JP2000355652A - Polyester amide resin composition and film or sheet using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition satisfactory in flexibility, heat resistance, and weather resistance by mixing a polyesteramide resin with a hindered phenolic compound and/or a phosphorous ester compound. SOLUTION: This composition comprises 100 pts.wt. polyesteramide resin containing both an aliphatic ester structure and an aliphatic amide structure and 0.03-1.2 pts.wt. hindered phenolic compound and/or phosphorous ester compound. It is desirable that the composition further contains 0.03-1.0 pt.wt. hindered amine light stabilizer. The polyesteramide resin is obtained, for example, by mixing at least either an aliphatic aminocarboxylic acid or an aliphatic lactam with an aliphatic dicarboxylic acid and an aliphatic diol, subjecting the mixture to a dehydration reaction, and polymerizing the product in a vacuum. Alternatively, it is obtained by mixing an aliphatic dicarboxylic acid with an aliphatic diol and an aliphatic diamine, subjecting the mixture to a dehydration reaction, and polymerizing the product under reduced pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biodegradable polyesteramide resin composition having improved heat resistance and weather resistance when used as a product, and a film sheet using the same, and relates to a masking film and a riverbed. It is used for agricultural applications such as stretch films for sheets and pallets and silage films, packaging applications, and civil engineering applications.

[0002]

2. Description of the Related Art Aliphatic polyesters, starches and the like are known as biodegradable resins, but have the disadvantage of poor flexibility.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a composition which satisfies flexibility, heat resistance and weather resistance by using a specific biodegradable resin.

[0004]

According to the present invention, a hindered phenol compound and / or a phosphite ester are added to 100 parts by weight of a polyesteramide resin having an aliphatic ester structure and an aliphatic amide structure. A polyesteramide resin composition characterized in that the compound is compounded in an amount of 0.03 to 1.2 parts by weight.

[0005] Further, the present invention relates to a polyester amide resin having an aliphatic ester structure and an aliphatic amide structure, wherein 100 parts by weight of a hindered phenol compound and / or a phosphite compound is added to 0.03 parts by weight. ~
1.2 parts by weight, hindered amine light stabilizer 0.03 to
1.0 part by weight of the polyester amide resin composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The polyesteramide resin containing an aliphatic ester structure and an aliphatic amide structure used in the present invention has an average molecular weight of 10,000 to 300,000, preferably 20,000 to 150,000. The method for producing the polyesteramide resin includes at least one of an aliphatic aminocarboxylic acid and an aliphatic lactam.
It can be produced by mixing a seed, an aliphatic dicarboxylic acid, and an aliphatic diol, dehydrating, and polymerizing under reduced pressure.

The polyester amide resin containing an aliphatic ester structure and an aliphatic amide structure used in the present invention is prepared by mixing an aliphatic dicarboxylic acid, an aliphatic diol and an aliphatic diamine, and subjecting the mixture to a dehydration reaction. It can also be produced by polymerizing under reduced pressure.

Further, the polyesteramide resin can be polymerized from at least one of an aliphatic aminocarboxylic acid or an aliphatic lactam, an aliphatic dicarboxylic acid, an aliphatic diol, and an aliphatic diamine.

As the above-mentioned aliphatic aminocarboxylic acid or aliphatic lactam, those having a linear aliphatic chain or a cyclic aliphatic chain having 4 to 20 carbon atoms, such as aminocaproic acid, ω-lauryl lactam, ε-caprolactam, etc. Examples of the aliphatic dicarboxylic acid include those having a linear aliphatic chain having 2 to 12 carbon atoms such as adipic acid, succinic acid, and oxalic acid, and the aliphatic diols having 2 to 10 carbon atoms.
Diols having a linear aliphatic chain of, for example, ethylene glycol, 1,3-propanediol, 1,4
-Butanediol, 1,6-hexanediol and the like, as the aliphatic diamine, a linear aliphatic diamine having 2 to 10 carbon atoms is preferable, for example, hexamethylene diamine,
Butylene diamine can be mentioned. It is also possible to use an oligomer raw material in which a plurality of components have been reacted in advance, such as by reacting an aliphatic dicarboxylic acid with an aliphatic diol and using it as an acid terminal ester oligomer. Furthermore, a small amount of an aromatic component or an alicyclic component can be used as long as biodegradability is not impaired.

