JPH11320776A - Laminated film and bag - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent antiblocking properties, antistatic properties, and transparency by laminating respectively specified amounts of a polyolefin resin, an aromatic vinyl elastomer, spherical resin particles of specified particle size and sphericity, and others in turn. SOLUTION: A polyolefin resin composition of a polyolefin resin A, 100, 2-10 pts.wt. of an aromatic vinyl elastomer, 0.03-0.5 pt.wt. of spherical resin fine particles C of 0.5-8 μm average particle size and of 0.8 or above sphericity of the formula: f=[M/(π/4)]<0.5> /Nmax , 0.03-0.4 pt.wt. of a higher fatty acid amide D, and 0.05-1.5 pts.wt. of an aliphatic monocarboxylic acid partial ester of a tetra-hexavalent polyol, an amorphous polyolefin or linear polyethylene resin, and a polyolefin resin composition comprising 100 pts.wt. of A, 0.01-0.5 pt.wt. of C, and 0.01-0.3 pt.wt. of D are laminated in turn. In the formula, M represents an optional cross-sectional area mm<2> of the fine particles; Nmax represents the longest diameter of the cross section.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated film and a bag manufactured from the laminated film.

[0002]

2. Description of the Related Art Polyolefin resin films are widely used as packaging films because of their easy workability and low cost. However, when a polyolefin-based resin is processed into a film, the film is liable to cause blocking, which may impair workability during film forming and high-order processing. In addition, when the film is used, for example, for packing or wrapping, troubles such as poor opening of the bag are likely to occur. In addition, since the polyolefin resin is hydrophobic, it has a strong chargeability, and a single-layer or multi-layer film formed from the resin is likely to cause a problem such as dust adhesion during the processing step or use.

[0003] In order to solve such disadvantages, there has been proposed a method for improving the slipperiness of a film by blending fine particles of silicic anhydride, kaolinite, zeolite or the like with a polyolefin resin. In addition, Japanese Patent Publication No. 5-28262 and Japanese Patent Publication No.
Japanese Patent Application Laid-Open No. 11550 and Japanese Patent Application Laid-Open No. Hei 7-258487 propose that a non-melting silicone resin is blended with a polypropylene polymer.

[0004] However, such a film to which only the non-melting type silicone resin fine particles are added has a certain effect in terms of blocking resistance, but in terms of the slipperiness of the film, it has been required to increase the speed of recent packaging. There is almost no effect in the machine, and in order to obtain a sufficient effect, a large amount of the fine particles must be added, and there is a disadvantage that the transparency is significantly impaired. Furthermore, when these non-melting silicone resins are blended with a polypropylene polymer, the former has a problem that the refractive index is significantly different from the latter refractive index of 1.5, so that the transparency is impaired.

Japanese Patent Application Laid-Open No. 7-138415 proposes a composition in which a silicone-based graft polymer is blended with a polyolefin-based resin, but depending on the shape, particle size, and refractive index of the silicone-based graft polymer. Transparency and slipperiness may decrease. Further, this composition is also unsuitable for a film which requires a high degree of transparency, since transparency is reduced by the blending of the polymer.

Japanese Patent Application Laid-Open No. 9-165519 discloses that 100 parts by weight of a thermoplastic resin has an average particle size of 0.1 to 2 parts by weight.
Although 0.1 to 10 parts by weight of 0 μm crosslinkable spherical fine particles are blended, when the blending amount in this range is used, the use of crosslinked spherical fine particles having an average particle diameter of more than 10 μm causes a significant decrease in transparency. Even with particles having the following particle sizes, a decrease in transparency due to a large dividend as described above was inevitable. Further, bags made from these films have a problem that the coefficient of kinetic friction is still too large and the opening of the bags is not sufficient.

There is a method of kneading a known cationic or anionic surfactant as a kneading type antistatic agent into a polyolefin resin in order to prevent the film from being charged. However, when the surfactant is kneaded, the obtained film is inferior in heat resistance, and the appearance quality is deteriorated due to coloring. As a way to overcome this,
JP-A-8-59852 proposes a method in which spherical organic fine particles are combined with a specific amide and blended into a polyolefin resin. However, even if such a combination alone can provide an antistatic effect, bags made from this film have the same kinetic friction coefficient as described above, and the opening of the bags is not sufficient. There was a problem that the durability of the prevention performance was poor.

[0008] Further, when the articles to be packaged are stacked in bags, they often collapse, and in order to prevent this, the surface is subjected to corona discharge treatment or chemically roughening treatment. Have been done. However, these methods require costly equipment and require a long curing time in order to stably obtain the effect of preventing collapse of the load.

[0009]

SUMMARY OF THE INVENTION In view of the above-mentioned drawbacks, an object of the present invention is to provide a laminated film having excellent anti-blocking properties, antistatic properties and transparency, and anti-blocking properties and antistatic properties obtained from the laminated film. An object of the present invention is to provide a bag which is excellent in the properties, transparency, opening property and load-carrying prevention property.

