JPH08198703A - Cut flower-prolonging agent - Google Patents

Abstract

PURPOSE: To obtain a cut flower-prolonging agent containing a water-soluble polymer having a specific nitrogen-containing heterocyclic compound as a struc tural unit as an active ingredient, having high prolonging effect, especially on rose, chrysanthemum and Gerbera hybrida, etc., having high bent neck preventing effect and hardly causing environmental pollution. CONSTITUTION: This cut flower-prolonging agent contains a water-soluble polymer having a nitrogen-containing heterocyclic compound as a structural unit as an active ingredient. The water-soluble polymer is e.g. a water-soluble polymer obtained by reaction of an imidazole compound of formula I (R<1> is H, an alkyl or phenyl; R<2> and R<3> are each H, methyl, an aldehyde, etc.) with a compound selected from a group comprising an epihalohydrin of formula II (X is a halogen), an alkylene dihalide of the formula X-B-X' (B is an alkylene; X and X' are each a halogen), a diepoxide of formula III (D is a direct bond, an alkylene, etc.) and a dihalogenoalkyl ether of the formula X-(R<4> -O)n -R<5> -X [R<4> and R<5> are each an alkylene; X is a halogen; (n) is 1-12]. The cut flower prolonging agent exhibits effect capable of prolonging admiring period from bud to 8/10 bloom.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a life-prolonging agent (freshness-maintaining agent) for fresh flowers, especially cut flowers. More specifically, during the transportation of cut flowers after harvest, at the distribution stage such as retail,
At the consumer stage after distribution, it is possible to significantly extend the viewing period of cut flowers by the effect of preventing deterioration of freshness due to withering of petals and leaves of cut flowers, yellowing of leaves, etc. and the effect of suppressing over-opening. It relates to an inexpensive agent for extending the life of cut flowers.
In particular, the life prolonging agent of the present invention has not been a conventional life prolonging agent,
Excellent effect on roses and chrysanthemums.

[0002]

2. Description of the Related Art In recent years, the consumption of cut flowers has tended to increase for purposes such as business use, work flowers, household use, etc., and brings more moisture to people's lives. At this time, it is very necessary to prevent the deterioration of freshness at the time of distribution from the production area distant to the consumption area or at the consumer stage, and the development of life-prolonging agents is very important because of the differentiation of the production area. Is. Drugs that extend the life span of cut flowers can be broadly divided into two types depending on the stage of use. That is, there are a pretreatment agent used by a producer for landing immediately after harvest and a post-treatment agent used in addition to ikebana (water for flowering) at the retail and consumer stages.

Post-treatment agents are mainly composed of nutrients such as bactericides, surfactants, inorganic salts, sugars and nitrogen, and various products are currently on the market. Furthermore, as the pretreatment agent,
An aqueous solution of silver thiosulfate complex salt (hereinafter abbreviated as STS)
It is said that cut flowers have a long life-prolonging effect. Vee
n (H.Veen and S.C.Vand
e Geijn "Mobility and Ioni
c Form of Silver as Relat
ed toCongevity of Cut Car
countries, Planta 140, 93-96 (1
Since 978),), various kinds of STS agents have been marketed in Japan and are widely used for cut flowers with high ethylene sensitivity known as plant aging hormones such as carnation, sweet pea, delphinium, gypsophila and the like. However, there is concern about environmental pollution due to silver.

On the other hand, various products are commercially available as life-prolonging agents (freshness-maintaining agents) for rose, chrysanthemum, gerbera, etc., for which the effect of STS agents is weak. In addition, a water-soluble quaternary ammonium-containing polysaccharide (or an aqueous solution containing a water-soluble quaternary ammonium-containing hydroxyalkyl polysaccharide) is used as an active ingredient (JP-A-1-121201), and abscisic acid is used as an active ingredient. Thing (JP-A-2-2895
No. 01) has been reported.

