WO2006038507A1

WO2006038507A1 - Polyamide resin molding material for film and process for producing the same

Info

Publication number: WO2006038507A1
Application number: PCT/JP2005/017852
Authority: WO
Inventors: Hajime Ooyama; Morio Tsunoda
Original assignee: Mitsubishi Engineering-Plastics Corporation
Priority date: 2004-10-06
Filing date: 2005-09-28
Publication date: 2006-04-13
Also published as: CN100532455C; CN101031617A; TW200628550A; TWI370832B

Abstract

A polyamide resin molding material for films which is obtained by mixing (A) 90-99 parts by weight of polyamide resin pellets, (B) 10-1 part by weight of a masterbatch comprising a polyamide resin and, compound therewith, 2-8 wt.% inorganic particles and 1-5 wt.% bisamide compound, and (C) 0.005-0.1 part by weight of a bisamide compound powder, the sum of (A) and (B) being 100 parts by weight. The polyamide resin molding material for films is suitable for use in producing a polyamide resin film which is excellent in transparency, slip properties, and printability and which, even when having been formed continuously, is less apt to have appearance defects such as die lines or fisheyes.

Description

Specification

Polyamide resin molding material for film and method for producing the same

Technical field

The present invention relates to a polyamide resin molding material suitable for producing a polyamide resin film excellent in transparency, slipperiness, printability, appearance and productivity, and a film obtained therefrom.

Background art

[0002] Polyamide resin films are excellent in gas barrier properties, mechanical 'thermal properties, etc., and therefore are mainly composed of food packaging, single layer films, multilayer films with other resins, and other materials. It is used in a wide range of applications as a laminated film. The transparency of the polyamide resin film is an important characteristic because it greatly affects the appearance of the contents. In general, a film having good transparency is desired. In addition, if the slipperiness is poor, the film may be caught during bag making, or the ink may be misaligned during multicolor printing. For this reason, the slipperiness of the film is an extremely important characteristic of film productivity, quality and commercial value. Thus, it is necessary to achieve both transparency and slipperiness of the film, but the surface of the film with good transparency is smooth. The smooth surface of the film is slippery.

[0003] Various methods have been attempted in the past to improve a strong polyamide-resin film. For example, a method of blending inorganic particles such as silica and talc (for example, see Patent Document 1), a method of blending a specific bisamide (for example, see Patent Document 2), and the like are known. However, in the method of blending inorganic particles, if the surface activity of the inorganic particles is high, the thermal stability of the polyamide resin becomes poor, and granular defects called fish eyes, It is difficult to stably and continuously produce a film having an excellent appearance that easily causes streak-like appearance defects. In view of this, it has been proposed to treat the surface of silica when typical silica is blended as inorganic particles for film (see, for example, Patent Document 3). By blending such treated inorganic particles and bisamide, comparatively good results were obtained in terms of transparency and slipperiness. [0004] On the other hand, as a general method of blending fine inorganic particles such as silica with polyamide resin, (1) a method of attaching inorganic particles to the pellet surface using static electricity, (2) a low viscosity on the pellet surface A method of adhering inorganic particles using a liquid, (3) A method of manufacturing a masterbatch in which inorganic particles are kneaded at a high concentration and blending with polyamide resin, (4) Inorganic particles during polymerization of polyamide resin Addition methods and the like have been adopted.

[0005] However, even when the inorganic particles and bisamide for improving the film are blended by the methods (1), (2) and (3), the dispersion of the inorganic particles in the polyamide resin is insufficient. For this reason, the resulting film cannot avoid the generation of fish eyes. On the other hand, in the method (4), the inorganic particles are dispersed sufficiently well, but the thermal stability of the polyamide resin is deteriorated, and burning is mixed into the pellets after the polymerization for a long time. There is a risk of appearance defects such as eyes and die lines. Therefore, in the conventional general method of blending inorganic particles, stable production for a long time without appearance defects is difficult.

[0006] Patent Document 1: Japanese Patent Publication No.54-4741

Patent Document 2: Japanese Patent Publication No. 44-9825

Patent Document 3: Japanese Patent Application Laid-Open No. 63-251460

Disclosure of the invention

Problems to be solved by the invention

[0007] The present invention overcomes the disadvantages of the polyimide resin for film produced by the conventional method of blending inorganic particles as described above, and has excellent transparency, slipperiness and printability, and continuous film formation. An object of the present invention is to provide a polyamide resin molding material for a film that does not easily cause appearance defects such as die lines and fish eyes even if it is performed.

Means for solving the problem

[0008] As a result of diligent investigations to solve the above problems, the present inventors have determined that each of the inorganic particles by a masterbatch, a predetermined amount of bisamide by a masterbatch, and the remainder of the bisamide in powder form, respectively. It has been found that the above-mentioned problems can be solved by blending with rosin, and the present invention has been completed.