[0010]

The laminated film of the present invention has a polyolefin resin (A) of 100 parts by weight, a vinyl aromatic elastomer (B) of 2 to 10 parts by weight, and an average particle size of 0.5 to 8 μm. F = [M / (π / 4)] ^0.5 / Nmax (where M is an arbitrary cross-sectional area mm ² of the fine particles, Nmax
Represents the longest diameter mm of the section. A) spherical resin fine particles (C) having a sphericity f of 0.8 or more
03 to 0.5 parts by weight, higher fatty acid amide (D) 0.03 to
A polyolefin-based resin composition layer (x) comprising 0.4 parts by weight and 0.05 to 1.5 parts by weight of an aliphatic monocarboxylic acid partial ester (E) of a 4- to 6-valent polyol, propylene and / or butene-1 Resin layer (y) composed of an amorphous polyolefin resin having a content of 50% by weight or more or a linear polyethylene resin polymerized using a metallocene catalyst, and 100 parts by weight of polyolefin resin (A), average F = [M / (π / 4)] ^0.5 / Nmax (where M is an arbitrary cross-sectional area mm ² of the fine particles, Nmax
Represents the longest diameter mm of the section. A) spherical resin fine particles (C) having a sphericity f of 0.8 or more
01 to 0.5 part by weight and higher fatty acid amide (D) 0.01
To 0.3 part by weight of a polyolefin resin composition layer
(z) are sequentially laminated.

The polyolefin resin used in the present invention
(A) is a polymer mainly composed of an olefin monomer,
For example, polyethylene, polypropylene, poly (4-methyl-1-pentene), ethylene-propylene copolymer,
Examples include an ethylene-propylene-diene monomer copolymer and an ethylene-vinyl acetate copolymer.

The vinyl aromatic elastomer (B) used in the present invention comprises a vinyl aromatic compound (F) and a conjugated diene.
(G) is copolymerized with F- (GF) _l (l represents an integer of 1 or more) or (FG) _m (m represents an integer of 1 or more). Block copolymers or random copolymers and hydrogenated products of these copolymers,
And FG type copolymers are preferred.

The vinyl aromatic compound includes, for example, styrene, t-butyl styrene, α-methyl styrene, p-methyl styrene, 1,1-diphenyl styrene and the like, and styrene and α-methyl styrene are preferred. Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 2-methyl-1,3-
Examples thereof include pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, and chloroprene, and 1,3-butadiene and isoprene are preferred.

The vinyl aromatic elastomer (B) is preferably a styrene-butadiene random copolymer, a styrene-isoprene-styrene block copolymer or a hydrogenated product thereof. As the hydrogenated product of the styrene-isoprene-styrene block copolymer, a styrene-ethylene-propylene-styrene copolymer and a hydrogenated styrene-isoprene-styrene block copolymer having 3,4 isoprene bonds are particularly preferable.

The spherical resin fine particles (C) used in the present invention
Has an average particle size of 0.5 to 8 μm, and f = [M / (π / 4)] ^0.5 / Nmax (where M is an arbitrary cross-sectional area mm ² of the fine particles, Nmax
Represents the longest diameter mm of the section. ) Are spherical resin fine particles having a sphericity f of 0.8 or more.

When the average particle size of the spherical resin fine particles (C) is small, the slipperiness is reduced, and when the average particle size is large, the transparency is reduced. Therefore, the average particle size is limited to 0.5 to 8 μm, preferably 1.5 to
３3 μm.

As the spherical resin fine particles (C), a true spherical one is excellent for imparting effects such as good slipperiness and high transparency. In the sphericity f defined above, M is a cross-sectional area (mm ² ) when cut at an arbitrary angle including the center of the fine particles.
And Nmax represents the longest diameter (mm) in the cross section. The sphericity f is 0.8 or more, preferably 0.85 or more.

The resin forming the spherical resin fine particles (C) is not particularly limited, but is preferably generally available, has excellent dispersibility in the polyolefin resin, and is close to the refractive index of the polyolefin resin. Resin, silicone rubber, polyamide, condensation type resin having a triazine ring, cross-linked polymethyl methacrylate, cross-linked polystyrene and the like.

Above all, when the sliding property is particularly important,
Silicone resin and silicone rubber are preferable, and when transparency is important, cross-linked polymethyl methacrylate and silicone acrylic copolymer are preferable.

In particular, as spherical resin fine particles (C) capable of achieving both slipperiness and transparency, an organopolysiloxane represented by the following general formula (I) and a non-crosslinkable radical polymerizable copolymerizable therewith are used. What was obtained by copolymerizing a reactive monomer and a crosslinkable radical polymerizable monomer is preferable.

