JPH02111760A - Hydantoin derivative - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula (R1 is H or OCH3; R2 is 8-20C alkyl). EXAMPLE:5-Benzylidene-3-octadecylhydantoin. USE:An additive for heat-sensitive recording materials and ultraviolet absorber. PREPARATION:5-Benzylidenehydantoin or 5-(3,4-dimethoxybenzylidene)hydantoin is obtained by a method for reacting hydantoin with benzaldehyde or veratrum aldehyde in the presence of an amino acid, etc., at 40-100 deg. in water or an aqueous solution for 1-10hr, etc., and the resultant compound is then reacted with an 8-20C alkyl halide in the presence of an alkali, such as NaOH, in a polar aprotic solvent at 50-200 deg.C for 5min-4hr to afford the compound expressed by the formula.

Description

[Detailed description of the invention] [Industrial application field 1 The present invention is based on Hidan! - Regarding in derivatives.

The compounds of the invention are extremely useful as additives for heat-sensitive recording materials and as UV absorbers.

[Prior art] A heat-sensitive recording layer containing a basic dye and a color developer that reacts with F111 dye 14 when heated to develop color is provided on a sheet base material (paper, polyester sheet, etc.), Heat-sensitive recording materials with surface protective layers formed according to
Widely used in thermal recording devices such as automatic ticket vending machines and various printers.

In recent years, as devices have been improved, diversified, and improved in performance, there has been a demand for highly sensitive heat-sensitive recording materials capable of high-speed recording, and quality requirements have become increasingly strict.

As a heat-sensitive recording material, it is required to have high whiteness and excellent stability in the colored and non-colored areas.
Up to now, there has been a method of adding stearic acid amide, etc. (Japanese Unexamined Patent Publication No. 139740/1983), and a method of adding p-
Method using benzyl hydroxybenzoanthate etc.
4-74762), a method of adding an aliphatic dibasic acid i5 and a dibasic acid aryl ester derivative (JP-A-5
8-71191), etc. have been proposed. Although these methods showed improvement in color development sensitivity, they were not satisfactory in terms of whiteness and stability of non-color development areas.

On the other hand, in the field of cosmetics, many ultraviolet absorbers have been developed to prevent the harmful effects of ultraviolet rays on the skin.

Currently, benzophenone derivatives, salicylic acid derivatives, oochinic acid derivatives, para-amino acid derivatives, oxic acid derivatives, etc. are used as ultraviolet absorbers. Also, in the field of resins, various ultraviolet absorbers are used to prevent oxidative deterioration. Among these, there are very few that have the efficacy, safety, solubility, and stability of JIE.

[Problems to be Solved by the Invention] As described above, in heat-sensitive recording materials, color development sensitivity and
Problems include the fact that there is no material that satisfies both the whiteness and stability of the non-color-developing area, and the lack of UV absorbers that have sufficient effects.

It is an object of the present invention to provide additives for heat-sensitive recording materials and ultraviolet absorbers that solve these problems.

[Means for Solving the Problems] The present inventors have studied the binding of a hydantoin derivative represented by the following general formula in order to develop a highly stable heat-sensitive recording material with excellent sensitivity and background whiteness. It has been found that it is extremely useful as an additive for materials. It has also been revealed that this hydantoin derivative has a high effect as an ultraviolet absorber.

Specifically, the hydantoin derivative of the present invention is represented by the general formula: [%] (wherein R1 is a hydrogen atom or a methoxy group, and I (2 represents an alkyl group of 8 to 20).

The present invention also provides an additive for heat-sensitive recording materials containing a hydantoin derivative represented by the general formula "Nijigami" as an active ingredient, and an ultraviolet absorber containing a hydantoin derivative represented by the general formula "P+P+" as an active ingredient.

The hydantoin derivative represented by the above general formula of the present invention is:
All are Dj-order compounds.

As a production method, for example, hydantoin is reacted with benzaldehyde or veratrumaldehyde to obtain 5-penzylidenehycuntoin or 5-(:1,4-dimethoxybenzylidene)hydantoin, which is then converted into an alkyl halide having 8 to 20 carbon atoms. There are ways to react with this.

