JP5089047B2 - Crystalline resin composition and crystalline resin film - Google Patents

Description

  The present invention relates to a crystalline resin composition and a crystalline resin film, and more particularly to a crystalline resin composition and a crystalline resin film excellent in gas barrier properties, transparency, and slipperiness.

  Polyamide film, which is a typical example of crystalline resin film, is excellent in gas barrier properties and mechanical and thermal characteristics. Therefore, it can be used as a single layer film, multilayer film with other resin, laminated film with other materials, etc. It is used for a wide range of applications, mainly. The transparency of the polyamide film is an important characteristic because it greatly affects the appearance of the contents, and in general, a film having good transparency is desired. Also, if the slipperiness is poor, the film may be caught during bag making, or printing misalignment may occur during multicolor printing. For this reason, the slipperiness of the film is an extremely important characteristic in terms of film productivity, quality, and commercial value. Thus, it is necessary to achieve both transparency and slipperiness. However, both characteristics are contradictory properties such that the surface of a film with good transparency is smooth and the smooth film surface is poorly slipped.

  Various methods have been tried to improve the slipperiness of polyamide films. For example, a method of blending talc, silica and other inorganic filler fine particles has been proposed (Patent Document 1).

  In addition, it has been proposed to use amorphous aluminosilicate (zeolite) whose surface is treated with a silane coupling agent with the aim of achieving both transparency and slipperiness as much as possible (Patent Document 2). According to this proposal, by using the surface-treated zeolite particles, a polyamide film excellent in transparency and slipperiness can be obtained as compared with the case where inorganic particles such as silica and talc are used. The slipperiness is still insufficient and further improvement is eagerly desired.

Japanese Patent Publication No.54-4741 JP-A-1-156333

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a crystalline resin composition and a crystalline resin film excellent in gas barrier properties, transparency, and slipperiness.

  As a result of intensive studies to achieve the above object, the present inventors have obtained the following knowledge. That is, one cause of the decrease in transparency caused when the slipperiness of the film is improved by blending the inorganic filler fine particles is that between the particles and the resin around them in the stretching process during film formation. In addition, voids formed by the formation of voids. Such voids are less likely to occur in crystalline resins, such as polyester resins, which have a relatively low intermolecular force due to hydrogen bonding because the internal stress generated during stretching is relatively low. However, a resin having a high intermolecular force due to hydrogen bonding, such as a polyamide resin, has a high internal stress generated at the time of stretching, and voids are easily generated between the particles and the resin as a matrix, and voids are easily generated. Moreover, in a gas barrier (low oxygen permeable) film such as a polyamide resin film, the formation of voids forms a gas passage, resulting in a decrease in gas barrier properties (higher oxygen permeability). ).

  As a result of further studies based on the above findings, the present inventors have improved the slipperiness of the film by forming a macro rough surface and a micro rough surface using two kinds of particles having different particle sizes. In this case, spherical particles are used for large particles that are close to the macro rough surface, and polyhedral particles are used for small particles that contribute to the micro rough surface, thereby maintaining transparency and slipping while maintaining gas barrier properties. The knowledge that the resin composition for crystalline resin films which made compatibility compatible was obtained was acquired.

  This invention is completed based on said various knowledge, The 1st summary is the porous filler (B) 0.01-0.5 with respect to 100 weight part of crystalline resin (A). The porous filler (B) containing parts by weight is a spherical porous filler (B-1) having an average particle diameter of 1.5 to 6 μm and a polyhedral porous filler having an average particle diameter of 0.4 to 1.5 μm ( B-2), and the weight ratio is in the range of 1/90 ≦ (B-1) / (B-2) ≦ 1/1.

The second gist of the present invention resides in a crystalline resin film formed by molding the above crystalline resin composition, and the third gist of the present invention is a thickness of 15 μm. The oxygen permeation amount at 23 ° C. and 65% RH is 50 ml / [m ² · day · atm] or less, the haze is 2.5% or less, and the coefficient of static friction between films is 0.5 or less at 23 ° C. and 65% RH. It exists in the crystalline resin film characterized by being 0.6 or less under 90 degreeCRH.

  According to the present invention, a crystalline resin composition and a crystalline resin film excellent in gas barrier properties, transparency, and slipperiness are provided. Furthermore, the crystalline resin film of the present invention has good suitability for secondary processing such as printing, bag making, laminating and the like, and can be used for food packaging and other wide applications.

