years, from the viewpoint of safety for the human body and the environment, there are countries that have stricter regulations by the Positive List System for compounds that can be used as antibacterial and antifungal agents. As a result, effective antibacterial and antifungal agents that have been previously available cannot be used. On the other hand, with the compounds listed on the positive list, there is a problem that the antibacterial and antifungal effect cannot be obtained as a gel-type deodorant for the above reasons. .

As such, in the gel form deodorant, it is not possible to use the antibacterial and antifungal method employed in other gel formulations, and it is necessary to suppress the growth of bacteria or mold by other methods, and There has been a demand for the development of technologies for suppressing the occurrence or propagation of bacteria and fungi.

JP 2001-157706 A

The present invention has been made in view of the above situation, and in a deodorizing agent made by dispersing an adsorbent in a gel, without being affected by the adsorbent, from the start of use to the end of the boil, to provide a technique for suppressing the growth of bacteria and mold that's the task.

The present inventors have intensively searched for components that exhibit antibacterial and antifungal action without being affected by the adsorbent dispersed in the gel in a gel form deodorant. It was found that 3-alkylamino-1,2-propanediol has such properties, and by blending it with a gel-type deodorant, it is possible to effectively inhibit the generation and growth of bacteria and mold in the gel, thereby completing the present invention. made it

That is, the present invention provides the following components (A) to (D):

(A) adsorbent

(B) gelling agent

(C) Antibacterial and antifungal agent

(D) solvent

containing, component (C),

(C1) the general formula (I):

(wherein, R ¹ represents an alkoxy group having 1 to 3 carbon atoms, and R ² represents a hydrogen atom or a hydroxyl group); and/or

(C2) the general formula (II):

(wherein R ³ represents an alkyl group having 10 to 14 carbon atoms)

It is a gel-type deodorant, characterized in that it contains one or two or more of the compounds represented by

The gel-form deodorant of the present invention can prevent the occurrence and proliferation of bacteria and mold from the start of use to the end of use, and at the same time suppress a decrease in the function of the adsorbent, thereby maintaining the deodorizing effect.

The gel deodorant of the present invention contains component (A) an adsorbent, (B) a gelling agent, (C) an antibacterial/anti-fungal agent, and (D) a solvent.

Examples of the component (A) adsorbent include a conventionally known carbon-based adsorbent such as activated carbon such as coconut shell activated carbon, and charcoal such as charcoal; and silica-based adsorbents such as zeolite, silica gel, and layered zinc aluminosilicate, and one or more of these may be used. Among these, carbon-based adsorbents are preferable from the viewpoints of maintaining the deodorizing effect and stability of the gel, and in particular, it is more preferable to use (a1) activated carbon and (a2) non-charcoal in combination. In addition, it is preferable to use the adsorbent having a particle size of 100 mesh or more from the viewpoint of gel formation and adsorption capacity.

The content of the adsorbent (A) in the gel deodorant of the present invention is not particularly limited, but is usually 0.1 to 10% by mass (hereinafter only expressed as "%"), preferably 0.5 to 5%. (A) As the adsorbent, when (a1) activated carbon and (a2) binchotan are used in combination, the mixing mass ratio ((a1):(a2)) is preferably 2:1 to 1:1, and 3:2 to 1:1 is more preferable.

As the component (B) gelling agent, conventionally known ones such as carrageenan, gellan gum, agar, gelatin, guar gum, pectin, locust bean gum, xanthan gum, sodium alginate, and cellulose derivatives can be used, and one or two or more of these can be used. is available. Examples of the cellulose derivative include hydroxypropylmethylcellulose, hydroxyethylcellulose, and carboxymethylcellulose, and among these, hydroxypropylmethylcellulose is preferable. Among these, (b1) carrageenan and (b2) hydroxypropylmethylcellulose are preferable from a viewpoint of gel stability etc., and it is preferable to use these in combination.

The content of the component (B) gelling agent in the gel deodorant is not particularly limited, but is usually 0.1 to 10%, preferably 0.5 to 5%. As component (B), when (b1) carrageenan and (b2) hydroxypropylmethylcellulose are used together, the compounding mass ratio ((b1):(b2)) 10:1 to 1:1, and 7:1 to 2 It is preferable to combine them in a ratio of 1:1.