The reaction between hydantoin and aldehyde is 1, for example, JP-A-60
2:3306: The method shown in Publication No. 3, that is, the method of reacting in water or an aqueous solution at 40 to 100°C for 1 to 10 hours in the presence of an amino acid or its salt, etc., 5
-Reaction of arylidenehydantoin and alkyl halide is described, for example, in Encycl, Chem, l'ech.

3rd Ed, Vnl, 12 p., 695, there is also the chisel method of I<tsuka, but as an effective method, 5-arylidenehydantoin is mixed with sodium hydroxide and potassium carbonate in a polar aprotic solvent. Examples include a method of reacting with an alkyl halide at 50 to 200°C for 5 minutes to 4 hours.

When the hydantoin derivative thus obtained is used as an additive in a heat-sensitive recording layer that involves the reaction between a colorless or light-colored basic dye and a color developer, it is also possible to use it in combination with 2-L. Furthermore, various known thermofusible substances can also be used in combination within a range that does not impede the effects of the present invention.

The amount of the additive having the above-mentioned specific structure used according to the present invention is not necessarily limited, but is generally 0.10 to 1 part (E!! is used in an amount of about 1.0 to 5.0 parts by weight. Examples of colorless to light-colored basic dyes constituting the recording layer of the heat-sensitive recording material include the following.

3.3-bis(p-dimethylaminophenyl)=6-dimethylaminophthalide, 3.3-bis(p-dimethylaminophenyl) phthalide.

3-(p-dimethylaminophenyl)-3-(1,2-
dimethylindol-3-yl)phthalate.

3-(p-dimethylaminophenyl)-3(2-methylindol-3-yl)phthalide, 3.3-bis(1,2-dimethylindol-;3-yl)-5-dimethylaminophthalide.

3.3-bis(l,2-dimethylindole-coyl)
-6-dimethylaminophthalide.

3.3-bis(9-ethylcarbazol-3-yl)-
6-dimethylaminophthalide, 3.3-bis(2-phenylindol-3-yl)-
6-dimethylaminophthalide, 3-p-dimethylaminophenyl-3-(l-methylpyrrol-3-yl)-6-dimegluami, triarylmethane dyes such as Noclide, 4,4'-bis-dimethylaminobenz Hydryl benzyl ether.

N-halophenyl-leukoolamine, N-2,4,
Diphenylmethane dyes such as 5-trichlorophenylleucoauramine, thiazine dyes such as benzoylleucomethylene blue p-nitrobenzoylleucomethylene pur, and 3-medylose bilodinaphthobilane.

3-ethyl-spiro-dinaphthopyran 3-phenyl-spiro-dinaphthopyran.

3-benzyl-spiro-dinaphthopyran, 3-methyl-
Naphtho(6°-methoxybenzo)spiropyran, 3.3°-cyclolospirodinaphthopyran.

Spiro dyes such as 3-propyl-spiro-dibenzobilane, rhodamine-B-anilinolactam, rhodamine (p-nitroanilino)lactam, rhodamine (0-chloroanilino)lactam, rhodamine B (p
-lactam dyes such as chloroanilino)lactam, 3-dimethylamitrimethoxyfluorane, and 3-diethylamino-6-methoxyfluorane.

3-diethylamino-7-methquine fluorane, 3-diethylamino-7-lyrolofluorane, 3-diethylamino-6-methyl-7-chlorofluorane.

3-diethylamino-6,fucymethylfluoran, 3-(N-ethyl-p-toluidino)-7-methylfluoran.

3-diethylamino-? -N-acetyl-N-methylaminofluorane, 3-diethylamino-7-N-methylaminofluorane.

3-diethylamino-7-diethylaminofluorane.

3-diethylamino-? -N-Mejiru N-benzylaminofluorane, 3-diethylamino-? -1'J-chloroethyl N-
Methylaminofluorane, 3-diethylamino-7-N-diethylaminofluorane, 3-(N-ethyl-p-toldino)-f;-medyl-
7-phenylaminofluorane, 3-(N-ethyl-p
-toluidino)-6-methyl-7-(p-toluidino)
Fluorane.

3-diethylamino-5-medy-7-phTnylaminofluoran 3-dibutylamino-〇-methyl-7-phenylaminofluoran, 3-diethylamino-7-(2-carbomethoxyphenylamino)fluoran.