[0005]

However, none of the effects of these life prolonging agents (keeping freshness) are satisfactory. That is, those containing a bactericide as a main component are less likely to sustain their effects on consumers after distribution, and those containing silver in the component are not considered to be environmentally friendly in terms of waste liquid, and thus ethylene action inhibitors. However, there is still room for improvement in the case where the main component of is is that the stem conduit is closed by bacteria in the live water, leading to deterioration of freshness due to poor water supply.

The present invention solves the above-mentioned problems and has a particularly high life-prolonging (keeping freshness) effect on roses, chrysanthemums, gerberas, etc., to which the effect of the silver thiosulfate complex (STS agent) is small, and a particularly remarkable vent. Shows a neck (breaking neck) prevention effect and an effect of extending the viewing period from the buds to the eight-minute blooming, and has little environmental pollution (inexpensive)
The purpose is to provide a life-saving agent for cut flowers.

[0007]

The object of the present invention is achieved by a life-prolonging agent for cut flowers, which comprises, as an active ingredient, a water-soluble polymer having a nitrogen-containing heterocyclic compound as a structural unit. Hereinafter, the present invention will be described in detail. The life prolonging agent used in the present invention contains a water-soluble polymer having a nitrogen-containing heterocyclic compound as a structural unit as an active ingredient.

Specifically, a water-soluble polymer obtained by reacting at least one compound selected from the group consisting of epihalohydrin, alkylenedihalide, diepoxide and dihalogenoalkyl ether with a imidazole compound, a ring of dialkyldiallylammonium halide. Examples thereof include a water-soluble polymer obtained by chemical polymerization, a water-soluble polymer obtained by reacting a dialkyldiallylammonium halide with sulfur dioxide, a quaternary ammonium compound of a vinylpyridine polymer, and a vinylpyrrolidone polymer.

The imidazole compound, which is a raw material for the water-soluble polymer having a nitrogen-containing heterocyclic compound as a structural unit, is
The following general formula (1)

[0010]

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(In the formula, R ¹ is hydrogen, or has 1 to 1 carbon atoms.
8 straight or branched chain alkyl and phenyl groups,
R ² and R ³ are represented by hydrogen or a methyl group, a hydroxymethyl group, a carboxyl group, an aldehyde group), and specific examples include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-hexylimidazole, 2-phenylimidazole, 2-methyl-4-
Methylimidazole, 2-methylimidazole-5-carboxylic acid, 4-methyl-5-hydroxymethylimidazole and the like, and these imidazole compounds can be used in combination.

The epihalohydrin has the general formula (2)

[0013]

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(In the formula, X is halogen), specifically, the halogen is usually fluorine, chlorine, bromine or iodine, but epichlorohydrin is preferable for economic reasons. Further, as the alkylene dihalide, a compound represented by the general formula (3)

[0015]

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(Wherein B is a linear or branched alkylene group having 1 to 20 and X and X'are the same or different halogens), and specifically, dichloroethane, dichloropropane, Examples thereof include dichlorobutane, dichlorohexane, dibromoethane, bromochloropropane, dibromopropane, dibromohexane and dichlorononane. In particular, dihalopropane, especially 1,3-dichloropropane, is preferred for its reactivity with amines and economical reasons.

As the diepoxide, the general formula (4) is used.

[0018]

[Chemical 4]

{Wherein D is a direct bond or has 1 carbon atom
4 straight-chain or branched alkylene groups, or the general formula (5)

[0020]

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[Wherein m is an integer of 1 to 4]}, specifically, 1,3-butadiene diepoxide, 1,4-pentadiene diepoxide, 1 , 5-hexadiene diepoxide, 1,6-heptadiene diepoxide, 1,7-
Examples include octadiene diepoxide, ethylene glycol diglycidyl ether, triethylene diglycidyl ether, and the like.

