JP2003276116A - Resin film and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film having excellent thermal bondability such as low temperature sealability. <P>SOLUTION: A polysilane is held at least at a thermally bonding site of the film. The film may be laminated on a base film to form a composite film. The polysilane may be, for example, a polysilane having at least one unit of a structural unit represented by formula (1), wherein R<SP>1</SP>to R<SP>3</SP>are the same or different, and are each an alkyl group, an aryl group, etc., and m, n and p are each a positive integer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to thermal bondability (particularly,
The present invention relates to a film having excellent heat sealability), a method for producing the film, and a method for lowering the thermal bonding temperature of the film.

[0002]

2. Description of the Related Art Paper, synthetic resin film or sheet, and bag-shaped molded products such as aluminum foil are used as packaging materials for liquids, powders and solids for foods, beverages, sundries and the like. In particular, packaging bags made of synthetic resin are excellent in low cost and water resistance and are used in many applications. Among the properties required of such a synthetic resin packaging material, thermal bonding is one of the important properties.

Particularly, in terms of thermal bondability, it is required that (1) low temperature bonding (low temperature sealing) is possible, (2) sufficient sealing strength is obtained, and (3) wide sealing temperature range is provided. To be done. Various resin films such as low density polyethylene (LDPE) film and polypropylene (PP) film are widely used as heat-bondable synthetic resin films. However, low density polyethylene (LDP
E) The film does not have a sufficient low-temperature sealing property and reduces the productivity of the packaging material. In addition, since the polypropylene (PP) film is inferior in heat bonding property, in general, in order to supplement the heat bonding property, the polypropylene (PP) film is added to the LDPE.
Alternatively, it is used as a film obtained by coating or laminating an ethylene-α-olefin copolymer.

However, these films are not yet sufficiently heat-bondable, and from the viewpoints of expanding the fields of application and improving productivity, resin films further excellent in heat-bonding properties, especially low-temperature heat-sealing properties are required. ing.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a resin film excellent in heat bonding such as low temperature sealing property, a composite film formed from this resin film, and a method for producing these films. To do.

Another object of the present invention is to produce a film which can be bonded at high speed and strongly and has high productivity by a simple method.

Yet another object of the present invention is to provide a method of lowering the thermal bonding temperature of a film.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, when the polysilane is held on the resin film by coating or containing, the fluidity of the film is improved. The present invention has been completed by finding that a film excellent in heat bondability (for example, low temperature sealing property) can be obtained.

That is, the resin film of the present invention is a heat-bondable (for example, heat-sealable) resin film, and holds polysilane in at least a heat-bonding portion of the film. The polysilane is at least one of structural units represented by the following formulas (1) to (3).
It may have one unit.

[0010]

[Chemical 2]

(Wherein R ^{1 to} R ³ are the same or different and are a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkenyl group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkenyl group or an aryl group. , An aryloxy group, an aralkyl group, an aralkyloxy group or a silyl group, and m, n, and p are positive integers) The resin film is an olefin resin (for example, polyethylene resin), a vinyl resin, or styrene. It may be composed of at least one thermoplastic resin selected from a series resin, an aliphatic polyamide series resin, a polyester series resin, and a polycarbonate series resin.

The resin film may have a polysilane layer formed on at least the surface of the heat-bonding portion, or may contain polysilane in the heat-bonding portion. When the resin film forms a polysilane layer, the coating amount of polysilane at the thermal bonding site may be about 0.1 to 50 g / m ² , and the thermal bonding site may not contain polysilane. In this case, the content ratio of polysilane may be about 0.1 to 50 parts by weight with respect to 100 parts by weight of the resin. The resin film can be manufactured by holding polysilane in at least a thermal bonding site of the resin film.

In the present invention, a composite film may be composed of a base film and the resin film laminated on the base film. The base film is at least one selected from polypropylene resin, aliphatic polyamide resin, aromatic polyester resin, polyimide resin, polycarbonate resin, and cellulose resin.
It may be composed of one kind of thermoplastic resin. The composite film can be manufactured by laminating a base material film and a resin film.

The present invention also includes a method for holding the polysilane at least at the thermal bonding site to lower the thermal bonding temperature of the resin film.

In the present specification, polysilane and oligosilane are collectively referred to as "polysilane".

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION [Resin Film] The resin film of the present invention can be heat-bonded, and holds polysilane at least at a heat-bonding site. Therefore, in the present invention, probably because the fluidity of the resin film is improved, the thermal bonding property (particularly, the low temperature sealing property) of the resin film is improved. In the present invention, the term “thermal bonding” means bonding or welding by heat, and may be bonding by an external heating method (heat sealing, impulse sealing, etc.) or bonding by an internal heating method (ultrasonic bonding). , High-frequency bonding, etc.).