3-(N-ethyl-N-1so-amyl)amino: 1
-(N-cyclohexyl-N-methylamino)-6-medy-7-phenylaminofluorane, :l-pyrrolidino-6-methyl-7-phenylaminofluorane, 3-piperidino-6-methyl-7 -Phenylaminofluorane.

3-diethylamino-6-methyl-7-xylidinofluorane.

:;-Diezylamino-7-(o-chloro[1phenylamino)fluoran.

; 1-dibutylamino-7-(o-chlorophenylamino)fur Aran.

:)-pyrrolidino-6-methyl-7-p-butylphenylaminofluorane 3-(N-methyl-N-n-amyl)amino 6-methyl-phenylaminofluorane, 3-(N-ethyl-
N-n-amyl)amino-6-methyl-7-phenylaminofluorane.

-6-methyl-7-phenylaminofluorane, 3-(
N-methyl-N-n-hexyl)amino-6-methyl-
7-phenylaminofluorane, 3-(N-ethyl-N
-n-hexyl)amino-6-methyl-7-phenylaminofluorane, 3-(N-ethyl-N-β-ethylhexyl)amino-6-methyl-7-phenylaminofluorane.

3-(N-Methyl-N-tetrahydrofurfurylamino)-6-methyl-7-phenylaminofluorane.

3-(N-ethyl-N-tetrahydrofurfurylamino)-6-methyl-7-phenylaminofluorane.

2.2-bis[4-[6°-(N-cyclohexyl-N
-methylamino)-3°-methylspiro[phthalide-3
,9°-xanthine 1-2′-ylaminocophenyl 1
propane.

2.2-bis[4-[6'-(N-cyclohexyl-N
-methylamino)-3゛-methylspiro(phthanodo-3
, 9'-ki→)'enteno)-2'-, ylamino]phenyl 1-butane cap.

In combination with the above-mentioned basic dyes, the color developer used in [11] is not particularly limited, and has the property of liquefying, vaporizing, or dissolving with increasing temperature;
Various color developers are used that have the property of developing color when in contact with the basic dye (F).

As a typical example.

4-tert-butylphenol.

a-Naphthol.

β-Naphthol.

4-A7delphenol.

4-tert-octylphenol, 4.4°-8ec-butylidene diphenol.

4-]J Nylphenol 4.4'-dihydroxy-diphenylmethane.

2.2-bis(4-hydroxyphenyl)propane, 4-Hydroxyacetophenol.

'I　-tert-Okujiriki Decor.

2.2°-dihydrocodiphenol, 2.2′-methylenebis(4-medy-6-Lert-isobutylphenol).

4.4'-isopropylidene bis(2tcrt-butylphenol), 2.2'-methylenebis(chlorophenol).

2°2°-bis(3-methyl-4-hydroxy)propane, 1.1-bis(4-hydroxyphenyl)ethane.

2.2-bis(4-hydroxyphenyl)-4-methylpentane.

4.4°-benzylidene bisphenol, hydroquinone, 4.4°-cyclohexylidene diphenol, 4.4°-dihydroxycyphenylsulfide, 4.4°-thiobis(6-t,erL-butyl-3-methyl phenol), 3,4-dihydroxydiphenyl-p-tolylsulfone.

4-Hydroxy-4'-chlorodiphenylsulfone.

4-hydroxy-4°-isopropoxydiphenyl sulfone, bis(3-allyl-4-hydroxyphenyl)-sulfone, 3-chloro-4-hydroxydiphenyl sulfone, 4.4′-dihydroxydiphenyl sulfone, hydroquinone monobenzyl ether, 4-hydroxybenzophenone, 2.4-dihydroxybenzophenone.

2.4.4'-trihydroxybenzophenone, 2.2
°, 4.4°-tetrahydroxybenzophenone.

dimethyl 4-hydroxyfucurate, Methyl 4-hydroxybenzoate, J-Tyl 4-hydroxybenzoate propyl monohydroxybenzoate, 3CC-Butyl monohydroxybenzoate.

Pentyl hydroxybenzoate.

One person! Roxyan, 9. Phenyl fragrant, -hydroxyan, 0. Benzyl fomarate, -tolyl hydroxybenzoate.

Chlorophenyl hydroxybenzoate, phenylpropyl hydroxybenzoate, phenethyl hydroxy'alpha hydrocyanate - p-methoxybenzyl hydroxybenzoate, p-chlorobendi4-hydroxybenzoate.