The refractive index of the spherical resin fine particles (C) is 1.45.
~ 1.52 is preferred. If the refractive index is outside the above range,
Since there is too much difference in the refractive index between the polyolefin-based resin (A) and the spherical resin fine particles (C), high transparency may not be obtained. The more preferable range of the refractive index of the spherical resin fine particles (C) is from 1.48 to 1.50.

[0022]

Embedded image

The groups R in the general formula (I) are the same or different and are a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. Examples of such R include, for example, methyl, ethyl, propyl, isopropyl, n-
Alkyl groups such as butyl group and n-hexyl group; aryl groups such as phenyl group, tolyl group and naphthyl group; aralkyl groups such as phenethyl group and benzyl group; 3-chloropropyl group, 3,3,3-trifluoropropyl And substituted alkyl such as a group. Among these, a methyl group, a butyl group, and a phenyl group are particularly preferable, and 50 mol% or more of the total R is a methyl group in order to impart sufficient sliding properties and blocking resistance.

The group X in the general formula (I) represents a radical polymerizable functional group-containing organic group, and preferably a group represented by the general formula (II)

Embedded image (Wherein, R ¹ represents a divalent organic group having 3 to 20 carbon atoms which may contain a hetero atom, and R ² represents a hydrogen atom or a methyl group, respectively) or the general formula (III)

Embedded image Is a group represented by

In the above general formula (II), -R in the formula
^{As 1} -,-(CH ₂ ) _3- , -CH ₂ CH (CH
_{3) CH 2 -, - (} CH 2) 4 -, - (CH 2) 6 -,
— (CH ₂ ) ₃ O (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —
(C ₂ H ₄ O) _2- and the like.

N in the general formula (I) is an integer of 5 to 200. If n is less than 5, the slipperiness decreases, and if it exceeds 200, the transparency decreases.

The non-crosslinkable radical polymerizable monomer copolymerizable with the organopolysiloxane represented by the general formula (I) includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl ( Alkyl (meth) acrylates such as (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; Examples include alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate; cyclohexyl (meth) acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate. These (meth) acrylates may be used alone or in combination of two or more.

In addition, as long as the effects of the present invention are not impaired, radical polymerizable monomers other than those described above can be used in combination with the above (meth) acrylates. Such monomers include, for example, maleic acid, fumaric acid,
Unsaturated acids such as (meth) acrylic acid; (meth) acrylamides such as N-methylol (meth) acrylamide; 3-trimethoxysilylpropyl (meth) acrylate, 3-triethoxysilylpropyl (meth) acrylate, 3- Dimethoxymethylsilylpropyl (meth)
Radical polymerizable silane compounds such as acrylate, vinyltriethoxysilane, 4-vinylphenyltrimethoxysilane, and vinylmethyldimethoxysilane; styrene, acrylonitrile, vinylpyridine, vinylpyrrolidone,
Examples include vinyl alkyl ethers, radically polymerizable macromonomers of polyoxyalkylenes having one radically polymerizable group in the molecule, and polycaprolactone.

Examples of the crosslinkable radical polymerizable monomer copolymerizable with the organopolysiloxane represented by the general formula (I) include, for example, ethylene glycol di (meth)
Acrylate, diethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, allyl (meth)
Radical polymerizable monomers having two or more ethylenically unsaturated groups in one molecule such as acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and divinylbenzene are exemplified.

In order to produce the above-mentioned spherical resin fine particles (C) which are compatible with both slipperiness and transparency, an organopolysiloxane represented by the above general formula (I) and a non-crosslinkable radical copolymerizable monomer can be used. A solution or a non-aqueous dispersion containing the copolymer obtained by solution polymerization of the monomer and the crosslinkable radical copolymerizable monomer, and drying the spherical fine particles by spray drying. A method of dehydrating and drying the copolymer fine particles obtained by turbid polymerization, a method of drying the copolymer obtained by emulsion polymerization of the above monomers by a spray drying method, or a method of slowly coagulating from the above emulsion reaction liquid. After washing and drying the slurry-like copolymer thus obtained, a method of obtaining spherical fine particles by crushing with a jet mill or the like, previously preparing crosslinked fine particles by suspension polymerization or emulsion polymerization of the copolymerizable monomer, This fine particle table After reacting the emulsion polymerization of the organopolysiloxane, and a method of taking out the particles dried.

In the copolymerization, the charged weight ratio of the organopolysiloxane represented by the above formula (I) / non-crosslinkable radical polymerizable monomer and crosslinkable radical polymerizable monomer is preferably (5 to 5). 70) / (95-30).

When the amount of the organopolysiloxane to the radical polymerizable monomer is reduced, the effect of imparting slipperiness is reduced, and when the amount is increased, fine particles having a refractive index in the range of 1.45 to 1.52 are obtained. It becomes difficult to be.

