JPH0559274A - Polyamide resin film - Google Patents

Abstract

PURPOSE:To obtain a polyamide resin film excelling in transparency, slip and printability and difficultly undergoing surface defects such as die lines. CONSTITUTION:A polyamide resin film prepared by molding a resin composition prepared by mixing 100 pts.wt. polyamide resin with 0.01-1 pt.wt. bisamide compound (ethylene-bisstearamide), 0.01-1 pt.wt. partial ester compound (monoglyceride) of a tri- to hexa-hydric aliphatic alcohol with a 10-22C fatty acid and 0.01-0.5 pt.wt. inorganic filler particles (silica).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polyamide resin film. More specifically, the present invention relates to a polyamide resin film that has few defects in appearance during film production and is excellent in transparency, slipperiness, and printing characteristics.

[0002]

2. Description of the Related Art Polyamide resin films are excellent in gas barrier properties and mechanical and thermal properties, so that they are mainly used for food packaging, such as single layers, multi-layer films with other resins, and laminated films with other materials. Is used in a wide range of applications. If the film made of such a polyamide resin has poor slipperiness, the film may be caught during bag making, or ink misalignment may occur during multicolor printing. Therefore, the slipperiness of the film is an extremely important characteristic from the viewpoint of the productivity, quality and commercial value of the film.

Therefore, various methods have been tried so far in order to improve the slipperiness of the polyamide resin film. For example, a method of blending inorganic filler particles (Japanese Patent Publication No. 54-4741), a method of blending polyethylene (Japanese Patent Publication No. 53-45226) and the like have been proposed.

[0004]

However, in the former method of blending the inorganic filler particles, the transparency of the obtained film is lowered and the commercial value is remarkably lowered, so that the blending amount is restricted, and The slipperiness of the film cannot be sufficiently improved only by blending the inorganic filler particles.

The film obtained from the composition also includes
A streak-like appearance defect called a die line is likely to occur, and it is difficult to stably and continuously produce a film having an excellent appearance. In particular, when silica-based inorganic particles are mixed, although relatively good results can be obtained with respect to the transparency and slipperiness of the obtained film, appearance defects such as die lines are extremely likely to occur, and the appearance is good. It is difficult to stably produce a film.

In addition, the latter method of blending polyethylene also causes a significant decrease in the transparency of the film and, at the same time, has the drawback that the strength of the film decreases. On the other hand, it is known that the transparency of the obtained film can be improved by blending a bisamide compound, but the blending of the bisamide compound causes a change in the surface characteristics of the film, resulting in adhesion of the printing ink during printing of the film. It has a drawback that the property is deteriorated and a printing defect is likely to occur. For this reason, it has been the actual situation that a polyamide resin film which is less likely to cause a defective appearance and has high productivity and which is excellent in transparency, slipperiness, and printability has not been industrially obtained.

[0007]

Means for Solving the Problems The present inventors have overcome the drawbacks of such conventional polyamide resin films, and are excellent in transparency, slipperiness, and printing characteristics, and are made of polyamide resin As a result of intensive studies to provide a film, a polyamide resin, a bisamide compound, a partial ester of a polyhydric aliphatic alcohol and a fatty acid, and by molding a film using a resin composition containing inorganic filler particles, The inventors have found that the objectives have been achieved and have reached the present invention.

That is, the gist of the present invention is: (1) 0.01 to 1 part by weight of a bisamide compound (2) trihydric aliphatic alcohol and 10 to 22 carbon atoms per 100 parts by weight of polyamide resin. Partial ester compound with fatty acid 0.01 to 1 part by weight (3) Inorganic filler particles 0.01 to 0.5 parts by weight A polyamide resin film formed by molding a resin composition is prepared.

The present invention will be specifically described below. As the polyamide resin used in the present invention, a polyamide resin obtained by polycondensation of a lactam having 3 or more membered rings, a polymerizable ω-amino acid, a dibasic acid and a diamine can be used. Specifically, polymers such as ε-caprolactam, aminocaproic acid, enanthlactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone and α-piperidone, hexamethylenediamine, nonamethylene. Diamine,
Undecamethylenediamine, dodecamethylenediamine,
Polymers obtained by polycondensing a salt of a diamine such as metaxylylenediamine and a dicarboxylic acid such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane dibasic acid, and glutaric acid, or a copolymer thereof. ,
For example, nylon 4, 6, 7, 8, 11, 12, 6 ・
6, 6/10, 6/11, 6/12, 6T, 6/6 ・
6, 6/12, 6 / 6T, 6I / 6T and the like. The bisamide compound used in the present invention means the following general formula (I) or (II)

[0010]

[Chemical 1]

(In the formula, R ¹ represents a divalent hydrocarbon residue, R ² and R ³ represent a monovalent hydrocarbon residue, and R ⁴ and R ⁵ represent a hydrogen atom or a monovalent hydrocarbon residue. ) Is a compound represented by.

