JP2018103467A - Multilayer polypropylene-based stretched film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multilayer polypropylene-based stretched film which has heat fusion bonding strength durable even during high-speed automatic packaging, and is excellent in smoothness.SOLUTION: The multilayer polypropylene-based stretched film containing a base material layer 3 and a heat fusion bonding layer 2 is provided, in which the heat fusion bonding layer 2 is in the outermost layer of the film, the base material layer 3 contains a polypropylene-based resin, component (A) being aliphatic amine-ethylene oxide adduct fatty acid ester, component (B) being glycerol fatty acid ester and component (C) being aliphatic amine-ethylene oxide adduct, two kinds of compounds of mono- and di-fatty acid ester are contained in the component (A) with a weight ratio (mono/di) of 50/50 to 90/10, and two kinds of compounds of glycerol mono- and di-fatty acid ester are contained in the component (B) with a weight ratio (mono/di) of 95/5 to 5/50.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a multilayer polypropylene-based stretched film.

  Since polypropylene has good transparency, rigidity, and moisture resistance, its films and molded products are widely used for packaging materials such as foods and clothing, home appliance parts, automobile interior materials, and the like. In particular, films having a heat-sealing layer are widely used because they do not require post-processing such as laminating and can be used alone for packaging.

  For a film having a heat-sealing layer, a polymer having a melting point lower than that of a base material layer such as a polyethylene-polypropylene copolymer is usually used for the heat-sealing layer, and the surface layer becomes flexible so that the friction of the film There is a tendency for the coefficient to increase, and a device for improving smoothness by using a lubricant, an anti-blocking agent or the like has been devised. However, in polypropylene films used for automatic packaging machines that have recently been accelerated at high speeds, the side surface may be insufficiently heat-sealed depending on the packaging conditions when the material to be packaged is packaged at high speed. Therefore, a packaging film that can provide stable heat-sealing strength even under high-speed packaging is desired.

  On the other hand, polypropylene resin is hydrophobic and the wettability of the resin surface is remarkably low, so that water condensed on the inner surface of the film is exposed under conditions exposed to a large amount of moisture such as packaging of moisture-containing foods (fruits, vegetables, meat, etc.). Adhesion and fogging occur. Due to cloudiness, for example, the contents cannot be seen in food containers and the like, and not only the commercial value is reduced, but also condensation of water droplets may adhere to the stored food, thereby promoting the quality change of the food. In order to solve these problems, a method is adopted in which an antifogging agent composed of various surfactants is blended in a resin so that water droplets are not formed on the surface by increasing the wettability of the resin surface.

In recent years, the development of catalysts and processes for obtaining highly ordered polypropylene resins has made it possible to efficiently obtain polypropylene that is even more excellent in rigidity and transparency than before. On the other hand, however, it has become a problem that the performance of the kneading type antifogging agent becomes difficult to express due to the increase in crystallinity of the resin.
In order to solve this problem, attempts have been made to increase the transfer rate of the internal surfactant to the surface by increasing the concentration of these additives or increasing the heat setting time after the molded product is produced. However, attempts to improve performance by increasing the concentration and extending the heat setting time often cause excessive bleeding phenomenon on the surface of the surfactant, and a decrease in transparency due to the anti-bleeding antifogging agent is seen, There was a problem in dealing with the high-speed automatic packaging machine as described above due to deterioration of heat-fusibility and deterioration of smoothness.
Further, the anti-fogging agent that is excessively bleeded may cause a decrease in the anti-fogging property due to the transfer from the outer surface of the film to the inner surface due to close contact during film winding.

  In order to solve this problem, in the multilayer film, in general, the antifogging agent is contained only in the base material layer, and the device has been devised to delay the transition to the surface layer, but during high temperature storage such as summer, In many cases, it was insufficient to suppress the bleeding phenomenon.

  Patent Document 1 proposes a method in which organic polymer fine particles having a predetermined particle diameter and inert fine particles such as inorganic fine particles are added to a resin for forming a heat-fusible layer. It is difficult to uniformly disperse these complicated fine particles in a polypropylene resin, and even if it can be dispersed, it is insufficient as an anti-blocking effect against excessive bleeding. Further, in Patent Document 2, an attempt is made to suppress the migration of the antifogging agent by adhesion by changing the resin composition of the outer surface and the inner surface, but the work increases in order to change the resin composition to be used, It cannot cope with excessive bleeding caused by ordinary antifogging agents.

Japanese Patent Laid-Open No. 2003-237827 JP-A-2006-97536

  An object of this invention is to provide the multilayer polypropylene-type stretched film excellent in the heat-seal | strengthening strength and smoothness which can be endured also at the time of high-speed automatic packaging.

As a result of intensive studies, the inventors of the present invention have a multilayer polypropylene-based stretched film containing a base material layer and a heat fusion layer, wherein the heat fusion layer is an outermost layer of the film, and the base material layer It was discovered that a multilayered polypropylene-based stretched film containing a specific component in a multilayer polypropylene-based stretched film excellent in heat-sealing strength and smoothness that can withstand even during high-speed automatic packaging was achieved. .
That is, the multilayer polypropylene-based stretched film of the present invention is a multilayer polypropylene-based stretched film containing a base layer and a heat-seal layer, and the heat-seal layer is the outermost layer of the film, and the base layer Is a polypropylene resin, a component (A) that is an aliphatic amine ethylene oxide adduct fatty acid ester, a component (B) that is a glycerin fatty acid ester, and a component (C) that is an aliphatic amine ethylene oxide adduct. The component (A) is an aliphatic amine ethylene oxide adduct mono-fatty acid ester represented by the following general formula (1), and an aliphatic represented by the following general formula (2) Component (A-2) which is an amine ethylene oxide adduct difatty acid ester,
The weight ratio (A-1 / A-2) of the component (A-1) and the component (A-2) is 50/50 to 90/10,
The component (B) includes a component (B-1) that is a glycerin monofatty acid ester and a component (B-2) that is a glycerin difatty acid ester,
The weight ratio (B-1 / B-2) of the component (B-1) and the component (B-2) is 95/5 to 50/50, and the component (C) is represented by the following general formula (3) ).

（式中、Ｒ^１及びＲ^２は、それぞれ独立して、アルキル基、アルケニル基、アルカジエニル基またはアルキニル基である。Ｒ^１の炭素数は８〜２２、Ｒ^２の炭素数は７〜２１である。ａ及びｂはオキシエチレン基の平均付加モル数を示し、ａ及びｂは０以上であり、ａ＋ｂは２〜３を満足する数である。）

(In the formula, R ¹ and R ² are each independently an alkyl group, an alkenyl group, an alkadienyl group, or an alkynyl group. R ¹ has 8 to 22 carbon atoms, and R ² has 7 to 21 carbon atoms. A and b represent the average number of moles of oxyethylene group added, a and b are 0 or more, and a + b is a number satisfying 2 to 3.)

（式中、Ｒ^３及びＲ^４は、それぞれ独立して、アルキル基、アルケニル基、アルカジエニル基又はアルキニル基である。２つあるＲ^４は互いに同一であっても異なっていてもよい。Ｒ^３の炭素数は８〜２２であり、Ｒ^４の炭素数は７〜２１であり、ｃ及びｄはオキシエチレン基の平均付加モル数を示し、ｃ及びｄは０以上であり、ｃ＋ｄ=２〜３を満足する数である。）

(In the formula, R ³ and R ⁴ are each independently an alkyl group, an alkenyl group, an alkadienyl group, or an alkynyl group. Two R ^{4 s} may be the same as or different from each other. R ³ The carbon number of R ⁴ is 8 to 22, the carbon number of R ⁴ is 7 to 21, c and d represent the average number of moles added of the oxyethylene group, c and d are 0 or more, and c + d = 2 to 2 It is a number that satisfies 3.)

（式中、Ｒ^５はアルキル基、アルケニル基、アルカジエニル基又はアルキニル基であり、Ｒ^５の炭素数は８〜２２であり、e及びfはオキシエチレン基の平均付加モル数を示し、ｅ及びｆは０以上であり、ｅ＋ｆ＝２〜３を満足する数である。）

(In the formula, R ⁵ represents an alkyl group, an alkenyl group, an alkadienyl group or an alkynyl group, R ⁵ has 8 to 22 carbon atoms, e and f represent the average number of added moles of the oxyethylene group, and e and f is 0 or more and is a number satisfying e + f = 2 to 3.)