Penkumechishi/Nbisu 4-hydroxyan, 151 apricot acid.

Propyl gallic acid, l☆Lauryl edible acid Sudearyl gallate phenolic compounds such as An, 13. hydrocyanic acid.

p-Lert-butylbenzoic acid.

Trichlorbenzoic acid.

Terephthalic acid, 1-sec-butyl-4-hydroxyan, 2,6 #
, 3-cyclohexyl-4-hydroxybenzoic acid 3.5-dimethyl-4-hydroxybenzoic acid.

salicylic acid.

3-isopropylsalicylic acid, 3-t, crL-butylsalicylic acid, : I-pendylsalicylic acid, 3-(α-methylbenzyl)salicylic acid.

°(-chloro-5-(α-methylbenzyl)1-nolycylic acid, ;1,5-di-tcrL-butylsalicylic acid, phenyl-5-(a, α-dimethylbenzyl)salicylic acid.

; (Aromatic carboxylic acids such as 5-di-a-methylbenzylsalidylic acid, these phenol/P1 compounds, and aromatic carboxylic acids such as zinc, magnesium, aluminum, calcium, titanium manganese, tin, nickel, etc.) Examples include acidic substances such as salts with valent metals.

The ratio of basic dye to color developer is generally 1 part dye to 1 part dye.
The developer is used in an amount of 1.0 to 5.0 parts, preferably 1.5 to 3.0 parts. It should be noted that, of course, two or more of the basic dye and the color developer may be used in combination as necessary.

Basic dyes, color developers, and inorganic pigments may be added to the heat-sensitive recording material. Examples of inorganic pigments include calcium carbonate, aluminum hydroxide, talc, kaolin, diatomite, titanium oxide, and magnesium carbonate. , silicon oxide, etc.

In addition, the Je recording layer should be properly coated to prevent sticking when it comes into contact with a recording head or the like.

Dispersions of salts such as lead stearate and calcium stearate may be added to heat-sensitive recording materials as a binder to improve adhesion to substrates such as paper, and water as a dispersion medium. When used, starch, hydroxycellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, styrene-maleic anhydride copolymer, etc. are contained in an amount of 2 to 40% by weight, preferably 5 to 25% by weight of the total solids. When using an organic solvent such as , toluene, methyl ethyl ketone, etc. as a dispersion medium, methyl methacrylate resin etc. should be used in an amount of 10 to 50% of the total solids.
, preferably 20 to 40% by weight. Of course, the binder is not limited to these.

In order to prepare a heat-sensitive recording material using the various heat-sensitive coloring layer forming components described above, the commonly known method can be used. For example, basic dye 14, υn coloring agent,
Heat-fusible substances, pigments, and other additives are added to the binder and additives, either alone or with the salt dye alone, and the remaining components are mixed together with a polyvinyl alcohol aqueous solution, etc. It is added to an aqueous medium and pulverized and dispersed using a dispersion machine such as a ball mill or an ATRIU to prepare a coating liquid.Then, each dispersion liquid is mixed to prepare a heat-sensitive coloring layer coating liquid. Apply on a support such as paper according to the technique and dry.

The amount of coating liquid applied to a support such as paper is not particularly limited, and is generally 2 to 12 g/dry weight.
m", preferably in the range of 3 to 10 g/m2. The support is not particularly limited, and 5 papers, 1 synthetic fiber paper, 1 synthetic resin film, etc. can be used as appropriate.

Furthermore, it is possible to provide an overcoat layer on the recording layer for purposes such as protecting the recording layer, and on the other hand, it is of course possible to provide an undercoat layer on the support. Known technology can be added.

[Example] Hereinafter, specific examples of the synthesis of hydantoin derivatives of the present invention and examples of their use will be described in detail.

However, these are examples to facilitate understanding of the present invention, and the present invention is not limited to these alone, and is not limited thereto in any way.

(Synthesis Example 11 A 500 mQ separable flask equipped with a 5-benzylidenehydantoin total thermometer, a flow cooler, and a stirrer was set in a constant temperature bath.