  Hereinafter, the present invention will be described in detail. In general, examples of the crystalline resin include polyolefin (polyethylene, polypropylene, etc.), polyamide, polyester, etc. In the present invention, a resin having an intermolecular force larger than that of the polyolefin resin or the polyester resin is preferable. Resin is optimal.

  In the present invention, examples of the polyamide resin include polyamide resins obtained by polycondensation of lactam having three or more members, polymerizable ω-amino acid, dibasic acid and diamine. Specifically, polycondensates such as ε-caprolactam, aminocaproic acid, enanthractam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone, α-piperidone; hexamethylenediamine, nona Obtained by polycondensation of diamines such as methylenediamine, undecamethylenediamine, dodecamethylenediamine, and metaxylenediamine with dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane dibasic acid, and glutaric acid. These polymers are copolymers of these. For example, polyamide 4, 6, 7, 8, 11, 12, 6 · 6, 6 · 10, 6 · 11, 6 · 12, 6T, 6/6 · 6, 6/12, 6 / 6T, 6I / 6T Etc. Two or more of these can be mixed and used. Of these, polyamide 6 resin and polyamide 6/66 copolymer resin are particularly preferred from the viewpoint of the thermal and mechanical properties of the resulting film.

  The viscosity number of the polyamide resin is usually 115 to 300, preferably 120 to 250, as a value measured in 96% by weight sulfuric acid at a concentration of 1% by weight and a temperature of 23 ° C. according to JIS-K-6933-99. If the viscosity number is too low, the resulting film has insufficient mechanical properties, and if it is too high, film formation becomes difficult.

In the present invention, examples of the porous filler include porous silica, calcium carbonate, zeolite, silica gel and the like. Among them, the use of the primary particles constituting the porous filler having substantially the same shape and size, the effect of the present invention becomes remarkable, especially as the porous filler used in the present invention, Zeolite is preferred. The pore volume of these porous fillers is usually 10 ml / 100 g or more, preferably 30 ml / 100 g or more as DBP oil absorption, and the upper limit is usually 100 ml / 100 g, preferably 80 ml / 100 g, more preferably 60 ml / 100 g. Moreover, a specific surface area is 10 m < ² > / g or more normally, Preferably it is 30 m < ² > / g or more, The upper limit is 100 m < ² > / g normally, Preferably it is 50 m < ² > / g, More preferably, it is 40 m < ² > / g.

In the present invention, the zeolite may be amorphous or crystalline, but amorphous zeolite is preferred as measured by the X-ray method. When a zeolite having a crystal structure as measured by the X-ray method is used, the stretching stability is lowered, and stretching breakage tends to occur frequently. The composition of the amorphous zeolite is represented by the formula: xMO.Al ₂ O ₃ .ySiO ₂ .zH ₂ O. In the formula, M represents an alkali metal or an alkaline earth metal, x represents a number from 0.01 to 2, y represents 1 to 100, and z represents a number from 0.1 to 5, respectively.

  In the present invention, two kinds of porous fillers having different particle sizes and shapes are used. One porous filler is spherical, and the other porous filler is polyhedral.

  The spherical porous filler used in the present invention is preferably as the particle shape is close to a true spherical shape. In the present invention, the degree of sphericalness can be expressed by a spherical ratio defined in the following formula (1), and the value is usually 0.90 to 1.0, preferably 0.93 to 1.0. is there. When the spherical ratio is less than 0.90, the slipperiness of the film is inferior, which is not preferable.

  In the present invention, the polyhedral porous filler is meaningful in terms of a shape having corners, and the polyhedron is a regular polyhedron such as a regular tetrahedron, a regular hexahedron, a regular octahedron, a regular dodecahedron, and a regular icosahedron. It is not limited, A quasi-regular polyhedron may be sufficient. Examples of the quasi-regular polyhedron include various “cut corner types” lacking corners, various “star-shaped regular polyhedrons”, “polygonal columns”, and the like. The number of faces is not particularly limited, but is usually 4 to 20, preferably 4 to 8. The shape of the polyhedron can be confirmed by a micrograph, and a porous filler in which 90% or more is a hexahedron is particularly preferable.

