JPH0557294B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a thermoplastic resin laminated film that is easily slippery and has excellent adhesive properties, particularly a thermoplastic resin laminated film that has good adhesive properties to hydrophilic polymers, hydrophobic polymers, and inorganic materials. Regarding film. (Prior art) Thermoplastic resin films such as polyester, polyamide, and polypropylene (especially polyester films such as polyethylene terephthalate)
is a base film for magnetic tape, with excellent mechanical strength, heat resistance, chemical resistance, transparency, and dimensional stability.
It is widely used in applications such as insulating tape, photographic film, tracing film, and food packaging film. However, these thermoplastic resin films usually lack adhesion to hydrophilic polymers, hydrophobic polymers, and inorganic materials. Therefore, when a magnetic material, a photosensitive agent, a matting agent, etc. are to be laminated on this film, it is necessary to apply a corona discharge treatment to the surface of the film and then provide an anchor coat layer. Furthermore, even if this film is used as a food packaging film and a printing layer or heat-sealing layer is provided, the adhesion between these layers and the thermoplastic resin film is weak.
Heat seal strength may decrease. In order to improve the adhesion of thermoplastic resin films, in addition to corona discharge treatment, the film is subjected to physical treatments such as ultraviolet irradiation treatment, plasma discharge treatment, flame treatment, and corona discharge treatment under a nitrogen atmosphere. A method is proposed. Chemical treatment methods such as alkali treatment and primer treatment, as well as the combination of these and physical treatment methods, are also used. However, none of these methods can sufficiently improve the adhesion of thermoplastic resin films. In particular, the adhesion between the hydrophilic polymer or hydrophobic polymer and the film is insufficient. Furthermore, among the above-mentioned various treatments, especially primer treatment generally reduces the slipperiness of the resulting film, resulting in poor workability such as winding performance. (Problems to be Solved by the Invention) The present invention solves the above-mentioned conventional problems, and its purpose is to provide a hydrophilic polymer,
The object of the present invention is to provide a thermoplastic resin laminated film that has good adhesion to both hydrophobic polymers and inorganic substances and is easily slippery. (Means for Solving the Problems) The present invention provides at least one of a water-soluble resin, a water-emulsifiable resin, and a water-dispersible resin, a specific organic boron polymer compound, and polyvinyl alcohol on the surface of a thermoplastic resin film. By laminating a composition containing the composite as a main component, the adhesion between a hydrophilic polymer, a hydrophobic polymer, or an inorganic substance and a thermoplastic resin film can be significantly improved, and the film also has excellent slipperiness. It was completed based on the inventor's knowledge. The thermoplastic resin laminated film of the present invention has at least one of a water-soluble resin, a water-emulsifiable resin, and a water-dispersible resin on at least one side of the thermoplastic resin film, and an organic boron polymer compound represented by the following formula () and This is a thermoplastic resin laminated film in which a composition containing a polyvinyl alcohol composite as a main component is laminated, whereby the above objects are achieved: Here, p is 10 to 10000; q is 0 or 1; when q is 1, A is -(X) _l -(Y) _n -(Z) _o -, and X and Z are one Y is an oxygenated hydrocarbon group having a terminal ether residue and a total number of carbon atoms of 100 or less,

[Formula] Group (where R is a hydrocarbon group having 1 to 34 carbon atoms) or

[Formula] group (wherein R' is a hydrocarbon group having 2 to 13 carbon atoms), and l, m and n are each independently 0 or 1. The organic boron polymer compound () forming the above-mentioned composite used in the thermoplastic resin laminate film of the present invention can be prepared by the following method. (1) React the following compound () having two glycerin residues at the end of the molecule with boric acid, boric acid triester, or boric anhydride: Here, q is 0 or 1; when q is 1, A is −(X) _l −(Y) _n −(Z) _o −, and X and Z
is an oxygen-containing hydrocarbon group with one terminal ether residue and the total number of carbon atoms is 100 or less, Y is