As the polysilane that can be used in the present invention, various polysilanes having a Si--Si bond, such as linear, branched, cyclic, and mesh-like can be used. For example, the above formulas (1) to (3) can be used. Examples thereof include polysilanes composed of at least one unit among the structural units represented by. Specifically, for example, (i) the linear or cyclic polysilane represented by the above formula (1), (ii) the above formula (2)
A branched polysilane represented by the formula (polysilin) or a branched polysilane represented by the formula (3), (iii) a combination of structural units represented by the formulas (1) to (3) (for example, the above A combination of formula (1) and formula (2), a combination of formula (1) and formula (3), a combination of formula (1), formula (2) and formula (3)). And polysilane. You may use polysilane individually or in combination of 2 or more types.

In the above formulas (1) to (3), R ¹ and R ²
And as the substituent represented by R ³ , a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkenyl group,
Examples thereof include a cycloalkyl group, a cycloalkyloxy group, a cycloalkenyl group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group and a silyl group.

Alkyl groups include methyl, ethyl, and
Ropil, isopropyl, butyl, t-butyl, pentyl
C such as group_1-14Alkyl group (preferably C_1-10Alkyl
Group, more preferably C_1-6Alkyl group)
It Alkoxy groups include methoxy, ethoxy and pro
Poxy, isopropoxy, butoxy, t-butoxy,
C such as an ethyloxy group_1-14An alkoxy group (preferably
C_1-10An alkoxy group, more preferably C_1-6Arcoki
Si group). As the alkenyl group, vinyl,
C such as allyl, butenyl and pentenyl groups_2-14Alkenyl
A group (preferably C _2-10An alkenyl group, more preferably
C_2-6Alkenyl group). Cycloalkyl group
Is C such as cyclopentyl or cyclohexyl group.
_5-14Cycloalkyl group (preferably C_5-10Cycloalk
Group, more preferably C_5-8Cycloalkyl group)
You can The cycloalkyloxy group is
C such as ethyloxy and cyclohexyloxy groups_5-14Shi
Chloroalkyloxy group (preferably C_5-10Cycloalk
Ruoxy group, more preferably C_5-8Cycloalkyl
Xy group). As a cycloalkenyl group,
C such as cyclopentenyl group and cyclohexenyl group_5-14
Cycloalkenyl group (preferably C_5-10Cycloalkeni
Group, more preferably C_5-8Cycloalkenyl group)
Can be mentioned. Aryl groups include phenyl and naphthyl
C such as group_6-20Aryl group (preferably C_6-15Aryl
Group, more preferably C_6-12Aryl group)
It Aryloxy groups include phenoxy and naphthyl
C such as oxy group_6-20Aryloxy group (preferably C
_6-15An aryloxy group, more preferably C_6-12Ally
Luoxy group). As an aralkyl group,
C such as benzyl, phenethyl and phenylpropyl groups_6-20
Aryl-C_1-4Alkyl group (preferably C_6-10Ally
R-C_1-2And an alkyl group). Aralkyl Oki
Si groups include benzyloxy, phenethyloxy, and phenyloxy.
C such as phenylpropyloxy group_6-20Aryl-C_1-4
Alkyloxy group (preferably C_6-10Aryl-C_1-2
And an alkyloxy group). As a silyl group,
Si such as silyl group, disilanyl group and trisilanyl group
_1-10Silyl group (preferably Si_1-6Silyl group)
Wear.

These substituents may be any of substituents such as halogen atom (eg, chlorine atom, fluorine atom), alkyl group (eg, C _1-4 alkyl group such as methyl group), alkoxy group (eg, alkyl group). , A C _1-4 alkoxy group such as a methoxy group), an aryl group (a phenyl group, a naphthyl group, etc.)].

In the above formula (1), the combination of R ¹ and R ² may be a combination of aryl groups (phenyl group etc.), and a preferable combination is, for example,
(A) C _1-4 alkyl groups (particularly methyl groups), (b)
A combination of a C _1-4 alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) can be exemplified, and particularly a combination in which at least one of R ¹ and R ² is an aryl group (particularly a phenyl group) (for example, , A combination of the above (b) and the like) are preferable. Since such polysilane has a relatively low melting point, it is easy to realize the low temperature sealing property of the resin film. Further, preferred R ³ is a C _1-4 alkyl group (especially C _1-2 alkyl group such as methyl group) or an aryl group (especially phenyl group).

The types of R ¹ , R ² and R ³ may differ depending on the number of repeating structural units (the number of m, n and p).