  The aforementioned zeolite can be obtained, for example, by a method in which crystalline zeolite is synthesized using sodium silicate, silica sol or acidic clay as a raw material, and then the obtained crystalline zeolite is acid-treated.

  The synthesis of the crystalline zeolite is carried out by a known method in which the above raw material is acid-treated, and an alkali aluminate is added to the obtained silicic acid solution such as activated silicate gel and heated. The acid treatment of the crystalline zeolite is performed by adding 0.2 to 5 moles of acid to the base content (sodium) of the zeolite to be brought into sufficient contact, followed by filtration, washing with water and drying, and 300 to 600 ° C. Calcination and further pulverization and classification as necessary. The acid used for the acid treatment can be either an inorganic acid or an organic acid, but economically, a mineral acid such as hydrochloric acid, sulfuric acid or nitric acid is preferred.

  As the kind of zeolite, zeolite A, zeolite X, zeolite Y, zeolite P and the like are preferable from the viewpoint of ease of synthesis and treatment, and zeolite A is particularly preferable from the economical viewpoint. By selecting the above synthesis conditions, the particle size and shape of the crystalline zeolite obtained can be variously changed. In addition, in the acid treatment of the above crystalline zeolite, care must be taken so that the shape of the amorphous aluminosilicate (zeolite) such as a cubic shape or a spherical shape does not collapse.

  In the present invention, it is also possible to use a commercial product of zeolite. For example, cubic zeolite is sold under the trade name “Silton AMT” by Mizusawa Chemical Co., Ltd., and spherical zeolite is also sold by Mizusawa Chemical Co., Ltd. under the trade name “Silton JC”.

Cubic zeolite and spherical zeolite are not only different in shape but also different in composition. For example, the composition of the cubic “Silton AMT” is H ₂ O / Al ₂ O ₃ / SiO ₂ / Na ₂ O / CaO = 4.64 / 41.56 / 47.55 / 6.25 / 0. The composition of the spherical “Silton JC” is H ₂ O / Al ₂ O ₃ / SiO ₂ / Na ₂ O / CaO = 4.31 / 25.91 / 4.5.56 / 8.48 / 6.74, There is a difference in the composition ratio between Al ₂ O ₃ and SiO ₂ and the content of CaO.

  The oil absorption amount of zeolite is preferably 1 to 70 ml / 100 g as measured by JIS K-5101 method. If the oil absorption is too low, the stretching stability of the film is lowered, and if it is too high, the effect of improving the slipping property during stretching is small. The oil absorption is preferably 5 to 70 ml / 100 g.

In the crystalline resin composition of the present invention, the content of the porous filler (B) is 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the crystalline resin (A). When the content is less than 0.01 part by weight, the effect of improving the slipping property is reduced, and when it exceeds 0.5 part by weight, the transparency tends to deteriorate.
The content of the porous filler (B) is preferably 0.015 to 0.4 parts by weight, more preferably 0.02 to 0.3 parts by weight.

  In the present invention, two types of particles having different particle sizes are used to form a macro rough surface and a micro rough surface to improve the slipperiness of the film. Spherical particles are used for the large particles, and polyhedral particles are used for the small particles that contribute to the micro rough surface. That is, in the present invention, a spherical porous filler (B-1) having an average particle diameter of 1.5 to 6 μm and a polyhedral porous filler (B-2) having an average particle diameter of 0.4 to 1.5 μm are used. To do. In addition, the weight ratio between the two is adjusted to a range of 1/90 ≦ (B-1) / (B-2) ≦ 1/1.

  When the average particle size of the spherical porous filler (B-1) exceeds 6 μm, the transparency is lowered, and when it is less than 1.5 μm, the effect of improving the slipping property is not recognized. Further, when the average particle size of the polyhedral porous filler (B-2) exceeds 1.5 μm, the transparency is deteriorated, and when it is less than 0.4 μm, the effect of improving the slipping property is not exhibited. Further, when the weight ratio of the spherical porous filler (B-1) and the polyhedral porous filler (B-2) is larger than 1/1, the transparency is lowered, and when it is smaller than 1/90, the slipping property is not improved. The weight ratio of the spherical porous filler (B-1) and the polyhedral porous filler (B-2) is preferably 1/80 ≦ (B-1) / (B-2) <9/10, more preferably 1/70 ≦ (B-1) / (B-2) <8/10.