[0009] That is, the first gist of the present invention is that the total of (A) and (B) is 100 parts by weight, (A) 90 to 99 parts by weight of polyamide resin pellets, and (B) polyamide resin 2-8% by weight of inorganic particles and Master batch 10 to 1 parts by weight blended bisamide compound 1-5 wt ^_0/0, (C) Bisua bromide compound powder 0.1 005-0. 1 made by mixing parts by weight film for polyamide榭脂molding Lies in the material.

[0010] The second gist of the present invention is that the total of (A) and (B) is 100 parts by weight, (A) 90 to 99 parts by weight of polyamide resin pellets, and (B) inorganic particles in polyamide resin. and 2-8 weight ^_0/0 and bisamide compound 1-5 wt% masterbatch 10-1 parts by weight blended, (C) a bisamide compound powder 0.1 005-0. 1 part by weight of a film manufacturing extruder The present invention resides in a method for producing a polyamide resin film characterized in that the film is formed into a film.

[0011] The third gist of the present invention resides in a polyamide resin film in which the above-mentioned polyamide resin molding material strength is also formed.

[0012] It should be noted that the polyamide resin molding material for film according to the present invention includes the components (A), (B), and (C) as compounding, as is apparent from the description of the present specification. Preferably, it is a material that is uniformly stirred and mixed (referred to as “dry blend”) in a mixing device such as a tumbler mixer or a nauter mixer, and is used for film production as it is. A material that is supplied to a molding machine to form a film. A mixture obtained by stirring and mixing (A), (B), and (C) in a mixing apparatus as described above may be referred to as a dry blend.

The invention's effect

[0013] By using the polyamide resin molding material of the present invention, it is possible to continuously form a film for a long time without stopping production, and the resulting film has an appearance, transparency, The excellent slipperiness and printability can be expected to reduce the manufacturing cost and expand the application to food packaging of polyamide resin film.

BEST MODE FOR CARRYING OUT THE INVENTION

[0014] Hereinafter, the present invention will be described in detail. However, the description of the constituent elements described below is a representative example of embodiments of the present invention, and the present invention is not limited to these contents. In the present invention, (A) the polyamide resin used in the polyamide resin pellet is a polyamide obtained by polycondensation of ratata having a three-membered ring or more, polymerizable ω-amino acid, dibasic acid and diamine, and the like.榭脂 can be used. Specifically, ε-force prolatatam, aminocaproic acid, enantolactam and other ratatams; 7 aminoheptanoic acid, 11 aminoundeca Polymers of ω-amino acids such as acid, 9-aminononanoic acid, pyrrolidone, and α-piperidone; hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, Examples thereof include polycondensates of diamines such as metaxylene diamine and dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecanedioic acid, and glutaric acid, or copolymers thereof. More specifically, polyamide 4, 6, 7, 8, 11, 12, 6, 6, 6, 10, 11, 6, 12, 6Τ, 6/6-6, 6/12, 6 / 6Τ , 6ΙΖ6Τ 等力 Illustrated. These polyamide resin may be used alone or in combination of two or more. Among these polyamide resins, polyamide 6 resin and polyamide 6-66 copolymer resin can be preferably used from the viewpoint of thermal and mechanical properties of the obtained film.

[0015] The shape of the polyamide resin pellets (ペレット) in the present invention may be any of a sphere, a cylinder, a prism, and a plate, but the pellet volume is preferably about 0.5 to 10 cm ³ Zg. More preferably, it is l-8cm ³ Zg. For example, in the case of a cylinder, pellets having a length of 1 to 5 mm and a diameter of 1 to 4 mm are easy to handle in the production of the polyamide resin material of the present invention, and bite into the extruder during film formation. The stability force of is preferably used.

[0016] Further, in the polyamide resin used in the present invention, according to JIS K6933-99, the viscosity number measured at 96% sulfuric acid concentration 1% and the temperature at 23 ° C is usually 115 to 300, preferably It is in the range of 130-210. If the viscosity number is too low, the resulting film has insufficient mechanical properties, and if it is too high, film formation becomes difficult.

[0017] Furthermore, the amount of water extract measured in accordance with JIS K6920-1 which is a method for measuring the content of low molecular weight substances in the polyamide resin used in the present invention is usually 1% by weight or less, Preferably it is 0.5 weight% or less. When the amount of water extraction is large, low molecular weight materials such as monomers and dimers easily adhere to the periphery of the die mouth, and such low molecular weight materials come into contact with or adhere to the film. Appearance defects are likely to occur.

[0018] The kind of the inorganic particles used in the present invention is not particularly limited, and any of the conventionally used inorganic fillers can be selected and used. Specifically, silica-alumina clay minerals (hydrous aluminum silicates) typified by clay, kaolin, calcined kaolin, silica-magnesium typified by talc, calcium silicate, silica, zeolite, alumina, calcium carbonate Among these, among these, special In addition, talc, kaolin, calcined kaolin, silica and zeolite are also suitable for easy dispersibility. Of these, silica and zeolite are particularly suitable.