In the polysilane having the above structural unit, the values of m, n and p are, for example, 2 to 100, respectively.
00, preferably 3-1000, more preferably 3-
It is about 500 (for example, 3 to 100). In particular, in the linear polysilane represented by the formula (1), the value of m is 3
It is about 0 or less (for example, 2 to 30, preferably 3 to 25, more preferably about 4 to 20), and the above formula (1)
In the cyclic polysilane represented by, the value of m is about 12 or less (for example, 3 to 12, preferably 4 to 12, and more preferably about 5 to 10). Further, in the polysilane having the structural unit represented by the formula (2) or (3), n
Alternatively, p can be appropriately selected from the above range (particularly about 2 to 100, preferably about 2 to 50) as long as the polymerization operation and the like are not impaired. Furthermore, in the aspect (iii) having the plurality of structural units, the value of m + n + p is, for example,
It is 2 to 10000, preferably 3 to 1000, and more preferably 3 to 500 (for example, 3 to 100).
Further, the polysilane may be a copolymer.

The number average molecular weight of the polysilane is, for example, 300 to 40,000, preferably 400 to 2000.
It is 0, more preferably about 500 to 10,000.
A polysilane having such a number average molecular weight has a high affinity for a resin film (or a resin that constitutes the resin film), and not only makes it easy to hold the resin film, but also impairs transparency in a transparent resin film. This is convenient because it does not occur. In particular, such a polysilane can reduce the heat seal temperature and easily obtain high heat seal strength.

The terminal groups of the structural units represented by the above formulas (1) to (3) may be constituted by the above substituents R ¹ , R ² or R ³ , and a halogen atom (chlorine atom, bromine atom, iodine). Atom, etc.) or a silyl group substituted with the above-mentioned substituents R ¹ , R ² or R ³ and the like. Preferred terminal groups include alkyl groups (C _1-4 alkyl groups such as methyl group, ethyl group, t-butyl group, etc.), aryl groups (phenyl group, etc.), silyl groups having a substituent (trimethylsilyl group, t-group, etc.). tri C _6-10, such as triphenylsilyl group; tri C _1-4 alkylsilyl group such as butyl dimethylsilyl group
And an inert group such as an arylsilyl group).

A preferable polysilane is a linear or cyclic polysilane (for example, methylphenylpolysilane) in which at least one of the substituents R ¹ and R ^{2 in} the above formula (1) is an aryl group (particularly a phenyl group). is there. In the linear polysilane, the terminal group can be composed of the above-mentioned inactive group (trimethylsilyl group, triphenylsilyl group, etc.).

The polysilane can be prepared using various methods. For example, a method of dehalogenating a halosilane in the presence of an alkali metal (for example, "Kipping method" J. Am. Chem. Soc., 110, 124 (1988), Macromolecules, 2
3,3423 (1990), etc., a method of performing anionic polymerization of disilene cross-linked with biphenyl (eg, Macrolecul
es, 23,4494 (1990)), a method of dehalogenating halosilanes by electrode reduction (for example, J. Chem. Soc., Ch.
em.Commun., 1161 (1990), J.Chem.Soc., Chem.Commun., 89
7 (1992)), a method for dehalogenating a halosilane in the presence of magnesium (for example, WO98 / 29).
No. 476, etc.), a method of dehydrogenating a hydrosilane in the presence of a metal catalyst (for example, JP-A-4-334).
551), and ring-opening polymerization of cyclic silanes. Among these preparation methods, from the viewpoint of the purity of polysilane, the molecular weight distribution, the compatibility with the resin, the content of by-products (such as salts containing sodium ions and chloride ions), the production cost, the production From the viewpoint of safety, industrial production method, etc., the “method of dehalogenating halosilanes in the presence of magnesium” is preferable.

Among the polysilanes represented by the above formula (1), the cyclic polysilane may be obtained, for example, by partially cyclizing it in the process of synthesizing the linear polysilane.
For example, a cyclic polysilane having a number average molecular weight of about 1,000 or less is soluble in a solvent such as alcohol and can be easily separated from a linear polysilane. Further, the cyclic polysilane may be obtained by an intramolecular cyclization reaction of the polysilane, for example, a method by an intramolecular condensation reaction in which the terminals of the polysilane self-condense. Examples of the intramolecular condensation reaction include an intramolecular dehydrogenation reaction, an intramolecular dehalogenation reaction, an intramolecular dehydrohalogenation reaction, and an intramolecular dehydration reaction.