  In particular, in the present invention, spherical particles having no corners are used for large particles, and polyhedral particles having corners are used for small particles, so that the resin around the particles and matrix in the stretching process during film formation. This is significant in that the formation of voids is reduced as much as possible by reducing the chance of voids between them. As a result, according to the present invention, it is possible to obtain a resin composition for a crystalline resin film having both transparency and slipperiness while maintaining gas barrier properties.

  The particle size of the porous filler is easily measured by the Coulter counter method. In this method, a particle counter manufactured by Coulter Electronics Co., Ltd. is used, particles are dispersed in an electrically conductive liquid such as an electrolyte solution, and a suspension is prepared. In this method, the diameter distribution of particles is measured from the voltage that changes when passing through a hole and the number of changes. In addition, the average particle | grains of a polyhedral porous filler (B-2) are represented by the average particle diameter numerical value measured by the Coulter counter method.

  By observation with a SEM at a magnification of 5000 to 10000, the shape and size of the porous filler can be easily determined. Since the above-mentioned porous filler does not change its shape or size even when baked at 600 to 800 ° C., even if it is a film formed from the crystalline resin composition of the present invention, it is 600 to 800 ° C. If the ash content is dry ashed and the ash content is observed with an SEM, the shape and size of the porous filler can be easily identified.

  The crystalline resin composition of the present invention preferably contains a silane coupling agent (C). Examples of the silane coupling agent (C) include those having an organosiloxane group. Specific examples of the organo group include alkyl groups such as methyl, ethyl and propyl; alkenyl groups such as vinyl and allyl; cycloalkyl groups such as cyclopropyl and cyclohexyl; aryl groups and aralkyl groups such as phenyl and benzyl; γ-amino Aminoalkyl groups such as propyl, N- (β-aminoethyl) -γ-aminopropyl, and those containing functional groups such as chloro, thiol, epoxy such as γ-glycidoxy, γ-chloropropyl, γ-mercaptopropyl Is mentioned.

  Specific examples of the silane coupling agent (C) include trimethylmethoxysilane, vinyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-amino. Propyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, N, N′-bis (trimethylsilyl) acetamide, diethyltrimethylsilylamine, N, N′-bis (trimethylsilyl) trifluoroacetamide, stearyltrimethoxysilane and the like can be mentioned. In particular, aminosilanes such as γ-aminopropyltriethoxysilane are suitable.

  The amount of the silane coupling agent (C) is usually 0.01 to 60% by weight, preferably 0.05 to 40% by weight, more preferably 0.1 to 30% by weight, based on the porous filler (B). It is. When the amount of the silane coupling agent (C) used is less than 0.01% by weight, the effect of preventing the clouding of the film is hardly seen, and when it exceeds 60% by weight, the coupling agents tend to aggregate. It tends to remain as fish eyes in the film.

  In order to produce the crystalline resin composition of the present invention, the crystalline resin may contain a porous filler and a silane coupling agent, and the method is not particularly limited, and from the production of the crystalline resin to film formation. What is necessary is just to add a porous filler and a silane coupling agent in the arbitrary steps of, or to add the porous filler previously processed with the silane coupling agent. Specific examples of the case where the crystalline resin is a polyamide resin include the following methods.

(A) A silane coupling agent diluted with water is added to and mixed with the porous filler under heating and stirring to prepare a porous filler treated with the silane coupling agent. This is the initial stage in the polyamide resin production process ( Normal pressure), a method of adding between any time before the start of the polymerization reaction and before the start of the reduced pressure polymerization reaction.

(B) A method of dry blending the porous filler treated with the silane coupling agent with a polyamide resin, or a method of further melt-kneading the blend.

(C) A method of dry blending a porous filler and a silane coupling agent to a polyamide resin, or a method of further melt-kneading the blend.
(D) A method of producing a master batch containing a porous filler and a silane coupling agent at a high concentration by the method of (b) or (c), and mixing the master batch and the polyamide resin.

  From the viewpoint of good dispersion of the zeolite, the method (a) or (d) is preferable.

  Further, in the case of the crystalline resin composition of the present invention, particularly in the case of a polyamide resin composition, it is effective to add a bisamide compound (D) for the purpose of improving slipperiness and transparency in the water-cooled film forming method. . As the bisamide compound, a compound represented by the following general formula [I] or [II] is used.