Component (C) an antibacterial and antifungal agent, (C1) a cinnamaldehyde derivative and/or a cinnamic carboxylic acid derivative represented by the following general formula (I), and/or (C2) 3- represented by the following general formula (II) contains one or two or more of alkyl amino-1,2-propanediol:

(Wherein, R ¹ represents an alkoxy group having 1 to 3 carbon atoms, and R ² represents a hydrogen atom or a hydroxyl group)

(wherein R ³ represents an alkyl group having 10 to 14 carbon atoms)

As a cinnamaldehyde derivative represented by the above formula (I), specifically, o-methoxycinnamaldehyde, m-methoxycinnamaldehyde, p-methoxycinnamaldehyde, o-ethoxycinnamaldehyde, m-ethoxycinnam aldehyde, p-ethoxycinnamaldehyde, o-propoxycinnamaldehyde, m-propoxycinnamaldehyde, and p-propoxycinnamaldehyde are exemplified. Among them, methoxycinnamaldehyde (o-methoxycinnamaldehyde, m-methoxycinnamaldehyde, p-methoxycinnamaldehyde) is preferable from the viewpoint of antibacterial and antifungal effects and deodorizing effects, and in particular (c1) o-methoxycinnamaldehyde is preferred. As the o-methoxycinnamaldehyde, one commercially available from Wako Junyaku Kogyo Co., Ltd. may be used. In addition, o-methoxycinnamaldehyde is included in a lot of cinnamon, and cinnamon essential oil or extract can be used.

On the other hand, as a cinnamic acid derivative represented by formula (I), specifically, o-methoxycinnamic acid, m-methoxycinnamic acid, p-methoxycinnamic acid, o-ethoxycinnamic acid, m-ethoxycinnamic acid, p- ethoxycinnamic acid, o-propoxycinnamic acid, m-propoxycinnamic acid, and p-propoxycinnamic acid are exemplified.

The content of the component (C1) in the gel deodorant is not particularly limited, but is usually 0.01 to 10%, preferably 0.025 to 2%.

Further, as the 3-alkyl amino-1,2-propanediol represented by the formula (II), specifically, 3-decylamino-1,2-propanediol, 3-undecylamino-1,2- propanediol, 3-dodecylamino-1,2-propanediol, 3-tridecylamino-1,2-propanediol, and 3-tetradecylamino-1,2-propanediol are exemplified. Among them, (c2) 3-dodecylamino-1,2-propanediol is preferable from the viewpoints of antibacterial and antifungal effects and deodorizing effects.

The content of the component (C2) in the gel deodorant is not particularly limited, but is usually 0.01 to 2%, preferably 0.01 to 0.5%. In addition, it is preferable to use (c1) and (c2) together from the viewpoint of inhibiting the growth of bacteria and mold, maintaining the deodorizing effect, etc., in that case, the compounding mass ratio ((c1): (c2)) is 20:1 to 1:5 is preferable, and it is preferable to set it as the range of 10:1 - 1:3.

Moreover, by emulsifying and dispersing component (C1) and/or component (C2) in surfactant beforehand, preparation of the gel form deodorizing agent of this invention can be performed easily. As the surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl amino ether, polyethylene glycol fatty acid ester, polyoxyethylene polyoxypropylene glycol, sorbi Carbon fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil ether, sodium alkylsulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium dialkylsulfosuccinate, polyoxyethylene Alkyl ether phosphoric acid, polyoxyethylene alkyl phenyl ether phosphoric acid, palm oil fatty acid sodium methyl taurine (N-cocoyl-N-methyl taurine sodium), lauryl sulfate triethanolamine, sodium lauryl sulfate, lauroyl sarcosine sodium, laur Roylmethylβ-alanine sodium solution, lauroylmethyltaurine sodium solution, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, alkyldiaminoethylglycine hydrochloride solution, lauryldimethylamino Betaine acetate, etc. are mentioned. In addition, (c2) 3-dodecylamino-1,2-propanediol can be used also as a surfactant, so it is also possible to use (c1) and (c2) together to form an emulsified and dispersed state. Formulations in which o-methoxycinnamaldehyde and 3-dodecylamino-1,2-propanediol are blended with a surfactant, such as "GL-200" manufactured by BJ BIOCHEM, are also commercially available and may be used.