It is preferable that the base material layer further includes a component (D) that is a polyoxyethylene sorbitan fatty acid ester and / or a component (E) that is a polyglycerol fatty acid ester.
The weight ratio of the component (A) is 30 to 89% by weight with respect to the total weight of the component (A), the component (B), the component (C), the component (D), and the component (E). The weight ratio of the component (B) is 5 to 50% by weight, the weight ratio of the component (C) is 5 to 50% by weight, the weight ratio of the component (D) and / or the component (E) is 1 to It is preferable that it is 20 weight%.
The component (D) preferably has 1 to 30 moles of oxyethylene groups added to the sorbitan fatty acid ester and has a fatty acid residue having 8 to 22 carbon atoms.
The component (E) is an ester derivative of polyglycerin having an average degree of polymerization of 2 to 10 and preferably has a fatty acid residue having 8 to 22 carbon atoms.

The masterbatch of the present invention comprises a polypropylene resin, a component (A) that is an aliphatic amine ethylene oxide adduct fatty acid ester, a component (B) that is a glycerin fatty acid ester, and a component that is an aliphatic amine ethylene oxide adduct. A masterbatch containing (C),
The component (A) is an aliphatic amine ethylene oxide adduct mono-fatty acid ester represented by the following general formula (1), and an aliphatic amine ethylene represented by the following general formula (2) Component (A-2) which is an oxide adduct difatty acid ester,
The weight ratio (A-1 / A-2) of the component (A-1) and the component (A-2) is 50/50 to 90/10,
The component (B) includes a component (B-1) that is a glycerin monofatty acid ester and a component (B-2) that is a glycerin difatty acid ester,
The weight ratio (B-1 / B-2) of the component (B-1) and the component (B-2) is 95/5 to 50/50, and the component (C) is represented by the following general formula (3) It is a masterbatch which is a compound shown by this.

（式中、Ｒ^１及びＲ^２は、それぞれ独立して、アルキル基、アルケニル基、アルカジエニル基またはアルキニル基である。Ｒ^１の炭素数は８〜２２、Ｒ^２の炭素数は７〜２１である。ａ及びｂはオキシエチレン基の平均付加モル数を示し、ａ及びｂは０以上であり、ａ＋ｂは２〜３を満足する数である。）

(In the formula, R ¹ and R ² are each independently an alkyl group, an alkenyl group, an alkadienyl group, or an alkynyl group. R ¹ has 8 to 22 carbon atoms, and R ² has 7 to 21 carbon atoms. A and b represent the average number of moles of oxyethylene group added, a and b are 0 or more, and a + b is a number satisfying 2 to 3.)

（式中、Ｒ^３及びＲ^４は、それぞれ独立して、アルキル基、アルケニル基、アルカジエニル基又はアルキニル基である。２つあるＲ^４は互いに同一であっても異なっていてもよい。Ｒ^３の炭素数は８〜２２であり、Ｒ^４の炭素数は７〜２１であり、ｃ及びｄはオキシエチレン基の平均付加モル数を示し、ｃ及びｄは０以上であり、ｃ＋ｄ=２〜３を満足する数である。）

(In the formula, R ³ and R ⁴ are each independently an alkyl group, an alkenyl group, an alkadienyl group, or an alkynyl group. Two R ^{4 s} may be the same as or different from each other. R ³ The carbon number of R ⁴ is 8 to 22, the carbon number of R ⁴ is 7 to 21, c and d represent the average number of moles added of the oxyethylene group, c and d are 0 or more, and c + d = 2 to 2 It is a number that satisfies 3.)

（式中、Ｒ^５はアルキル基、アルケニル基、アルカジエニル基又はアルキニル基であり、その炭素数は８〜２２であり、e及びfはオキシエチレン基の平均付加モル数を示し、ｅ及びｆは０以上であり、ｅ＋ｆ＝２〜３を満足する数である。）

(In the formula, R ⁵ represents an alkyl group, an alkenyl group, an alkadienyl group or an alkynyl group, the carbon number thereof is 8 to 22, e and f represent the average number of added moles of the oxyethylene group, and e and f are It is 0 or more and is a number satisfying e + f = 2 to 3.)

The antifogging agent for thermoplastic resin film of the present invention is a component (A) which is an aliphatic amine ethylene oxide adduct fatty acid ester, a component (B) which is a glycerin fatty acid ester, and an aliphatic amine ethylene oxide adduct. Component (C),
The component (A) is an aliphatic amine ethylene oxide adduct mono-fatty acid ester represented by the following general formula (1), and an aliphatic amine ethylene represented by the following general formula (2) Component (A-2) which is an oxide adduct difatty acid ester,
The weight ratio (A-1 / A-2) of the component (A-1) and the component (A-2) is 50/50 to 90/10,
The component (B) includes a component (B-1) that is a glycerin monofatty acid ester and a component (B-2) that is a glycerin difatty acid ester,
The weight ratio (B-1 / B-2) of the component (B-1) and the component (B-2) is 95/5 to 50/50, and the component (C) is represented by the following general formula (3) ).

（式中、Ｒ^１、Ｒ^２はアルキル基、アルケニル基、アルカジエニル基またはアルキニル基でありその炭素数はＲ^１＝８〜２２、Ｒ^２＝７〜２１であり、ａおよびｂは０以上でａ＋ｂ＝２〜３を満足する数である。）

(Wherein R ¹ and R ² are an alkyl group, an alkenyl group, an alkadienyl group or an alkynyl group, the carbon number thereof is R ¹ = 8 to 22, R ² = 7 to 21, and a and b are 0 or more. a + b = 2 to 3)

（式中、Ｒ^３、Ｒ^４はアルキル基、アルケニル基、アルカジエニル基またはアルキニル基でありその炭素数はＲ^３＝８〜２２、Ｒ^４＝７〜２１であり、ｃおよびｄは０以上でｃ＋ｄ＝２〜３を満足する数である。）

(Wherein R ³ and R ⁴ are an alkyl group, an alkenyl group, an alkadienyl group or an alkynyl group, the carbon number thereof is R ³ = 8 to 22, R ⁴ = 7 to 21, and c and d are 0 or more. (c + d = 2 to 3)

（式中、Ｒ^５ はアルキル基、アルケニル基、アルカジエニル基またはアルキニル基であり、その炭素数は８〜２２であり、ｅおよびｆは０以上でｅ＋ｆ＝２〜３を満足する数である。）

(In the formula, R ⁵ represents an alkyl group, an alkenyl group, an alkadienyl group or an alkynyl group, the carbon number thereof is 8 to 22, and e and f are 0 or more and a number satisfying e + f = 2 to 3). )

  The multilayer polypropylene-based stretched film of the present invention is excellent in heat-sealing strength and smoothness that can withstand even during high-speed automatic packaging.

The top view of the multilayer polypropylene-type stretched film of Embodiment 1-5 of this invention. Sectional drawing which cut | disconnected the film of Embodiment 1 by the II-II line | wire of FIG. Sectional drawing which cut | disconnected the film of Embodiment 2 by the II-II line | wire of FIG. Schematic at the time of applying the film of Embodiment 1 for food packaging. Sectional drawing cut | disconnected by the III-III line | wire of FIG.

  The multilayer polypropylene film of the present invention will be described in detail.

[Multilayer polypropylene-based stretched film]
The multilayer polypropylene-based stretched film of the present invention has a base material layer and a heat fusion layer, and the heat fusion layer is in the outermost layer. Each layer will be described.

(Base material layer)
The base material layer essentially includes a polypropylene resin.
It is preferable that a propylene homopolymer is mainly used as the polypropylene resin.
The propylene homopolymer is preferably isotactic polypropylene obtained by a gas phase method.
The polypropylene resin preferably contains an amorphous polyolefin resin in addition to the propylene homopolymer.
As the amorphous polyolefin resin, propylene / ethylene copolymer, propylene / butene-1 copolymer, propylene / ethylene / butene-1 copolymer, propylene / pentene copolymer, ethylene / butene-1 copolymer, Used as a mixture of ethylene-propylene-butene-1 copolymer, ethylene-acrylic acid copolymer / ethylene-acrylic acid copolymer cross-linked ionomer, polybutene-1, butene-ethylene copolymer, etc. May be.
Furthermore, polyester-based resins, polyamide-based resins, polycarbonate-based resins, and the like can be used as long as the characteristics of the film are not impaired.

  Propylene / Butene-1 Copolymer, Propylene / Ethylene / Butene-1 Copolymer, Ethylene / Butene-1 Copolymer, Ethylene / Propylene / Butene-1 Copolymer and Butene / Ethylene Copolymer The content of -1 is preferably 3 to 7% by weight.