  Examples of the bisamide compound represented by the general formula [I] include alkylene bis fatty acid amides and arylene bis fatty acid amides obtained by reacting various diamines with fatty acids. Examples of the diamine include ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, octamethylene diamine, dodecamethylene diamine and other alkylene diamines, phenylene diamine, naphthalene diamine and other arylene diamines, xylylene diamine and other arylene alkyl diamines, and the like. Examples of the fatty acid include 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. Typical examples among these include N, N'-methylenebisstearic acid amide and N, N'-ethylenebisstearic acid amide.

  Examples of the bisamide compound represented by the general formula [II] include bisamides obtained by reacting various monoamines with dicarboxylic acids. Examples of the monoamine include alkylamines such as ethylamine, methylamine, butylamine, hexylamine, decylamine, pentadecylamine, octadecylamine and dodecylamine, arylamines such as aniline and naphthylamine, aralkylamines such as benzylamine, cyclohexylamine, etc. And cycloalkylamine. Examples of the dicarboxylic acid include terephthalic acid, p-phenylene dipropionic acid, succinic acid, and adipic acid. Among these, typical examples include dioctadecyl dibasic acid amides such as N, N′-dioctadecyl terephthalic acid amide. These bisamide compounds may be used in combination of two or more.

  The compounding quantity of the bisamide compound (D) is 0.01-1 weight part normally with respect to 100 weight part of polyamide resins, Preferably it is 0.02-0.5 weight part. When the blending amount is small, the effect of improving the slipperiness is not observed, and when it is too large, the printability of the film and the adhesiveness at the time of laminating are lowered, which is not preferable. In addition, you may use the said bisamide compound in combination of 2 or more types.

  The blending method of the bisamide compound is not particularly limited, and for example, a so-called external addition method in which dry blending is performed on a polyamide resin pellet-shaped raw material, a kneading method in which the pellet is melt-mixed, a so-called master compounding a high concentration raw material. Any method such as a batch method or an internal addition method added at the time of polymerization may be used.

  In the crystalline resin composition of the present invention, various additives well known to those skilled in the art can be blended in addition to the above components (A) to (D) as long as the effects of the present invention are not impaired. Examples of such additives include antioxidants such as hindered phenols, phosphate esters and phosphites, weather resistance improvers such as triazine compounds, colorants such as pigments and dyes, antistatic agents, Examples thereof include a lubricant and a surfactant. The method for blending these additives is not particularly limited, and any known method can be employed.

  The crystalline resin film of the present invention is obtained by molding the above-described crystalline resin composition of the present invention by employing a known film forming method. As a typical film forming method, the T-die method in which the cooling and solidification of the film-like material extruded from the T-die is cast by a chilled roll and cooled, the tube-like material is extruded from a die having an annular slit, and is put into the tube. Examples include an inflation method in which air is blown and expanded to form by cooling with air or water. The film thus formed is used as an unstretched film or as a stretched film through a stretching process such as uniaxial stretching or biaxial stretching.

The crystalline resin film of the present invention has an oxygen permeation amount of 50 ml / [m ² · day · atm] or less at 23 ° C. and 65% RH at a thickness of 15 μm, a haze of 2.5% or less, The friction coefficient is 0.5 or less at 23 ° C. and 65% RH, and 0.6 or less at 23 ° C. and 90% RH. The oxygen permeation amount is preferably 40 ml / [m ² · day · atm] or less, the haze is preferably 2.2% or less, and the static friction coefficient between films is 0.4 or less at 23 ° C. and 65% RH, It is 0.58 or less at 23 ° C. and 90% RH. These physical property values are values obtained by the measurement methods shown in the examples described later.

The crystalline resin film of the present invention may be a single layer film, a multilayer film by coextrusion with another resin, or a laminated film by lamination. The crystalline resin film of the present invention is excellent in gas barrier properties, transparency and slipperiness, and can be easily subjected to secondary processing such as bag making, printing and laminating, and is useful as a packaging film for a wide range of foods and the like. .
In addition, the thickness of the film in the present invention is usually less than 0.2 mm. Moreover, the minimum of thickness is 1 micrometer normally from a viewpoint of the difficulty of film forming.

  EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. The measurement methods employed in the following examples are as follows. The additive components used are as shown in Table 1 below.

