JP2000052516A - Laminated polyamide resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide laminated polyamide resin film good in impact resistance and transparency and especially good in slip properties under high humidity. SOLUTION: In a laminated polyamide resin film consisting of a resin layer (X) based on an aliphatic polyamide resin (a) and a resin layer (Y) mainly containing an aromatic polyamide resin component (b) and an aliphatic polyamide resin component (c) so that the repeating unit of the aromatic polyamide resin component (b) is 0.5 mol.% or more with respect to the total amt. of the repeating units of the total polyamide resin components in the resin layer and formed by laminating the resin layer (Y) to at least one surface of the resin layer (X), 0.2-10 wt.% of a bending fatigue resistance modifier (d) and 0.05-1.0 wt.% of inorg. and/or org. fine particles with a mean particle size of 0.5-5.0 μm are added to at least one of the resin layer (X) and the resin layer (Y) with respect to the total amt. of the constitutional components in the respective resin layers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide resin film having good impact resistance and good transparency and slipperiness for use in food packaging and the like.

[0002]

2. Description of the Related Art Polyamide resin films have been widely used in various applications including food packaging, because of their excellent mechanical properties, optical properties, thermal properties, chemical resistance and gas barrier properties. Have been. However, the conventional polyamide resin film has a high hygroscopicity as a disadvantage derived from the properties of the polyamide resin itself, and when used in a high humidity environment, absorbs moisture to increase the contact area, resulting in reduced slipperiness. However, there is a problem that handling operability during processing is significantly impaired.

[0003] In order to solve these problems, a method of reducing the coefficient of friction on the friction surface between films or between the film and another material has been studied. Specifically, a polyamide resin film contains a polyamide resin film. For example, a method of reducing the coefficient of friction of the film surface by adding inorganic particles or the like which are inert to the film, and a method of adding an organic surface lubricant to lower the surface energy are used.

However, in the above-mentioned conventional method, when the content of the inorganic particles is increased in order to reduce the friction coefficient, there is a problem that the transparency of the polyamide resin film is deteriorated. The coefficient of friction and the transparency of the film,
There is a trade-off relationship, and it is difficult to obtain a polyamide-based resin film that satisfies both the characteristics of easy sliding and transparency, especially a polyamide-based resin film that satisfies transparency and satisfies the sliding property under high humidity. Was. In addition, when a large amount of an organic surface lubricant is used, the surface energy of the film is excessively reduced, and the slip property is improved. On the other hand, there is a problem that the adhesive property when printing or laminating on the film surface is reduced, which is practical. Due to its characteristics, it has been difficult to increase the amount of the organic surface lubricant.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to a polyamide resin film having good impact resistance and good transparency and sliding properties, particularly a polyamide resin film having good sliding properties under high humidity. The purpose is to provide.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present invention has revealed that a polyamide resin having low water absorption and a fat having relatively good impact resistance and bending pin pole resistance. Without impairing the impact resistance by laminating the aromatic polyamide resin, it was found that transparency and slipperiness under high humidity can be simultaneously satisfied,
The present invention has been achieved.

That is, the present invention comprises a resin layer (X) containing an aliphatic polyamide resin (a) as a main component, an aromatic polyamide resin (b) component and an aliphatic polyamide resin (c) component. Mainly containing aromatic polyamide resin (b)
A resin layer (Y) in which the repeating unit of the component is 0.5 mol% or more based on the total amount of the repeating units of all the polyamide-based resin components in the resin layer, and at least one surface of the resin layer (X) A laminated polyamide resin film obtained by laminating a resin layer (Y), wherein at least one of the resin layer (X) and the resin layer (Y) has a resistance to the total amount of the constituent components in each resin layer. Flexural fatigue improver (d)
2 to 10% by weight, and an average particle size of 0.5 to 5.0 μm
Inorganic and / or organic fine particles of 0.05 to 1.
The present invention provides a laminated polyamide resin film containing 0% by weight.