  As a polypropylene resin, it is 0.5-15 weight part of amorphous polyolefin with respect to 100 weight part of propylene homopolymers, Preferably it is 1-5 weight part. If it is less than 0.5 part by weight, antifogging properties cannot be obtained, and if it exceeds 15 parts by weight, the bleedout to the surface of component (A), component (B) and component (C) described later is too early, and Unnecessary bleed-out is likely to occur, which is not preferable.

  The said base material layer contains the component (A), the component (B), and component (C) which are mentioned later essential. The total amount of component (A), component (B), component (C), component (D) and component (E) with respect to the base material layer is preferably 0.10 to 2.0% by weight, more preferably. Is 0.30 to 1.8% by weight, more preferably 0.50 to 1.5% by weight. If it is less than 0.10% by weight, smoothness may be insufficient. On the other hand, if the content is more than 2.0% by weight, the surface of the film may become sticky due to excess bleed and the thermal fusion strength may be lowered.

Further, the base material layer is not limited to stabilizers such as antioxidants and ultraviolet absorbers, lubricants, nucleating agents, pigments, inorganic fillers, plasticizers, and the like, as long as the effects of the present invention are not impaired. In addition, other polyolefin thermoplastic resin additives may be contained.
Examples of the antioxidant include phenolic antioxidants, phosphorous acid antioxidants, and acrylate antioxidants.

(Heat-fusion layer)
The heat-sealable layer is not particularly limited as long as it has heat-sealability. However, since the adhesiveness with the base material layer is excellent, a polymer structure mainly composed of polyolefin is preferable.
For example, homopolymers or copolymers such as ethylene, propylene, 1-butene, or a mixture thereof may be mentioned. For convenience in bag making, the melting point is preferably lower than the base material layer, more preferably 10 ° C. or higher. Lower is better. Although the physical property about a heat sealing | fusion layer is not specifically limited, In consideration of melting | fusing point of a base material layer, it is preferable that the melting | fusing point exists in the range of 90-145 degreeC.

  The heat-sealing layer can contain a propylene-based random copolymer as a main component and a polyethylene-based resin. The mixing ratio of the propylene random copolymer and the polyethylene resin is preferably 80 to 99% by weight of the propylene random copolymer and 1 to 20% by weight of the polyethylene resin. If the polyethylene resin is less than 1% by weight, a stable heat-sealing strength cannot be obtained, and if it exceeds 20% by weight, the transparency is undesirably lowered.

  The polyethylene resin used in the heat-sealing layer is preferably a linear low density polyethylene. The linear low-density polyethylene is a copolymer of ethylene and an α-olefin having 4 to 8 carbon atoms, and a copolymer of ethylene and octene-1 having 8 carbon atoms is preferable. The density is preferably 0.87 to 0.91 g / cm 3 and the MFR (temperature 190 ° C., load 21.2 N) is 2.0 to 5.0 g / 10 minutes, preferably 2.5 to 3.5 g / 10. Minutes.

  The propylene random copolymer used in the heat-fusible layer may be a propylene-ethylene random copolymer, a propylene-butene random copolymer, a propylene-ethylene-butene random copolymer, or a mixture thereof. preferable.

  The propylene-ethylene random copolymer preferably has an ethylene content of 1 to 6% by weight and a density of 0.89 to 0.92 g / cm 3. The MFR (temperature 230 ° C., load 21.2 N) is 6.0 to 8.0 g / 10 minutes, preferably 6.5 to 7.5 g / 10 minutes, and the melting point is 130 to 150 ° C., preferably 135. It should be ~ 145 ° C. When the ethylene content is less than 1% by weight, the heat-sealing strength tends to deteriorate, and when it exceeds 6% by weight, the smoothness is deteriorated. Further, the density, MFR, and melting point are suitable ranges for obtaining smoothness and heat fusion strength.

  The propylene-butene random copolymer preferably has a butene content of 4 to 8% by weight and a density of 0.89 to 0.92 g / cm 3. The MFR (temperature 230 ° C., load 21.2 N) is 1.0 to 10.0 g / 10 minutes, preferably 3.0 to 6.0 g / 10 minutes, and the melting point is 120 to 150 ° C., preferably 130. It should be ~ 140 ° C. If the butene content is less than 4% by weight, the heat-sealing strength tends to deteriorate, and if it exceeds 8% by weight, the smoothness is deteriorated. Further, the density, MFR, and melting point are suitable ranges for obtaining smoothness and heat fusion strength.

  The propylene-ethylene-butene random copolymer has an ethylene content of 2 to 5% by weight, a butene content of 4 to 8% by weight (the total content of propylene, ethylene and butene is 100% by weight), and a density of 0. The thing of 89-0.92g / cm3 is preferable. The MFR (temperature 230 ° C., load 21.2 N) is 4.0 to 8.0 g / 10 minutes, preferably 5.0 to 7.0 g / 10 minutes, and the melting point is 120 to 140 ° C., preferably It is good that it is 125-135 degreeC. If the ethylene content is less than 2% by weight, the fusing sealability tends to deteriorate, and if it exceeds 5% by weight, molding becomes difficult. On the other hand, if the butene content is less than 4% by weight, the heat-sealing strength becomes unstable, and if it exceeds 8% by weight, molding becomes difficult. Further, the density, MFR, and melting point are suitable ranges for obtaining smoothness and heat fusion strength.

  Moreover, as these mixtures, propylene-ethylene random copolymer and propylene-butene random copolymer, propylene-ethylene random copolymer, propylene-ethylene-butene random copolymer, propylene-butene random copolymer, Examples thereof include a propylene-ethylene-butene random copolymer, or a combination of a propylene-ethylene random copolymer, a propylene-butene random copolymer, and a propylene-ethylene-butene random copolymer. The mixing ratio here may be set as appropriate in consideration of the smoothness, rigidity, heat fusion strength, etc. of the film, and is not particularly limited.

As long as the effects of the present invention are not impaired, the heat-sealing layer is provided with stabilizers such as antioxidants and ultraviolet absorbers, lubricants, nucleating agents, pigments, inorganic fillers, plasticizers, and as necessary. Other polyolefin thermoplastic resin additives and the like may be contained.
Examples of the antioxidant include phenolic antioxidants, phosphorous acid antioxidants, and acrylate antioxidants.

(Layer structure)
The multilayer polypropylene-based stretched film of the present invention contains at least two layers of a base material layer and a heat fusion layer, and the outermost layer of the film is a heat fusion layer.
Hereinafter, description will be given with reference to the drawings as appropriate.
It should be noted that the dimensions such as thickness and size in each drawing are different from the actual ones.
FIG. 1 is a plan view of a multilayer polypropylene-based stretched film, and FIGS. 2 and 3 are enlarged cross-sectional views of the respective embodiments of the film.
As shown in FIG. 1, the multilayer polypropylene-based stretched film is formed in a long band shape in plan view. In the present specification, the long band shape means that the length in one direction is a sufficiently long rectangle compared with the length in the other direction, for example, the length in one direction is twice or more that in the other direction, Preferably it is 4 times or more. The long strip-shaped multilayer polypropylene-based stretched film is wound on a roll and is stored and transported.

(First embodiment)
FIG. 2 is a cross-sectional view of the first embodiment, and is in the form of base material layer 3 / heat fusion layer 2. There is no distinction between the upper surface and the lower surface, and the base material layer 3 may be the upper portion, and the heat fusion layer 2 may be the upper portion. A plurality of layers may be laminated on both the base material layer 3 and the heat sealing layer 2.
This first embodiment is obtained by a simple operation, and it is easy to control the transition of the antifogging agent contained in the base material layer to the heat fusion layer, and adjusts the heat fusion strength and smoothness. It is preferable because it is easy.
(Second Embodiment)
FIG. 3 is a cross-sectional view of the second embodiment, in the form of heat fusion layer 2 / base material layer 3 / heat fusion layer 2.
Since the second embodiment is a heat-sealing layer on both sides, it can be used without front and back classification at the time of bag making and, like the first embodiment, the anti-fogging agent heat-sealing layer contained in the base material layer. This is preferable because it is easy to control the transition to, and it is easy to adjust the thermal fusion strength and smoothness.
(Other embodiments)
The multilayer polypropylene-based stretched film of the present invention may be laminated in a form other than Embodiments 1 and 2 as long as the outermost layer of the film is a heat-sealing layer.