Specifically, when ε-caprolactam, adipic acid and 1,4-butanediol are polymerized,
[—CO— (CH ₂ ) ₄ —COO— (CH ₂ ) ₄ —O
-] Unit, an aliphatic ester structure consisting of [-CO-
(CH ₂ ) ₅ —NH—] having an aliphatic amide structure. The preferred weight ratio of the aliphatic ester structure is 2
0 to 70% by weight, the weight ratio of the aliphatic amide structure is 30 to
The weight ratio of the aliphatic ester structure is 30 to 60% by weight, and the weight ratio of the aliphatic amide structure is more preferably 40 to 70% by weight.

Further, hexamethylenediamine and adip
When acid and 1,4-butanediol are polymerized,
[-CO- (CH_Two)_Four-COO- (CH_Two)_Four-O
-] Unit, an aliphatic ester structure consisting of [-CO-
(CH_Two)_Four-CO-NH- (CH _Two)₆-NH-]
Having an aliphatic amide structure consisting of
The weight ratio of the stell structure is 50 to 90% by weight,
The weight ratio of the metal structure is 10 to 50% by weight.
More preferably, the weight ratio of the aliphatic ester structure is 55 to 80.
Weight%, weight ratio of aliphatic amide structure is 20-45 weight%
%.

The hindered phenol compound used in the present invention includes octadecyl-3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate, pentadecyl-3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate, triethylene glycol-bis [3- (3-t-butyl-5- Methyl-4-hydroxyphenyl) propionate],
1,6-hexanediol-bis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,
5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N , N-Hexamethylenebis (3,5-
Di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5
-Di-t-butyl-4-hydroxybenzyl) isocyanurate, 3,9-bis {1,1-dimethyl-2- [β
-(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl {-2,4,8,1
0-tetraoxaspiro (5,5) undecane, tetrakis [methylene-3 (3 ′, 5′-di-t-butyl-
4'-hydroxyphenyl) propyl] methane, 1,
1,3-tris (2-methyl-4-hydroxy-5-t
-Butylphenyl) butane, 4,4'-butylidenebis (3-methyl-6-t-butylphenyl) and the like.

The phosphite compound used in the present invention includes 2,2-methylenebis (4,6-
Di-t-butylphenyl) octyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-t- Butylphenyl) butane,
2,2-thio-diethylenebis [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate], dinonylphenylpentaerythritol diphosphite, distearylpentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,
6-di-t-butyl-4-methylphenyl), pentaerythritol-di-phosphite, diphenyldecyl phosphite, triphenyl phosphite, tris-nonylphenyl phosphite, tridecyl phosphite,
Tris (2-ethylhexyl) phosphite, tributyl phosphite, tris (dinonylphenyl) phosphite, trilauryl trithiophosphite, trilauryl phosphite, bis (neopentyl glycol)-
1,4-cyclohexanedimethylphosphite, distearylpentaerythritol diphosphite, diisodecylpentaerythritol diphosphite, tris (lauryl-2-thioethyl) phosphite, tetratridecyl-1,1,3-tris (2'- Methyl-5'-t-
Butyl-4'-oxyphenyl) butanediphosphite, tris (4-oxy-2,5-di-t-butylphenyl) phosphite, tris (4-oxy-3,5-di-t-butylphenyl) Phosphite, 2-ethylhexyl diphenyl phosphite, tris (mono, di-mixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, diphenyl bis [4,4'-n-butylidene bis (2-t-butyl-5-methylphenol)] thiodiethanol diphosphite, 4,4'-butylidenebis (3-methyl-
6-t-butylphenol-di-tridecyl) phosphite, bis (octylphenyl) bis [4,4'-n
-Butylidenebis (2-t-butyl-5-methylphenol)]-1,6-hexanediol diphosphite;
Phenyl-4,4'-isopropylidenediphenol
Pentaerythritol diphosphite, phenyldiisodecyl phosphite, tetratridecyl-4,4'-n
-Butylidenebis (2-t-butyl-5-methylphenol) diphosphite, tris (2,4-di-t-butylphenyl) phosphite, tristearyl phosphite, octyldiphenylphosphite, diphenyltridecylphosphite, phenyldi ( (Tridecyl) phosphite, tris (2-cyclohexylphenyl) phosphite, ditridecyl di (2-cyclohexylphenyl) hydrogenated bisphenol A diphosphite, di (2,
4-di-t-butylphenyl) cyclohexyl phosphite, 2,4-di-t-butylphenyl diisodecyl phosphite, tris (butoxyethoxyethyl) phosphite, diphenyl acid phosphite, bis (2-
Cyclohexylphenyl) acid phosphite, bis (2,4-di-t-butylphenyl) acid phosphite, bis (nonylphenyl) acid phosphite, dibenzyl acid phosphite, tetrakis- (2,4-di-t-) Butylphenyl) 4,4'-biphenylene phosphite.