[0008] In the present invention, "film" means
The thickness is not particularly limited, and includes a “sheet”.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the present invention, the aliphatic polyamide resin (a) mainly constituting the resin layer (X) is not particularly limited, but is preferably nylon 6, nylon 12, nylon 6.6, nylon 6.12, nylon 6. / 6/6 copolymer and nylon 6/12 copolymer are preferred, and these may be used alone or as a mixture of two or more.

In the present invention, the component (b) of the aromatic polyamide resin contained in the resin layer (Y) is not particularly limited, but is preferably terephthalic acid and / or isophthalic acid, and having 6 to 12 carbon atoms. Aromatic polyamide resin mainly composed of an aliphatic diamine is preferable, and nylon 6T obtained by polycondensation of terephthalic acid and hexamethylene diamine, and nylon 6I obtained by polycondensation of isophthalic acid and hexamethylene diamine are more preferable. . These may be used alone or as a mixture of two or more.

In the present invention, the aliphatic polyamide resin (c) component contained in the resin layer (Y) is not particularly limited, but preferably nylon 6 and / or nylon 66.

The resin layer (Y) in the present invention may contain mainly the aromatic polyamide resin (b) component and the aliphatic polyamide resin (c) component.
Is preferably mainly composed of the following polyamide resins. That is, specifically, a copolymer of an aromatic polyamide resin and an aliphatic polyamide resin, a mixture of an aromatic polyamide resin and an aliphatic polyamide resin, or an aromatic polyamide resin and an aliphatic polyamide resin What blended the aromatic polyamide resin and / or the aliphatic polyamide resin with the copolymer with resin is mentioned. Preferably, it contains a copolymer of an aromatic polyamide resin and an aliphatic polyamide resin.

In the present invention, the polyamide resin component mainly contained in the resin layer (Y) is based on the total amount of repeating units of all the polyamide resin components in the resin layer (Y).
It is necessary to make the repeating unit of the aromatic polyamide resin (b) component 0.5% by mole or more. When the content of the aromatic polyamide-based resin (b) is less than 0.5 mol%, the resin layer (Y) has high hygroscopicity, and a sufficient improvement in slipperiness cannot be obtained.

The laminated polyamide resin film of the present invention comprises, in at least one of the resin layer (X) and the resin layer (Y), a flex fatigue resistance improving agent (d ) 0.2 to 10% by weight.
The flex fatigue resistance improving agent (d) used in the present invention is not particularly limited, and compounds generally used can be used.
Preferably, the flex fatigue resistance improving agent (d) comprises at least one of block polyesteramide, block polyetheramide, polyetheresteramide-based elastomer, polyester-based elastomer, modified ethylene-propylene rubber, and ethylene / acrylate copolymer. It may consist of more than one compound.

The flex fatigue resistance improving agent (d) may be blended in only one of the resin layers (X) and (Y), or may be blended in both layers. When the flex fatigue resistance improving agent (d) is blended in both the resin layers (X) and (Y), the blending ratio between the layers is not particularly limited.

The compounding amount of the flex fatigue resistance improving agent (d) is 0.2% by weight in both the resin layers (X) and (Y).
If it is less than 10, the bending fatigue resistance of the laminated film is not improved, and the blending amount of the bending fatigue resistance improving agent (d) exceeds 10% by weight in any of the resin layers (X) and (Y). In this case, the transparency is reduced.

The laminated polyamide resin film of the present invention has an average particle size of 0.5 to 5 in at least one of the resin layer (X) and the resin layer (Y) based on the total amount of the constituent components in each resin layer. 0.0 μm of a particulate lubricant, that is, 0.05 to 1.0% by weight of inorganic and / or organic fine particles.

If the average particle size of the particle-based lubricant is less than 0.5 μm in both the resin layers (X) and (Y), the slipperiness is not improved, and the resin layers (X) and (Y) are not improved. If any of them exceeds 5.0 μm, the transparency will be reduced.