4 and 5 are diagrams showing an example when the film of the first embodiment is applied for food packaging. As shown in FIG. 5, by folding and fusing the heat fusion layer in the outermost layer of the film as the inner side of the bag, it becomes a packaging form and food can be wrapped.
FIG. 5 is an example in which the contact surface with a moisture generation product such as food is a heat-fusible layer, and the anti-fogging components (components (A) to (E) described later) contained in the base material layer. )) Can penetrate into the heat-sealing layer and bleed out to the surface, thereby preventing the clouding phenomenon due to moisture adhesion of food. Also in the second embodiment, the anti-fogging packaging bag that does not cause fogging due to moisture in the internal food is obtained by folding and fusing the heat-fusible layer as the inside of the bag as in FIG. It is done.

  The ratio of the thickness of the heat-seal layer to the thickness of the multi-layer polypropylene-based stretched film (heat-seal layer / multi-layer polypropylene-based stretched film) is not particularly limited. Is preferably 1/50 to 1/3, more preferably 1/50 to 1/5, and particularly preferably 1/30 to 1/10. If the thickness ratio of the seal layer is less than 1/50, the heat-sealing strength when the bag is processed may be insufficient. Further, if the thickness ratio of the seal layer is larger than 1/3, smoothness may be insufficient.

  As other layers other than the base material layer and the heat fusion layer, a gas barrier layer, an antifogging agent volatilization prevention layer, a polyamide resin layer, a metal vapor deposition layer, and the like may be laminated.

  The thickness of the multilayer polypropylene-based stretched film is not particularly limited, but is preferably 15 to 80 μm, and more preferably 15 to 60 μm, which facilitates a balance between smoothness and heat-sealing strength. When the thickness of the film is less than 15 μm, the ratio per surface area of the antifogging component decreases, so that the smoothness may be insufficient due to insufficient surface antifogging agent, and when the thickness exceeds 80 μm, A decrease in heat-sealing strength due to excessive bleeding may be observed.

  The dynamic friction coefficient of the multilayer polypropylene-based stretched film is preferably from 0.1 to 0.4, more preferably from 0.15 to 0.35, and even more preferably from 0.2 to 0.3. If it is less than 0.1, troubles such as collapse of the produced film roll occur, and if it exceeds 0.4, slipping is insufficient, and troubles such as film feeding failure occur. Bag making may not be possible.

  The surface tension of the multilayer polypropylene-based stretched film is preferably 38 to 44 mN / m. When the surface tension is less than 38 mN / m, the expression of antifogging properties may not be sufficient, and when printing, the adhesion of the printing ink may be inferior. When the surface tension exceeds 44 mN / m, bleeding out of the antifogging agent to the surface is severe, which may cause whitening and blocking, and may cause a decrease in thermal fusion strength.

[Method for producing multilayer polypropylene-based stretched film]
A method for producing a multilayer polypropylene-based stretched film is not particularly limited and a known method can be used. However, a step of forming a flat sheet having a multilayer structure by extrusion molding, and then successively biaxially stretching to form a film A stretching step.
The process of forming a flat sheet having a multilayer structure by extrusion is not particularly limited. However, in consideration of production efficiency, each layer of the multilayer is mixed and melted with an internal component in a separate extruder to perform coextrusion. A method of fusing by a method to obtain a fused sheet is preferable.

  A method in particular about mixing of the component (A) etc. in a base material layer is not limited. For example, after preparing a master batch containing a high concentration of component (A) and the like, a method of liquid-adding a mixture of components (A) to (E) melted into an extruder from the side of the extruder, a predetermined concentration The method of mixing with the base resin is mentioned so that, and the method using a masterbatch is preferable because of good workability and stability of concentration.

  The stretching process of biaxial stretching to form a film is a process in which the stretching sheet is subjected to a stretching process, and examples thereof include, but are not particularly limited to, methods such as sequential stretching, simultaneous stretching, and inflation. Although it does not specifically limit as extending | stretching conditions, About sequential extending | stretching, after heating normally the unstretched film to the temperature of 90-140 degreeC, extending 3-7 times in the longitudinal direction, and cooling, it is a tenter type. A method is adopted in which the film is guided to a stretching machine, heated to a temperature of 130 to 175 ° C., stretched 7 to 12 times in the width direction, and then wound after heat setting (heat treatment) at a predetermined temperature.

  The method for producing a multilayer polypropylene-based stretched film may be a post-processing step (corona treatment, settling, etc.) in a normal film, particularly at least for improving the film printability and bleeding of the antifogging component. It is preferable to perform a corona discharge treatment on one side.

[Component (A)]
Component (A) is an antifogging component used in the present invention (hereinafter, component (A), component (B), component (C), component (D) and component (E) are called antifogging components). Among them, it is a component having excellent compatibility with the polypropylene resin, and is used for controlling the dispersion state of the antifogging component in the polypropylene resin. Component (A) is an aliphatic amine ethylene oxide adduct fatty acid ester.
The multilayer polypropylene stretched film of the present invention essentially contains the component (A-1) represented by the general formula (1) and the component (A-2) represented by the general formula (2).

[Component (A-1)]
Component (A-1) is an aliphatic amine ethylene oxide adduct monofatty acid ester, which is a compound represented by the above general formula (1).
In the general formula (1), R ¹ represents an alkyl group, an alkenyl group, an alkadienyl group, or an alkynyl group. R ¹ has 8 to 22 carbon atoms.
The alkyl group may be linear or branched, and is preferably linear from the viewpoint of exerting the effect of the present application.
The number of carbon atoms of R ¹ is 8 to 22, 12 to 18, more preferably 14 to 18, more preferably 16 to 18. If the number of carbon atoms is less than 8, the compatibility with the polypropylene resin is poor, and the heat fusion strength is insufficient due to excessive bleeding. On the other hand, when the carbon number exceeds 22, smoothness is insufficient.

The number of carbon atoms in R ² is preferably 12 to 18, more preferably 14 to 18, particularly preferably 16 to 18. If the number of carbon atoms is less than 8, the compatibility with the polypropylene resin is poor and the heat fusion strength may be insufficient due to excessive bleeding. On the other hand, when the carbon number exceeds 22, smoothness may be insufficient.

  a and b show the average addition mole number of an oxyethylene group. a and b are 0 or more, and a + b is a number satisfying 2-3.

  Component (A-1) is not particularly limited, and examples thereof include lauryl diethanolamine monolaurate, lauryl diethanolamine monomyristate, lauryl diethanolamine monopalmitate, lauryl diethanolamine monostearate, lauryl diethanolamine monooleate, myristyl diethanolamine monolaurate, Myristyl diethanolamine monomyristate, myristyl diethanolamine monopalmitate, myristyl diethanolamine monostearate, myristyl diethanolamine monooleate, palmityl diethanolamine monolaurate, palmityl diethanolamine monomyristate, palmityl diethanolamine monopalmitate, palmityl diethanolamine monostearate , Palmityl diethanolamine monooleate, stearyl diethanolamine monolaurate, stearyl diethanolamine monomyristate, stearyl diethanolamine monopalmitate, stearyl diethanolamine monostearate, stearyl diethanolamine monooleate, oleyl diethanolamine monolaurate, oleyl diethanolamine monomyristate, oleyl Examples include diethanolamine monopalmitate, oleyl diethanolamine monostearate, oleyl diethanolamine monooleate and the like, and may be one or more.

[Component (A-2)]
Component (A-2) is an aliphatic amine ethylene oxide adduct difatty acid ester, which is a compound represented by the general formula (2).
In the general formula (2), R ³ represents an alkyl group, an alkenyl group, an alkadienyl group, or an alkynyl group. R ³ has 8 to 22 carbon atoms.
The alkyl group may be linear or branched, and is preferably linear from the viewpoint of exerting the effect of the present application.
The number of carbon atoms of R ³ is from 8 to 22, 12 to 18, more preferably 14 to 18, more preferably 16 to 18. If the number of carbon atoms is less than 8, the compatibility with the polypropylene resin is poor, and the heat fusion strength is insufficient due to excessive bleeding. On the other hand, when the carbon number exceeds 22, smoothness is insufficient.

R ⁴ preferably has 12 to 18 carbon atoms, more preferably 14 to 18 carbon atoms, and particularly preferably 16 to 18 carbon atoms. If the number of carbon atoms is less than 8, the compatibility with the polypropylene resin is poor and the heat fusion strength may be insufficient due to excessive bleeding. On the other hand, when the carbon number exceeds 22, smoothness may be insufficient.

  c and d show the average addition mole number of an oxyethylene group. c and d are 0 or more, and c + d is a number satisfying 2-3.

