JPH11309229A - Biodegradable green fork - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent natural environmental disruption caused by leaving a green fork as it is by including biodegradable resins in the green fork. SOLUTION: For example, about 400 g of L-lactide, about 0.04 g of octanoic acid primary tin, and about 0.12 g of lauryl alcohol are sealed in a thick stainless-steel polymerized container with an agitator. After vacuum-evaporating them, nitrogen gas is filled into them and they are reacted by heating to produce a polylactatic acid melting substance. This substance is cut by a pelletizer to obtain polylactatic acid pellet of molecular weight average of about 138 thousand. A green fork for golf is formed from this polylactatic acid by a normal injection molding machine. According to an examination of resolvability of the green fork after using it on golf green and burying it in compost, the green fork is excellent in practicality and resolvability and is resolved with no trace of the original form after at least one to six months. Environmental disruption can be prevented thereby.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a green fork used in golf, which is a molded product of a biodegradable resin.

[0002]

BACKGROUND OF THE INVENTION Golf green forks according to the present invention are typically made of moldable plastic. These can be freely picked up at golf courses, but are frequently used to repair holes called ball marks, which are formed when the ball is turned on the green and the green is dented into the shape of a ball by impact. The purpose is to fix the dented ball mark so as not to disturb the putting of other players.

A green fork is usually kept in a player's pocket or hung on a golf bag except when used on a green, but it is dropped from a pocket or dropped off a golf bag. In many cases, the ball mark is broken when it is inserted into the green and the ball mark is repaired, so that the ball mark is left in the golf course. Such a case is annoying and difficult to collect, leading to destruction of the natural environment.

Generally, plastics which can be molded include resins having excellent flexibility, heat resistance and water resistance, such as polyethylene, polypropylene, soft polyvinyl chloride and polyethylene terephthalate. Used in many. However, when these resins are discarded after use, they increase the amount of refuse and are hardly decomposed in the natural environment. Therefore, even if they are buried, they remain semi-permanently in the ground. In addition, abandoned plastics have caused problems such as spoiling the landscape and destroying the living environment of marine life.

On the other hand, as a biodegradable polymer of a thermoplastic resin, polylactic acid, a copolymer of lactic acid and another aliphatic hydroxycarboxylic acid, an aliphatic polyhydric alcohol and an aliphatic polycarboxylic acid are used. Polyester and the like have been developed. Some of these polymers are 100% biodegradable within months to one year in animals or, when placed in soil or seawater, begin to degrade within weeks in a humid environment, with about 1 It disappears in a few years from the year. Furthermore, the decomposition products have the property of becoming lactic acid, carbon dioxide, and water that are harmless to the human body. In particular, polylactic acid, in particular, has recently been able to produce L-lactic acid as a raw material in large quantities and at low cost by a fermentation method, has a high decomposition rate in compost, has resistance to mold, and has an odor resistance to food. Due to its excellent characteristics such as resistance and coloring resistance, its use is expected to expand.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a biodegradable golf green fork which does not destroy the natural environment even when left unattended.

[0007]

Means for Solving the Problems As a result of diligent studies, the present inventors have found that the above-mentioned object is satisfied by manufacturing a golf green fork using a biodegradable resin, thereby completing the present invention. Reached. That is, the present invention is specified by the matters described in the following [1] to [3]. [1] A green fork used in golf, comprising a biodegradable resin. [2] The biodegradable resin is an aliphatic polyester
The green fork according to [1].

[3] The green fork according to [2], wherein the aliphatic polyester comprises at least one blend composition selected from the group consisting of polylactic acid, polyglycolic acid, polycaprolactone, and polybutylene succinate.