The compounding amount of the particulate lubricant is as follows:
If the amount is less than 0.05% by weight in both layers of (Y), the slipperiness of the laminated film is not improved, and the blending amount of the particle-based lubricant is 1 in any of the resin layers (X) and (Y). .0
If the amount is more than 10% by weight, the transparency decreases.

The particle-based lubricant used in the present invention is not particularly limited, and a generally used particle-based lubricant can be used.
For example, inorganic particles such as silica, alumina and calcium carbonate, and organic particles such as cross-linked acrylic particles and cross-linked polystyrene particles can be mentioned.

In the present invention, the above-mentioned particle-based lubricant may be used alone or in combination of two or more.

The above-mentioned particle-based lubricant comprises a resin layer (X),
(Y) may be blended in only one of them, or may be blended in both layers. When the particle-based lubricant is blended in both the resin layers (X) and (Y), the blending ratio between the layers is not particularly limited.

In the present invention, the thickness and the thickness ratio of each layer of the resin layer (X) and the resin layer (Y) are not particularly limited, and may be appropriately set so as to have desired thickness and physical properties after lamination.

The laminated polyamide resin film of the present invention may be provided with a slipperiness imparting agent in one or both of the resin layer (X) and the resin layer (Y) to prevent blocking of the films and to improve slipperiness. May be blended. As the slipperiness imparting agent, for example, stearic acid amide, behenic acid amide, erucic acid amide, N-stearyl stearic acid amide, ethylene bisbehenic acid amide, higher fatty acid amides such as ethylene bisstearic acid amide and fatty acid metal salts, fatty acids An organic lubricant such as an ester may be used.

In the present invention, the kind of the above-mentioned slipperiness imparting agent to be blended is not particularly limited, and one kind may be used alone, or two or more kinds may be used in combination.

The blending ratio of the above-mentioned slip imparting agent is not particularly limited, and the type of polyamide resin used for each resin layer,
What is necessary is just to set suitably according to the thickness etc. of each layer.

The slipperiness imparting agent comprises a resin layer (X),
(Y) may be blended in only one of them, or may be blended in both layers. When the slipperiness imparting agent is blended in both the resin layers (X) and (Y), the blending ratio between the layers is not particularly limited.

In the present invention, various commonly used additives may be further added to the resin layers (X) and (Y) as long as the effects of the present invention are not impaired. For example, antioxidants, light stabilizers, anti-gelling agents, pigments, antistatic agents,
Surfactants and the like can be added.

The laminated polyamide resin film of the present invention has a resin layer (Y) on at least one surface of the resin layer (X).
Are laminated. That is, the layer configuration is (X)-(Y)
Or (Y)-(X)-(Y).
In the laminated polyamide-based resin film of the present invention, the surface on the side that requires slipperiness when used is the resin layer (Y).

The laminated polyamide resin film of the present invention may be formed by simultaneously forming and laminating each of the resin layers (X) and (Y) by coextrusion or the like. ) And (Y) may be separately formed into a film and later laminated by a laminating method or the like. As a film forming method, a generally used method such as a T-die method and an inflation method can be used. Each resin layer (X),
The materials constituting (Y) can be mixed simultaneously or sequentially, and mixed using a commonly used mixer or the like.

The laminated polyamide resin film of the present invention is preferably uniaxially or biaxially stretched after lamination. The stretching method is not particularly limited, and a generally used method can be used.

The laminated polyamide resin film of the present invention may be subjected to a surface treatment such as a corona discharge treatment or a plasma treatment within a range not to impair the function of the present invention.

Hereinafter, the present invention will be described in detail with reference to Test Examples and Examples. However, the present invention is not limited by the following Examples, and may be appropriately modified within a range that can be adapted to the gist of the present invention. It is also possible to implement by adding
All of them are included in the technical scope of the present invention. Test Examples The following tests were performed on the laminated polyamide resin films of Examples 1 to 6 and Comparative Examples 1 to 8. 1. Test Method (1) Transparency A haze value was measured with a haze tester of Toyo Seiki Seisakusho in accordance with JIS-K6714, and evaluated based on the following criteria. ：: good transparency (haze value is 5.0% or less) ×: poor transparency (haze value exceeds 5.0%)