  Specific examples of the component (A-2) include lauryl diethanolamine dilaurate, lauryl diethanolamine dimyristate, lauryl diethanolamine dipalmitate, lauryl diethanolamine distearate, lauryl diethanolamine dioleate, myristyl diethanolamine dilaurate, myristyl diethanolamine dimyristate, myristyl. Diethanolamine dipalmitate, myristyl diethanolamine distearate, myristyl diethanolamine diolate, palmityl diethanolamine dilaurate, palmityl diethanolamine dimyristate, palmityl diethanolamine dipalmitate, palmityl diethanolamine distearate, palmityl diethanolamine dioleo , Stearyl diethanolamine dilaurate, stearyl diethanolamine dimyristate, stearyl diethanolamine dipalmitate, stearyl diethanolamine distearate, stearyl diethanolamine dioleate, oleyl diethanolamine dilaurate, oleyl diethanolamine dimyristate, oleyl diethanolamine dipalmitate, oleyl diethanolamine distearate, An oleyl diethanolamine diolate etc. are mentioned, 1 type (s) or 2 or more types may be sufficient. Although there is no limitation in particular about the synthesis method of a component (A-1) and a component (A-2), a mixture is obtained by adjusting the reaction ratio of a fatty acid at the time of esterifying the alkyldiethanolamine and a fatty acid, or alkyldiethanolamine Can be obtained separately from each other after being reacted with the fatty acid.

  The weight ratio (A-1 / A-2) of the component (A-1) to the component (A-2) is 50/50 to 90/10, preferably 60/40 to 90/10, 63/37 to 86/14 is more preferable. If it is less than 50/50, the hydrophobicity of the antifogging component becomes strong, resulting in insufficient bleeding of the antifogging component, resulting in insufficient smoothness. On the other hand, if it exceeds 90/10, the compatibility of the anti-fogging component is lowered, so that the heat fusion strength is lowered.

[Component (B)]
Component (B) is a glycerin fatty acid ester, and is an excellent anti-fogging component used in the present invention, particularly an excellent smoothness component that promotes immediate bleed-out of the entire anti-fogging component.

When the component (B) has a fatty acid residue having 8 to 22 carbon atoms, it is preferable because of good compatibility with the thermoplastic resin, high transparency, and excellent smoothness and antifogging properties.
The number of carbon atoms of the fatty acid residue of component (B) is preferably 12-18, more preferably 14-18, and particularly preferably 16-18. When the number of carbon atoms is less than 8, the compatibility with the polypropylene resin is poor and a transparency failure may occur due to excessive bleeding. On the other hand, when the number of carbon atoms exceeds 22, immediate effects cannot be sufficiently exhibited and smoothness and antifogging properties may be insufficient.

  A component (B) contains a component (B-1) and a component (B-2) essential.

[Component (B-1)]
Component (B-1) is a glycerin monofatty acid ester.
Examples of the component (B-1) include glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin monostearate, glycerin monobehenate, and glycerin monooleate. There may be.

[Component (B-2)]
Component (B-2) is glycerin difatty acid ester.
Examples of the component (B-2) include glycerin dilaurate, glycerin dimyristate, glycerin dipalmitate, glycerin distearate, glycerin dibehenate, and glycerin dioleate. Also good.

  The weight ratio (B-1 / B-2) of the component (B-1) to the component (B-2) is 95/5 to 50/50, preferably 90/10 to 50/50, 80/20 to 60/40 is more preferable. In the case of more than 95/5, the heat fusion strength is lowered. On the other hand, when it is less than 50/50, smoothness is insufficient.

  Although there is no limitation in particular about the synthesis method of a component (B-1) and a component (B-2), For example, when making glycerol and a fatty acid esterify, or making a glycerol ester transesterify a fatty acid ester, for example. A mixture can be obtained by adjusting the reaction ratio. Moreover, about the composition obtained by each reaction, you may use it, mixing the purified product obtained separately.

[Component (C)]
Component (C) is an aliphatic amine ethylene oxide adduct, and is a component that imparts antifogging properties among the antifogging components used in the present invention. Contribute.
Component (C) is an ethylene oxide adduct of an aliphatic amine, which is a compound represented by the above general formula (3).

In general formula (3), R ⁵ represents an alkyl group, an alkenyl group, an alkadienyl group, or an alkynyl group.
R ⁵ has 8 to 22 carbon atoms, e and f are 0 or more, and e + f = 2 to 3 is satisfied.
R ⁵ is preferably an alkyl group or an alkenyl group, and is generally easily available and has good stability. The number of carbon atoms of R ⁵ is from 8 to 22, 8 to 18, more preferably 12 to 18, more preferably 16 to 18. When the carbon number of R ⁵ is less than 8, the compatibility with the polypropylene resin is poor, and the thermal fusion strength is insufficient due to excessive bleeding. On the other hand, if the number of carbon atoms in the R ⁵ is a 22 exceeds smoothness is insufficient.

Specific examples of the component (C) include, for example, lauryl diethanolamine, myristyl diethanolamine, palmityl diethanolamine, stearyl diethanolamine, etc., and may be one or more.
Although there is no limitation in particular about the manufacturing method of a component (C), For example, it can manufacture by making an ethylene oxide addition reaction to an aliphatic amine. Moreover, it can also be made to contain as an unreacted substance by adjusting a reaction ratio at the time of a synthesis | combination of a component (A).

[Component (D)]
Component (D) is an optional component, which is a polyoxyethylene sorbitan fatty acid ester. When component (D) is contained in the multilayer polypropylene film of the present invention, it suppresses excessive bleeding and reduces heat-fusibility. Can be prevented.
Component (D) is a sorbitan fatty acid ester having a polyoxyethylene group. The number of repeating units p of the oxyethylene group in the component (D) is not particularly limited, but is preferably 1 to 30, more preferably 3 to 25, and particularly preferably 10 to 22. When the number of repeating units p of the oxyethylene group is less than 1, the hydrophobicity is strong and the antifogging property may be inhibited. On the other hand, if the number of repeating units p of the oxyethylene group exceeds 30, the hydrophilicity becomes excessive and the compatibility with the polypropylene resin may be hindered.

The fatty acid constituting the component (D) is not particularly limited, and examples thereof include esters of fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid. But you can.
Component (D) may be any of monoesters, diesters, triesters, tetraesters, etc., and has an intermediate degree of esterification such as the reaction mole number of fatty acid to sorbitan is 1.5 or 2.5. Things can also be used. Moreover, you may be comprised from 1 type, or 2 or more types.

The number of carbon atoms of the fatty acid residue of component (D) is preferably 8 to 22, more preferably 12 to 18, still more preferably 14 to 18, and particularly preferably 16 to 18. When the number of carbon atoms is less than 8, the compatibility with the polypropylene resin is poor, and the heat fusion property due to excessive bleeding may be insufficient. On the other hand, when the carbon number exceeds 22, smoothness may be insufficient.
Examples of such fatty acid residues include fatty acid residues (D) represented by the following general formula (4).

R ⁶ CO- (4)
(In the formula, R ⁶ is an alkyl group, an alkenyl group, an alkadienyl group or an alkynyl group, and the carbon number thereof is 7 to 21.)
R ⁶ is preferably an alkyl group or an alkenyl group, which is generally easily available and has good stability.

Specific examples of component (D) include, for example, POE (p) sorbitan laurate, POE (p) sorbitan myristate, POE (p) sorbitan palmitate, POE (p) sorbitan stearate, etc. Or 2 or more types may be sufficient. Here, POE means a (poly) oxyethylene group, and p means the number of repeating units of the oxyethylene group, as described above.
The production method of component (D) is not particularly limited. For example, 1) esterification of sorbitan and fatty acid, and reaction of the resulting esterified product with ethylene oxide, or 2) fatty acid ester of sorbitan ester Transesterification, the resulting esterified product is reacted with ethylene oxide, 3) sorbitan is reacted with ethylene oxide, the resulting adduct is esterified with fatty acid, and 4) the sorbitan ester is ethylene oxide. Can be produced by subjecting the resulting adduct to transesterification with a fatty acid ester. Among these, the production method 1) is preferable.

[Component (E)]
Component (E) is a polyglycerin fatty acid ester and is an optional component.
When the component (E) is used in the multilayer polypropylene film of the present invention, it is possible to suppress excessive bleeding and prevent a decrease in heat fusibility.
Component (E) is an ester derivative of polyglycerol. Examples of the polyglycerin constituting the component (E) include diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nonaglycerin, decaglycerin, and the like. That's all. Component (E) is not particularly limited as long as it is a fatty acid ester, and examples thereof include esters of fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid, and the like. But you can.