In the present invention, it is preferable to use (c3) ethylenediamine disodium tetraacetate (EDTA) in combination as component (C) from the viewpoints of suppression of growth of bacteria and mold, long-term maintenance of the deodorizing effect, and the like. The content of EDTA is not particularly limited, but is usually 0.001 to 1%, preferably 0.01 to 0.1%. Although the content in particular in the gel-form deodorant of component (C) antibacterial/antifungal agent is not restrict|limited, Usually, it is 0.02 to 10 %, Preferably it is 0.04 to 3 %. In the present invention, as component (C), components other than (c1), (c2) and (c3) may be used, but it is preferable to use only (c1), (c2) and (c3).

As a component (D) solvent, glycols, such as alcohols, such as water, ethanol, and propanol, propylene glycol, and ethylene glycol, etc. are mentioned. In addition, 3-methoxybutanol, 1-methoxy-2-butanol, 1-methoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate A solvent having an antibacterial and antifungal effect such as these can also be used. Among these, (d1) water and (d2) ethanol are preferably used from the viewpoints of ease of gel adjustment, stability of the gel, clarity of the end point of use, and the like, and particularly, it is preferable to use them in combination.

The content of the component (D) in the gel deodorant is not particularly limited, but is usually 80 to 98%, preferably 85 to 95%. In general, in a gel deodorant, if the content of water increases, bacteria and mold are more likely to occur. It can suppress the occurrence and growth of mold. The upper limit is, for example, 95% or less, preferably 90% or less. Moreover, 0.1 to 15 % is preferable and, as for content in the case of using (d2) ethanol together, 1 to 10 % is more preferable. It is preferable to set it as 90:1-10:1, and, as for these compounding mass ratio ((d1):(d2)), 80:1-10:1 are more preferable. In the present invention, even without using the solvent having the antibacterial and antifungal effect, it is possible to suppress the generation and proliferation of bacteria and mold during the period of use.

In addition, various additives can be added to the gel-form deodorant of the present invention to the extent that it does not affect the gel formation. As an additive, alkali metal salts, such as sodium chloride, and alkaline-earth metal salts, such as calcium chloride, etc. are mentioned, for example as a gel strengthening agent. In addition, deodorant components such as surfactants, preservatives, ultraviolet absorbers, organic acids, pigments, fragrances, copper sulfate and plant extracts may be added.

The gel deodorant of the present invention can be prepared by mixing the components (A) to (D) and optional additives added as necessary according to a known method. For example, (B) gelling agent, (C) antibacterial/anti-fungal agent and surfactant are added to (D) solvent such as water, heated and stirred, and (A) powder adsorbent is dispersed in a small amount of water. It can be prepared by adding the above mixture, further stirring to obtain a homogeneous solution, finally pouring the solution into a container, cooling and gelling.

As a preferred aspect of the gel deodorant of the present invention, the following compositions can be exemplified.

(A) adsorbent

(a1) 0.3 to 3% activated carbon

(a2) 0.2 to 2% of bincho charcoal

(a1):(a2) = 3:2 to 1:1

(B) gelling agent

(b1) 0.4 to 5% carrageenan

(b2) hydroxypropylmethylcellulose 0.1 to 2%

(b1):(b2) = 10:1 to 1:1

(C) Antibacterial and antifungal agent

(c1) 0.025 to 2% of o-methoxycinnamaldehyde

(c2) 3-dodecylamino-1,2-propanediol 0.001 to 1%

(c3) EDTA 0.01 to 0.1%

(c1):(c2) = 20:1 to 1:5

(D) solvent

(d1) 87 to 90% water

(d2) ethanol 1 to 10%

(d1):(d2) = 90:1 to 10:1

[Example]

Next, Examples and Test Examples are given and the present invention will be described in more detail, but the present invention is not limited to these Examples in any way.

Example 1

According to the composition shown in Table 1, a gel-form deodorant was prepared by the following method.

ingredient Invention 1 Comparison 1 Comparison 2 Comparison 3 One GL-200 ^※1 0.3 — — — 2 parabens — — 0.3 — 3 sodium benzoate — — — 0.3 4 carrageenan 2 2 2 2 5 charcoal 0.4 0.4 0.4 0.4 6 activated carbon 0.6 0.6 0.6 0.6 7 copper sulfate 0.05 0.05 0.05 0.05 8 Bamboo Extract ^※2 0.1 0.1 0.1 0.1 9 Hydroxypropylmethylcellulose 0.4 0.4 0.4 0.4 10 sodium chloride 0.5 0.5 0.5 0.5 11 EDTA 0.04 0.04 0.04 0.04 12 95% ethanol 7 7 7 7 13 water 88.61 88.91 88.61 88.61 Sum 100 100 100 100 ※1: o-methoxycinnamaldehyde content 15 to 40%, 3-dodecylamino-1,2-propanediol content 5 to 30%, BJ BIOCHEM
※2: GT-C12WBB097, manufactured by Ewoo chem

[quite]

Components 1 to 11 were dispersed in components 12 to 13, heated and stirred at 70° C., poured into a glass beaker, and gelled by standing at room temperature to obtain a gel deodorant.