[0019] These inorganic particles do not contain particles having a particle size of 10 μm or more and have an average particle size of 0.4 to 6

Those in the range of / z m are preferred. If the particle size is large, it will cause the generation of fish eyes. If the particle size is too large, the dispersibility will be poor, and it will be easy to cause fishery due to secondary aggregation of inorganic particles.

[0020] Further, as the inorganic particles, the above-mentioned particles are used alone or in combination of two or more. The amount thereof, the total polyamide榭脂, i.e. 100% on the total weight of the poly amide榭月fact occupied in the molding material of the present invention, 0.02 to 0.8 wt ^_0/0, preferably 0. 05～ Selected in the range of 0.5% by weight. If the amount of the inorganic particles is small, the improvement of the slipperiness of the resulting film is not observed, and if the amount is too large, the transparency is lowered.

As the silica preferably used as the inorganic particles of the present invention, any of so-called wet silica and dry silica can be used, and the specific surface area by the BET method is usually 50 m ² Zg or more, preferably 100 m ^2. The oil absorption measured according to JIS K5101-13 is usually 50 mlZlOOg or more.

[0022] The zeolite that is preferably used as the inorganic particles of the present invention may be either amorphous or crystalline, but is preferably zeolite that is amorphous as measured by the X-ray method. Use of zeolite, which has a crystal structure as measured by the X-ray method, reduces the stretching stability of the resulting film and tends to cause frequent stretching breaks. There is no particular limitation on the shape of zeolite, but it may be spherical or polygonal fine particles. Preferably, it has a spherical or cubic shape.

[0023] The amount of oil absorption measured by ZEOLITE by the JIS K5101-13 method is usually 1 to 70 mlZlOg, preferably 5 to 70 mlZlOOg. If the oil absorption is too low, the stretching stability will decrease, and if it is too high, the effect of improving the slipping property will be small when stretched. Also, the chemical composition of zeolite is: Si O force 0-60% by weight, Al O force ¾0-45% by weight, Na O 6-9% by weight, CaO 0-8%

2 2 3 2

It is preferred to be weight%! /.

[0024] When the inorganic particles used in the present invention are surface-treated with a known surface treatment agent such as a silane coupling agent (silane treatment agent) or a titanium-based treatment agent, good dispersion is obtained. It is preferable because the transparency of the resulting film is improved at the same time that the properties are obtained. The type of surface treatment agent and the surface treatment method are not particularly limited, but treatment with a silane coupling agent is preferred. In particular, when surface-treated silica or zeolite is used as the inorganic particles, favorable results are obtained in terms of transparency and slipperiness of the resulting film.

[0025] The silane coupling agent preferably used in the present invention has an organosiloxane group. Specific examples of the organo group include alkyl groups such as methyl, ethyl and propyl; alkenyl groups such as butyl and allyl; cycloalkyl groups such as cyclopropyl and cyclohexyl; aryl groups such as phenyl and benzyl; γ-Aminopropyl, Ν- (β-aminoethyl) Contains functional groups such as chloro, thiol, and epoxy, such as aminoalkyl groups such as γ-aminominopropyl, γ-glycidoxy, γ-chloropropyl, and γ mercaptopropyl. There is a whip.

[0026] Specifically, trimethylmethoxysilane, butyltriethoxysilane, γ-chloropropyl methoxytrimethoxysilane, γ-aminopropyltriethoxysilane, Ν- (j8-aminoethyl) -aminopropyltrimethoxysilane , _Ί -Mercaptopropyltrimethoxysilane, γ- _{Dalicydoxypropyltrimethoxysilane} , γ-methacryloxypropyltrimethoxysilane, hexamethyldisilazane, Ν, Ν, monobis (trimethylsilyl) urea, Ν, Ν, Examples thereof include monobis (trimethylsilyl) acetamide, jetyltrimethylsilylamine, Ν, Ν, -bis (trimethylsilyl) trifluoroacetamide, stearyltrimethoxysilane, and the like. In particular, aminosilanes such as γ aminopropyltriethoxysilane are suitable.

[0027] The amount of the silane coupling agent used is usually 1 to 99% by weight, preferably 2 to 70% by weight, more preferably 5 to 40% by weight, based on the inorganic particles. If the amount of the silane coupling agent used is less than 1% by weight relative to the inorganic particles, the effect of preventing film turbidity will be reduced. On the other hand, if it exceeds 99% by weight, the coupling agents will easily aggregate. There are features that cause poor appearance such as fish eyes in the film.

[0028] The method of surface treatment of inorganic particles with a silane coupling agent is not particularly limited, and is a method known per se. Specifically, for example, inorganic particles treated with a silane coupling agent are added to the inorganic particles with a silane coupling agent diluted with water under heating. Prepared and dried, blended during the production of the masterbatch (B), melt-kneaded, or dry blending of inorganic particles, silane coupling agent and polyamide resin, and blending For example, a method of melt-kneading a product to produce a master batch can be used.