The higher fatty acid amide (D) used in the present invention
Is a component blended for improving the slipperiness of the obtained film, for example, lauric amide, myristic amide, palmitic amide, stearic amide, behenic amide (C ₂₁ H ₄₃ CONH ₂ ), etc. Oleic amides, erucamides (C ₂₁ H)
₄₁ CONH ₂ ) and the like; unsaturated higher fatty acid amides such as methylenebisstearic acid amide and ethylenebisstearic acid amide; These higher fatty acid amides (D) may be used alone or in combination of two or more.

The higher fatty acid amide represented by Ra CONH ₂ is preferably a higher fatty acid amide in which the hydrocarbon group Ra has 16 to 24 carbon atoms, particularly preferably a monocarboxylic acid amide, and particularly, transparency and immediate action. In view of this, erucamide is most preferred.

The aliphatic monocarboxylic acid partial ester (E) of the 4- to 6-valent polyol used in the present invention is for imparting an antistatic property, and comprises a 4- to 6-valent polyol and an aliphatic monocarboxylic acid. It is obtained by partial esterification with a carboxylic acid and has at least one free hydroxyl group in the molecule.

Examples of the above 4- to 6-valent polyol include polyhydric alcohols such as pentaerythritol, sorbitol and glucose; cyclic ether polyhydric alcohols obtained by dehydration of sorbitol such as sorbitan and sorbite; diglycerin, ethylene glycol diethylene glycol Polyether tetraols such as glyceryl ether; polyether pentaols such as triglycerin; and polyether hexaols such as tetraglycerin and dipentaerythritol.

As the aliphatic monocarboxylic acid, an aliphatic monocarboxylic acid having 8 to 20 carbon atoms is preferable, and examples thereof include lauric acid, myristic acid, palmitic acid, and stearic acid.

Among such partial esters, those having 3 or 4 free hydroxyl groups and 1 or 2 aliphatic monocarboxylic acid ester groups in the molecule, such as sorbitan monoester, diglycerin monoester, Preferred are triglycerin monoester, triglycerin diester, tetraglycerin diester and the like.

When a partial ester obtained from a divalent or trivalent polyol is used as a partial ester of an aliphatic monocarboxylic acid of a polyol, an antistatic effect may not be sufficiently exerted, and a polyol having a valence of 7 or more may be used. When the partial ester obtained from the above is used, problems may occur in post-processing after film formation.

The polyolefin resin composition layer (x) in the present invention comprises the above-mentioned polyolefin resin (A), vinyl aromatic elastomer (B), spherical resin fine particles (C), higher fatty acid amide (D) and aliphatic Carboxylic acid partial ester
(E), the smaller the amount of the vinyl aromatic elastomer (B) added, the easier it is to slide, the more likely it is for the bag to collapse when stacked in a bag, and the larger the amount, the softer the film and blocking. The amount is 2 to 10 parts by weight, preferably 3 to 5 parts by weight, based on 100 parts by weight of the polyolefin resin.

The smaller the amount of the spherical resin fine particles (C), the lower the slipperiness. The larger the amount, the better the slipperiness and blocking resistance. However, it is difficult to obtain high transparency. ) 0.03 to 0.5 part by weight, preferably 0.1 to 0.4 part by weight, per 100 parts by weight.

If the amount of the higher fatty acid amide (D) is too small, the lubricity is not improved, and if it is too large, it bleeds out and lowers the transparency or adheres to the roll during film formation. The resulting film becomes contaminated, so that the content is preferably 0.03 to 0.4 parts by weight, preferably 0.1 to 0.3 parts by weight, per 100 parts by weight of the polyolefin resin (A).
Parts by weight.

When the amount of the aliphatic monocarboxylic acid partial ester (E) of the 4- to 6-valent polyol is small, the antistatic effect cannot be obtained, and when the amount is large, the transparency decreases with time. It is 0.05 to 1.5 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the polyolefin resin (A).

The polyolefin-based resin composition layer (z) in the present invention comprises the above-mentioned polyolefin-based resin (A), spherical resin fine particles (C) and higher fatty acid amide (D). Is less, the slipperiness is reduced, and if it is increased, the slipperiness and the anti-blocking property are improved, but it is difficult to obtain high transparency. Therefore, 0.01 to 0 based on 100 parts by weight of the polyolefin resin (A). 0.5 parts by weight, preferably 0.05 to 0.4 parts by weight.

If the amount of the higher fatty acid amide (D) is too small, the lubricating property is not improved, and if it is too large, it bleeds out and lowers the transparency or adheres to the roll during film formation to obtain the higher fatty acid amide (D). The resulting film becomes contaminated, so the polyolefin resin (A) is used in an amount of 0.01 to 0.3 parts by weight, preferably 0.1 to 0.3 parts by weight, per 100 parts by weight.
Parts by weight.