Further, the terminal group is the above-mentioned silyl group (tri-C _1-4 alkylsilyl group such as trimethylsilyl group, tri-C _6-10 arylsilyl group such as triphenylsilyl group).
The polysilane can be prepared by, for example, a method of combining polysilane and a blocking agent, for example, by preparing polysilane by the above-mentioned method and reacting the produced polysilane with a silyl compound as a blocking agent. For the reaction between the polysilane and the silyl compound, depending on the end of the polysilane, for example, dehydrohalogenation reaction, dehydrogenation reaction, dehalogenation reaction, detrifluoromethanesulfonic acid reaction, dehydration reaction, etc. can be used. Halogen reaction is available. Examples of the silyl compound include silylating agents corresponding to the silyl group (for example, halosilanes (for example, halotri C _1-4 alkylsilane such as chlorotrimethylsilane and chloro-t-butyldimethylsilane) and halotrialkyl such as chlorotriphenylsilane). C _6-10 monohalosilane such as aryl silane, etc.), silyl triflate acids)
And silanes, but halosilanes are preferable.

The form of polysilane is not particularly limited as long as it can be applied to the resin film, but it may be powdery in general.

The resin constituting the resin film (hereinafter sometimes referred to as heat-sealable resin) is not particularly limited as long as it can be heat-bonded (for example, heat-sealable), and examples thereof include olefin resin and vinyl. Examples of the thermoplastic resin include thermoplastic resins, styrene resins, aliphatic polyamide resins, polyester resins, and polycarbonate resins. You may use these resins individually or in combination of 2 or more types. When a plurality of resins are used in combination, the resin composition may form a composite resin composition such as a polymer alloy.

Examples of the olefin resin include C
_Homogeneous or copolymer of _2-6 olefins (low density polyethylene (LDPE), linear low density polyethylene (LLDP)
E), polyethylene such as medium density polyethylene and high density polyethylene, polyethylene resin such as ethylene-propylene copolymer; polypropylene resin such as polypropylene, unstretched polypropylene, propylene-ethylene copolymer and propylene-butene copolymer. Etc.), C
_2-6 Copolymer of olefin and copolymerizable monomer (ethylene- (meth) acrylic acid copolymer, ionomer resin,
Ethylene- (meth) acrylic acid ester copolymer etc.)
And so on.

As the vinyl-based resin, a halogen-containing vinyl-based resin (for example, a homopolymer of a halogen-containing monomer such as polyvinyl chloride; vinyl chloride-vinyl acetate copolymer, vinyl chloride- (meth) acrylic acid ester). Copolymers of halogen-containing monomers and copolymerizable monomers such as copolymers), vinyl ester resins (homopolymers of vinyl ester monomers such as polyvinyl acetate; ethylene-vinyl acetate) Copolymer, vinyl acetate-vinyl chloride copolymer,
Examples thereof include copolymers of vinyl ester-based monomers such as vinyl acetate- (meth) acrylic acid ester copolymers and copolymerizable monomers).

Examples of the styrene resin include styrene-acrylonitrile copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), styrene- (meth) acrylic acid ester copolymer, styrene-maleic anhydride. Examples thereof include a copolymer of a styrene-based monomer such as a copolymer and another copolymerizable monomer.

Examples of the aliphatic polyamide resin include an aliphatic diamine component (alkylenediamine such as tetramethylenediamine and hexamethylenediamine) and an aliphatic dicarboxylic acid component (alkylenedicarboxylic acid such as adipic acid, sebacic acid and dodecanedioic acid). Etc.) (eg, nylon 610, nylon 612, etc.), lactam (ω-laurolactam, etc.) or aminocarboxylic acid (ω-aminoundecanoic acid, etc.), homopolymer or copolymer (eg, nylon 11, nylon, etc.) 12, etc.), a copolyamide in which these polyamide components are copolymerized (for example,
Nylon 6/11, Nylon 6/12, Nylon 66 /
11, nylon 66/12, etc.) and the like.

As the polyester resin, aliphatic glycol (ethylene glycol, propylene glycol,
A polymer obtained by a condensation reaction of a C _2-6 alkylene glycol such as butanediol and hexanediol, a polyoxy C _2-4 alkylene glycol, etc.) with an aliphatic dicarboxylic acid or an acid anhydride thereof (adipic acid, etc.), poly Aliphatic polyester-based resins such as caprolactone resins (polymers obtained by ring-opening polymerization of lactones such as ε-caprolactone); poly C _2-4 alkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate, polyethylene naphthalate, etc. Examples of the aromatic polyester resin include The aliphatic polyester may be a non-crystalline resin or an aromatic dicarboxylic acid may be copolymerized.

Examples of the polycarbonate resin include aromatic dihydroxy compounds (bisphenol compounds such as bisphenol A and bisphenol S) and
Aromatic polycarbonates (bisphenol A type polycarbonates) obtained by reaction with phosgene or carbonic acid diesters (diaryl carbonates such as diphenyl carbonate, dialkyl carbonates such as dimethyl carbonate) can be exemplified.

