JP2945329B2 - Gardening ties - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for improving the flexibility and the flexibility, and at the same time, achieving a balance between the properties at a low cost.
In particular, the present invention relates to a tying cord for horticultural use which is useful as a runner stopper for picking strawberry seedlings.

[0002]

2. Description of the Related Art For example, in the cultivation of strawberries, a runner of an elongated strawberry is fixed in a seedling pot containing sterilized soil with a runner stopper such as a wire-containing vinyl string, and rooting is performed at the stopped portion. Then, a method of obtaining strawberry seedlings by cutting before and after the runner is employed. It is desirable to bury the seedling-raising pots after the seedlings are taken out in the soil together with runner stoppers and allow them to be naturally decomposed. For this reason, the use of a biodegradable polyester resin as a material has been studied.
However, the conventional biodegradable polyester resin itself has a high price of 900 to 2,000 yen / kg, so it is difficult to use it for the above applications, and attempts have been made to add a filler to lower the price. However, when the addition amount was increased, the physical properties, particularly the elongation, were remarkably reduced, and the material became brittle, so that practicality as a runner stopper could not be expected. On the other hand, a runner stopper made of paper has been used, but if the end of the string is cut, the strawberry runner is damaged at this point, causing anthrax.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to suppress the deterioration of physical properties and to maintain the function as a tying cord for horticulture even when the amount of filler is increased to lower the price. And a tying cord for horticulture.

[0004]

The tie for horticulture of the present invention comprises a filler described later and 0.5 to 5 parts by weight of a surface treating agent based on 100 parts by weight of a biodegradable aliphatic polyester resin .
It is obtained by adding 10 to 150 parts by weight of the mixture . this
The mixture comprises at least one filler selected from calcium carbonate, clay, talc, aluminum hydroxide and magnesium hydroxide , and a titanate coupling agent,
Aluminum coupling agents, those combination with at least one surface treatment agent selected from an acetylene glycol and its derivatives; silica, ceramic balloon, surface-treated with at least one filler selected from glass balloons and glass beads combinations of an epoxy-based silane coupling agent as agent; and
And at least one surface treatment agent selected from starch and acetylene glycol and its derivatives as a filler
A combination is used. A tie for horticulture made of these materials can be filled with a filler at a high level and has a good balance of physical properties.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The biodegradable aliphatic polyester resin used in the tying cord for horticulture of the present invention may be any one having biodegradability.
Specifically, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, dodecanoic acid, malic acid, tartaric acid, polycarboxylic acids such as citric acid and anhydrides thereof, Ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, decanediol, glycerin,
Polycondensation products with polyhydric alcohols such as trimethylolpropane; ring-opening polymers of cyclic esters such as lactide and ε-caprolactone, which are cyclic dimers of lactic acid; hydroxy acids such as lactic acid, hydroxybutyric acid, and hydroxyvaleric acid And the like, and are used as one kind or as a mixture of two or more kinds.

The filler includes an inorganic filler and an organic filler. Examples of the inorganic filler include calcium carbonate, clay, talc, aluminum hydroxide, magnesium hydroxide, silica, ceramic balloon, glass balloon, and glass beads. Examples of the organic filler include starches such as grains such as wheat and corn, and potatoes such as potato, sweet potato, tapioca and the like. Its particle size is 0.1 ~
100 μm is preferable, and these fillers may be used alone or in combination.
It is used as a mixture of more than one species, and the properties can be complemented by mixing.

[0007] Of these, regarding calcium carbonate,
Any of heavy, light and colloidal materials having an average particle size of 0.1 to 6 μm may be used, but it is preferable that the surface treatment with fatty acid or the like is not performed. The difference in specific surface area depending on the particle size affects the viscosity and physical properties at the time of molding. Therefore, it is desirable that the amount of calcium carbonate having a small particle size be smaller than the amount of calcium carbonate having a large particle size. Clay, talc, aluminum hydroxide, magnesium hydroxide or silica having the same particle size and surface treatment as calcium carbonate are also used.