Polyolefin resin layer in the present invention
(y) indicates that the content of propylene and / or butene-1 is 5
It is composed of an amorphous polyolefin resin having a content of 0% by weight or more or a linear polyethylene resin polymerized using a metallocene catalyst.

The above-mentioned amorphous polyolefin resin includes polypropylene, polybutene-1, propylene and butene-1.
Of propylene and / or butene-1 and other α
-A copolymer with an olefin, wherein the content of propylene or butene-1 or the total content of propylene and butene-1 is 50% by weight or more. When the content of propylene and butene-1 decreases, the compatibility with the polyolefin resin decreases. In the case of a copolymer of propylene, butene-1 and another α-olefin, the content of propylene is preferably less than 50% by weight.

The above-mentioned amorphous polyolefin resin has a boiling n-heptane insoluble content, that is, a Soxhlet extraction insoluble content with boiling n-heptane of 70% by weight or less, preferably 60% by weight or less. Boiling n-heptane insoluble matter is 70
If it is larger than the percentage by weight, the ratio of the amorphous portion becomes small, and the flexibility of the obtained film decreases.

The number average molecular weight of the amorphous polyolefin resin is preferably 1,000 to 200,000. When the number average molecular weight is less than 1000, mechanical strength is insufficient,
If it exceeds 200,000, it becomes difficult to form a film. Therefore, it is more preferably from 1500 to 10,000.

Examples of the amorphous polyolefin resin include polybutene-1, butene-1 / ethylene copolymer, propylene / butene-1 copolymer, propylene / butene-1 / ethylene terpolymer, Butene-1 / hexene-1 / octene-1 terpolymer, butene-1 /
Hexene-1 / 4-methylpentene-1 terpolymer and the like, and propylene / butene-1 copolymer is particularly preferable from the viewpoint of improving the flexibility of the film.

The amorphous polyolefin resin may be used in combination with the polyolefin resin (A). When used together, the amount of the amorphous polyolefin-based resin decreases and the flexibility of the film decreases. Therefore, the amorphous polyolefin-based resin is 20 to 100% by weight, and the polyolefin-based resin (A) is 80 to 0% by weight. More preferably, the amorphous polyolefin resin is 25 to 100% by weight, the polyolefin resin (A) is 75 to 0% by weight, still more preferably the amorphous polyolefin resin is 50 to 100% by weight, Resin (A) is 50 to 0% by weight.

Examples of the linear polyethylene resin polymerized using the metallocene catalyst include polyethylene,
Ethylene and propylene, butene-1, pentene-1,
Hexene-1,4-methyl-1-pentene, octene-
Copolymers with an α-olefin such as 1 are exemplified.

When the MFR of the linear polyethylene resin is low, the fluidity is low and the productivity is low. When the MFR is high, the MFR of the linear polyethylene resin is liable to draw down during molding and becomes difficult to produce. 5.0 is preferred, and more preferably 0.6 to 3.0.

The above-mentioned linear polyethylene resin is polymerized using a metallocene catalyst containing a transition metal element or the like as a polymerization catalyst. The metallocene generally refers to a compound having a structure in which a transition metal element is sandwiched between unsaturated compounds or the like in which π electrons are localized (hereinafter, referred to as “ligand”).

Examples of the transition metal constituting the metallocene include tetravalent transition metals such as titanium, zirconium, nickel, palladium, hafnium, and platinum. Examples of the compound serving as the ligand include cyclopentadiene, a hydrocarbon group, a substituted hydrocarbon group, a cyclopentadiene substituted with a hydrocarbon group-substituted metalloid group, a cyclopentadiene oligomer, an indene, a hydrocarbon group, a substituted hydrocarbon group, And indene substituted by a hydrocarbon-substituted metalloid group.

Examples of the hydrocarbon group for substituting the above cyclopentadiene include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, an isoamyl group, a hexyl group,
Examples thereof include an isobutyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cetyl group, a 2-ethylhexyl group, and a phenyl group.

In addition to these π-electron unsaturated compounds, the above-mentioned ligands include, for example, monovalent anion ligands such as chlorine and bromine, divalent anion chelate ligands, hydrocarbons, alkoxides, arylamides, aryloxides, aryloxides A phosphide, a silyl group, a substituted silyl group, or the like may be coordinated with the transition metal.

Examples of the metallocene catalyst include cyclopentadienyl titanium tris (dimethylamide), methylcyclopentadienyl titanium tris (dimethylamide), bis (cyclopentadienyl) titanium dichloride and dimethylsilyltetramethylcyclopentane. Dienyl-tert-butylamidozirconium dichloride, dimethylsilyltetramethylcyclopentadienyl-tert-butylamidohafnium dichloride, dimethylsilyltetramethylcyclopentadienyl-pn-butylphenylamidozirconium chloride, methylphenylsilyltetramethyl Cyclopentadienyl-tert-butylamidohafnium dichloride, indenyl titanium tris (dimethylamide),
Indenyl titanium tris (diethyl amide), indenyl titanium tris (di-n-propyl amide),
Indenyl titanium bis (di-n-butylamide),
Indenyl titanium bis (di-n-propylamide)
And the like.