As the component (E), those having various degrees of esterification can be used, and any of monoesters, diesters, triesters, tetraesters, etc. can be used. Those having an intermediate degree of esterification such as 2.5 can also be used. Moreover, you may be comprised from 1 type, or 2 or more types.
There is no limitation in particular about the average degree of polymerization of the polyglycerol which comprises a component (E), the esterification degree of a component (E), etc.

The average degree of polymerization of polyglycerol is preferably 3 to 10, more preferably 4 to 8, and particularly preferably 4 to 6. If the average degree of polymerization of polyglycerin is less than 3, bleeding may occur and heat fusion may be impaired. On the other hand, if the average degree of polymerization of polyglycerin exceeds 10, bleeding may occur and smoothness may be inhibited.
In the component (E), when the degree of esterification (the number of moles of fatty acid that reacts with 1 mol of polyglycerol) is y and the average degree of polymerization of polyglycerol is x, the relationship of y ≦ x + 2 holds. y is preferably y <x. In this case, the antifogging component has good hydrophilicity and excellent immediate effect. Further, in the case of 4 ≦ x ≦ 6, it is particularly preferable that 1 ≦ y ≦ 3 because the balance between the immediate effect and the suppression effect against excessive bleeding can be obtained. When y ≧ x, the hydrophobicity of the antifogging component becomes too high, and the immediate effect may be impaired.

  The number of carbon atoms of the fatty acid residue constituting the component (E) is preferably 8 to 22, more preferably 12 to 18, still more preferably 14 to 18, and particularly preferably 16 to 18. When the number of carbon atoms exceeds 8, the compatibility with the polypropylene resin is poor, and poor heat fusion due to excessive bleeding may be caused. On the other hand, if the carbon number exceeds 22, the antifogging property may be insufficient.

  Although there is no limitation in particular about the manufacturing method of a component (E), For example, polyglycerol and a fatty acid can be esterified, or it can manufacture by making a polyglycerol ester transesterify a fatty acid ester.

(Composition of anti-fogging ingredients)
The multilayer polypropylene-based stretched film of the present invention contains the component (A), the component (B) and the component (C) as essential components for the antifogging component, and the component (D) or the component (E) as an optional component. May be contained.

  The weight ratio of component (A) is preferably 30 to 89% by weight with respect to the total amount of component (A), component (B), component (C), component (D) and component (E), More preferably, it is 35-80 weight%, Most preferably, it is 40-70 weight%. When the blending ratio of the component (A) is less than 30% by weight, the compatibility with the polypropylene resin is deteriorated, and the film anti-fogging component is excessively bleed and the film transparency is deteriorated and the heat fusion strength is sometimes lowered. On the other hand, if the blending ratio of component (A) is more than 89% by weight, smoothness may be lowered.

  The blending ratio of component (B) is preferably 5 to 50% by weight based on the total amount of component (A), component (B), component (C), component (D) and component (E), More preferably, it is 8-40 weight%, Most preferably, it is 10-25 weight%. If the blending ratio of the component (B) is less than 5% by weight, the immediate effect of bleed may be inhibited and the smoothness may be lowered. On the other hand, when the blending ratio of the component (B) is more than 50% by weight, the film transparency may be deteriorated or the heat-sealing strength may be lowered due to excessive bleeding of the antifogging component.

  The blending ratio of the component (C) is preferably 5 to 50% by weight based on the total amount of the component (A), the component (B), the component (C), the component (D) and the component (E). More preferably, it is 8-40 weight%, Most preferably, it is 10-30 weight%. Smoothness may fall that the mixture ratio of a component (C) is less than 5 weight%. On the other hand, if the blending ratio of component (C) is more than 50% by weight, the surface of the film may become sticky due to excess bleed and the thermal fusion strength may be lowered.

  When the film of this invention contains a component (D) or a component (E), the weight ratio of a component (D) and a component (E) is a component (A), a component (B), a component (C), a component Preferably it is 1-20 weight% with respect to the total amount of (D) and a component (E), More preferably, it is 3-15 weight%, Most preferably, it is 5-10 weight%. When the blending ratio of the component (D) and the component (E) is less than 1% by weight, the film anti-fogging component may be excessively bleed, resulting in deterioration of film transparency and thermal fusion strength. On the other hand, when the blending ratio of the components (D) and (E) is more than 20% by weight, the smoothness may be deteriorated due to bleed suppression more than necessary.

〔Master Badge〕
The masterbatch of the present invention is a masterbatch containing a polypropylene resin, component (A), component (B), and component (C),
The component (A) is an aliphatic amine ethylene oxide adduct mono-fatty acid ester represented by the general formula (1), and an aliphatic amine ethylene represented by the general formula (2). Component (A-2) which is an oxide adduct difatty acid ester,
The weight ratio (A-1 / A-2) of the component (A-1) and the component (A-2) is 50/50 to 90/10,
The component (B) includes a component (B-1) that is a glycerin monofatty acid ester and a component (B-2) that is a glycerin difatty acid ester,
The weight ratio (B-1 / B-2) of the component (B-1) and the component (B-2) is 95/5 to 50/50, and the component (C) is represented by the following general formula (3) ).
About a component (A), a component (B), a component (C) component (A-1) component (A-2) component (B-1) component (B-2), what was described with the film mentioned above. Can be used.

The shape of the masterbatch is preferably similar to that of the raw material resin from the viewpoint of effectively expressing the effect of the present application by ensuring uniform mixing with the raw material resin, and generally sold resin shapes In view of the above, a cylindrical similar shape is more preferable.
The diameter of the master batch is preferably 1 mm to 5 mm, more preferably 2 mm to 4 mm in consideration of uniform mixing properties.
Bulk density of the masterbatch, in view of the uniform mixability, preferably 0.5~0.7g / cm ^3, more preferably 0.55~0.60g / cm ^3.
The water content of the masterbatch is preferably less than 1000 ppm in order to prevent thermal decomposition of the antifogging component during mixing with the raw material resin and to prevent alteration of the blend composition of the present application.

  The polypropylene resin constituting the master batch is obtained by polymerizing a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-ethylene-α-olefin ternary random copolymer, and a monomer mainly composed of propylene. Polypropylene copolymer obtained by producing a copolymer component obtained by polymerizing a monomer comprising propylene, ethylene, and / or an α-olefin having 4 to 12 carbon atoms in multiple stages of at least two stages Examples include coalescence. A propylene homopolymer, a propylene-ethylene random copolymer, or a propylene-ethylene-α-olefin ternary random copolymer is preferable. These may be used alone or in combination of two or more.

Examples of the α-olefin include α-olefins having 4 to 12 carbon atoms, such as 1-butene, 2-methyl-1-propene, 1-pentene, 2-methyl-1-butene, and 3-methyl-1. -Butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3 , 3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl- 1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, di Examples thereof include ethyl-1-butene, 1-nonene, 1-decene, 1-undecene and 1-dodecene. Preferred is 1-butene, 1-pentene, 1-hexene or 1-octene, and more preferred is 1-butene or 1-hexene from the viewpoints of copolymerization properties, economy and the like.
The content of ethylene and / or α-olefin in the copolymer is usually 0.1 to 20% by weight, preferably 1 to 10% by weight.

  In the case of a propylene homopolymer, the maximum peak temperature of the crystal melting heat by the differential scanning calorimetry of the thermoplastic resin masterbatch composition containing a low bleed antistatic agent is preferably 165 ° C or higher.

[Manufacturing method of masterbatch]
There is no restriction | limiting in particular about the manufacturing method of the masterbatch of this invention, It can manufacture by a well-known method as a manufacturing method of the masterbatch which used the conventional polyolefin as base resin. For example, a material obtained by homogenizing the above raw materials with a known mixing apparatus (eg, tumbler mixer, super mixer, Henschel mixer, screw blender, ribbon blender, etc.) is melt kneaded (eg, a single screw extruder, a multi-screw machine having two or more screws). And a kneading method using a screw extruder, a Banbury mixer, a kneader, or the like.

  The kneaded master batch is preferably in the form of pellets, which makes the master batch easier to handle. The method of pelletization is arbitrary, and a known method is used. For example, there is a method of hot cutting or strand cutting simultaneously with kneading using the melt kneading machine or while extruding what has been kneaded in advance with, for example, a feeder ruder.