[0029] The blending amount of the inorganic particles in the master batch (B) of the present invention is 2 to 8% by weight. If the amount of inorganic particles is less than 2% by weight, a large amount of masterbatch is used, resulting in poor thermal stability during film production and a reduction in film quality. On the other hand, when the content is more than 8% by weight, the dispersion of the inorganic particles is lowered and the appearance of the film such as fish eye is deteriorated. The blending amount of the inorganic particles in the master batch is more preferably 2.5 to 7.5% by weight, particularly preferably 3 to 7% by weight.

[0030] As the bisamide compound to be blended for the purpose of improving slipperiness and transparency over the material of the present invention, a compound represented by the following general formula [I] or [II] is used.

[0031] [Chemical 1]

In the formula, R ¹ represents a divalent hydrocarbon residue, R ² and R ³ represent a monovalent hydrocarbon residue, R ⁴ and R ⁵ represent a hydrogen atom, or a monovalent hydrocarbon residue. .

[0033] Examples of the bisamido compound of the general formula [I] include alkylene bis fatty acid amides and arylene bis fatty acid amides obtained by reaction of diamine and monocarboxylic acid. Examples of the diamine include ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, otatamethylene diamine, dodecamethylene diamine etc. And arylene alkyldiamines such as arylenediamine and xylylenediamine. Monocarboxylic acids include fatty acids such as stearic acid, hexanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, arachidic acid, behenic acid, oleic acid, elaidic acid, and montanic acid. Can be mentioned. Among these, N, N'-methylenebis Mention may be made of the tea amide and N, N'-ethylenebisstearic amide.

[0034] The bisamido compound represented by the general formula [Π] is obtained by the reaction of a monoamine and a dicarboxylic acid. Examples of the monoamine include alkylamines such as ethylamine, methylamine, butylamine, hexylamine, decylamine, pentadecylamine, octadecylamine, dodecylamine, aralkylamines such as a-line and naphthylamine, aralkylamines such as benzylamine, and cyclohexylamine. Examples of the dicarboxylic acid include terephthalic acid, p-phenylene dipropionic acid, succinic acid, and adipic acid. Among these, representative examples include dioctadecyl dibasic acid amides such as N, N′-dioctadecyl terephthalic acid amide.

[0035] One of these bisamido compounds may be used, or two or more may be used in combination. In the present invention, the bisamidite compound is characterized by being divided and mixed in the master notch of the component (B) and the bisamidyl compound powder of the component (C). (B) component of the bi Suamido compound as the amount in (master batch), 1 to 5 wt ^_0/0, the amount of component (C) (powder) is, (A) component and (B) It is 0.005 to 0.1 part by weight with respect to 100 parts by weight of the total of the components, and the blending amount of the entire polyamide resin molding material of the present invention is preferably 0.005 with respect to the total polyamide resin. It is in the range of ~ 0.6% by weight, more preferably 0.02 to 0.5% by weight. If the blending amount is small, the effect of improving the slipperiness is not observed, and if it is too large, the printability of the film and the adhesiveness at the time of laminating process are lowered, which is not preferable.

[0036] In the material of the present invention, the bisamide compound is blended mainly for the purpose of improving the transparency and slipperiness of the film, but the bisamide in the component (B) is the dispersibility of the inorganic particles. In addition to the purpose of improvement, the bisamide powder as component (C) is essential for the stability of biting into the extruder. Therefore, in the component (B), the blending ratio (weight ratio) of the inorganic particle Z bisamide compound is preferably in the range of 1 to 5. When the blending ratio is less than 1 and the blending amount of the bisamide compound is 5% by weight or more, the dispersibility of the inorganic particles, which is difficult to stably melt and knead during the production of the masterbatch, is also lowered. If the blending ratio is larger than 5, the resulting film is difficult to disperse, and poor appearance tends to occur.

[0037] The production method of the masterbatch that is the component (B) of the present invention is not particularly limited, and is produced by a known method, preferably in the form of pellets. For example, a certain amount of polyamide Master blend pellets can be obtained by dry blending the resin, inorganic particles and bisamide compound, then melting and kneading with an extruder, and pelletizing with a conventional method. At that time, in order to make the inorganic particles uniformly adhere to the surface of the polyamide resin pellet and facilitate dispersion, it is also preferable to wet the polyamide resin surface with water or a liquid surfactant, and then perform dry blending and melt-kneading. . Further, the shape and size of the masterbatch pellets are the same as or similar to those of the polyamide resin pellets (A). From the viewpoint of preventing separation of the masterbatch and the polyamide pellets.

[0038] The molding material of the present invention comprises the three components of polyamide resin, inorganic particles and bisamide compound as essential components. Conventionally, the production of such a three-component composition is usually performed by dry blending the three components together or by adding inorganic particles internally during the polymerization of the polyamide and dry blending the biamide compound. Has been manufactured by a method. Therefore, in the present invention, by blending these three components as follows, it is possible to suppress the appearance failure of the resulting film, and at the same time, excellent transparency, slipperiness and printability can be obtained.