Preferred resins are olefin resins (particularly low density polyethylene, linear low density polyethylene,
Polyethylene such as medium density polyethylene and high density polyethylene, polyethylene resin such as ethylene-propylene copolymer, unstretched polypropylene, polypropylene resin such as propylene-ethylene copolymer), aliphatic polyamide resin (nylon 6/11) Etc.).

The resin film of the present invention only needs to hold the polysilane at least at the heat-bonding site, and the holding form is not particularly limited. For example, (1) polysilane may be contained in the heat-bonded portion of the resin film,
(2) A polysilane layer may be formed on at least the surface (or the surface of the thermal bonding site) of the resin film, and the polysilane may be retained by combining these forms. In these holding modes, the polysilane may hold the polysilane layer at least in the heat-bonding site, and for example, the polysilane may be held in the entire resin film, or partially corresponding to the heat-bonding site. You may hold | maintain polysilane.

In the resin film, the proportion of polysilane can be selected according to the type of resin, the bonding temperature, the holding form and the like. For example, when the retention form of polysilane is the content form of the above (1), 0.1 to 50 parts by weight, preferably 0.5 to 40 parts by weight of polysilane, relative to 100 parts by weight of the resin constituting the film, It may be preferably about 1 to 20 parts by weight. Further, the holding form is the above (2).
In the case of the above coating form, a small amount of polysilane to be coated may be used. For example, the coating amount of polysilane on the surface of the thermal bonding site is 0.1 to 50 g / m ² , preferably 0.5 to 2
0 g / m ² (e.g., 1~10g / m ^2), more preferably 1 to 10 g / m ² (e.g., 2~5g / m ²⁾ may be about.

The thickness of the resin film is, for example, 5 to 100 μm, preferably 1 depending on the structure and form of the film.
It can be selected from the range of 0 to 50 μm (for example, 10 to 30 μm), and more preferably 15 to 35 μm (for example, 15 to 25 μm).

[Composite Film] In the present invention, a composite film may be composed of a base film and the resin film laminated on the base film. In the composite film, the resin film may form a coating layer (or a coating layer). The coating layer is, for example, a film-forming resin containing polysilane (for example,
The heat-sealable resin or the like) or the like.

The base film is not particularly limited as long as it does not impair the heat-bonding property of the composite film, and includes resin, paper (kraft paper, pure white roll paper, fine paper, art paper, glassine paper, etc.), metal (aluminum). , Copper, etc.) and the like.

Resin that constitutes the base film (base resin)
May be made of a resin having a melting point (or glass transition point) higher than that of the resin constituting the resin film (heat-sealable resin), and the heat-sealable resin (for example,
Olefin resin such as polypropylene resin, aliphatic polyamide resin such as nylon 6/11, polyester resin such as polyethylene terephthalate) or heat resistant resin. The base resin is
You may comprise a base film individually or in combination of 2 or more types. When two or more kinds of resins are combined and configured, the resin composition may form a composite resin composition such as a polymer alloy.

Examples of the heat-resistant resin include vinyl alcohol resins (polyvinyl alcohol, ethylene-vinyl alcohol copolymers, etc.), styrene resins (polystyrene, styrene-styrene-monomers such as styrene-α-methylstyrene copolymers). Homopolymer or copolymer), aliphatic polyamide resin (nylon 6, nylon 46, nylon 66, etc.), aromatic polyamide resin (polymetaxylylene adipamide, etc.), polyimide resin (polyimide resin, polyamideimide resin) , Polyesterimide resins, etc.), cellulose resins [eg, cellulose esters such as cellulose acetate, cellulose butyrate, cellulose acetate propionate; regenerated cellulose resins such as cellophane (normal cellophane, moisture-proof cellophane, etc.)], poly Urethane-based resins, such as biodegradable resin (such as polylactic acid-based resin such as polylactic acid) can be exemplified.

Preferred base resins are polypropylene resins (polypropylene etc.), aliphatic polyamide resins (nylon 6 etc.), aromatic polyester resins (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate etc.), polyimide resins. , Polycarbonate resins, and cellulose resins. Specifically, when the resin film is made of polyethylene resin (high density, medium density, low density polyethylene, linear low density polyethylene, etc.), the base resin is polypropylene resin or aliphatic polyamide. Resin,
It may be an aromatic polyester resin or a polyimide resin.

The base film may be a monolayer film or a laminated film. The thickness of the base film is not particularly limited, and is, for example, 5 to 1000 μm.
m, preferably 10 to 500 μm, more preferably 1
It is from 0 to 200 μm, usually from 15 to 100 μm.
In the composite film, the thickness of the resin film is
The thickness is 0.5 to 30 μm, preferably 1 to 20 μm, and more preferably 1 to 15 μm.