  In this case, the cutting may be performed in water or may be performed while blowing air. Furthermore, after uniform mixing, it may be formed into a sheet with two rolls or the like and pelletized with a sheet pelletizing machine.

  Although there is no restriction | limiting in particular as a shape of a pellet at this time, The diameter 0.5-5mm, length 0.5-5mm cylindrical pellet, and the flat disk type | mold pellet of diameter 0.5-5mm are mentioned.

  The master batch of the present invention may contain additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, a flame retardant, a nucleating agent, and a pigment as necessary.

[Anti-fogging agent]
The antifogging agent of the present invention comprises a component (A), a component (B), and a component (C),
The component (A) includes the component (A-1) represented by the general formula (1) and the component (A-2) represented by the general formula (2), and the component (A-1 ) And the component (A-2) (A-1 / A-2) is 50/50 to 90/10,
The component (B) includes a component (B-1) and a component (B-2),
The weight ratio (B-1 / B-2) of the component (B-1) and the component (B-2) is 95/5 to 50/50, and the component (C) is represented by the general formula (3). ) Is an antifogging agent for thermoplastic resin films.
About a component (A), a component (B), a component (C) component (A-1) component (A-2) component (B-1) component (B-2), what was described with the film mentioned above. Can be used.

  The thermoplastic resin to which the antifogging agent for thermoplastic resin film can be applied is not particularly limited, but for example, polyolefin resin, polystyrene resin, acrylic resin, vinyl resin, polyamide resin, polyester resin, polyacetal resin, polycarbonate resin, heat Examples thereof include a plastic polyurethane resin, a fluororesin, and a mixture of two or more thereof.

  Examples of the polyolefin resin include homopolymers of α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 4-methyl-1-pentene, copolymers of the α-olefins, Examples thereof include a copolymer of a monomer other than an α-olefin copolymerizable with the α-olefin and an α-olefin, a mixture thereof, and the like. Examples of the monomer other than the α-olefin copolymerizable with the α-olefin include vinyl acetate, maleic acid, methacrylic acid, methyl methacrylate, and ethyl methacrylate.

  Examples of the polystyrene resin include a styrene homopolymer, a copolymer of a monomer copolymerizable with styrene and styrene, and the like. Specific examples include polystyrene, acrylonitrile-styrene resin (AS), and acrylonitrile-butadiene-styrene resin (ABS).

  Examples of the vinyl resin include diene polymers such as butadiene resin and polyisoprene resin.

  Examples of the polyamide resin include nylon.

  Examples of the polyester resin include aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polybutylene adipate, polyethylene succinate, polybutylene succinate, polyethylene succinate, polybutylene succinate adipate, and polyethylene succinate adipate. And aliphatic polyesters such as polycaprolactone and polylactic acid.

  Examples of the polyacetal resin include formaldehyde or trioxane polymers.

  Examples of the polycarbonate resin include a condensate of bisphenol A and phosgene and a condensate of bisphenol A and carbonic acid diester.

  Examples of the thermoplastic polyurethane resin include a reaction product of an organic diisocyanate and a polymer diol.

  An example of the fluororesin is a polymer of a fluorine-containing monomer.

  Among these, as the crystalline thermoplastic resin contained in the masterbatch of the present invention, a polyolefin resin is preferable, and polypropylene and polyethylene having a glass transition point lower than room temperature are more preferable. Among these, polypropylene is preferable because it is easy to control the balance between smoothness and heat fusion strength.

The present invention will be described in detail in the following examples and comparative examples, but the present invention is not limited to these examples.
The physical properties of the polypropylene-based stretched film in the examples were evaluated by the following methods.

(Film heat fusibility)
The conditions of a temperature of 140 ° C., a pressure of 1 kg / cm ² , and a heat fusion time of 1 second using a heat sealer as the seal surface is the anti-fogging surface (heat fusion layer surface) of the polypropylene-based stretched film after storage at 40 ° C. for 10 days. In processing. The film is cut into a width of 15 mm, the adhesive strength of the seal is measured using a tensile tester, and the relative strength when the adhesive strength of the antifoggant-free film is taken as 100 is shown. Evaluation is based on the evaluation criteria shown below.
○: 85 or more ×: less than 85

(Film smoothness)
For a polypropylene-based stretched film, the dynamic friction coefficient (μd) after storage at 40 ° C. for 1 day was measured using a friction measuring device TR-2 (manufactured by Toyo Seiki). JIS K7125-ISO 8295 (plastic-film and sheet-friction coefficient) Measure according to the test method). The measurement conditions were as follows: temperature and humidity 20 ° C. × 45% R.D. H. It is. Evaluation is based on the evaluation criteria shown below.
○: 0.1 to 0.4
Excessive smoothness: 0 or more and less than 0.1 Insufficient smoothness: More than 0.4

(Film defogging)
A glass beaker having a capacity of 100 ml was charged with 60 ml of 30 ° C. water, and the mouth of the beaker was sealed and sealed with the heat-sealed layer surface of the stretched film after storage at 40 ° C. for 1 day. Subsequently, it puts in a 5 degreeC thermostat, observes the adhesion state of the water droplet to the film inner surface 24 hours later, and evaluates based on the evaluation criteria shown below.
○: No water droplets and the entire surface is wet.
(Triangle | delta): Although it is not cloudy, it is in the state where a big water droplet is scattered.
X: The whole is cloudy white and the contents are difficult to see.

(Film transparency)
After the polypropylene-based stretched film is stored at 40 ° C. for 10 days, the color difference / turbidity measuring device (manufactured by Nippon Denshoku Industries Co., Ltd.) is used to determine the Haze value of the film and ΔHaze (the Haze value before and after lightly washing the film surface with ethanol). Measure the difference. ΔHaze is evaluated based on the evaluation criteria shown below.
○: 0.0 or more and less than 0.6 Δ: 0.6 to 0.9
×: More than 0.9

(Film production)
Example 1
The components (A) to (E) as anti-fogging components at the blending ratio shown in Table 1 were mixed so as to be 10% by weight with respect to polypropylene (homopolymer, MFR = 2.5 g / 10 min), and biaxial A strand was obtained by melt-kneading at 230 ° C. in an extruder. The obtained strand was cut with a pelletizer to prepare a master batch. The master batch was obtained as a cylinder-like shape having a diameter of about 3 mm and a height of about 3 mm, and had a bulk specific gravity of 0.57 g / cm ³ and a water content of 40 ppm.

(Embodiment 1)
Next, the obtained master batch and a separately prepared polypropylene homopolymer were mixed so as to have the ratio shown in Table 1, to prepare an extrusion raw material, put into one twin-screw extruder, put into another extruder Is a polypropylene-ethylene-1-butene random copolymer, co-extruded at a melting temperature of 230 ° C. using the former as a base material layer and the latter as a heat-sealing layer, and having a thickness of 300 μm with a cooling drum at 40 ° C. It was collected on a roll as a sheet. After cutting this unstretched sheet to 3 cm x 3 cm, while heating to 150 ° C, it was stretched by a batch-type simultaneous stretching apparatus at a magnification of 3 times in the longitudinal direction and 5 times in the width direction, 9 cm x 15 cm, thickness A film having a thickness of 20 μm (base layer: 18 μm, thermal fusion layer: 2 μm) was obtained.
The heat-bonded layer of the stretched film thus obtained was subjected to corona discharge treatment so that the surface tension was 40 dyne / cm, and heat-set at 40 ° C. for 8 hours. The wearing strength was evaluated. The results are shown in Table 2.

(Example 1-2)
(Embodiment 2)
The above masterbatch and a separately prepared polypropylene homopolymer were mixed so as to have the ratio shown in Table 1, the extrusion raw material was adjusted, and the mixture was put into one twin-screw extruder, and the other two extruders were polypropylene- An ethylene-1-butene random copolymer was introduced, and the former was used as a base material layer and the latter as a heat sealing layer, and the heat sealing layer was in contact with both sides of the base material layer at a melting temperature of 230 ° C. The sheet was extruded and collected on a roll as a sheet having a thickness of 300 μm using a cooling drum at 40 ° C. After cutting this unstretched sheet to 3 cm x 3 cm, while heating to 150 ° C, it was stretched by a batch-type simultaneous stretching apparatus at a magnification of 3 times in the longitudinal direction and 5 times in the width direction, 9 cm x 15 cm, thickness A film of 22 μm (base layer: 18 μm, double-sided heat-sealing layer: 2 μm each) was obtained.
The heat-bonded layer of the stretched film thus obtained was subjected to corona discharge treatment so that the surface tension was 40 dyne / cm, and heat-set at 40 ° C. for 8 hours. The wearing strength was evaluated. The results are shown in Table 2.