Examples of the bisamide compound represented by the general formula (I) include alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, octamethylenediamine, dodecamethylenediamine, phenylenediamine and naphthalenediamine. Diamines such as arylene diamines, arylene diamines such as xylylenediamine and stearic acid, hexanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, arachidic acid, behenic acid, oleic acid, elaidic acid, montan Examples include alkylene bis fatty acid amides and arylene bis fatty acid amides obtained by reaction with a fatty acid such as an acid. Typical of these are:
N, N'-methylenebisstearic acid amide and N,
N'-ethylene bis stearic acid amide can be mentioned.

Examples of the bisamide compound represented by the general formula (II) include ethylamine, methylamine, butylamine, hexylamine, decylamine, pentadecylamine, octadecylamine, dodecylamine and other alkylamines, aniline, naphthylamine and the like. Selected from those obtained by reacting arylamines, aralkylamines such as benzylamine, monoamines such as cycloalkylamines such as cyclohexylamine with dicarboxylic acids such as terephthalic acid, p-phenylenedipropionic acid, succinic acid and adipic acid. Among them, dioctadecyl dibasic acid amide such as N, N′-dioctadecyl terephthalic acid amide can be mentioned as a typical one.

These bisamide compounds may be used alone or in combination of two or more.
The blending amount of the bisamide compound is 0.01 to 1 part by weight, preferably 0.0, to 100 parts by weight of the polyamide resin.
5 to 0.5 parts by weight. If this amount is too small, the transparency of the resulting film will decrease, and if it is too large, the printability will decrease.

The inorganic filler particles used in the present invention are not particularly limited, but any one can be selected and used from those conventionally used as fillers for resins. Specifically, clay, carion, silica-alumina-based clay minerals represented by calcined kaolin (hydrous aluminum silicates), silica-magnesium represented by talc, further calcium silicate, silica, alumina, Examples include calcium carbonate,
Among these, talc, kaolin, calcined kaolin or silica is particularly preferable from the viewpoint of easy dispersibility. Among them, silica is particularly preferably used because the resulting film has excellent transparency and good slipperiness.

These inorganic filler particles have a particle size of 10 μm.
does not contain particles larger than m and has an average particle size of 0.5 to 6 μm
Those within the range are preferable. If the particle size is large, it causes generation of fish eyes, and if the particle size is too small, dispersibility becomes poor, and fish eyes are likely to be caused by secondary aggregation of the filler, which is not preferable. Further, when these inorganic filler particles are surface-treated with a well-known surface treatment agent such as a silane treatment agent or a titanium treatment agent, good dispersibility can be obtained, and at the same time, transparency is improved. .. Further, in order to further improve the dispersibility, it is also extremely effective to mix an inorganic filler with a polyamide resin forming raw material during polymerization of the polyamide resin and disperse the inorganic filler in the resin in advance for use.

These inorganic filler particles are used alone or in combination of two or more, and the blending amount is
0.01 to 0.5 per 100 parts by weight of polyamide resin
Parts by weight, preferably 0.05 to 0.25 parts by weight.
If the blending amount is small, the slipperiness of the obtained film is not improved, and if the blending amount is too large, the transparency is lowered. Trivalent to hexavalent aliphatic alcohol used in the present invention and carbon number 1
Specific examples of the partial ester compound with 0 to 22 fatty acids include aliphatic alcohols such as glycerin, trimethylpropane, pentaerythritol, mesoerythritol, and sorbitol. Also, carbon number 10
Examples of the -22 fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. The carbon skeleton of the fatty acid may have a substituent such as a hydroxyl group.