In the above metallocene compound, the type of the metal or the structure of the ligand is changed, or the metallocene catalyst is combined with a specific co-catalyst (co-catalyst) to form the metallocene compound.
The effect as a catalyst in the polymerization of various olefins can be exhibited more effectively. For example, methylaluminoxane (MAO) as a co-catalyst for the metallocene catalyst,
The polymerization may be carried out in a catalyst system to which a boron compound or the like has been added. When such a cocatalyst is used, the use ratio of the cocatalyst is a molar ratio of the metallocene compound: the cocatalyst =
The ratio is preferably 10: 100,000, more preferably 1:50 to 5,000.

The conditions for the above polymerization are not particularly limited, but in the presence of the above metallocene catalyst, for example, a solution polymerization method using an inert medium, a bulk polymerization method substantially free of an inert medium, a gas phase polymerization method, etc. Can be used.
The temperature at the time of the polymerization is not particularly limited, but generally, it is preferably about -100 to 300 ° C, and the pressure is preferably about normal pressure to about 100 kg / cm ² .

The above-mentioned metallocene catalysts have the feature that the properties of the active sites are homogeneous, and since each active site has the same activity, the molecular weight, molecular weight distribution, composition and homogeneity of the composition distribution of the polymer to be synthesized are obtained. Sex is enhanced. Therefore,
The polyolefin polymerized using the metallocene catalyst has a narrow molecular weight distribution, and in the case of a copolymer, the copolymer component is introduced at almost the same ratio to any molecular weight component.

Examples of the linear polyethylene resin polymerized using the metallocene catalyst include affinity and engagement manufactured by Dow Chemical Co., Ltd., and Ethon manufactured by Exxon Chemical Co., Ltd.
XACT, Evolue manufactured by Mitsui Petrochemical, Umerit manufactured by Ube Industries, etc. are on the market.

The linear polyethylene resin polymerized by using the metallocene catalyst is the same as the polyolefin resin (A)
May be used in combination. When used in combination, when the amount of the linear polyethylene resin is reduced, the feeling of the film is reduced. Therefore, the linear polyethylene resin is preferably 50 to 100% by weight and the polyolefin resin (A) is preferably 50 to 0% by weight.

The above polyolefin resin composition layer (x),
(z) and the polyolefin-based resin layer (y) may further contain a plasticizer, a light stabilizer, an antioxidant, a coloring agent, a processability improver, an antistatic agent, and an ultraviolet absorber as long as the properties are not deteriorated. Etc. may be added as needed.

The laminated film of the present invention comprises the above-mentioned polyolefin resin composition layer (x) and polyolefin resin layer (y)
And the polyolefin resin composition layer (z) are sequentially laminated, the thickness of each layer is not particularly limited,
It is preferable that the (y) layer occupies 50 to 90%, and the (x) layer and the (z) layer occupy about the other half, from the viewpoints of texture and transparency.

The method for producing the laminated film is not particularly limited, and it may be produced by any conventionally known method using the above-mentioned polyolefin-based resin composition. Is kneaded in a heated and melted state using a kneader such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneading roll, a Brabender, a kneader, and the obtained kneaded product is used using a conventional extruder or the like. By extruding, it can be formed into a film. In particular, it is preferable to form a film by a T-die method in order to smooth the surface, suppress generation of crystals, and obtain high transparency. In this case, after a single-layer film is manufactured, the film may be laminated by a method such as heat fusion or adhesion with an adhesive, but it is preferable that the film is manufactured by a co-extrusion method.

The invention according to claim 5 is a bag in which the laminated film according to claims 1 to 4 is formed such that the polyolefin resin composition layer (z) is on the inside. A conventionally known method may be adopted as a method for manufacturing a bag.For example, one film may be folded or two films may be stacked so that the polyolefin-based resin composition layer (z) of the film is inside. Bonding methods such as heat fusion bonding and bonding with an adhesive may be used.

[0068]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples. First, the method for producing the spherical resin fine particles (C) of the present invention will be described.

(Particle 1) A mixture of 90 parts by weight of methyl methacrylate and 5 parts by weight of butanediol diacrylate was added to a siloxane (a) represented by the following chemical formula.

Embedded image Was added, and these were copolymerized by emulsion polymerization. The obtained copolymer was dried by a spray-drying method and pulverized with a jut mill to obtain fine particles 1.

(Fine particles 2) Methyl methacrylate 65 parts by weight, butyl acrylate 6 parts by weight, styrene 5 parts by weight, acrylic acid 1 part by weight, and allyl methacrylate 3
A siloxane represented by the following chemical formula is added to a mixture of parts by weight.
(b)

Embedded image Was added in the same manner as in the production of the fine particles 1 except that these were copolymerized by emulsion polymerization.
I got

(Fine particles 3) Methyl silicone fine particles (average composition formula CH ₃ SiO _1.5 , average particle size 3 μm, sphericity 0.93).