(Examples 2 to 22, Examples 2-2 and 3-2, Comparative Examples 1 to 5)
In the same manner as in Example 1 except that the components used in Example 1 for Component (A) to Component (E) were replaced with the components described in Table 1, Examples 2 to 22 and Comparative Examples 1 to 2 were used. A stretched film was prepared for No. 5 and evaluated for antifogging properties, transparency, and heat fusion strength. In Embodiment 2, stretched films were prepared and evaluated for Examples 2-2 and 3-2. The results are shown in Table 2.

As can be seen from Tables 1 and 2, it was confirmed that the multilayer polypropylene-based stretched film of the present invention has excellent smoothness and does not cause a decrease in heat-sealing strength.
On the other hand, since the film of Comparative Example 1 does not contain the component (A), the compatibility with the resin is insufficient, and it is considered that the heat fusion strength is reduced by the additive excessively bleeding on the surface. Since the film of Comparative Example 2 did not contain the component (B), an immediate effect was not obtained, and the smoothness decreased due to the lack of smooth components. Since the film of Comparative Example 3 did not contain component (C), sufficient smoothness could not be obtained. In Comparative Example 4 and Comparative Example 5, the ratios of Component A-1 and Component B-1 were small, so the hydrophobicity of the antifogging component became strong, and the smoothness was insufficient due to insufficient bleeding of the antifogging component.

1 Film 2 Heat Fusion Layer 3 Base Material Layer 4 Heat Seal (Heat Fusion)

Claims (7)

A multilayer polypropylene-based stretched film containing a base material layer and a heat-fusible layer,
The thermal fusion layer is on the outermost layer of the film;
The base material layer is a polypropylene resin, a component (A) that is an aliphatic amine ethylene oxide adduct fatty acid ester, a component (B) that is a glycerin fatty acid ester, and a component that is an aliphatic amine ethylene oxide adduct ( C) and
The component (A) is an aliphatic amine ethylene oxide adduct mono-fatty acid ester represented by the following general formula (1), and an aliphatic amine ethylene represented by the following general formula (2) Component (A-2) which is an oxide adduct difatty acid ester,
The weight ratio (A-1 / A-2) of the component (A-1) and the component (A-2) is 50/50 to 90/10,
The component (B) includes a component (B-1) that is a glycerin monofatty acid ester and a component (B-2) that is a glycerin difatty acid ester,
The weight ratio (B-1 / B-2) of the component (B-1) and the component (B-2) is 95/5 to 50/50, and the component (C) is represented by the following general formula (3) The multilayer polypropylene-type stretched film which is a compound shown by this.

(In the formula, R ¹ and R ² are each independently an alkyl group, an alkenyl group, an alkadienyl group, or an alkynyl group. R ¹ has 8 to 22 carbon atoms, and R ² has 7 to 21 carbon atoms. A and b represent the average number of moles of oxyethylene group added, a and b are 0 or more, and a + b is a number satisfying 2 to 3.)

(In the formula, R ³ and R ⁴ are each independently an alkyl group, an alkenyl group, an alkadienyl group, or an alkynyl group. Two R ^{4 s} may be the same as or different from each other. R ³ The carbon number of R ⁴ is 8 to 22, the carbon number of R ⁴ is 7 to 21, c and d represent the average number of moles added of the oxyethylene group, c and d are 0 or more, and c + d = 2 to 2 It is a number that satisfies 3.)

(In the formula, R ⁵ represents an alkyl group, an alkenyl group, an alkadienyl group or an alkynyl group, the carbon number thereof is 8 to 22, e and f represent the average number of added moles of the oxyethylene group, and e and f are It is 0 or more and is a number satisfying e + f = 2 to 3.)   The multilayer polypropylene-based stretched film according to claim 1, wherein the base material layer further comprises a component (D) that is a polyoxyethylene sorbitan fatty acid ester and / or a component (E) that is a polyglycerol fatty acid ester.   The weight ratio of the component (A) is 30 to 89% by weight with respect to the total weight of the component (A), the component (B), the component (C), the component (D), and the component (E). The weight ratio of the component (B) is 5 to 50% by weight, the weight ratio of the component (C) is 5 to 50% by weight, the weight ratio of the component (D) and / or the component (E) is 1 to The multilayer polypropylene-based stretched film according to claim 1 or 2, which is 20% by weight.   The multilayer polypropylene-based stretched film according to claim 2 or 3, wherein the component (D) has 1 to 30 moles of oxyethylene groups added to sorbitan fatty acid ester and has a fatty acid residue having 8 to 22 carbon atoms. .   The multilayer polypropylene-based stretched film according to any one of claims 2 to 4, wherein the component (E) is an ester derivative of polyglycerol having an average degree of polymerization of 2 to 10, and has a fatty acid residue having 8 to 22 carbon atoms. . A masterbatch comprising a polypropylene resin, a component (A) that is an aliphatic amine ethylene oxide adduct fatty acid ester, a component (B) that is a glycerin fatty acid ester, and a component (C) that is an aliphatic amine ethylene oxide adduct Because
The component (A) is an aliphatic amine ethylene oxide adduct mono-fatty acid ester represented by the following general formula (1), and an aliphatic amine ethylene represented by the following general formula (2) Component (A-2) which is an oxide adduct difatty acid ester,
The weight ratio (A-1 / A-2) of the component (A-1) and the component (A-2) is 50/50 to 90/10,
The component (B) includes a component (B-1) that is a glycerin monofatty acid ester and a component (B-2) that is a glycerin difatty acid ester,
The weight ratio (B-1 / B-2) of the component (B-1) and the component (B-2) is 95/5 to 50/50, and the component (C) is represented by the following general formula (3) A master batch which is a compound represented by

(In the formula, R ¹ and R ² are each independently an alkyl group, an alkenyl group, an alkadienyl group, or an alkynyl group. R ¹ has 8 to 22 carbon atoms, and R ² has 7 to 21 carbon atoms. A and b represent the average number of moles of oxyethylene group added, a and b are 0 or more, and a + b is a number satisfying 2 to 3.)

(In the formula, R ³ and R ⁴ are each independently an alkyl group, an alkenyl group, an alkadienyl group, or an alkynyl group. Two R ^{4 s} may be the same as or different from each other. R ³ The carbon number of R ⁴ is 8 to 22, the carbon number of R ⁴ is 7 to 21, c and d represent the average number of moles added of the oxyethylene group, c and d are 0 or more, and c + d = 2 to 2 It is a number that satisfies 3.)

(In the formula, R ⁵ represents an alkyl group, an alkenyl group, an alkadienyl group or an alkynyl group, the carbon number thereof is 8 to 22, e and f represent the average number of added moles of the oxyethylene group, and e and f are It is 0 or more and is a number satisfying e + f = 2 to 3.) A component (A) that is an aliphatic amine ethylene oxide adduct fatty acid ester, a component (B) that is a glycerin fatty acid ester, and a component (C) that is an aliphatic amine ethylene oxide adduct,
The component (A) is an aliphatic amine ethylene oxide adduct mono-fatty acid ester represented by the following general formula (1), and an aliphatic amine ethylene represented by the following general formula (2) Component (A-2) which is an oxide adduct difatty acid ester,
The weight ratio (A-1 / A-2) of the component (A-1) and the component (A-2) is 50/50 to 90/10,
The component (B) includes a component (B-1) that is a glycerin monofatty acid ester and a component (B-2) that is a glycerin difatty acid ester,
The weight ratio (B-1 / B-2) of the component (B-1) and the component (B-2) is 95/5 to 50/50, and the component (C) is represented by the following general formula (3) An antifogging agent for a thermoplastic resin film, which is a compound represented by

(Wherein R ¹ and R ² are an alkyl group, an alkenyl group, an alkadienyl group or an alkynyl group, the carbon number thereof is R ¹ = 8 to 22, R ² = 7 to 21, and a and b are 0 or more. a + b = 2 to 3)

(Wherein R ³ and R ⁴ are an alkyl group, an alkenyl group, an alkadienyl group or an alkynyl group, the carbon number thereof is R ³ = 8 to 22, R ⁴ = 7 to 21, and c and d are 0 or more. (c + d = 2 to 3)

(In the formula, R ⁵ is an alkyl group, an alkenyl group, an alkadienyl group or an alkynyl group, R ⁵ has 8 to 22 carbon atoms, and e and f are 0 or more and satisfy e + f = 2 to 3). is there.)

Images