The dihalogenoalkyl ether has the general formula (6)

[0023]

[Chemical 6]

(In the formula, R ⁴ and R ⁵ are linear or branched alkylene groups having 1 to 4 carbon atoms, X is halogen, and n is n.
Is an integer of 1 to 12). Specifically, when n = 1, 2,2'-dichloroethyl ether, 2,2'-dibromoethyl ether, 3,3'-dichloropropyl. Ether, 2,3-dichloropropyl ether, 4,4′-dibromobutyl ether, etc., and when n = 2 or more, a dehydration reaction from an ethylene oxide polymer having a degree of polymerization of up to 10 and a halogenated alkyl alcohol. And the like, and particularly 2,2'-dichloroethyl ether (hereinafter referred to as dichloroethyl ether) is preferable for at least economic reasons.

The epihalohydrin, alkylenedihalide, diepoxide, and dihalogenoalkyl ether may be used alone or in admixture of two or more kinds for each component. The dialkyldiallylammonium halide has the general formula (7)

[0026]

[Chemical 7]

(Wherein R ⁶ and R ⁷ are hydrogen, an allyl group, a linear or branched alkyl group having 1 to 8 carbon atoms, and X is a halogen), and dimethyldiallylammonium chloride, Examples thereof include methyl ethyl diallyl ammonium chloride, methyl phenyl diallyl ammonium bromide, methyl propyl diallyl ammonium bromide, ethyl t-butyl diallyl ammonium bromide, ethyl octyl diallyl ammonium bromide and the like.

The quaternary ammonium compound of the vinyl pyridine polymer is represented by the general formula (8)

[0029]

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(Wherein R ⁸ is a linear or branched alkyl group having 1 to ⁸ carbon atoms, or a benzyl group, X is halogen, and n is the degree of polymerization of the polymer). Poly (N-methyl-4-vinylpyridinium chloride), poly (N-ethyl-4-vinylpyridinium bromide), poly (N-butylpyridinium bromide), poly (N-hexylpyridinium chloride),
And poly (N-benzylpyridinium chloride).

The vinylpyrrolidone polymer has the general formula (9)

[0032]

[Chemical 9]

(Wherein n represents the degree of polymerization of the polymer), and examples thereof include poly (N-vinyl-2-pyrrolidone). The water-soluble polymer having a nitrogen-containing heterocyclic compound as a structural unit can be made into a solid by removing the solvent (usually water), or a solution produced as an aqueous solution as it is, or if necessary. It is preferably diluted or concentrated before use.

When the above water-soluble polymers are mixed and used, the ratio of use is not particularly limited. The life prolonging agent of the present invention can be used in both cases of pretreatment and posttreatment of cut flowers. When the life prolonging agent of the present invention is used as a pretreatment agent, the above water-soluble polymer is usually added in an amount of 10 to 500,000 ppm, preferably 50 to 50 ppm.
000 ppm, more preferably 100 to 5,000 pp
Immerse the cut flowers after harvest in m.

When used as a post-treatment agent, the above water-soluble polymer is usually added to water for arranging flowers in an amount of 5 to 5000 pp.
m, preferably 5-1000 ppm, more preferably 1
It suffices if it is present at 0 to 500 ppm. The present invention is
Although it may be used in any of the post-treatments, it is particularly effective as a pre-treatment agent.

The cut flower life-prolonging agent of the present invention contains, if necessary, inorganic metal salts such as aluminum sulfate and potassium aluminum sulfate, sugars such as glucose, fructose, sorbitol and sucrose, nitrogen, various fungicides, and cytocanin. , Plant hormones such as gibberellin, abscisic acid, and folic acid may be added.

[0037]

The present invention will be described in more detail with reference to the following examples and test examples.
It is not limited to these.