The amount of the hindered phenol compound and / or phosphite compound is 0.03-1.2 parts by weight, preferably 0.05-1. The range is 0 parts by weight. If the amount is less than this, the thermal stability tends to decrease. If the amount is too large, the appearance of the molded article is impaired or the cost is increased, which is not preferable.

It is preferable to use a hindered amine light stabilizer in the present invention. For example, poly [$ 6-
(1,1,3,3-tetramethylbutyl) imino-1,
3,5-triazine-2,4-diyl {(2,2,
6,6-tetramethyl-piperidyl) imino {hexamethylene} (2,2,6,6-tetramethyl-piperidyl) imino}], poly [{6- (1,1,3-trimethylpentyl) imino-1 , 3,5-Triazine-2,4
-Diyl {(N-methyl-2,2,6,6-tetramethyl-piperidyl) imino} octamethylene {(N-methyl-2,2,6,6-tetramethyl-piperidyl) imino}], 2 , 2,6,6-tetramethylpiperidinyl-4-benzoate, bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 1,3
8-triaza, 7,7,9,9-tetramethyl-3
-N-octyl-spiro [4,5] decane-2,4-dione, 1,2,3,4-tetra (4-carbonyloxy-2,2,6,6-tetramethylpiperidine) -butane, tri -(4-acetoxy-2,2,6,6-tetramethylpiperidine) -amine, 4-acetoxy-2,
2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine,
4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,
2,6,6-tetramethylpiperidine, tris (2,
2,6,6-tetramethyl-4-piperidine) phosphite, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, 1,3,8-triaza-7,
7,9,9-Tetramethyl 2,4-dioxosepyro [4,5] decane, (2,2,6,6-tetramethylpiperidine) -4-spiro-2 '-(6', 6'-dimethylpiperidine ) -4'-Spiro-5 "-hindantoin, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, dimethyl-1- (2-succinate)
(Vidroxyethyl) -4-hydroxy-2,2,6,6
-Tetramethylpiperidine polycondensate, tetrakis (2,
2,6,6-tetramethyl-4-piperidyl) 1,2,2
Examples thereof include 3,4-butanetetracarboxylate and tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate.

The amount of the hindered amine light stabilizer is in the range of 0.03 to 1.0 part by weight, preferably 0.05 to 0.8 part by weight, per 100 parts by weight of the resin component. If the amount is less than this, the weather resistance tends to decrease, and if it is too large, the appearance of the molded article is impaired or the cost is increased, which is not preferable.

In the above-mentioned blending, other biodegradable polymer materials may be added as long as the effects of the present invention are not impaired. In addition, plasticizers, fillers, lubricants, reinforcing agents, Ni-based quenchers, sulfur-based antioxidants, benzotriazole-based and benzophenone-based ultraviolet absorbers for the purpose of adjusting moldability and other physical properties of films and sheets. It is also possible to add additives such as fungicides, pigments, fluorescent agents and the like, and modifiers.