[4] The biodegradable resin is (A) 100 parts by weight of an aliphatic polyester, and (B) polyalkylene glycol, polyvinyl alcohol and starch having a structural unit represented by the formula (1) or (1). The green fork according to any one of [1] to [3], which is a resin composition comprising 1 to 100 parts by weight of at least one selected from the group consisting of:

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. [Resin used in the present invention] As the biodegradable resin used in the present invention, aliphatic polyester, polysaccharide,
Other degradable resins are mentioned, and aliphatic polyester is particularly desirable. Examples of the aliphatic polyester include polylactic acid, polyglycolic acid, polycaprolactam, polyethylene oxalate, polybutylene oxalate, polyneopentyl glycol oxalate, polyethylene succinate, polybutylene succinate, polyhydroxybutyric acid, and β-hydroxybutyric acid And a copolymer of β-hydroxyvaleric acid and the like, and these can be used alone or as a blend of two or more. Among them, polylactic acid, polyglycolic acid, polycaprolactone, and polybutylene succinate are particularly preferred. For example, those obtained by increasing the molecular weight by using an isocyanate compound or by cross-linking may be used.

Examples of the polysaccharide include starch, modified starch, cellulose, modified cellulose such as cellulose acetate, chitin, chitosan and the like. Other general-purpose resins having degradability include polyethylene glycol, polypropylene glycol, PVA, and modified PVA.

As the biodegradable resin, commercially available resins may be used. For example, Biopol (manufactured by Zeneca), bacterial cellulose (manufactured by Biomaterial), pullulan (manufactured by Hayashibara Shoji), curdlan ( Takeda Pharmaceutical Co., Ltd.), polylactic acid (Cargill, Ecochem), Lacty (Shimadzu), Lacia (Mitsui Chemicals),
Cell Green (manufactured by Daicel Chemical), Tone (manufactured by Union Carbide), Bionore (manufactured by Showa Polymer),
Matterby (manufactured by Novamont) and the like.

These biodegradable resins may be used alone or as a mixture of two or more. In addition, starch, modified starch, polyvinyl alcohol, polyalkylene glycol such as polyethylene glycol and polypropylene glycol, and the like can be added to the biodegradable resin. Degradability can be promoted by adding these compounds.

The biodegradable resin according to the present invention contains various additives (antioxidant, ultraviolet absorber, heat stabilizer, flame retardant, internal release agent, inorganic additive, antistatic agent, surface wetting improving agent). ,
(An incineration aid, a lubricant such as a pigment) and the like can be added. Examples of the inorganic additives include silica, calcium carbonate, talc, kaolin, kaolinite, and zinc oxide, and silica is particularly preferred. These can be used as one kind or as a mixture of two or more kinds. The golf green fork of the present invention can easily produce the biodegradable resin described above by ordinary injection molding.

[0015]

EXAMPLES The present invention will be described below in detail with reference to examples, but is not limited thereto without departing from the technical scope of the present invention. Production Example 1 400 g of L-lactide and stannous octoate 0.1 g
04 g and lauryl alcohol 0.12 g were sealed in a thick cylindrical stainless steel polymerization vessel equipped with a stirrer and degassed under vacuum for 2 hours. After replacing with nitrogen gas, 200 ℃
The mixture was heated and stirred at / 10 mmHg for 2 hours. After completion of the reaction, a melt of polylactic acid was extracted from the lower outlet, air-cooled, and cut with a pelletizer. The resulting polylactic acid had a yield of 340 g, a yield of 85%, and a weight average molecular weight (M
w) 138,000.

Production Example 2 In a reactor equipped with a Dien-Stark trap, 9
10 kg of 0% L-lactic acid and 45 g of tin powder are charged, and 150 ° C.
After distilling water while stirring at / 50 mmHg for 3 hours, the mixture was stirred at 150 ° C / 30 mmHg for 2 hours to oligomerize. 21.1 kg of diphenyl ether was added to this oligomer, and an azeotropic dehydration reaction at 150 ° C./35 mmHg was performed. The distilled water and the solvent were separated by a water separator, and only the solvent was returned to the reactor. Two hours later, the organic solvent to be returned to the reactor was passed through a column packed with 4.6 kg of molecular sieve 3A, and then returned to the reactor.
The reaction was carried out at 17 mmHg for 20 hours to obtain a polylactic acid solution having a weight average molecular weight (Mw) of 150,000. 44 kg of dehydrated diphenyl ether was added to this solution to dilute it, and then cooled to 40 ° C., and the precipitated crystals were filtered. 12 kg of 0.5 N HCl and 12 k of ethanol
g, and the mixture was stirred at 35 ° C. for 1 hour, and then filtered.
5. Dry at 50 mmHg, polylactic acid powder 1 kg (85% yield) was obtained. This powder was melted and pelletized by an extruder to obtain polylactic acid. The weight average molecular weight (Mw) of this polymer was 1470,000.