[0039] That is, a masterbatch (B) was prepared by blending 2 to 8% by weight of inorganic particles and 1 to 5% by weight of a bisamide compound in polyamide, and the masterbatch (B) and bisamide compound powder (C) were prepared. And 3 types of polyamide rosin pellets (A). The amount of masterbatch (B), of the total amount of the polyamide榭脂pellets (A), 1 to 10 weight ^_0/0, preferably 2 to 8 wt%. When the content is less than 1% by weight, the inorganic particles are dispersed unevenly in the film, resulting in uneven transparency. If it is more than 10% by weight, the thermal stability deteriorates during film production, and poor film appearance tends to occur. The blending amount of the bisamide compound powder (C) is 0.005 to 0.1 parts by weight, preferably 0.01 to 0.08 parts by weight per 100 parts by weight of the total amount of the components (A) and (B). is there. Less than 005 wt.%! / ヽ and stable bite into the extruder during the manufacture of FINOLEM is not guaranteed, and if more than 0.1 wt.%, Stable bite into the beam extruder A failure occurs.

[0040] The polyamide used in the polyamide resin pellet (A) and the master notch (B) may be the same or different. If they are different, the melting point or melt viscosity of the polyamide in the masterbatch (B) is preferably lower than those of the polyamide resin pellet (A). In addition, the bisamide compound in the master batch (B) and the bisamide compound in the bisamide compound powder (C) The compound may be the same or different.

[0041] The material according to the present invention is manufactured by mixing the components (A), (B), and (C).

. Mixing is possible at any point before film production by conventional methods, for example (

A), (B) and (C) are dry blended and supplied to the hopper of an extruder for film production, and (A), (B) and (C) are separately supplied to the hopper of a film production extruder. For example, a method using a fixed amount feeder can be preferably used.

[0042] In addition to the components (A), (B), and (C), which are essential components, the material of the present invention can contain additives within a range that does not impair the effects of the present invention. For example, in order to further improve the appearance defect prevention effect, it contains a partial ester compound of tri- to hexavalent aliphatic alcohol and C10-22 fatty acid and magnesium metal salt of Z or hydroxy fatty acid Let me do it. Examples of the aliphatic alcohol of a partial ester compound of a tri- to hexavalent aliphatic alcohol and a fatty acid having 10 to 22 carbon atoms include glycerin, trimethylpropane, pentaerythritol, mesoerythritol, and sorbitol. Carbon number

Examples of the fatty acids 10 to 22 include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and the like. A substituent such as a hydroxyl group may be present in the carbon skeleton of the fatty acid. Such an ester compound of an aliphatic alcohol and a fatty acid needs to be substantially a partial ester, and preferably 30% or more of the total hydroxyl groups in the polyhydric alcohol are not esterified and remain. Is used. Among them, glycerin monostearate, glycerin distearate, glycerin monobehenate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol monobehenate, pentaerythritol dibehenate, etc. Is preferred. Such partial ester compounds can be used alone or in combination of a plurality of compounds.

[0043] Further, the magnesium metal salt of hydroxy fatty acid is a salt of hydroxycarbonic acid having 12 to 30 carbon atoms and magnesium, for example, by direct reaction with hydroxycarboxylic acid and magnesium oxide or hydroxide. Can be obtained. In this case, a better result can be obtained by adding magnesium oxide or hydroxide in excess to synthesize a highly basic hydroxy fatty acid magnesium salt. Specifically, lauric acid, myristic acid , A magnesium salt of a compound obtained by hydroxylating an aliphatic carboxylic acid such as palmitic acid, stearic acid or behenic acid. If the fatty acid has a small number of carbon atoms, a predetermined effect cannot be obtained. If the number of carbon atoms is too large, the transparency of the resulting film is lowered, which is not preferable. For this reason, carbon number is normally selected in the range of 12-30, Preferably 12-24. The blending amount of the partial ester compound of aliphatic alcohol and fatty acid and the magnesium salt of hydroxy fatty acid is usually from 0.01 to 0.7 parts by weight, preferably from 0.03 to 0.7 parts per 100 parts by weight of the polyamide resin. 0. 4 parts by weight. If the blending amount is small, the effect of improving the appearance of the resulting film is insufficient, and if the blending amount is too large, the printing characteristics deteriorate.

[0044] The combination of the partial ester of the polyhydric alcohol and the magnesium metal salt of the hydroxy fatty acid may be a so-called external addition method in which dry blending is performed on the pelletized raw material of polyamide resin, a kneading method in which melt mixing is performed, or a high concentration Either a so-called master one-batch method in which the raw materials contained in the compound are blended or an internal addition method to be added during polymerization can be used. In particular, it is preferable to simultaneously add to the master batch (B) and melt knead.