The ceramic balloon, glass balloon or glass beads may have a particle size of about 100 μm or less. These spherical fillers have a small increase in viscosity at the time of filling. In particular, since ceramic balloons and glass balloons are hollow, the specific gravity is small, and the addition of the biodegradable resin also reduces the specific gravity, which is advantageous in terms of cost. In addition, when a round ceramic balloon or glass balloon is used, no directionality appears in the added biodegradable resin, so that there is an advantage that a product having no directionality can be obtained at the time of molding.

[0009] Starch takes various shapes depending on the type of material, the contents of amylose and amylopectin, the degree of polymerization thereof are different, and the particle size varies, but the average particle size is 100 µm.
It is sufficient if it is about the following. Further, since starch has lubricity, lubrication during molding can be imparted without adding a lubricant to the mixture with the resin, which is advantageous in terms of labor and cost for compounding.

[0010] As a surface treating agent is mixed with these fillers, ceramic balloons, glass balloons, for glass beads and silica epoxy silane coupling agent (Table 1), for these other inorganic fillers titanate coupling agent (Table 2), aluminum coupling agent (Table 3), also acetylene glycol
Has the derivative (Table 4), respectively used. Among these, the epoxy-based silane coupling agent and the titanate-based coupling agent take a form in which the inorganic portion of each coupling agent is oriented toward the inorganic filler and the organic portion is directed toward the resin. That is, a structure in which an inorganic substance is wrapped with an organic substance is obtained, uniform dispersion becomes possible, and a decrease in physical properties can be minimized due to interaction with the resin.

[0011]

[Table 1]

[0012]

[Table 2]

[0013]

[Table 3]

[0014]

[Table 4]

On the other hand, acetylene glycol or a derivative thereof is used as a surface treatment agent for starch. Acetylene glycol is a powerful surfactant that is oriented to the OH groups in the starch and the organic part is directed toward the resin, so it is thought that the uniform dispersion and interaction in the resin will cause a decrease in physical properties. Can be Dispersing an organic powder such as starch uniformly in a resin cannot be expected from a general surface treatment agent, and is a great effect of acetylene glycol.

Regarding the method of surface treatment of these fillers, any method such as a wet method (a method by hydrolysis), a dry method, and an integral blend on a mixing roll can be used. The addition amount of the surface treatment agent in the range of 0.5 to 5 parts by weight is sufficient. This is 0.5 weight
If the amount is less than 5 parts by weight , the effect as a surface treatment agent cannot be expected so much. If the amount exceeds 5 parts by weight , the cost becomes high and the economy is inferior.

The tying cord for horticulture of the present invention is based on 100 parts by weight of the biodegradable aliphatic polyester resin described above.
The mixture of surface treatment agent and filler of the combination is used in the range of 10 to 150 parts by weight depending on the required properties,
If the amount is less than 10 parts by weight, the effect on the viscosity adjustment, fluidity, adhesiveness, strength, etc. by adding the mixture is reduced, and if it exceeds 150 parts by weight, the viscosity becomes too high and moldability,
The physical properties are remarkably reduced and the practicality is lost.

Since the biodegradable aliphatic polyester resin to which the above-mentioned mixture is added must not normally cause photodegradation during use, for example, an ultraviolet absorber, an antioxidant, etc. may be added. And a plasticizer for imparting flexibility may be added.

Further, the biodegradable aliphatic polyester resin generally has a calorific value about half that of polyethylene or the like.
With the biodegradable aliphatic polyester resin to which the mixture is added , the calorific value is even smaller (1/3 to 1/4), and there is no problem in incineration treatment in an incinerator. Can also be expected to have a secondary effect that decomposition by microorganisms is further promoted.

The tie for horticulture of the present invention may be in the form of a tape in addition to a tube. In the case of tube, outer diameter: 1-4mm, inner diameter: 0.5-3mm, thickness: 0.2-1.8mm
If the material is in the form of a tape, width: 2 to 20 mm, thickness:
The one having a thickness of 0.1 to 1 mm is desirable from the viewpoint of workability of attaching a vine or the like to a support, and a surface having a smooth surface is preferable to prevent damage due to contact with the vine or the like.