(Fine particles 4) 6 parts by weight of the above siloxane (a) was added to a mixture of 90 parts by weight of methyl methacrylate and 4 parts by weight of butanediol diacrylate, and these were copolymerized by emulsion polymerization. After diluting the emulsified reaction solution to 50% by weight with deionized water, a 20% by weight aqueous solution of sodium sulfate is added at 80 ° C. to coagulate the copolymer, and the mixture is washed with water.
After dehydration and drying, fine particles
I got

(Fine Particles 5) To a mixed solution of 90 parts by weight of methyl methacrylate and 5 parts by weight of butanediol diacrylate, 5 parts by weight of the siloxane (a) was added, and these were copolymerized by suspension polymerization. The obtained copolymer was washed with water, dehydrated and dried to obtain fine particles 5.

(Fine particles 6) 30 parts by weight of the above siloxane (a) was added to a mixture of 60 parts by weight of methyl methacrylate, 19 parts by weight of ethyl methacrylate and 1 part by weight of ethylene glycol diacrylate, and these were copolymerized by emulsion polymerization. I let it. The obtained copolymer was dried by a spray-drying method and crushed by a hammer mill to obtain fine particles 6.

(Fine particles 7) Average particle diameter 2 μm, sphericity 0.
9 silicone rubber fine particles. The spherical resin particles obtained
Table 1 shows the physical properties of (C).

[0076]

[Table 1]

Next, a performance evaluation method will be described. With respect to the films and bags obtained in the examples and comparative examples, evaluation tests were performed on the following evaluation items by the following method.

(1) Transparency: Haze (JIS K710
It was evaluated by the measurement in 5). (2) Slipperiness: The kinetic friction coefficient was evaluated by measuring (ASTM-D1894).

(3) Bag Opening Property: The bags were evaluated according to the following criteria. 4: Open easily with fingers 3: Feel a little resistance when opened with fingers 2: Feel considerable resistance when opened with fingers 1: Difficult to open mouth

(4) Load collapse property: A shirt was inserted into a bag made, and five bags were stacked and tilted at 5 degrees to evaluate the state of the load collapse. ○: Does not cause collapse of cargo △: May cause collapse of cargo due to weight ×: Causes collapse of cargo

(5) Modulus of elasticity: Measured according to JIS K7133. (6) Initial antistatic property: After the bag was kept in an oven at 45 ° C. for 70 hours, the surface specific resistance value of the outer surface of the bag was measured according to JIS-K6911.

(7) Film appearance: Fine irregularities and spots due to spherical resin fine particles and higher fatty acid amide on the film surface were visually observed and evaluated according to the following criteria. 4: no unevenness or spots at all 3: slight unevenness or spots, but no practical problem 2: many unevenness or spots observed 1: many unevenness or spots, practical use impossible

(8) Stability over time: After the bags were kept in an oven at 45 ° C. for 6 months, the degree of yellowing was observed. ：: No yellowing, and antistatic properties are maintained. Δ: No yellowing, but antistatic performance is deteriorated. X: Yellowing is observed.

(9) Blocking property: 50 bags are stacked 40
After holding for 24 hours in an oven at 75 ° C and 75% humidity,
It was left at room temperature for hours and evaluated according to the following criteria. 3: There is no blocking between the bags, and the contacted surface slides freely. 2: There is almost no blocking between the bags, but the contact surface is hard to slip. 1: There is blocking between the bags, and it is difficult to peel off the contact surface.

Examples 1 to 7, Comparative Examples 1 to 13 A vinyl aromatic elastomer was added to 100 parts by weight of a random copolymerized polypropylene having an MFR of 6.0 g / 10 min.
(B), spherical resin fine particles (C), higher fatty acid amide (D) and aliphatic monocarboxylic acid partial ester (E) shown in Table 1 were blended in predetermined amounts shown in Table 2, and then mixed at 210 ° C. for 10 minutes. By kneading, a composition for the polyolefin-based resin composition layer (x) was obtained. Random copolymerized polypropylene with MFR of 6.0 g / 10 min, propylene / butene-1 copolymer which is an amorphous polyolefin-based resin (weight ratio 65/35, number average molecular weight 6500, boiling n-heptane insoluble matter 5% by weight) And a linear polyethylene resin (octene-1 content 7.5% by weight,
(Density 0.915 g / cm ³ , MFR 1.0 g / 10 min)
Was mixed in a predetermined amount as shown in Table 2, and kneaded at 210 ° C. for 10 minutes to obtain a composition for a polyolefin-based resin composition layer (y).