(2) Sliding property The coefficient of kinetic friction between the surfaces of the resin layers (Y) not subjected to the surface activation treatment of the laminated film was determined by ASTM-D-189.
According to the four laws, (A) 50% RH and (B) 65%
The measurement was performed in a humidity atmosphere of RH, and the evaluation was performed based on the following criteria. (2-1) Slippery in a 50% RH atmosphere ○: Good slipperiness (dynamic friction coefficient (A) is 1.0 or less) ×: Poor slipperiness (dynamic friction coefficient (A) exceeds 1.0) (2-2) Slip property under high humidity (under a humidity atmosphere of 65% RH) ○: Good slip property (dynamic friction coefficient (B) / dynamic friction coefficient (A))
×: 1.5 or less) ×: poor slipperiness (dynamic friction coefficient (B) / dynamic friction coefficient (A))
Exceeds 1.5)

(3) Bending Fatigue Resistance Using a gelbo flex tester manufactured by Rikagaku Kogyo KK, bending fatigue resistance was measured by the following method. That is,
The other end was fixed to the fixed head side having a diameter of 3.5 inches, and the other end was fixed to the movable head side. The first 3.5 inches of the stroke give a 440 degree twist, followed by 2.5 inches of linear and horizontal motion, with bending fatigue to complete the entire stroke at a rate of 40 times / minute, 1000 times.
The number of pinholes generated in the film was counted, and the bending fatigue resistance was evaluated based on the following criteria. The measurement was performed in an environment at 25 ° C. ：: Bending fatigue resistance is good (the number of pinholes is 20/7 inch square or less) ×: Bending fatigue resistance is poor (the number of pinholes exceeds 20/7 inch square)

2. Test results Table 1 shows the test results. Table 1 shows that the films of the examples were excellent in all of the slipperiness, transparency, and bending fatigue resistance.

[0037]

[Table 1]

[0038]

EXAMPLES Example 1 As a resin layer (X), 94.4 parts by weight of nylon 6, 5 parts by weight of polylaurin tactam / polyether copolymer (Daiamide, manufactured by Daicel Huls Co., Ltd.), and an average particle diameter of 1 were used. 0.4 part by weight of porous silica having a thickness of 0.6 μm and 0.2 part by weight of ethylene bisstearic acid amide were mixed and blended, and then melt-mixed using a 60 mm extruder with barrel temperatures of 260, 265 and 270 ° C. On the other hand, as the resin layer (Y), 2 parts by weight of nylon 6T / nylon 6 copolymer (copolymerization ratio 50/50 molar ratio)
8 parts by weight of nylon 6 were blended, and the barrel temperature was 290, 3
The mixture is melt-mixed using a 30 mm extruder at 00 and 305 ° C., and has a layer configuration of outermost layer (Y) / intermediate layer (X) / innermost layer (Y), and a thickness ratio of resin layer (Y) :( X) : (Y) =
The mixture was melt coextruded and laminated with a T die at a die temperature of 300 ° C. so that the ratio became 1.5: 7.0: 1.5, and cooled on a rotating drum at 20 ° C. to obtain an unstretched polyamide film having a thickness of 180 μm. This unstretched film was longitudinally stretched 3.0 times at 50 ° C. Then stretched 4.0 times in the transverse direction at 125 ° C.
The film was heat-set at ℃ to obtain a 15 μm thick biaxially stretched film.