(1) Gas barrier property (oxygen permeability):
In accordance with ASTM D-3985, “OXY-TRAN100 type” manufactured by Mondan Control was used, and the oxygen permeation amount ml / [m ² · day · atm] was measured in an environment of 24 ° C. and 65% RH. .

(2) Haze:
Haze was measured using a Tokyo Denshoku Co., Ltd. haze meter.

(3) Coefficient of static friction between films:
The coefficient of static friction (μS) was measured by a parallel displacement method under the conditions of relative humidity of 65% and 90% and a temperature of 23 ° C.

(4) Spherical ratio:
The projected area of 500 particles and the circle equivalent area of the maximum diameter on the projected surface were obtained from an image taken by observing spherical porous particles with an SEM at a magnification of 5000 to 10,000 times, and calculated by the above-described equation (1).

(5) DBP oil absorption:
It measured based on JIS6220.

Examples 1-2 and Comparative Examples 1-3 :
Each of the four types of zeolite, a predetermined amount of silane coupling agent, and water 6 times the weight of the total amount are mixed in a super mixer while heating to 80 ° C., and the zeolite is evaporated while evaporating the water. Was processed. Subsequently, it dried at 120 degreeC and obtained 4 types of surface-treated zeolite fine particles.

The obtained surface-treated zeolite fine particles were added to 100 parts by weight of the finally obtained polyamide 6 resin during the polymerization of caprolactam so as to be parts by weight shown in Table 2, and polymerized by a conventional method. A number 6 polyamide 6 resin was obtained. The obtained zeolite particle-containing polyamide 6 resin was treated in boiling water according to a conventional method to extract and remove low molecular weight substances, and dried in a vacuum dryer.

The bisamide compound was added so as to have the weight parts shown in Table 2 with respect to 100 parts by weight of polyamide 6 resin, and a T-die type film forming machine having an extruder diameter of 40 mm was used. A film original having a thickness of 135 μm was formed at 30 ° C. Furthermore, this film original film was simultaneously biaxially stretched at 3Ox3 times in length and breadth at 80 ° C and then heat-set at 200 ° C to obtain a biaxially stretched film having a thickness of 15 µm. The evaluation results on the obtained stretched film are shown in Table 2 .

Table 2 or Luo following it is clear. That is, films produced from the compositions of Examples 1 and 2 using two types of zeolites having different shapes and particle sizes in the combinations defined in the present invention are excellent in gas barrier properties, transparency and slipperiness. . On the other hand, films obtained from the compositions of Comparative Examples 1 and 2 using any one kind of zeolite are inferior in slipperiness and / or transparency. Moreover, the film obtained from the composition of Comparative Example 3 in which the two types of combinations are outside the scope of the present invention is inferior in transparency and slipperiness .

Claims (8)

A spherical porous material having an average particle size of 1.5 to 6 μm, containing 0.01 to 0.5 parts by mass of the porous filler (B) with respect to 100 parts by mass of the crystalline resin (A). Filler (B-1) and a polyhedral porous filler (B-2) having an average particle diameter of 0.4 to 1.5 μm, and the mass ratio is 1 / 2.5 ≦ (B-1) / (B -2) Ri range der of ≦ 1/1, the crystalline resin composition crystalline resin characterized in that it is a polyamide resin. The crystalline resin composition according to claim 1, wherein the porous filler is a zeolite. Furthermore, the crystalline resin composition of Claim 1 or 2 containing 0.01-60 mass% silane coupling agent (C) with respect to a porous filler (B). The crystalline resin composition according to claim 3 , wherein the silane coupling agent (C) is an aminosilane coupling agent. Furthermore, the crystalline resin composition as described in any one of Claims 1-4 containing 0.01-1 mass part bisamide compound (D) with respect to 100 mass parts of crystalline resin (A). Crystalline resin film characterized by comprising molding a crystalline resin composition according to any one of claims 1 to 5. The crystalline resin film according to claim 6 , which is a stretched film. Oxygen permeation at 23 ° C. and 65% RH at a thickness of 15 μm is 50 ml / [m ² · day · atm] or less, haze is 2.5% or less, and the coefficient of static friction between films is 0 at 23 ° C. and 65% RH. The crystalline resin film according to claim 6 or 7 , which is 0.5 or less and 0.6 or less at 23 ° C and 90% RH.