JP2931275B2 - Starch-based compositions for making environmentally degradable alpha-olefin polymer molding materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biodegradable and photodegradable α-olefin polymer material, and more particularly to a starch for producing the biodegradable and photodegradable α-olefin polymer material. It relates to a base composition.

[0002]

2. Description of the Related Art α-olefin polymers such as low density polyethylene (LDPE) and high density polyethylene (HDP)
Polyethylene and polystyrene, including E) and linear low density polyethylene (LLDPE), are used extensively in the manufacture of packaging materials such as bags, bottles, thin films and the like. Most of these packaging materials are ultimately dumped in landfills or incinerated in incinerators. Therefore, there is a need for the production of polymeric materials that are industrially biodegradable, i.e., environmentally friendly. Many attempts have been made so far, for example, US Pat.
No. 281681, 5324794, 5334700
Nos. 5,367,003, 5,367,033, 53914
Nos. 23 and 5424345 show the results.

[0003]

It is an object of the present invention to provide a biodegradable and photodegradable, essentially environmentally degradable, starch-based composition for the preparation of α-olefin polymer molding materials. To provide. It is another object of the present invention to provide a starch-based masterbatch for making environmentally degradable α-olefin polymer molding materials.

[0004] It is yet another object of the present invention to provide α-olefin polymer materials and products that are degradable in the environment in which they are manufactured.

[0005]

SUMMARY OF THE INVENTION In order to achieve the objects of the present invention, an α-degradable α in an environment prepared according to the present invention.
-A starch-based composition for producing an olefin polymer molding material comprises 95-99 wt% of starch and a compound represented by the general formula 1 (wherein R ₁ and R ₂ are hydrogen, or both R ₁ and R ₂ =
O) is a titanate coupling agent of 0.2
-0.8 wt%, 0.1-2 wt% of paraffin, and 0.1-2 wt% of fatty acids.

The fatty acid is preferably a C ₁₂ -C ₂₀ fatty acid. The present invention separately comprises 50-80 wt% of the starch-based composition and α-olefin polymer 18-4.
Α-olefin polymer pellets decomposable in an environment consisting of 9.8 wt%, a photosensitizer 0.1-1.0 wt%, and a photosensitizer co-catalyst 0.1-1.0 wt%; A starch-based masterbatch useful for making powders is presented.

The α-olefin polymer containing the starch-based masterbatch comprises low density polyethylene (LDPE), linear low density polyethylene (LLD)
PE) and mixtures of LDPE and LLDPE (but not limited to), and LDPE: L
LDPE = LD having a weight ratio of 10:70 to 45:30
More desirably, it includes (but is not limited to) a mixture of PE and LLDPE.

[0008] The present invention further provides an α-olefin polymer molding material which is degradable in an environment made from the starch-based composition or directly from the starch-based masterbatch. . The α-olefin polymer material decomposable in the environment comprises 15-49 wt% of the starch-based composition, 50.8-84.8 wt% of the α-olefin polymer, and 0. 1-1.
0 wt% and 0.1-1.0 wt% of a photosensitizer promoter.

The α-olefin polymer contained in the α-olefin polymer molding material which can be decomposed in the environment includes low-density polyethylene (LDPE), high-density polyethylene (HDPE), and linear low-density polyethylene ( LLDP
E), polystyrene, a mixture of LDPE and LLDPE,
Mixture of LLDPE and polystyrene and LDPE, LL
Desirably, but not limited to, a mixture of DPE and polystyrene. Further, the α-olefin polymer is LDPE: LLDPE = 10: 70 to 45: 3.
A mixture of LDPE and LLDPE having a weight ratio of 0, LL
DPE: polystyrene = a mixture of LLDPE and polystyrene having a weight ratio of 5:80 to 30:25, or LDP
E: LLDPE: polystyrene = 10: 70: 800-
LDPE, LLDPE with a weight ratio of 43:30:60
And more preferably a mixture of styrene and polystyrene.