Next, spherical resin fine particles (C) and higher fatty acid amides (D) shown in Table 1 were blended in predetermined amounts shown in Table 2 with 100 parts by weight of random copolymerized polypropylene having an MFR of 6.0 g / 10 minutes. Thereafter, the mixture was kneaded at 210 ° C. for 10 minutes to obtain a composition for a polyolefin-based resin composition layer (z). Each of the obtained compositions is applied to a polyolefin resin composition layer.
The composition for (Y) was formed into a middle layer by cooling it to 30 ° C. with a cooling roll by a T-die method at a temperature of 30 ° C., and a transparent three-layer film having a thickness of 50 μm (the thickness ratio of each layer was 1: 4: 1)
I got The obtained film was folded so that the polyolefin-based resin composition layer (z) was inside, and both sides were heat-sealed to obtain a bag.

The performance of the obtained film and bag was evaluated.
The results are shown in Table 3. The abbreviations in the following table are as follows.

In the column of the vinyl aromatic elastomer (B), HSBR is hydrogenated styrene-butadiene random copolymer (manufactured by Nippon Synthetic Rubber Co., Dynalon 1320P, styrene content 10%, MFR 3.5), and SEPS is polystyrene. -Ethylene-propylene-styrene block copolymer (Kuraray Co., Ltd., Septon 2007, styrene content 3
0%, MFR7) and HSIPS are hydrogenated styrene-isoprene-styrene block copolymers (Kuraray Co., Ltd., Hypla HVS-3, styrene content 20%, MFR6) having isoprene 3,4 bonds.

In the section of fatty acid amide (D), amide 1
Is erucamide, and amide 2 is erucamide 7
It is a mixture of 5% by weight and 25% by weight of behenamide.

In the column of the partial ester (E), AS1 is diglycerin monostearate, AS2 is glycerin monostearate, and AS3 is stearyldiethanolamine.

[0091]

[Table 2]

[0092]

[Table 3]

[0093]

Since the constitution of the laminated film of the present invention is as described above, it is excellent in blocking resistance, antistatic property and transparency. Further, the bag obtained from this film is excellent in blocking resistance, antistatic property, transparency, opening property and anti-collapse property.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 25:10 55:00)

Claims (5)

[Claims] 1. A polyolefin resin (A) 100 parts by weight, a vinyl aromatic elastomer (B) 2 to 10 parts by weight,
The average particle diameter is 0.5 to 8 μm, and f = [M / (π / 4)] ^0.5 / Nmax (where M is an arbitrary cross-sectional area mm ² of the fine particles, Nmax
Represents the longest diameter mm of the section. A) spherical resin fine particles (C) having a sphericity f of 0.8 or more
03 to 0.5 parts by weight, higher fatty acid amide (D) 0.03 to
A polyolefin-based resin composition layer (x) comprising 0.4 parts by weight and 0.05 to 1.5 parts by weight of an aliphatic monocarboxylic acid partial ester (E) of a 4- to 6-valent polyol, propylene and / or butene-1 Content of 50% by weight
A polyolefin resin layer (y) composed of a linear polyethylene resin polymerized using an amorphous polyolefin resin or a metallocene catalyst as described above, and 100 parts by weight of the polyolefin resin (A), and an average particle size of 0.5 to F = [M / (π / 4)] ^0.5 / Nmax (where M is an arbitrary sectional area mm ² of fine particles, Nmax
Represents the longest diameter mm of the section. A) spherical resin fine particles (C) having a sphericity f of 0.8 or more
01 to 0.5 part by weight and higher fatty acid amide (D) 0.01
To 0.3 part by weight of a polyolefin resin composition layer
(z) is sequentially laminated. 2. The spherical resin fine particles (C) are represented by the general formula (I): (Wherein, R is the same or different from each other, and has 1 to 1 carbon atoms)
2 represents a substituted or unsubstituted monovalent hydrocarbon group, and at least 50 mol% of all Rs are methyl groups. X represents a radical polymerizable functional group-containing organic group, and n represents an integer of 5 to 200. ), A non-crosslinkable radical polymerizable monomer copolymerizable therewith, and a crosslinkable radical polymerizable monomer, and having a refractive index of 1.45 to 1. The laminated film according to claim 1, which is a particle having 52. 3. The method according to claim 1, wherein the organic group X in the organopolysiloxane represented by the general formula (I) is represented by the general formula (II): (Wherein, R ¹ represents a divalent organic group having 3 to 20 carbon atoms which may contain a hetero atom, and R ² represents a hydrogen atom or a methyl group, respectively) or the general formula (III): The laminated film according to claim 2, which is a group represented by the formula: 4. The laminated film according to claim 1, wherein the higher fatty acid amide (D) is a monocarboxylic acid amide having 16 to 24 carbon atoms in the hydrocarbon group. 5. A bag formed by laminating the polyolefin resin composition layer (z) of the laminated film according to any one of claims 1 to 4 inside.