[Production Example of Nitrogen-Containing Polymer] Sample A 2-Methylimidazole and a mixture of epichlorohydrin and 1,3-dichloropropane whose molar ratio was adjusted to 1: 1 in advance had a molar ratio of 1: 1. Until 50% 2-
A mixture of epichlorohydrin and propylene dichloride was added to an aqueous solution of methylimidazole while maintaining the reaction temperature at 80 ° C, and the mixture was stirred and reacted to obtain a mixed reaction composition (intrinsic viscosity (25 ° C) = 0.08). Was diluted with water to obtain a sample having a purity of 50% as Sample A.

Sample B A 50% aqueous solution of 2-methylimidazole was added to a 50% aqueous solution of dichloroethyl ether and ethylene glycol diglycidyl ether, the molar ratio of which was adjusted to 1: 0.1, until the molar ratio became 1: 1. % 2-Methylimidazole aqueous solution with a mixture of dichloroethyl ether and ethylene glycol diglycidyl ether at a reaction temperature of 80 ° C.
Sample B was prepared by diluting the mixed reaction composition (intrinsic viscosity (25 ° C.) = 0.06) obtained by adding and stirring while maintaining at 50% to make it 50% pure.

Sample C 20 to 30 equimolar amounts of N-methyldiallylamine and methyl chloride were added to isopropyl alcohol.
After reacting at 0 ° C. for 2 weeks with stirring and mixing, isopropyl alcohol was stripped off to obtain a 50% aqueous solution of N, N′-dimethyldiallylammonium chloride. Add 1% ammonium persulfate to this and add 5
The polymerization reaction composition (intrinsic viscosity (25 ° C.) = 0.22) obtained by stirring and mixing at 0 to 60 ° C. for 2 days was designated as Sample C.

Sample D Ethyl alcohol was mixed with 4-vinylpyridine and 2,2'-azobisisobutyronitrile in an amount corresponding to 0.2% by weight of 4-vinylpyridine.
After reacting at ˜90 ° C. for 6 hours with stirring and mixing, this was added into water to obtain a precipitate of poly (4-vinylpyridine). Furthermore, equimolar amounts of poly (4-vinylpyridine) and benzyl bromide were added to dimethylformamide, and the mixture was reacted at 90 ° C. for 4 hours with stirring and mixing, and then this was added to ethyl acetate to give poly (N- Benzyl-
4-vinylpyridine) precipitate (intrinsic viscosity (25 ° C.) =
1.21) was obtained. The obtained precipitate was filtered and dried, and then water was added to make 50% pure poly (N-benzyl-4-vinylpyridine) aqueous solution as Sample D.

Sample E A polymer obtained by the reaction of N, N'-dimethyldiallylammonium chloride and sulfur dioxide (trade name "PAS-A-5" manufactured by Nitto Boseki Co., Ltd.) and Sample C were prepared.
Sample mixed at a ratio of 1: 0.5 (weight ratio) (purity 47
%) Was designated as Sample E.

Sample F Poly (N-vinyl-2-pyrrolidone) (manufactured by Wako Pharmaceutical Co., Ltd.) and Sample D were mixed at a ratio of 1: 1 and diluted with water to have a purity of 50%. Was designated as Sample F.

Examples of the present invention will be described below. Example 1: Sample A was diluted 1000 times with water to 500 pp
An aqueous solution of m. Example 2: Sample B was diluted 1000 times with water to 500 pp
An aqueous solution of m. Example 3: Sample C was diluted 1000 times with water to 500 pp
An aqueous solution of m. Example 4: Sample D was diluted 1000 times with water to 500 pp
An aqueous solution of m. Example 5: Sample E was diluted 1000 times with water to 500 pp
An aqueous solution of m. Example 6: Sample F was diluted 1000 times with water to 500 pp
An aqueous solution of m. Example 7: Sample C 500 ppm and aluminum sulfate 10
Aqueous solution containing 0 ppm. Example 8: Sample C 500 ppm and glucose 500 pp
An aqueous solution containing m.