Example 2 As a resin layer (X), 94.4 parts by weight of nylon 6, 5 parts by weight of polylaurin lactam / polyether copolymer (Daiamide, manufactured by Daicel Huls Co., Ltd.), average particle diameter 1.6 μm 0.4 parts by weight of porous silica and 0.2 parts by weight of ethylene bisstearic acid amide were mixed and mixed by a blender, and then melt-mixed using a 60 mm extruder with barrel temperatures of 260, 265 and 270 ° C. As a resin layer (Y), 100 parts by weight of a nylon 6T / nylon 6 copolymer (specific polymerization ratio: 50/50 molar ratio) was blended and melted using a 30 mm extruder with barrel temperatures of 300, 305 and 310 ° C. Mix, outermost layer (Y)
/ Intermediate layer (X) / innermost layer (Y) with a thickness ratio of resin layer (Y) :( X) :( Y) = 1.5: 7.0: 1.
5 and co-extruded and laminated with a T-die having a die temperature of 310 ° C., cooled on a rotating drum at 40 ° C.
An 80 μm unstretched polyamide film was obtained. This unstretched film was longitudinally stretched 3.0 times at 70 ° C. Then 1
The film was stretched 4.0 times in the transverse direction at 25 ° C. and heat-set at 215 ° C. to obtain a biaxially stretched film having a thickness of 15 μm.

Example 3 In the method of Example 1, as the resin layer (Y), 2 parts by weight of nylon 6T / nylon 6 copolymer (copolymerization ratio 50/50 molar ratio), polylaurin lactam / polyether copolymer A biaxially stretched film having a thickness of 15 μm was obtained in exactly the same manner as in Example 1 except that 5 parts by weight of a coalesced product (manufactured by Tycel Huls Co., Ltd., diamide) and 93 parts by weight of nylon 6 were mixed.

Example 4 In the method of Example 2, 95 parts by weight of a nylon 6T / nylon 6 copolymer (copolymerization ratio 50/50 molar ratio) and a polylaurin lactam / polyether copolymer were used as the resin layer (Y). (Daicel, manufactured by Huls Co., Ltd., diamide) A biaxially stretched film having a thickness of 15 μm was obtained in the same manner as in Example 2 except that 5 parts by weight was blended.

Example 5 In the method of Example 1, the resin layers (X) and (Y) had a two-layer structure of the innermost layer (X) / the outermost layer (Y), and the thickness ratio was changed to the resin layer (X). ): A biaxially stretched film having a thickness of 15 μm was obtained in the same manner as in Example 1 except that (Y) was set to 7: 3.

Example 6 In the method of Example 2, the layer structure of the resin layers (X) and (Y) was changed to a two-layer structure of the innermost layer (X) / the outermost layer (Y), and the thickness ratio was changed to the resin layer (X). ): A biaxially stretched film having a thickness of 15 μm was obtained in the same manner as in Example 2 except that (Y) was set to 7: 3.

Comparative Example 1 In the method of Example 1, 100 resin was used as the resin layer (Y).
A biaxially stretched film having a thickness of 15 μm was obtained in exactly the same manner as in Example 1 except that nylon 6 in parts by weight was used.

Comparative Example 2 In the method of Example 1, 100 resin was used as the resin layer (Y).
The use of parts by weight of nylon 6 and the layer structure of the resin layers (X) and (Y) are changed to the innermost layer (X) / the outermost layer (Y).
And a thickness ratio of the resin layer (X) :( Y) =
Except for 7: 3, the thickness is 1 in the same manner as in Example 1.
A 5 μm biaxially stretched film was obtained.

Comparative Example 3 The procedure of Example 1 was repeated except that the blending amount of the polylaurin lactam / polyether copolymer was changed to 11 parts by weight.
A biaxially stretched film having a thickness of 15 μm was obtained in exactly the same manner as in Example 1.

Comparative Example 4 Biaxial stretching of 15 μm in thickness was performed in the same manner as in Example 1 except that the amount of the polylaurin lactam / polyether copolymer was changed to 0.1 part by weight. A film was obtained. .

Comparative Example 5 The procedure of Example 1 was repeated, except that the composition of the inorganic particles was changed to 0.4 parts by weight of porous silica having an average particle diameter of 6.0 μm. A 15 μm thick biaxially stretched film was obtained.

Comparative Example 6 The procedure of Example 1 was repeated, except that the composition of the inorganic particles was changed to 0.4 parts by weight of porous silica having an average particle diameter of 0.4 μm. A 15 μm thick biaxially stretched film was obtained.