Water 200mI2. Hydantoin 50, Og (=0.50
mol), benzaldehyde 53.0g (=0.
50 mol), glycine 2B, lg (=0
．． : 18 molL caustic soda 7, 5 g I = 0
．． 19Ill'ol) and stirred at 70 to 75°C for 7 hours.

Room? After cooling to a flat state, the crystals are collected by centrifugation and 5-
Benzylidenehydantoin 85.5f: The yield was 90.9% based on the obtained 6-hydantoin.

(Synthesis Example 2) Synthesis of 5-(:1,4-dimethoxybenzylidene)hydantoin In Synthesis Example 1, glycine was replaced with alanine 26, 8
IC (=O,: 10 mol), caustic soda to calcium hydroxide 8.6 g (=mouth, I5 mol), benzaldehyde to bellatol aldehyde 124.6 g (=
0.75 mol) and stirred at 80°C for 4 hours. During this period, the p of the reaction solution was 19.4 to 9.2. After cooling to room temperature, the crystals were collected by centrifugation and
-(3,4-dimethoxybenzylidene)hydantoin 1
04.5g ('4).84.2 for hydantoin
% yield.

(Example 1) A lβ separable flask equipped with a thermometer, a reflux condenser, and a stirrer was set in a constant temperature bath.

5-Benzylidenehydantoin obtained in (Synthesis Example 1) 04. l Og (=0.511 mol),
DMF 400g, n-octadecyl chloride 144,
Add 5 g (=0.501101) and 41.5 g (=0.30 mol) of potassium carbonate to make 90~l.
After stirring at OO°C for 3 hours to remove potassium chloride and unreacted potassium carbonate produced by the 4 reactions, D under reduced pressure
MF was distilled off to obtain a French-colored crude crystal. The crude crystals were recrystallized from 300 g O) M e OH to obtain 188.2 g of white crystals (85.4% of theoretical It).

This spectra include infrared absorption spectrum (IR), mass spectrum (MS'), nuclear magnetic resonance spectrum ('H-NM
As a result of structural analysis using a method such as R), it was recognized by GII to be 5-benzylidene-3-octadecylhydantoin (see Table 1! I?1).

(Example 2) In (Example 1), 130.5 g of n-hexadecyl chloride was used instead of n-octadecyl chloride.
(Example 1) except that (0.50+mol) was used.
) was performed. 170.6 g of white crystals were obtained (827% of theory).

This product was analyzed in the same manner as in Section A and was confirmed to be 5-pendinothene-3-hexadecylhydantoin (see Table 1).

(Example 3) 5-(3,4-dimethoxybenzylidene)hydantoin 124,,1 which was replaced with (!1) in (Synthesis Example 2) instead of 5-benzylidenehydantoin in (Example 1)
except that g [= [1,511n+ol] was used.

Perform the same operation as in (Example 1) to obtain 200 white crystals.
．． 8 g was obtained (E\theoretical amount 80.2%).

As a result of the second analysis as described above, it was confirmed to be 5-(3,4-dimethoxybenzylidene)-3-octadecylhydantoin (Table 1, 9jjQ).

(Example 4) In (Example 1), 5-(:1,4-dimethoxybenzylidenehydantoin 124, 1 g) obtained in (Synthesis Example 2) was used instead of 5-benzylidenehydantoin.
= 0.50 mol), n-tetradecyl chloride 130,5 instead of n-octadecyl chloride
The same operation as in Example 1 was performed except that 185.g (=0.50 mol) of white crystals was used. sg was 1°I (836% of theory).

This is 5-(3,4-dimethoxybenzylidene)
It was confirmed to be -3-tetradecyl chloride (see 1 J).

The measured values of the compounds obtained in (Example 1) to (Example 4) and other compounds obtained in the same manner are shown below.

(hereinafter 1τ: jz white) (Usage example 1) <Dispersion liquid A> 2.2-bis[4-[6°-(N-cyclohexyl-N
-methylamino)-3゛-methylspiro[phthalide-3
,9°-xanthine]-2°-ylamino1 phenyl]
1 part of 25 weight propane! 5% polyvinyl alcohol aqueous solution 25 Water
50 <Dispersion B> 3.4-dihydroxyphenyl-P-1-lylsulfone
25 Part by weight 15% polyvinyl alcohol aqueous solution 25 Water
50 <Dispersion C> 5-benzylidene-3-n-octadecylhydantoin 25; P placement part 15%
Polyvinyl alcohol aqueous solution ura 25 water
5()
[These compositions were ground and dispersed for 24 hours using a throat conditioner to form dispersions A, R, C,
adjusted.