The polyesteramide resin containing an aliphatic ester structure and an aliphatic amide structure of the present invention and the above-mentioned additives may be mixed at the time of extrusion processing. Is good. After being pelletized, the film is manufactured by an extruder, by a T-die, or by inflation molding. Calender molding is also possible.

When the composition of the present invention is formed into a film sheet by the above-mentioned method, the thickness thereof is usually 15 to 10
00 μm, preferably in the range of 20 to 500 μm.

With the composition of the present invention, a biodegradable film sheet obtained as described above is manufactured and used for various applications.

[0021]

The present invention is not limited by the following examples. The measurement and evaluation shown in the examples were performed under the following conditions.

Weather resistance test (1): Sunshine W. O.
The sample was placed in H, and the time until the sample was destroyed due to weather resistance deterioration was measured.

Weather resistance test (2): Sunshine W. O.
A sample was placed in H with an aluminum plate attached to the back side, and the time until destruction of the sample due to weather resistance deterioration was measured.

Example 1 A fatty acid having an aliphatic ester structure of 5 was prepared by polymerizing adipic acid, 1,4-butanediol and ε-caprolactam.
A hindered phenolic compound (trade name "AO-80" manufactured by Asahi Denka Co., Ltd.) is added to 100 parts by weight of a polyesteramide resin (melting point: 137 ° C.) having a weight of 0% by weight and an aliphatic amide structure of 50% by weight. 2 parts by weight and a phosphite compound ("2112" manufactured by Asahi Denka Co., Ltd.)
One part by weight was blended to prepare a pellet. These pellets were formed into a film having a thickness of 100 μm using a T-die type 30 mmφ extruder. In this film evaluation, the weather resistance test (1) was 120 hours, and the weather resistance test (2) was 100 hours.

Comparative Example 1 A film was prepared in the same manner as in Example 1 except that the hindered phenol compound and the phosphite compound were not blended. In this film evaluation, the weather resistance test (1) was 80 hours, and the weather resistance test (2) was 50 hours.

Example 2 0.1 part by weight of a hindered phenolic compound (trade name "AO-60" manufactured by Asahi Denka Co., Ltd.) was added to 100 parts by weight of the polyesteramide resin used in Example 1; Acid ester compound ((Asahi Denka Co., Ltd., trade name “211
2 ") 0.1 parts by weight and a hindered amine light stabilizer (trade name" LS- ", manufactured by Ciba Specialty Chemical Co., Ltd.)
944 "), and 0.3 parts by weight were blended to prepare pellets. The pellets are extruded by a 30 mm φ extruder
A film having a thickness of 100 μm was prepared. In this film evaluation, the weather resistance test (1) was 250 hours, and the weather resistance test (2) was 180 hours.

Example 3 0.1 part by weight of a hindered phenolic compound (trade name "AO-80" manufactured by Asahi Denka Co., Ltd.) was added to 100 parts by weight of the polyesteramide resin used in Example 1, Acid ester compound ((Asahi Denka Co., Ltd., trade name “211
2 ") 0.1 parts by weight, hindered amine light stabilizer (trade name" LS-94 "manufactured by Ciba Specialty Chemical Co., Ltd.)
4 ") 0.3 parts by weight and a benzotriazole-based ultraviolet absorber (trade name" VS-550 ", manufactured by Kyodo Yakuhin).
One part by weight was blended to prepare a pellet. These pellets were formed into a film having a thickness of 100 μm using a T-die type 30 mmφ extruder. In this film evaluation, the weather resistance test (1) was 350 hours, and the weather resistance test (2) was 190 hours.

Comparative Example 2 In Example 3, the additive was a benzotriazole-based ultraviolet absorber (trade name “VS-55” manufactured by Kyodo Yakuhin KK).
0 ") A film was prepared in the same manner as in Example 3, except that only 0.2 parts by weight was blended. In this film evaluation, the weather resistance test (1) was 100 hours, and the weather resistance test (2) was 60 hours.