[0010] Starches suitable for use in the present invention include modified starch and non-modified starch, but non-modified starch such as corn starch is preferred. The photosensitizer may be any known in the art, and typical photosensitizers include transition metal salts of dibutylthioaminoformic acid, for example, iron salts. The photosensitizer co-catalyst may be any of those known in the art, and typical examples thereof include stearates such as zinc stearate and calcium stearate.

[0011] An appropriate process for the production of a masterbatch based on this starch is the following:
99 parts and a general formula 1 (wherein R ₁ and R ₂ are hydrogen or R
A titanate coupling agent 0.2-0.8 parts represented by ₁ and R ₂ are both = O), paraffin 0.1-2
And 0.1-2 parts of a fatty acid, and 5-80 parts of the above mixture by weight is mixed with the α-olefin polymer 18-4.
9.8 parts, 0.1-1.0 part of the photo-enhancing agent, and 0.1-1.0 part of the photo-enhancing agent co-catalyst are mixed at a temperature of 120 ° C to 150 ° C, Desirably knead for 5-10 minutes, thoroughly mix all components to form a melt, and cool the resulting melt mixture to pellets.

The in-environmentally degradable α-olefin polymer molding composition of the present invention can be prepared using the starch-based masterbatch and using conventional compounding processes. The α-olefin polymer molding material decomposable in the environment according to the present invention can be used for producing bags, bottles, spongy sheets, films and the like by ordinary plastic molding techniques.

[0013]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described further by the following examples. Parts and percentages in each example are by weight unless otherwise indicated. The following examples are only meant to illustrate the invention, but not to limit it. Example 1 LLDPE masterbatch decomposable in the environment 100 parts of potato flour, 0.1 part of paraffin, 0.2 part of C ₁₈ fatty acid, and titanate coupling agent (R ₁ and R ₂
(O = 0.4) were thoroughly mixed and ground. After kneading 75 parts of the obtained mixture, 24.5 parts of LLDPE, 0.3 part of iron salt of dibutylthioaminoformic acid and 0.2 part of zinc stearate in a sealed kneader at 140 ° C. for 8 minutes. The mixture was cooled and the cooled mixture was ground to particles.

EXAMPLE 2 100 parts of LLDPE / LDPE masterbatch starch decomposable in the environment, 0.2 parts of paraffin, 0.3 parts of lauric acid, and a titanate coupling agent (both R1 and R2) (Hydrogen) and 0.2 part were thoroughly mixed and ground.
75 parts of the obtained mixture, 12.25 parts of LLDPE,
12.25 parts of LDPE, 0.3 part of iron salt of dibutylthioaminoformic acid, and 0.4 part of zinc stearate were kneaded in a sealed kneader at 140 ° C. for 8 minutes, cooled, and cooled. Crushed into particles.

Example 3 LLDPE / LDPE Film Decomposable in Environment The LLDPE masterbatch prepared in Example 1, which is decomposable in environment, LLDPE, and LDPE are 35: 5.
It was fed in a ratio of 0:15 to a blown film molding machine operated at a temperature profile of 130-180 ° C., where the melt index of the LLDPE and LDPE was 2.43 and 2.06 respectively. Tables 1 and 2 show the properties of the obtained film.

[0016]

[Table 1]

[0017]

[Table 2]

Example 4 LLDPE / LDPE film decomposable in the environment LLDPE / L decomposable in the environment prepared in Example 2
The DPE masterbatch and LDPE are supplied at a ratio of 70:30 into a blown film molding machine operated at a temperature profile of 130-180 ° C., and the LDPE is formed in the molding machine.
Had a melt index of 2.06. Tables 1 and 2 show the photodegradation properties of the obtained films.

Example 5 LLDPE / Polystyrene Sheet Decomposable in the Environment The LLDPE masterbatch decomposable in the environment prepared in Example 1 and polystyrene in a ratio of 25:75 at a temperature profile of 170-180 ° C. It was supplied to an operated extruder and finished into a sheet product. Tables 3 and 4 show the biodegradation properties of the obtained sheet product and the LLDPE masterbatch decomposable in the environment prepared in Example 1.