Test Example 1

Each gel-form deodorant prepared in Example 1 was heated to 80° C. again to dissolve it, and then poured into a sterilized petri dish by 30 g each, and cooled and solidified. A sterilized round piece of paper with a diameter of 10 mm was inoculated with 50 μl of each of the following three types of bacteria or mold suspensions, and then this paper piece was brought into contact with the gel in a petri dish and left still. After 1, 2, and 3 days from standing, each piece of paper was collected and suspended in 10 ml of sterile physiological saline. 100 μl of this physiological saline solution was inoculated into TSA medium for bacteria and SDA medium for fungi, and then cultured in an incubator for 48 hours and 72 hours for bacteria, and visually observed the growth of bacteria and fungi, as follows. It was evaluated according to the criteria. These results are shown in Table 2.

[Test bacteria/fungi]

Bacteria: Bacterial solution prepared by mixing the following three types of bacteria in a 1:1:1 ratio

Pseudomonas aeruginosa ( KCTC 2513)

Staphylococcus Aureus ( Staphylococcus Aureus , KCTC 3881)

E. coli ( Escherichia Coli , KCTC 2571)

Mold 1: Candida Albicans ( KCTC 7965)

Mold 2: Aspergillus niger ( Aspergillus Niger , KCTC 6317)

[Evaluation standard]

+: Growth of fungus and mold is confirmed.

±: Very little growth of bacteria/fungi was observed.

-: Growth of fungus and mold is not confirmed.

Invention 1 Comparison 1 Comparison 2 Comparison 3 fungus 1 day later - + + + 2 days later - + + + 3 days later - + + + mold 1 1 day later - + + + 2 days later - + + + 3 days later - + + + mold 2 1 day later - + + + 2 days later - + + + 3 days later - + + +

In Comparative Products 1 to 3, growth of both bacteria and mold was confirmed, whereas in Product 1 of the present invention, generation of bacteria and mold was completely prevented.

Test Example 2

Each gel-form deodorant prepared in Example 1 was dried until the weight became 1/2, and a gel-form deodorant in the state of the latter period of use was created. The gel was cut with a sterile knife and placed on a sterile petri dish. A sterilized round piece of paper with a diameter of 10 mm was inoculated with 50 µl each of a suspension of three types of bacteria or mold as in Test Example 1, and then this piece of paper was brought into contact with the gel in a petri dish and left still. After 1, 2, and 3 days from standing, each piece of paper was collected and suspended in 10 ml of sterile physiological saline. 100 μl of this physiological saline solution was inoculated into TSA medium for bacteria and SDA medium for fungi, and then cultured in an incubator for 48 hours and 72 hours for bacteria, visually observing the growth of bacteria and fungi, and testing It evaluated in the same manner as in Example 1. These results are shown in Table 3.

Invention 1 Comparison 1 Comparison 2 Comparison 3 fungus 1 day later + + + + 2 days later - + + + 3 days later - + + + mold 1 1 day later - + + + 2 days later - + + + 3 days later - + + + mold 2 1 day later + + + + 2 days later - + + + 3 days later - + + +

For all comparative products, antibacterial and antifungal effects were not confirmed, whereas in this invention product 1, bacteria and mold 2 survived at the time point 1 day later, but died after 2 days, and at the end of use It was also confirmed that the antibacterial and antifungal effects were maintained.

Example 2

About this invention product 1 obtained in Example 1, the deodorization test was implemented by the test method shown below. A result is shown in Table 4.

[Test Methods]

The product 1 of the present invention prepared in Example 1 was cut into cubes of 2 cm square, respectively, and this was used as a sample. This sample was placed in a 2-liter desiccator, and ammonia and hydrogen sulfide were injected as malodorous gases. The concentration after injection of the malodorous gas (initial concentration; A (ppm)) and the concentration after 180 minutes (B (ppm)) were measured with a detection tube, and the deodorization rate was calculated using the following formula. The deodorization rate was similarly calculated|required also about the blank which did not put a sample in the desiccator.

ammonia smell hydrogen sulfide smell Invention 1 100 100 blank 0 0

For Product 1 of the present invention, a decrease in the deodorizing effect during the period of use was not confirmed.