In the composite film, when the resin film forms a coating layer (coating layer), the proportion of polysilane may be the same as in the holding mode of (1) (for example, the coating film). Formable resin 100
0.1 to 50 parts by weight, preferably 0.
5 to 40 parts by weight, more preferably 1 to 20 parts by weight). The thickness of the coating layer (resin film layer) is
For example, 0.1 to 50 μm, preferably 1 to 30 μm,
More preferably, it is about 3 to 10 μm.

In the composite film, an adhesive layer may be interposed between the base film layer and the resin film layer. The adhesive layer is a homopolymer or copolymer of olefin (polyethylene, ethylene-vinyl acetate copolymer, modified polyolefin having a functional group introduced), rubber polymer such as butene-based copolymer, polyethyleneimine, modified It can be composed of polyester, modified cellulose, or the like. The thickness of the adhesive layer is not particularly limited and is, for example, 0.5 to 20 μm.
m, preferably about 0.5 to 15 μm.

The resin film and / or the base material film (hereinafter sometimes simply referred to as a film) may contain various additives such as plasticizers [polyester plasticizers (for example, 1,3- Butanediol-adipic acid copolymer etc.) and other oligomer type plasticizers; phthalate ester plasticizers such as dioctyl phthalate; polyethylene glycol adipic acid etc.], stabilizers (epoxy compounds such as epoxidized soybean oil, carbodiimide etc.) Imide compounds, etc.), antioxidants (2,6-di-t-butyl-4-methylphenol (BHT), butylhydroxyanisole (BHA) and other phenolic antioxidants, etc.), UV absorbers, charging Anti-foaming agent, lubricant, anti-blocking agent (silica, talc, etc.), anti-fog agent (glycerin fatty acid ester) Citric acid esters such as monostearyl citrate), colorants (titanium oxide, carbon black, ultramarine etc.), other resins (biodegradable resins such as aliphatic polyester, polyvinyl alcohol, polyhydroxybutyrate-hydroxy burr) Rate, starch-based polymer, etc.) and the like.

The surface of the film (for example, the substrate film) may be surface-treated (for example, corona discharge treatment, undercoat treatment, etc.). Further, the surface of the base film may be vapor-deposited with a metal or a metal oxide, or may be printed.

The film (for example, the base film) may be unstretched, or may be stretched (uniaxially stretched, biaxially stretched, etc.) or rolled.

The heat-bonding temperature range (sealing temperature range) of the film varies depending on the type of resin.
The temperature is 50 to 250 ° C., preferably 70 to 230 ° C., and more preferably 80 to 200 ° C.

The film of the present invention has a low thermal bonding temperature,
High low temperature sealability. For example, in the film,
The thermal bonding temperature that can be lowered can be adjusted according to the amount of polysilane retained, the type of resin constituting the film, and the like, and is, for example, 3 to 30 ° C., preferably about 5 to 20 ° C., more preferably 5 to 15 ° C. It is about ℃.

[Production Method of Resin Film and Composite Film] The resin film of the present invention can be easily produced by holding polysilane in at least the heat-bonding site of the resin film. The resin film containing the polysilane (the resin film in the form of (1) above) is produced, for example, by film-forming a resin composition obtained by mixing or adding polysilane to the resin forming the resin film. You may. In this method, the resin and the polysilane are mixed by a mixer (for example, a ribbon blender,
Tumble mixer, Henschel mixer, etc.) or a kneading machine (eg, open roller, kneader, Banbury mixer, extruder, etc.). In this method, as a film forming method, a conventional method (for example, a casting method, a T-die method, a melt extrusion method such as an inflation method, a calender method, etc.) can be used.
The preferred film forming method is the melt extrusion method.

The resin film forming the polysilane layer (the resin film in the form of (2) above) is, for example, applied to at least the heat-bonded portion of the resin film by a conventional method (for example, spraying, coating, It may be produced by applying polysilane by dipping or the like. In this method, polysilane may be mixed with a solvent and applied. Examples of the solvent include hydrocarbons (aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene), alcohols (ethanol, propanol, etc.) , Ethers (dimethyl ether, diethyl ether, tetrahydrofuran, etc.), ketones (acetone,
Ethyl methyl ketone, etc., esters (ethyl acetate,
Butyl acetate, etc.), cellosolves (methyl cellosolve,
Ethyl cellosolve) and carbitols (such as carbitol). You may use these solvent individually or in combination of 2 or more types.

The composite film can be produced by laminating the base film and the resin film.
For laminating (laminating) the resin film, a conventional laminating method such as extrusion laminating or laminating method (such as dry laminating) via an adhesive layer can be used.