The ester compound of such an aliphatic alcohol and a fatty acid needs to be substantially a partial ester, and preferably 30% or more of all hydroxyl groups in the polyhydric alcohol remain without being esterified. What is used is used. Among them, glycerin monostearate, glycerin distearate, glycerin monobehenate,
Glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate,
Pentaerythritol monobehenate, pentaerythritol dibehenate and the like are preferably used. These partial ester compounds can be used alone or in combination of two or more compounds, and the compounding amount thereof is 0.01 to 1 part by weight, preferably 0.05 to 0. 5 parts by weight. If the compounding amount is small,
The effect of improving the appearance of the obtained film is not observed, and if the blending amount is too large, the printing characteristics deteriorate.

There is no particular limitation on the method for preparing the resin composition which is the base material of the film of the present invention, and the resin composition can be prepared according to a commonly used method. For example, a polyamide resin pellet may be dry-blended with a bisamide compound, a partial ester compound, and inorganic filler particles at a predetermined ratio, or may be melt-mixed with an extractor. Further, it is effective to add the inorganic filler at the time of polymerization as described above.

In addition to the above-mentioned compounds, various additives well known to those skilled in the art, such as hindered phenols, antioxidants such as phosphoric acid ester and phosphorous acid ester, and triazine-based materials are added to the resin base material. Weather resistance improver such as compounds,
Colorants such as pigments and dyes, antistatic agents, lubricants and the like may be contained. The resin composition thus prepared is
The polyamide resin film of the present invention can be formed by a known film forming method. As a film forming method, a T-die method, an inflation method or the like is applied, and it is used as an unstretched film or a stretched film after a stretching step such as uniaxial stretching or biaxial stretching. Especially, a suitable effect is obtained when manufacturing a water-cooled blown film. This water-cooled blown film is obtained by extracting the resin composition through a circular die from an extractor at a temperature in the range of 220 to 280 ° C.,
After contacting the surface of a water-cooled ring flowing at a temperature of 10 to 30 ° C, it is rapidly cooled and solidified, and after being taken up by a pinch roll, the water adhering to the film surface is dried in an oven at a temperature of 50 to 80 ° C. Then, it can be manufactured by winding on a frame.

The polyamide resin film of the present invention may be a monolayer film or a laminated film formed by coextrusion or lamination.

[0022]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto without departing from the gist thereof. The physical properties of the film were determined by the methods described below. (1) Transparency The haze value was measured using a haze meter manufactured by Tokyo Denshoku Co., Ltd. (2) Sliding property The static friction coefficient (μs) was measured by a parallel movement method under the conditions of relative humidity of 65% and temperature of 23 ° C. (3) Printability It was judged by the water droplet contact angle of the film. (4) Presence or absence of die line It was judged by visual observation of the film.

Examples 1 to 7 and Comparative Examples 1 to 9 Commercially available nylon 6 resin (Novamid 1020 manufactured by Mitsubishi Kasei Co .; Novamid is a registered trademark), or nylon 6
/ 66 copolymer resin (Novamid 20 manufactured by Mitsubishi Kasei Co., Ltd.)
20) 100 parts by weight of the additives shown in Table 1 were blended in the ratio shown in Table 2 to obtain a film having a thickness of 25 μ and a width of 10 cm by a water cooling inflation method at a take-up speed of 25 m / mi.
The film was formed by n. In addition, 1 hour, 2 hours, 4
Using the film after the lapse of time, the presence or absence of streak-like appearance defects called die lines was visually observed. Also, after the start of film formation,
Haze value, static friction coefficient,
The water drop contact angle was measured. The results are shown in Table 2. Table 2
In the above, the compounding amount is parts by weight based on 100 parts by weight of the polyamide resin.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

The polyamide resin film of the present invention is
It has excellent properties such as excellent transparency, slipperiness and printability, and less likely to cause defective appearance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical indication C08K 5/20 KKX 7167-4J // C08L 77:00 (72) Inventor Tomoaki Kinmasa Chigasaki, Kanagawa 370 Enzo, Ichi, Japan Chibasaki Plant of Mitsubishi Kasei Co., Ltd.

Claims (1)

[Claims] 1. To 100 parts by weight of a polyamide resin, (1) a bisamide compound: 0.01 to 1 part by weight (2) a partial ester of a tri- to hexavalent aliphatic alcohol and a fatty acid having 10 to 22 carbon atoms. Compound: 0.01 to 1 part by weight (3) Inorganic filler particles: A polyamide resin film formed by molding a resin composition containing 0.01 to 0.5 part by weight.