Next, 10 parts by weight of liquid A>, 25 parts by weight of liquid <mouth>, 30 parts by weight of liquid <C>, and 3 parts by weight of 50% calcium carbonate dispersion.
0 parts by weight and 5 parts by weight of a 15% polyvinyl alcohol aqueous solution were mixed and stirred to obtain a clear liquid. The obtained ri3 liquid is
0 g/m'' base paper was coated with a wire bar to a drying rate of 1 Og/m'' and dried.

C usage example 2) Dispersion D> 5-(3,4-dimethoxybenzylidene)-:1-n
-Octadecylhydantoin 2Sffim portion 15
% polyvinyl alcohol water? 8 liquid 25 water
50
[Dispersion liquid <D> was prepared in the same manner as in (Use example 1).

<A> 1 night 101 ■... part, <8> liquid 25 (n view, <D>
A thermosensitive recording paper was prepared in the same manner as in (Use Example 1) except for using 30 parts by weight of the liquid.

(Use example 3) <Dispersion E> 3-(N-cycloheyasil-N-methylamino)-6-
Methyl-7-phenylaminofluorane 25 parts by weight 15% polyvinyl alcohol aqueous solution 25 Water
5
0//〈11〃UraF〉 Erosion f acid stearyl 25 inn Gunbu 15% polyvinyl alcohol aqueous solution 25〃Water
50
〃Dispersion G〉 5-Benzylidene-3-hexadecylhydantoin

25 ・Rid part 15% polyvinyl alcohol water ffi liquid 25 u water
50//Dispersion E
, F, G in the same way as (V! River 1), <+>
＞= I Oi[1tflll+, <Fo>=25r
rt part, <G> liquid 30 parts by weight, others (Use example 1)
Thermosensitive recording paper was prepared in the same manner.

(Comparative example 1) <C> tone? In the solution, stearic acid amide 1φ was used instead of 5-benzylidene-3-octadecylhydantoin.
A thermal recording paper was prepared in the same manner as in Use Example 1, except that 4 f Comparative Example 2) A thermal recording paper was prepared in the same manner as in Use Example 1, except that dispersion <C> was omitted.

The five types of heat-sensitive recording materials obtained in this way were tested at a temperature of 110°C using a thermal gradient tester to give l Kg/
A pressure of 1 cm" was applied for 0.2 seconds, and the resulting male-colored image was measured using a Macbeth densitometer.

The whiteness was measured using a Hunter whiteness meter.

In addition, the thermal stability test (1)
The whiteness after being left at 0°C for 124 hours was measured using a Hunter whiteness tester. The results are shown in Table 2.

(The following is a blank space) It can be seen that usage examples 1 to 3 in Table 2 have a better balance between color density and thermal stability than comparative examples 1.2.

Next, maximum absorption wavelengths and molar extinction coefficients of representative compounds among the hydantoin derivatives of the present invention are shown.

(Example 5) (Hereinafter blank) According to (Example 5), the hydantoin derivative of the present invention is
The absorption wavelength is in the UVA region, and the molar extinction coefficient is 2XlO
Since it has a high value exceeding ', it can be seen that it is highly effective as an ultraviolet absorber.

[Effects] The hydantoin derivatives of the present invention are novel compounds, and as clarified in the examples, these compounds improve the whiteness and thermal stability of non-color-forming areas while improving the color-forming sensitivity of heat-sensitive recording materials. It has an excellent effect on

In addition, as a UV absorber, there are still no suitable UV absorbers for UVA (long wavelength ultraviolet 400~
It is a compound that has a high absorption rate in the region of 320 nm), and is extremely useful in the fields of cosmetics, synthetic resins, etc.

Claims (3)

[Claims] (1) Hydantoin derivative represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 represents a hydrogen atom or a methoxy group, and R_2 represents an alkyl group having 8 to 20 carbon atoms.) (2) An additive for heat-sensitive recording materials containing the hydantoin derivative according to claim 1 as an active ingredient. (3) An ultraviolet absorber containing the hydantoin derivative according to claim 1 as an active ingredient.