Comparative Example 7 The procedure of Example 1 was repeated, except that the amount of the porous silica having an average particle diameter of 1.6 μm was changed to 1.1 parts by weight. An axially stretched film was obtained.

Comparative Example 8 The procedure of Example 1 was repeated except that the amount of the porous silica having an average particle diameter of 1.6 μm was changed to 0.04 parts by weight. An axially stretched film was obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shigeru Yoneda 2-1-1 Katata, Otsu City, Shiga Prefecture Inside Toyobo Co., Ltd. Research Institute (72) Masazumi Imanishi 2-1-1 Katata, Otsu City, Shiga Prefecture No. Toyobo Co., Ltd. Research Laboratory (72) Inventor Masayoshi Sato 2-1-1 Katata, Otsu-shi, Shiga F-term in Toyobo Co., Ltd. Research Laboratory (Reference) 3E086 AD01 BA04 BA15 BA33 BB01 BB22 BB41 BB55 BB62 BB74 CA01 4F100 AA20 AD03 AK01A AK01B AK01C AK41A AK41B AK41C AK41J AK46A AK46B AK46C AK46J AK47B AK48A AK48B AK48C AK54A AK54B AK54C AK54J AK64A AK64B AK64C AK71A AK71B AK71C AL01A AL01B AL01C AL02A AL02B AL02C AL05A AL05B AL05C AL06A AL06B AL06C AL09A AL09B AL09C BA02 BA03 BA06 BA07 BA10A BA10C CA23A CA23B CA23C CA24A CA24B CA24C DE01A DE01B DE01C EH20 GB23 JK10 JK16 JK20A JK20B JK20C JN01 YY00A YY00C 4J002 BB073 BB153 BC024 BG004 BP023 BP033 CF003 CL01W CL03W CL03X CL05W CL073 CL083 DE146 DE236 DJ016 EP017 FD174 FD176 FD177 FD203 GG02

Claims (6)

[Claims] 1. A resin layer (X) containing an aliphatic polyamide resin (a) as a main component, and an aromatic polyamide resin (b).
Component and an aliphatic polyamide resin (c) component, and the repeating unit of the aromatic polyamide resin (b) component is 0.5 mol based on the total amount of the repeating units of all the polyamide resin components in the resin layer. % Of the resin layer (Y), and a laminated polyamide resin film obtained by laminating the resin layer (Y) on at least one surface of the resin layer (X). And in at least one of the resin layers (Y), 0.2 to 10% by weight of a flex fatigue resistance improving agent (d) and an average particle size of 0.5 to 5 based on the total amount of the constituent components in each resin layer. A laminated polyamide resin film containing 0.05 to 1.0% by weight of 0.0 μm inorganic and / or organic fine particles. 2. The laminated polyamide resin film according to claim 1, wherein at least one of the resin layer (X) and the resin layer (Y) contains a slipperiness imparting agent. 3. The method according to claim 1, wherein the aliphatic polyamide resin (a) is nylon 6, nylon 12, nylon 6.6, nylon 6.6.
12, nylon 6/6/6 copolymer, nylon 6/12
The laminated polyamide resin film according to claim 1 or 2, wherein the laminated polyamide resin film is mainly composed of at least one kind of a copolymer. 4. An aromatic polyamide resin (b) component comprising:
Terephthalic acid and / or isophthalic acid and carbon number 6
The laminated polyamide resin film according to any one of claims 1 to 3, wherein the laminated polyamide resin film is an aromatic polyamide resin mainly including an aliphatic diamine of 1 to 12. 5. The laminated polyamide resin film according to claim 1, wherein the component (c) of the aliphatic polyamide resin is nylon 6 and / or nylon 66. 6. The flex fatigue resistance improving agent (d) is selected from block polyesteramide, block polyetheramide, polyetheresteramide elastomer, polyester elastomer, modified ethylene propylene rubber, and ethylene / acrylate copolymer. The laminated polyamide resin film according to any one of claims 1 to 5, wherein the laminated polyamide resin film is at least one compound.