Examples of the extrusion laminating method include:
A method of melt-extruding a resin (or a resin composition) forming the other film into one of the base film and the resin film to form a film, or a resin forming the resin film (or a resin composition) ), A resin (or a resin composition) that constitutes the base film, and (a resin that constitutes the adhesive layer if necessary) are melted by separate extruders to form a common die (T die, etc.). It includes a co-extrusion laminate that conducts extrusion film formation.

In the case of a composite film in which a resin film forms a coating layer (coating layer), for example, a base film is coated with a film-forming resin containing polysilane (such as the heat-sealing resin). Can be obtained by In this method, for coating, a conventional coating processing method such as roll coating (gravure coating, Meyer bar coating, doctor blade coating, reverse roll coating, dip coating, air knife coating, etc.) and calendar coating can be used.

The resin film and composite film of the present invention can be applied to various heat-bonding methods (heat-sealing method, impulse-sealing method, ultrasonic bonding, high-frequency bonding, etc., especially heat-sealing method), and can be used for foods, beverages, It is useful as various packaging films for miscellaneous goods, agricultural films, architectural films, decorative films, and the like.

[0061]

INDUSTRIAL APPLICABILITY The present invention can provide a resin film excellent in thermal bonding such as low-temperature sealing property because it holds polysilane, and a composite film composed of this resin film. Further, a film having high productivity and capable of high-speed bonding can be produced by a simple method of holding polysilane on the film. Further, in the present invention, the low temperature sealing property of the film can be improved by lowering the thermal bonding temperature.

[0062]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples.

Example 1 50 parts by weight of ethanol was mixed with 50 parts by weight of poly (methylphenylsilane) having a terminal trimethylsilyl group introduced (number average molecular weight of 650) and dissolved to prepare a coating solution. As a test piece, a strip-shaped high-density polyethylene resin film (10 cm × 1 cm × thickness 20 μm; resin film 1) was applied on one surface by an applicator to a thickness of 10 μm.
After coating the coating solution with, and allowing it to stand at room temperature for 10 minutes to be naturally dried, a strip-shaped high-density polyethylene resin film (10
cm × 1 cm × thickness 20 μm; resin film 2) was placed on top of each other, and the two films were placed under predetermined conditions (pressure 5 kg / cm ² , pressurizing time 10 seconds, heating at 95 to 260 ° C. in 5 minute increments). Both resin films were fused (bonded) while heating the outer surface.

Of the temperatures at which the resin film is completely fused (bonded), the lowest temperature is defined as the lowest fusion temperature T _1, and the lowest fusion temperature T when the coating solution is fused without being applied.
₂ the temperature difference between T ₂ -T _1: was measured ([Delta] T fusing temperature decrease).

Example 2 Both resin films were fusion-bonded in the same manner as in Example 1 except that the resin film 2 was a medium-density polyethylene resin film, and T ₂ -T ₁ (ΔT: fusion-bonding lowering temperature) was measured. did.

Example 3 Both resin films were fused in the same manner as in Example 1 except that the resin film 2 was a low-density polyethylene resin film, and T ₂ -T ₁ (ΔT: fusion temperature) was measured. did.

[0067] Example 4 resin film 1 a medium density polyethylene resin film, except that the resin film 2 to the medium-density polyethylene resin film fused both resin film in the same manner as in Example 1, T ₂ -T ₁ (ΔT: fusion lowering temperature) was measured.

Example 5 Both resin films were fused together in the same manner as in Example 1 except that the resin film 1 was a medium density polyethylene resin film and the resin film 2 was a low density polyethylene resin film, and T ₂ -T ₁ (ΔT: fusion lowering temperature) was measured.

Example 6 Both resin films were fused in the same manner as in Example 1 except that the resin film 1 was a medium density polyethylene resin film and the resin film 2 was a polypropylene resin film.
T ₂ −T ₁ (ΔT: fusion-bond lowering temperature) was measured.

Example 7 Both resin films were fused in the same manner as in Example 1 except that the resin film 1 was a low density polyethylene resin film and the resin film 2 was a low density polyethylene resin film, and T ₂ -T ₁ (ΔT: fusion lowering temperature) was measured.

Example 8 Except that the resin film 1 was a polypropylene resin film and the resin film 2 was a polypropylene resin film,
Both resin films were fused together in the same manner as in Example 1 to give T ₂
−T ₁ (ΔT: fusion-bond lowering temperature) was measured.

Example 9 Both resin films were fused in the same manner as in Example 1 except that the resin film 1 was an acrylonitrile butadiene styrene (ABS) resin film and the resin film 2 was an acrylonitrile butadiene styrene (ABS) resin film. , T ₂ −T ₁ (ΔT: fusion lowering temperature) were measured.