Example 3

Formulation example:

According to the composition of Table 5, a gel deodorant was prepared in a polypropylene container. While this deodorant exhibited a good deodorizing effect, it was possible to obtain a formulation with high utility value without any growth of bacteria or mold on the surface of the gel from immediately after preparation to the end of use.

ingredient gel deodorant One o-Methoxycinnamaldehyde ^※1 0.1 2 3-Dodecylamino-1,2-propanediol 0.05 3 carrageenan 2 4 charcoal 0.4 5 activated carbon 0.6 6 copper sulfate 0.05 7 Bamboo Extract ^※2 0.1 8 Hydroxypropylmethylcellulose 0.4 9 sodium chloride 0.5 10 EDTA 0.04 11 95% ethanol 7 12 water 88.76 Sum 100 ※1: Wako Junyaku Kogyo Co., Ltd. product
※2: GT-C12WBB097, manufactured by Ewoo chem

The gel-type deodorant of the present invention is useful as a gel-type deodorant that can be applied under a wide range of conditions, since there is no growth of bacteria or the generation of mold during the period of use, and the deodorizing effect can be maintained.

Claims (15)

As a deodorant in gel form,
The following components (A) to (D):
(A) adsorbent
(B) gelling agent
(C) Antibacterial and antifungal agent
(D) solvent
containing, wherein component (C) comprises:
(C1) the general formula (I):

(wherein, R ¹ represents an alkoxy group having 1 to 3 carbon atoms, R ² represents a hydrogen atom or a hydroxyl group) one or two or more compounds; and
(C2) the general formula (II):

(wherein R ³ represents an alkyl group having 10 to 14 carbon atoms)
A gel-type deodorant comprising one or two or more compounds represented by . The method according to claim 1, wherein (C1) is the following component (c1):
(c1) o-methoxycinnamaldehyde
Phosphorus, deodorant in gel form. The method according to claim 1, wherein (C2) is the following component (c2):
(c2) 3-dodecylamino-1,2-propanediol
Phosphorus, deodorant in gel form. The deodorant in gel form according to claim 1, wherein component (C) contains (c1) and (c2) in a mass mixing ratio of 20:1 to 1:5. 5. The composition according to any one of claims 1 to 4, wherein component (C) comprises the following components (c3);
(c3) EDTA
A deodorizing agent in gel form further comprising a. The gel deodorant according to any one of claims 1 to 4, wherein the component (A) adsorbent is one or more selected from the group consisting of activated carbon, charcoal, zeolite, silica gel and layered zinc aluminosilicate. 7. The method according to claim 6, wherein component (A) comprises the following components (a1) and (a2):
(a1) activated carbon
(a2) charcoal
A deodorizing agent in the form of a gel containing. The deodorizing agent in a gel form according to claim 7, wherein the components (a1) and (a2) are contained in a mass mixing ratio of 3:2 to 1:1. 5. The component (B) gelling agent according to any one of claims 1 to 4, wherein the gelling agent is selected from the group consisting of carrageenan, gellan gum, agar, gelatin, guar gum, pectin, locust bean gum, xanthan gum, sodium alginate and cellulose derivatives. One or two or more selected, gel-type deodorants. 10. The method according to claim 9, wherein component (B) comprises the following components (b1):
(b1) carrageenan
A deodorizing agent in the form of a gel containing. 11. The method of claim 10, wherein component (B) comprises the following components (b2):
(b2) hydroxypropylmethylcellulose
A deodorizing agent in gel form further comprising a. The deodorizing agent in a gel form according to claim 11, wherein the components (b1) and (b2) are contained in a mass mixing ratio of 10:1 to 1:1. 5. The composition according to any one of claims 1 to 4, wherein component (D) comprises the following components (d1) and (d2):
(d1) water
(d2) ethanol
A deodorizing agent in the form of a gel containing. 14. The deodorizing agent in a gel form according to claim 13, wherein the components (d1) and (d2) are contained in a mass mixing ratio of 90:1 to 10:1. The deodorizing agent in a gel form according to claim 13, wherein the content of component (d1) is 85 to 95 mass %.