Comparative Example 1: Tap water Comparative Example 2: Commercial product A (main component is silver nitrate, RNA degradation product,
Trishydroxymethylaminomethane) Comparative Example 3: Commercial product B (main component is aluminum sulfate, fungicide) Comparative Example 4: Commercial product C (main components are propenyl, sodium phosphonate, fungicide) Comparative Example 5: Trimethylstearyl ammonium Chloride (Tokyo Kasei Co., Ltd.) 500 ppm aqueous solution.

Comparative Example 6: Hydroxyethyl cellulose Hydroxypropyl trimethyl ammonium chloride (manufactured by Lion Corporation) 500 ppm aqueous solution. Comparative Example 7: Polyvinyl alcohol polymerization degree of about 500 (manufactured by Wako Pure Chemical Industries, Ltd.) 500 ppm. Comparative Example 8: Polyethylene glycol 20000 (manufactured by Wako Pure Chemical Industries, Ltd.) 500 ppm was used. In addition, tap water was used for dilution in both Examples and Comparative Examples.

Test Example 1. Freshness-keeping effect on roses After harvesting roses (variety: Roterose) at a producer, Examples 1 to 8 and Comparative Example 1 at 8 ° C. in the dark for 5 hours.
Each aqueous solution of ~ 8 is immersed as a pretreatment agent, dry-transported (one night) in a cardboard box, and inserted in groups of 5 in a plastic container containing 2 liters of tap water, 25 ° C, 70% R
Storage tests were conducted in duplicate for each of H and light conditions of 1200 lux (12 hr / 12 hr). The degree of flowering and the degree of bent neck were observed every day. The results are shown in Table 1. Table 1
Medium, the degree of flowering is the flowering stage (I-VIII) shown in Figure 1.
The vent neck is about the vent neck shown in FIG.
+++) was used as an index.

[0048]

[Table 1]

As is clear from Table 1, the cut flower life-prolonging agent of the present invention is found to have an excellent effect of delaying the flowering of cut flowers such as roses, prolonging the period of appreciation, and preventing bent necks. Was given.

[0050]

EFFECTS OF THE INVENTION The agent for prolonging the life of cut flowers of the present invention has an excellent effect of preventing bent neck, and prevents the deterioration of freshness due to the petals of cut flowers, wilting of leaves, yellowing of leaves and the like, and delays flowering, thereby cutting flowers. It is possible to significantly extend the viewing period. Further, the cut flower life-prolonging agent of the present invention is transparent and odorless when diluted to a use concentration, and is harmless to many plants and humans and livestock.

[Brief description of drawings]

[Fig. 1] Evaluation index of Test Example 1 and the degree of flowering of roses

[Fig. 2] Evaluation index of Test Example 1 and the degree of a bent neck

Claims (3)

[Claims] 1. A cut flower prolonging agent containing a water-soluble polymer having a nitrogen-containing heterocyclic compound as a structural unit as an active ingredient. 2. The water-soluble polymer is epihalohydrin,
Alkylene dihalide, diepoxide, a water-soluble polymer obtained by the reaction of at least one compound selected from the group of dihalogenoalkyl ethers and an imidazole compound, a water-soluble polymer obtained by cyclopolymerization of a dialkyldiallylammonium halide, Water-soluble polymer obtained by reaction of dialkyldiallylammonium halide with sulfur dioxide, vinylpyridine polymer 4
The cut flower life-prolonging agent according to claim 1, which is a polymer selected from a quaternary ammonium compound and a vinylpyrrolidone polymer. 3. A polycondensate of 2-methylimidazole with at least one member selected from epichlorohydrin, dihalopropane, ethylene glycol diglycidyl ether and dihaloethyl ether, and polydimethyl. The cut flower life-prolonging agent according to claim 1 or 2, which is selected from diallylammonium halides, polycondensates of dimethyldiallylammonium halide and sulfur dioxide, quaternary ammonium compounds of vinylpyridine polymers, and vinylpyrrolidone polymers.