[0021]

EXAMPLES The present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited to the description of the examples. Example 1 Aliphatic polyester resin: Bionole 3010 (manufactured by Showa Polymer Co., Ltd., trade name, copolymer of 1,4-butanediol and succinic acid and / or adipic acid) 100 parts by weight, as a titanate coupling agent 120 parts by weight of heavy calcium carbonate having an average particle diameter of 2 μm, 2 parts by weight of stearic acid, and calcium alkylbenzenesulfonate: 7764 (trade name, manufactured by Akishima Chemical Industry Co., Ltd.) to which 1 part by weight of tetraisopropylbis (dioctylphosphite) titanate is added. 3 parts by weight,
The resin was kneaded with a mixing roll at 90 ° C. until 5 minutes after the resin was melted, and was taken out in a sheet form. This was placed in a mold having a thickness of 2 mm and pressed at 130 ° C. for 5 minutes to obtain a sheet having a thickness of 2 mm. A punch test sample was prepared from this sheet using a No. 2 dumbbell specified in JIS, and a tensile test was performed at a speed of 200 mm / min. The strength, elongation, and 100% modulus were measured. The results are shown in Table 5. Was.

On the other hand, after cooling the above-mentioned sheet-like material to room temperature, it is pulverized to produce a pellet, and the pellet is used by using the pellet.
Using a 50 mm extruder, a tube with a smooth surface of 2.5 mm in outer diameter and 1.5 mm in inner diameter was extruded at a cylinder temperature of 130 ° C. and a die temperature of 135 ° C. This was cut into a length of 10 cm and bent in a U-shape at the center to prepare a tying cord for horticulture of the present invention.
On the other hand, the runner was extended to a polyethylene pot filled with sterilized soil for picking up strawberries, and the horticultural tying string was pierced into the soil to fix the runner. Seven to ten days later, roots emerged from the fixed part of the runner.
In this state, when the runners before and after were further cut after 100 days, a sub-strain with good root growth without damaging the runner was obtained.

Example 2 Aliphatic polyester resin: Bionole 3010 (supra) 100
Parts by weight and ethylene oxide adduct of acetylene glycol: Surfynol 440 (trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
Corn starch with an average particle size of 15 μm added with 1 part by weight 1
00 parts by weight (manufactured by Nippon Flour Milling Co., Ltd.) were kneaded with a mixing roll at 90 ° C. until 5 minutes after melting of the resin. This was taken out in the form of a sheet, a punch test sample was prepared in the same manner as in Example 1, and the same measurement was performed. The results shown in Table 5 were obtained. The sheet was cooled to room temperature and then pulverized to prepare pellets. Tubes having the same dimensions were prepared using the pellets in the same manner as in Example 1. As a result, a tube having fine irregularities on the surface was obtained. (The irregularities were also obtuse and soft without any problems). From this, a tying cord for horticulture was produced in the same manner as in Example 1 and used for fixing a runner for removing strawberry seedlings. As a result, a good child strain was obtained in the same manner.

Example 3 Aliphatic polyester resin: Bionole 3010 (supra) 100
Parts by weight, high molecular weight epoxy silane coupling agent: MA
C2101 (manufactured by Nippon Unicar, trade name) A glass balloon having an average particle diameter of 50 μm to which 1 part by weight is added: X-39 (manufactured by Asahi Glass Co., Ltd., trade name) 60 parts by weight, stearic acid 2 parts by weight, and calcium alkylbenzene sulfonate ： 7764 (see above)
3 parts by weight were kneaded with a mixing roll at 90 ° C. until the resin melted for 5 minutes. This was taken out in the form of a sheet, and
A sample for a punching test was prepared in the same manner as described above, and the same measurement was performed. The results shown in Table 5 were obtained. The sheet was cooled to room temperature and then pulverized to produce pellets. Tubes having the same dimensions were produced using the pellets in the same manner as in Example 1. As a result, a tube having a smooth surface was obtained. From this, a tying cord for horticulture was prepared in the same manner as in Example 1 and used for fixing a runner for removing strawberry seedlings.
In the same course, good offspring were obtained.