Example 10 Example 1 was repeated except that the resin film 1 was an acrylonitrile butadiene styrene (ABS) resin film and the resin film 2 was a polyethylene terephthalate resin film.
Both resin films are fused in the same manner as above, and T ₂ −T ₁ (Δ
T: fusion lowering temperature) was measured.

Example 11 Both resin films were fused in the same manner as in Example 1 except that the resin film 1 was a polyethylene terephthalate resin film and the resin film 2 was a polycarbonate resin film, and T ₂ -T ₁ (ΔT: The fusion lowering temperature) was measured.

Example 12 Except that the resin film 1 was a polyvinyl chloride resin film and the resin film 2 was a polyvinyl chloride resin film,
Both resin films were fused together in the same manner as in Example 1 to give T ₂
−T ₁ (ΔT: fusion-bond lowering temperature) was measured.

The results are shown in Table 1.

[0077]

[Table 1]

As can be seen from the table, the thermal bonding temperature of the film coated with polysilane was lower than that of the film not coated with polysilane.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hironori Sakamoto             4-1-2 Hirano-cho, Chuo-ku, Osaka City, Osaka             Gas Co., Ltd. (72) Inventor Hiroyuki Nishimura             4-1-2 Hirano-cho, Chuo-ku, Osaka City, Osaka             Gas Co., Ltd. (72) Inventor Shinichi Kawasaki             4-1-2 Hirano-cho, Chuo-ku, Osaka City, Osaka             Gas Co., Ltd. F-term (reference) 4F006 AA12 AA15 AA16 AA17 AA22                       AA35 AA36 AA38 AA58 AB39                       BA13 CA07 DA04                 4F100 AJ04C AK01A AK01C AK03A                       AK04A AK05 AK06 AK07                       AK07C AK11A AK12A AK14A                       AK15 AK21A AK41A AK42                       AK43C AK45A AK45C AK48A                       AK48C AK49C AK52B AK62A                       AK66A AK74 AT00A AT00C                       BA01 BA02 BA03 BA07 BA10A                       BA10C BA15 CC00B EH46B                       GB15 GB23 JL11 JL12B                       YY00B                 4J002 AA011 BB031 BB051 BB061                       BB071 BB081 BB121 BB151                       BB161 BB231 BC041 BC061                       BC071 BD041 BD081 BD091                       BF021 BF031 BN151 CF031                       CF061 CF071 CF191 CG011                       CL011 CL031 CL051 CP012                       FD020 FD030 FD070 FD090                       FD200 GG02

Claims (16)

[Claims] 1. A resin film capable of being heat-bonded, wherein the resin film holds polysilane at least at a heat-bonding site of the film. 2. The resin film according to claim 1, which is heat sealable. 3. The resin film according to claim 1, wherein the polysilane has at least one unit among structural units represented by the following formulas (1) to (3). [Chemical 1] (In the formula, R ^{1 to} R ³ are the same or different and are a hydrogen atom,
A hydroxyl group, an alkyl group, an alkoxy group, an alkenyl group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkenyl group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, or a silyl group, m, n, p Is a positive integer) 4. The resin film according to claim 3, wherein the polysilane is a linear or cyclic polysilane represented by the formula (1). 5. The polysilane is a linear or cyclic polysilane having a structural unit represented by the formula (1), wherein R ¹
Is a C _1-4 alkyl group and R ² is a C _6-10 aryl group. 6. The thermoplastic resin composition according to claim 1, which is composed of at least one thermoplastic resin selected from olefin resins, vinyl resins, styrene resins, aliphatic polyamide resins, polyester resins, and polycarbonate resins. The resin film described. 7. The resin film according to claim 1, which is composed of a polyethylene resin. 8. The resin film according to claim 1, wherein a polysilane layer is formed on at least the surface of the heat-bonded portion. 9. The coating amount of polysilane at the heat-bonded portion is
0.1-50g / m ²The resin fill according to claim 1, which is
Mu. 10. The resin film according to claim 1, which contains polysilane in the heat-bonding site. 11. The resin film according to claim 1, which contains 0.1 to 50 parts by weight of polysilane with respect to 100 parts by weight of the resin. 12. A method for producing a resin film according to claim 1, wherein polysilane is held at least at a thermal bonding site. 13. A composite film comprising a base film and the resin film according to claim 1 laminated on the base film. 14. The base film is at least one thermoplastic resin selected from polypropylene-based resins, aliphatic polyamide-based resins, aromatic polyester-based resins, polyimide-based resins, polycarbonate-based resins, and cellulose-based resins. The composite film according to claim 13, which is constituted. 15. A method for producing a composite film according to claim 13, wherein the base film and the resin film according to claim 1 are laminated. 16. A method of lowering the thermal bonding temperature of a resin film by holding polysilane at least at a thermal bonding site.