Production Example 3 In a reactor equipped with a Dien-Stark trap,
50.5 kg of 1,4-butanediol and succinic acid
After 5 kg of tin powder and 45 g of tin powder were charged, water was distilled off while stirring at 100 ° C. for 3 hours, and the mixture was further stirred at 150 ° C./50 mmHg for 2 hours to oligomerize. 385 kg of diphenyl ether is added to this oligomer,
An azeotropic dehydration reaction of 5 mmHg was performed, and the distilled water and the solvent were separated by a water separator, and only the solvent was returned to the reactor. After 2 hours, the organic solvent to be returned to the reactor was passed through a column packed with 50 kg of molecular sieve 3A, and then returned to the reactor. The reaction was carried out at 130 ° C./17 mmHg for 15 hours, and the weight average molecular weight (Mw) was 14. A polybutylene succinate (hereinafter, abbreviated as PSB) solution of 100,000 was obtained. After 180 kg of dehydrated diphenyl ether was added to this solution for dilution, the solution was cooled to 40 ° C., and the precipitated crystals were filtered. To this powder were added 200 kg of 0.5 N HCl and 200 kg of ethanol, and the mixture was stirred at 25 ° C. for 1 hour, filtered, dried at 60 ° C./50 mmHg, and dried with PSB 91.
5 kg (94.8% yield) were obtained. The weight average molecular weight (Mw) of this PSB was 138,000.

Examples 1 to 5 and Comparative Example 1 A resin composition as shown in Table 1 was molded into a golf green fork as shown in FIG. 1 using a conventional injection molding machine. They were actually used on golf greens and buried in compost to check for degradability. Practicality ○ ・ ・ ・ No problem. ×: There is a problem (breaking, etc.) Degradability ◎: The original shape is not stopped in 1 to 6 months. ○: The original form is not stopped in 6 to 12 months. ×: No change in appearance for 12 months or more.

[0019]

[Table 1] Starch: PA # 220 (Nippon Food Processing Co., Ltd.) PEG: Sanyo Kasei # 4000S PP: Grand Polymer Co., Ltd. ).

[0020]

The golf green fork comprising the biodegradable resin obtained by the present invention is practical because it decomposes and does not become garbage even if left in the environment.

[Brief description of the drawings]

FIG. 1 is a perspective view of a golf green fork obtained in an embodiment of the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hisashi Aihara 1190 Kasama-cho, Sakae-ku, Yokohama City, Kanagawa Prefecture (72) Inventor Tomoyuki Nakata 1190 Kasama-cho, Sakae-ku, Yokohama City, Kanagawa Prefecture Mitsui Chemicals ( 72) Inventor Shoji Obuchi 1190 Kasama-cho, Sakae-ku, Yokohama City, Kanagawa Prefecture Inside Mitsui Chemicals, Inc.

Claims (4)

[Claims] 1. A green fork for use in golf, comprising a biodegradable resin. 2. The green fork according to claim 1, wherein the biodegradable resin is an aliphatic polyester. 3. The green fork according to claim 2, wherein the aliphatic polyester comprises at least one blend composition selected from the group consisting of polylactic acid, polyglycolic acid, polycaprolactone, and polybutylene succinate. 4. The biodegradable resin is composed of (A) 100 parts by weight of an aliphatic polyester and (B) polyalkylene glycol, polyvinyl alcohol and starch having a structural unit represented by the formula (1) or (1). The green fork according to any one of claims 1 to 3, wherein the resin composition comprises 1 to 100 parts by weight of at least one selected from the group consisting of: Embedded image (In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and n represents an integer of 1 to 5.)