[0045] In addition to the above-mentioned blends, various additives well known to those skilled in the art, for example, hindered phenol, anti-oxidation agents such as phosphate ester and phosphite ester, and weather resistance improvement of triazine compounds, etc. Contains colorants such as colorants, pigments and dyes, antistatic agents, lubricants, and surfactants.

In order to produce a polyamide resin film using the molding material of the present invention, (A), (B) and

The predetermined amount of component (C) and, if necessary, other additives may be dry blended in advance, or supplied to a molding machine for film production without preblending, and film formation may be performed according to a conventional method. The film forming method to which the molding material of the present invention is applied is a force to which any of the known film forming methods can be applied, preferably the T-die method, the inflation method and the like. The polyamide film of the present invention is used as an unstretched film or as a stretched film through a stretching process such as uniaxial stretching or biaxial stretching. The film using the molding material of the present invention may be a single-layer polyamide film or a laminated film with other resin by coextrusion or lamination.

[0047] The thickness of the polyamide resin film of the present invention is not particularly limited, but if it is thick, the gas-noirality is improved, but the transparency is lowered. The strength you have is reduced. In view of this point, the thickness of the polyamide resin monolayer is usually 2 to 100 μm for an unstretched film and usually 2 to 50 μm for a stretched film. The thickness is usually about 10 to 300 m, and the thickness of the polyamide resin layer is preferably in the same range as the thickness of the single layer. Example

[0048] Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples unless it exceeds the gist. The additive components used in the examples and comparative examples, the method for producing the surface-treated inorganic particles, and the method for evaluating the obtained film are as follows.

[0049] <Additive component>

(1) Polyamide resin: Polyamide-6, “Novamid (registered trademark) 1020J” manufactured by Mitsubishi Engineering Plastics Co., Ltd., Viscosity number 182, Pellet size: Cylindrical shape with a length of 3mm and a diameter of 2.5mm

[0050] (2) Inorganic particles 1: Silica, “Silysia 310” manufactured by Fuji Silysia Chemical Ltd., average particle size 2.5 m, specific surface area 300 m ² Zg, oil absorption 310 ml ZlOOg.

[0051] (3) Inorganic particles 2: Zeolite, “Silton JC20” manufactured by Mizusawa Chemical Co., Ltd., average particle size 2 .: L m, oil absorption 50 ml ZlOOg.

[0052] (4) Inorganic particles 3: calcined kaolin, “Satinton No. 5” manufactured by Engelnodne earth, average particle size of 0.8πι.

[0053] (5) Silane coupling agent: y-aminopropyltriethoxysilane, “A 1100” manufactured by Nippon Kayaku Co., Ltd.

[0054] (6) Bisamide compound: ethylenebisstearic acid amide, "Kao Wax EB" manufactured by Kao Corporation

J o

[0055] <Method for producing surface-treated inorganic particles>

An aqueous solution in which inorganic particles (silica or zeolite or calcined kaolin) and a silane coupling agent were diluted 6-fold with water was stirred and mixed in a supermixer while heating to 80 ° C to evaporate the water. Subsequently, it was dried at 120 ° C. to obtain surface-treated inorganic particles.

[0056] <Film Evaluation Method> (1) Haze: The haze value was measured using a haze meter manufactured by Tokyo Denshoku.

[0057] (2) Sliding property: The coefficient of static friction s) was measured by the parallel displacement method under the conditions of relative humidity of 65% and 90% and a temperature of 23 ° C. If the coefficient of static friction, which is an index of slipperiness, exceeds 1.0, it indicates a serious situation. For example, when a film having a static friction coefficient exceeding 1.0 is used as a packaging material using an automatic filling machine, the film may be attracted to the machine. Therefore, the maximum allowable value of the static friction coefficient is 1.0.

[0058] (3) Long-term continuous formability of film formation: After 2 hours, 4 hours, and 6 hours from the start of film formation by a T-die film forming machine, the central part of the film was cut into a 300 mm X 300 mm square, and the part The presence or absence of these lines was observed with the naked eye and evaluated according to the following criteria. At the same time, the presence or absence of biting into the extruder was also observed, and the stability was evaluated on a three-point scale.

[0059] [Table 1]

◯: Die line was not recognized.

Δ: Die line was partially recognized.

X: Die lines were observed over the entire film.

[0060] (4) Presence or absence of fish eyes: After biaxial stretching of the film 1 hour after the start of film formation, it was cut into a 300 mm x 300 mm square, and the presence or absence of fish eyes in the part was visually observed. Counted the number. Normally, fish eyes with a size of about 300 m or more can be counted.

[0061] Example 1:

Polyamide resin, surface-treated inorganic particles 1 (silica), and bisamide compound are dry blended at a compounding ratio of 92/5/3 (weight ratio), and a twin screw extruder (“TEX30” manufactured by Nippon Steel) The mixture was melt-kneaded at 250 ° C, pelletized and dried to obtain a masterbatch containing inorganic particles and bisamido compound. 1.5 parts by weight of the master batch and 0.05 parts by weight of the bisamide compound powder were dry blended with 100 parts by weight of polyamide resin to obtain a molding material for film.