Example 4 Polyester amide-based resin having an aliphatic amide structure of 70% by weight and an aliphatic ester structure of 30% by weight (melting point: 116), produced by polymerizing adipic acid, 1,4-butanediol and ε-caprolactam. C.), and a film having a thickness of 100 μm was prepared in the same manner as in Example 1. In this film evaluation, the weather resistance test (1) was 130 hours, and the weather resistance test (2) was 100 hours.

Example 5 Polyester amide resin having an aliphatic ester structure of 80% by weight and an aliphatic amide structure of 20% by weight (melting point) produced by polymerizing adipic acid, 1,4-butanediol and hexamethylenediamine 0.1 part by weight of a hindered phenol compound (trade name “AO-60” manufactured by Asahi Denka Co., Ltd.) and a phosphite compound (trade name (trade name, manufactured by Asahi Denka Co., Ltd., 100 parts by weight) "2112") 0.1
Parts by weight and hindered amine light stabilizer (trade name “LS-944” manufactured by Ciba Specialty Chemicals)
0.3 parts by weight were blended to prepare pellets. This pellet was extruded with a T-die type 30 mmφ extruder to a thickness of 100 μm.
m was prepared. In this film evaluation, the weather resistance test (1) was 150 hours, and the weather resistance test (2) was 120 hours.

Comparative Example 3 A film was prepared in the same manner as in Example 5 except that the hindered phenol compound and the phosphite compound were not blended. In this film evaluation, the weather resistance test (1) was 90 hours, and the weather resistance test (2) was 70 hours.

[0032]

According to the present invention, by adding a hindered phenol compound and / or a phosphite compound to a polyester amide resin containing an aliphatic ester structure and an aliphatic amide structure, the heating conditions are increased. Underwater degradation can be prevented, and the weather resistance can be significantly improved by adding a hindered amine light stabilizer.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/34 C08K 5/34 5/524 5/524 (72) Inventor Nobuaki Wada Kyobashi, Chuo-ku, Tokyo No. 18-1 Shiai Kasei Co., Ltd. (72) Inventor Michael Huicht, Germany 47239 Deusburg Düsseldorfstrasse 8, (72) Inventor Ralph Timmermann, Germany 47800 Krefeld Shiybler Jutler C81 (72) Inventor Borfgang Schulz-Syuritte 40707 Langenfeld Huon Kniprodebeek 7 F-term (reference) 4F071 AA54 AC11 AC12 AE05 AF52 AH01 AH04 BB06 BB09 BC01 BC12 4J001 DA01 DB02 DB04 EA02 EA06 EB06 EB06 EB08 EC07 EC08 ED05 ED06 ED07 ED08 GA11 JA12 4J002 CL031 CL051 EJ066 EU077 EU196 EW066 EW126 FD046 FD047

Claims (6)

[Claims] 1. A hindered phenolic compound and / or a phosphite compound are added in an amount of 0.03 to 1 to 100 parts by weight of a polyesteramide resin containing an aliphatic ester structure and an aliphatic amide structure. A polyester amide-based resin composition comprising 2 parts by weight. 2. A hindered phenol compound and / or a phosphite compound is used in an amount of from 0.03 to 1 per 100 parts by weight of a polyesteramide resin containing an aliphatic ester structure and an aliphatic amide structure. 2 parts by weight,
A polyesteramide-based resin composition containing 0.03 to 1.0 parts by weight of a hindered amine-based light stabilizer. 3. The method according to claim 1, wherein the polyesteramide resin is polymerized from at least one kind of aliphatic aminocarboxylic acid or aliphatic lactam, an aliphatic dicarboxylic acid, and an aliphatic diol. The polyesteramide resin composition according to claim 2. 4. The polyester amide resin composition according to claim 1, wherein the polyester amide resin is polymerized from an aliphatic dicarboxylic acid, an aliphatic diol, and an aliphatic diamine. object. 5. The method according to claim 1, wherein the polyester amide resin is polymerized from at least one kind of aliphatic aminocarboxylic acid or aliphatic lactam, an aliphatic dicarboxylic acid, an aliphatic diol, and an aliphatic diamine. The polyester amide-based resin composition according to claim 1 or 2, wherein 6. A film sheet comprising the polyester amide-based resin composition according to claim 1.