[0020]

[Table 3]

[0021]

[Table 4]

Biodegradability Test Determines the degree and rate of degradation of a plastic sample in activated sludge according to ASTM D5209-91. Activated sludge collected from a municipal landfill was cultivated by passing air through a glass container. The sample was left in the container and exposed to activated sludge, which was converted to organic compounds and carbon dioxide by biological action. Biodegradability was determined by the degree and rate of degradation by measuring the resulting soluble organics and carbon dioxide and measuring the weight loss of the sample.

LLDP of Example 1 used in this test
The E masterbatch was previously pressed into a thin sheet.
The control-1 sample used in this test used tissue paper and the control-2 sample used dead leaves. The embodiments of the invention described above are merely illustrative in all respects and do not limit the invention. Thus, the present invention may be embodied in other specific forms without departing from its essentials. Therefore, the present invention is limited only by the following claims.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ identification symbol FI // C08L 91/06 C08L 91/06 (58) Field surveyed (Int. Cl. ⁶ , DB name) C08L 3/00-3 / 20 C08K 5/057 C08K 5/09 C08K 5/521 C08L 23/00 C08L 91/06 C08J 5/00

Claims (12)

(57) [Claims] (1) 95-99% by weight of starch and a general formula: (Wherein R ₁ and R ₂ are hydrogen, or both R ₁ and R ₂ are ＯO)
A starch for producing an environmentally degradable α-olefin polymer molding material, comprising 0.8 wt%, paraffin 0.1-2 wt%, and fatty acid 0.1-2 wt%. Composition. 2. The environmentally degradable α according to claim 1, wherein the fatty acid is a C ₁₂ -C ₂₀ fatty acid.
Starch-based compositions for making olefin polymer molding materials. 3. The starch-based composition of claim 1, comprising 50-80% by weight, an α-olefin polymer of 18-49% by weight, a photosensitizer of 0.1-1.0% by weight; A starch-based composition for preparing an environmentally degradable α-olefin polymer molding material, comprising 0.1-1.0 wt% of a sensitizer promoter. 4. The α-olefin polymer may be a low density polyethylene (LDPE), a linear low density polyethylene (L
(LDPE) or a mixture of LDPE and LLDPE.
-Compositions based on starch for the production of olefin polymer molding materials. 5. The mixture of LDPE and LLDPE,
The starch-based composition for preparing an environmentally degradable α-olefin polymer molding material according to claim 4, wherein the LDPE: LLDPE has a weight ratio of 10:70 to 45:30. 6. The starch for preparing an environmentally degradable α-olefin polymer molding material according to claim 3, wherein the photosensitizer is a transition metal salt of dibutylthioaminoformic acid. Base composition. 7. The starch for preparing an environmentally decomposable α-olefin polymer molding material according to claim 3, wherein the photosensitizer promoter is a stearate. Composition. 8. The starch-based composition of claim 1 in an amount of 15-49 wt%, an α-olefin polymer in an amount of 50.8-84.8 wt%, and a photosensitizer in an amount of 0.1-1.0 wt%. And an environmentally decomposable α-olefin polymer molding material, comprising: 0.1 to 1.0 wt% of a photosensitizer promoter. 9. The α-olefin polymer may be a low-density polyethylene (LDPE) or a high-density polyethylene (HDP).
9. The decomposition according to claim 8, characterized in that: E), linear low density polyethylene (LLDPE), polystyrene, a mixture of LDPE and LLDPE, a mixture of LLDPE and polystyrene, or a mixture of LDPE, LLDPE and polystyrene. Possible α-olefin polymer molding materials. 10. The method according to claim 1, wherein the α-olefin polymer is LDP.
LDPE: LLDPE = 1 in a mixture of E and LLDPE
Having a weight ratio of 0:70 to 45:30 or LLDP
10. The environmentally degradable α-olefin polymer molding material according to claim 9, wherein the mixture of E and polystyrene has a weight ratio of LLDPE: polystyrene = 5: 80 to 30:25. 11. The environmentally degradable α-olefin polymer molding material according to claim 8, wherein the photosensitizer is a transition metal salt of dibutylthioaminoformic acid. 12. The environmentally decomposable α-olefin polymer molding material according to claim 8, wherein the photosensitizer promoter is a stearate.