[0062] This molding material is supplied to a hopper of a T-die type film-forming machine that has a T-die having a diameter of 600 mm and a T-die having a diameter of 600 mm. A film having a thickness of 135 m was formed at ° C. The bite into the extruder was stable and the film was formed smoothly. At that time, use the film 2 hours, 4 hours, 6 hours after the start of film formation The stability of the film formation for a long time was evaluated by observing with the naked eye the presence or absence of streaky appearance defects called die lines. In addition, the film 1 hour after the start of film formation was cut into a 120 mm x 120 mm square and simultaneously biaxially stretched 3 x 3 times at 80 ° C with a TM-Long biaxial stretching machine, and then 200 The film was heat fixed in a hot air oven at ° C for 30 seconds to obtain a biaxially stretched film with a thickness of 15 μm. The haze value and static friction coefficient of the stretched film were measured. The results are shown in Table 2.

[0063] Comparative Example 1:

Polyamide resin, surface-treated inorganic particles 1 (silica), and bisamide compound were dry blended at a blending ratio of 99.83 / 0.075 / 0.095 (weight ratio) to obtain a molding material for film. Using this molding material, a film was formed and evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0064] Comparative Example 2:

Surface-treated inorganic particles 1 (silica) was added in an amount of 0.05 to 5% by weight with respect to polyamide 6 during polymerization of polyamide 6, and polymerized by a conventional method to obtain polyamide 6 resin having a viscosity number of 182. . A film molding material was obtained by dry blending the silica-containing polyamide 6 rosin pellets (3 mm in length and 2.5 mm in diameter) into a bisamide compound in an amount of 0.095% by weight. Using this molding material, film formation and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 2.

[0065] Comparative Example 3:

Polyamide rosin and surface-treated inorganic particles 1 (silica) were dry blended at a blending ratio of 95Z5 (weight ratio), and melt-kneaded in the same manner as in Example 1 to obtain a master batch in which inorganic particles were blended. 1.5 parts by weight of the master batch and 0.095 parts by weight of the bisamide compound powder were dry blended with 100 parts by weight of polyamide resin to obtain a molding material for film. Using this molding material, film formation and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 2.

[0066] Comparative Example 4:

Polyamide, surface-treated inorganic particles 1 (silica), and a bisamide compound were dry blended at a blending ratio of 87Z10Z3 (weight ratio), and melt-kneaded in the same manner as in Example 1 to blend inorganic particles and a bisamide compound. A master batch was obtained. 0.775 parts by weight of the masterbatch Then, 0.0725 parts by weight of bisamide compound powder and 100 parts by weight of polyamide resin were dry blended to obtain a molding material for film. Using this molding material, film formation and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 2.

[0067] Comparative Example 5:

Polyamide rosin, surface-treated inorganic particles 1 (silica), and bisamide compound were dry blended at a blending ratio of 88.67 / 5 / 6.33 (weight ratio), and melt-kneaded in the same manner as in Example 1 to make inorganic A master batch containing the particles and the bisamide compound was obtained. 1.5 parts by weight of the master batch and 100 parts by weight of polyamide resin were dry blended. Next, using this blend, film formation and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 2.

[0068] Example 2:

A film molding material was obtained in the same manner as in Example 1 except that the inorganic particles 1 (silica) used in Example 1 were changed to surface-treated inorganic particles 2 (zeolite), and a film was formed. Evaluation was performed. The results are shown in Table 3.

[0069] Comparative Example 6:

In the same manner as in Comparative Example 1, except that the inorganic particles 1 (silica) used in Comparative Example 1 were changed to surface-treated inorganic particles 2 (zeolite), a film molding material was obtained, and a film was formed. Evaluation was performed. The results are shown in Table 3.

[0070] Comparative Example 7:

In the same manner as in Comparative Example 2 except that the inorganic particles 1 (silica) used in Comparative Example 2 were changed to surface-treated inorganic particles 2 (zeolite), a film molding material was obtained, and a film was formed. Evaluation was performed. The results are shown in Table 3.

[0071] Comparative Example 8:

A molding material for a film was obtained in the same manner as in Comparative Example 3 except that the inorganic particles 1 (silica) used in Comparative Example 3 were changed to surface-treated inorganic particles 2 (zeolite), and a film was formed. Evaluation was performed. The results are shown in Table 3.

[0072] Example 3:

0.5 parts by weight of master notch containing inorganic particles 1 (silica) and bisamido compound of Example 1 and male particles containing inorganic particles 2 (zeolite) of Example 2 and bisamidi compound 1.0 part by weight of the star batch and 0.05 part by weight of the bisamide compound powder were dry blended with 100 parts by weight of polyamide resin to obtain a molding material for film. Using this molding material, film formation and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 4.