Comparative Example 1 In the same manner as in Example 1, except that the heavy calcium carbonate was not treated with titanate, the mixture was uniformly kneaded with a mixing roll. This was taken out in the form of a sheet, a punch test sample was prepared in the same manner as in Example 1, and the same measurement was performed. The results shown in Table 5 were obtained. The sheet was cooled to room temperature and then pulverized to produce pellets. A pellet having the same dimensions was extruded using the pellet in the same manner as in Example 1, but the appearance of the tube was poor and the tube was bent into a U-shape. Sometimes it broke.

Comparative Example 2 In the same manner as in Example 2, except that the corn starch was not treated with acetylene glycol, the corn starch was uniformly kneaded with a mixing roll. This was taken out in the form of a sheet, a punch test sample was prepared in the same manner as in Example 1, and the same measurement was performed. The results shown in Table 5 were obtained.
Further, the sheet-like material was cooled to room temperature and then pulverized to prepare a pellet, and a tube having the same dimensions was extruded using the same in the same manner as in Example 1, but compared with a corn starch treated with acetylene glycol. The surface was rough and rough. Also, it was bent when bent in a U-shape.

Comparative Example 3 The procedure of Example 3 was repeated, except that the glass balloon was not treated with the epoxy silane coupling agent. This was taken out in the form of a sheet, a punch test sample was prepared in the same manner as in Example 1, and the same measurement was performed. The results shown in Table 5 were obtained. The sheet was cooled to room temperature and then pulverized to prepare pellets. Using the pellets, a tube having the same dimensions was extruded in the same manner as in Example 1, and a tube with a smooth surface was obtained. The tube was less stretched and broke when bent in a U-shape.

[0028]

[Table 5]

COMPARATIVE EXAMPLE 4 When a 10-cm long cord for horticultural use was bent into a U-shape, a hard wrinkle was formed on the inside, and the runner was rubbed when the runner was moved by the wrinkle. I attached it. When the runner was repeatedly wetted with water and dried, the paper was peeled and became hard, and similarly the runner was damaged.

Further, the tie for horticulture of the present invention obtained in the above Examples 1 to 3 and the tie for paper horticulture obtained in Comparative Example 4 were buried in humus and 55% RH at 23 ° C. When left in a constant temperature room, the decomposition of the tying cord for horticulture of the present invention was considerably advanced, but the decomposition of the tying cord for paper horticulture was not so advanced.

[0031]

As described above, the tying cord for horticulture of the present invention has a small physical property deterioration even when a large amount of a filler is filled therein. If it is an agent, it will be even faster because the microorganisms help the decomposition. In addition, the calorific value when incinerated is about 1/2 that of the conventional biodegradable resin, and there is an advantage that the incinerator is not damaged. It can also be used to treat vines such as melons, watermelons, pumpkins, sweet potatoes, and other fruits and vegetables, in addition to stopping strawberry runners. When it is stretched, it becomes a flexible string, so it can be used as a binding string for vegetables and flowers such as tomatoes and cucumber using columns, and for fruit trees such as young trees and shelves using grapes and kiwi.

Continuation of the front page (56) References JP-A-4-318042 (JP, A) JP-A-8-1226437 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) A01G 9 / 12

Claims (3)

(57) [Claims] 1. Calcium carbonate, clay, talc, hydroxylated based on 100 parts by weight of a biodegradable aliphatic polyester resin.
Selected from aluminum and magnesium hydroxide
At least one filler and 0.5 to 5 parts by weight of titanate
Coupling agent, aluminum coupling agent, acetyl
Less selected from lene glycol and its derivatives
With one of the mixture from 10 to 150 parts by weight of the surface treatment agent, horticultural binding string, characterized by comprising the addition. 2. 100% by weight of a biodegradable aliphatic polyester resin
At least one member selected from the group consisting of silica, ceramic balloon, glass balloon and glass beads
Of a filler of 0.5 to 5 parts by weight of an epoxy silane coupling agent as a surface treatment agent 10 to 150 parts by weight
And a tying strap for horticulture. 3. 100% by weight of a biodegradable aliphatic polyester resin
Parts by weight of a mixture of starch as a filler and 0.5 to 5 parts by weight of at least one surface treating agent selected from acetylene glycol and derivatives thereof 10 to 150 parts by weight
And a tying strap for horticulture.