[0073] Example 4:

A film molding material was obtained in the same manner as in Example 1 except that the inorganic particles 1 (silica) used in Example 1 were changed to surface-treated inorganic particles 3 (calcined kaolin). Went. The results are shown in Table 5.

[0074] [Table 2]

[0075] [Table 3] Example 2 Comparative Example 6 Comparative Example 7 Comparative Example 8 Polyamide 92-95 Inorganic particles

5 ― ― 5 (Zeolite)

Bisamide 3 ― ―

Master Badge

1.5-1.5

(MB2) Blending amount

Polyamide 100 99.8 99.925 100 Bisamide 0.05 0.095 0.095 0.095 Zeolite ― 0 A.075 0.075

O C

Polyamide 101.38 101.3 σ8 101.38 101.38 Final inorganic particles

0.075 0.076 0.076 0.075 Composition (Zeolite)

Bisamide 0.095 0.097 0.096 0.095 Hedge 1.8 2.0 1.5 1.8 Slip (65%) 0.4 0.6 0.5 0.4 Slip (90%) 0.8 2.0 1.4 0.8 Number of fishey 17 32 86 Die line (after 2 hours) 〇〇〇 Die line ( 4 hours later) ○ Δ ○ ○ Die line (after 6 hours) ○ X Δ Δ Biting stability ○ Δ ○ ○ 4]

Five]

As apparent from Table 2, the film of Example 1 formed using the molding material for film of the present invention was the film of Comparative Examples 1 to 3 formed using a material having the same additive composition. Compared with the film quality, the film quality such as transparency, slipperiness, presence of fish eyes and die lines was excellent, and the long-term stability of the film formation was also good.

[0079] The film formed from the material of Comparative Examples 4 and 5 in which the blending amount of the inorganic particles and the bisamido compound in the master batch is out of the scope of the present invention is stable in fish eyes and long-term film formation. Problems occur. For this reason, the ratio of inorganic particles to bisamide compounds in the masterbatch affects the dispersion of inorganic particles, and coarse particles due to aggregation are It is presumed that this will affect the generation of die and the generation of die lines due to the turbulent flow of grease near the die outlet.

[0080] Films obtained from the materials of Examples 2 to 4 using zeolite, zeolite and silica, and kaolin instead of silica are excellent in quality and stable in film formation as in Example 1. It was.

[0081] From the above, it has been found that the molding material of the present invention is excellent in transparency and slipperiness of the obtained film, can prevent appearance defects such as die lines, and can be continuously stable for a long time. It was. In addition, since it is excellent in slipperiness, it is apparently excellent in printability. Industrial applicability

[0082] The molding material for polyamide resin film of the present invention is excellent in long-term continuous film-forming stability, and the resulting film has good transparency, slipperiness and printability, and has poor appearance such as die lines. Since it has few excellent characteristics, it is useful for a wide range of food packaging and the like.

[0083] While the present invention has been described in connection with the most practical and preferred embodiments at present, the present invention is not limited to the embodiments disclosed herein. However, it is understood that the scope of the present invention can be changed as appropriate without departing from the gist or philosophy of the invention that can be read, and that such changes are also within the technical scope of the present invention. There must be. This application is based on a Japanese patent application (Japanese Patent Application No. 2004-293153) filed on October 6, 2004, which is incorporated by reference in its entirety.

Claims

The scope of the claims

[1] The total of (A) and (B) is 100 parts by weight, (A) 90 to 99 parts by weight of polyamide resin pellets, and (B) 2 to 8% by weight of inorganic particles in polyamide resin and bisamide compound 1 A polyamide resin composition for film, comprising 10 to 1 part by weight of master batch mixed with ˜5% by weight and 0.005 to 0.1 part by weight of (C) bisamide compound powder.

[2] The polyamide resin composition for film according to claim 1, wherein the inorganic particles are at least one selected from silica, zeolite and kaolinka.

[3] The polyamide resin molding material for film according to claim 1 or 2, wherein the inorganic particles are surface-treated with a silane coupling agent.

[4] When the total of (A) and (B) is 100 parts by weight, (A) 90 to 99 parts by weight of polyamide resin pellets

(B) 10 to 1 part by weight of a masterbatch in which 2 to 8% by weight of inorganic particles and 1 to 5% by weight of a bisamide compound are mixed with polyamide resin, and (C) bisamide compound powder 0.005-0. A method for producing a polyamide resin film, wherein a part by weight is supplied to an extruder for film production to form a film.

[5] The total of (A) and (B) is 100 parts by weight.

(B) 10 to 1 part by weight of a masterbatch in which 2 to 8% by weight of inorganic particles and 1 to 5% by weight of a bisamide compound are mixed with polyamide resin, and (C) bisamide compound powder 0.005-0. The method for producing a polyamide resin film according to claim 4, wherein the weight parts are uniformly mixed in advance and then supplied to an extruder for film production.

[6] A polyamide resin film in which the polyamide resin molding material strength according to any one of claims 1 to 3 is also molded.