[Formula] Group (where R is a hydrocarbon group having 1 to 34 carbon atoms) or

[Formula] is a group (where R' is a hydrocarbon group having 2 to 13 carbon atoms), and l, m and n are each independently 0
or 1. As the boric acid triester, an ester of boric acid and a lower alcohol having 4 or less carbon atoms is used. With respect to 1 mole of compound (), boric acid and boric acid triester are reacted in a proportion of 1 mole, and boric anhydride is reacted in a proportion of 0.5 mole. (2) Perform a polyetherification reaction by adding ethylene oxide, etc. to di(glycerin) borate or a diol containing di(glycerin) borate residues and having a total number of carbon atoms of 206 or less. Alternatively, dicarboxylic acid having 3 to 36 carbon atoms; (ester of lower alcohol having 4 or less carbon atoms and the above dicarboxylic acid; dicarboxylic acid having 3 to 36 carbon atoms; An acid halide; or a diisocyanate having 4 to 15 carbon atoms is reacted in an equimolar amount. In the preparation methods (1) and (2) above, two or more types of raw materials may be used as a mixture. For example, ,
Two or more compounds having different groups represented by -{A} _q - may be used together as the compound of the above formula (). Examples of the organic boron polymer compounds obtained in this way include the following compounds: Polyvinyl alcohol (PVA) that forms a complex with the above organoboron polymer compound () is obtained from polyvinyl acetate with a saponification degree of 70 to
PVA with a concentration of 100 mol% and a degree of polymerization of 100 to 3000 is used. The saponification degree of PVA is preferably 85 mol% or more,
The degree of polymerization is 200 or more. A complex of the organic boron polymer compound (2) and PVA is formed by mixing the two in a solution or suspension state and heating as necessary. The mixing ratio of the organic boron polymer compound (2) and PVA at this time is 5:95 to 95:5, preferably 10:90 to 50:50 by weight. Specifically, for example, a PVA aqueous solution is prepared, and the organic boron polymer compound () is added dropwise to the solution while stirring. The reaction temperature at this time is 20
-100°C, preferably 50-80°C. Although the detailed structure of the formed complex is unknown, for example,
It is thought that the structure is such that PVA chains are crosslinked by an organic boron polymer compound. Among the resins contained in the composition used in the film of the present invention, any of natural polymer compounds, semi-synthetic polymer compounds, and synthetic polymer compounds can be used as the water-soluble resin. Examples of natural polymer compounds include starches, sodium alginate, and proteins (gelatin, etc.). Examples of semi-synthetic polymer compounds include cellulose resins such as carboxycellulose, and starch resins such as soluble starch. Examples of synthetic polymer compounds include poly(meth)acrylates, poly(meth)acrylate-containing copolymers, polyethylene oxide, and modified products of the above polymers. Furthermore, synthetic polymer compounds include epoxy resins prepared using polyhydric alcohols such as ethylene glycol and pentaerythritol; acrylic resins containing a high content of hydrophilic groups such as sulfonic acid groups, phosphinate groups, and ammonium groups Examples include resins, polyester resins, polyurethane resins, and polyamide resins. Materials for water-emulsifiable resins and water-dispersible resins include polybutadiene, poly(styrene-butadiene), poly(acrylonitrile-butadiene).
Rubber resins such as polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride and their copolymers; acrylic acid, methyl methacrylate, hydroxymethyl acrylate, styrene, glycidyl methacrylate, methyl acrylate, ethyl acrylate, etc. Acrylic resin prepared using; isophthalic acid, adipic acid,
Examples include polyester resins prepared using sebacic acid, ethylene glycol, diethylene glycol, neopentyl glycol, polyethylene glycol, polytetramethylene glycol, and the like; and polyurethane resins prepared using the above glycols and diisocyanates. In addition to the above, water-emulsifying resins and water-dispersible resins have hydrophilic groups in their molecules, so they exhibit dispersibility in aqueous solvents, or they have hydrophilic groups in their molecules, so they require a small amount of dispersion aid. Includes polymer compounds that exhibit dispersibility in aqueous solvents when added. Examples of the hydrophilic group include a phosphonic acid group, a phosphinic acid group, a sulfonic acid group, an ammonium group, and a carboxyl group. Examples of resins having such hydrophilic groups include polyesters, polyurethanes, polyamides, acrylic resins, epoxy resins, and polyolefin resins. The water-emulsifiable resin or water-dispersible resin is advantageously prepared, for example, by an emulsion polymerization method in which monomers are polymerized in an emulsified state. Of course, it is also possible to prepare the composition using other conventional methods, and in the case of a composition, the obtained polymer can be dispersed in water in an emulsified state using a surfactant or an organic solvent, and the film can be prepared as described below. can be conveniently used. Among the resins listed as the water-soluble resin, water-emulsifiable resin, and water-dispersible resin, polyester, polyurethane, and acrylic resin are particularly preferred. These will be described in more detail below. Among the carboxylic acid components and diol components that make up polyester, the carboxylic acid components include:
Terephthalic acid, isophthalic acid, orthophthalic acid,
Aromatic dicarboxylic acids such as 1,5-naphthalic acid;
p-oxybenzoic acid, p-(hydroxyethoxy)
Aromatic oxycarboxylic acids such as benzoic acid; aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid;
unsaturated aliphatic dicarboxylic acids such as fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid;
Examples include alicyclic dicarboxylic acids such as hexahydrophthalic acid; tri- and tetracarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid. Glycol components constituting the polyester include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-
hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol,
2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A,
Diols include ethylene oxide adducts of hydrogenated bisphenol A, propylene oxide adducts of hydrogenated bisphenol A, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Tri- and tetraols such as trimethylolethane, trimethylolpropane, glycerin, and pentaerythritol may be used in combination. In addition to the above, relatively high molecular weight diols include polyester polyols, including lactone-based polyester diols obtained by ring-opening polymerization of lactones such as ε-caprolactone. The resins contained in the composition used for the film of the present invention, such as polyester, polyurethane resins and acrylic resins described below, may have a hydrophilic group as described above. For example, hydrophilic groups suitable for polyester and polyurethane resins and compounds containing such groups are illustrated below. (1) -COOM (M represents a hydrogen atom, an alkali metal, tetraalkylammonium or tetraalkylsulfonium) polycarboxylic acid, glyceric acid, dimethylolpropionic acid, N,N-diethanolglycine,
Oxycarboxylic acids such as hydroxyethyloxybenzoic acid; aminocarboxylic acids such as diaminopropionic acid and diaminobenzoic acid and their derivatives. (2)

[expression] or

[Formula] (R ₁ to _{R 3} each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aralkyl group) N-methyldiethanolamine, 2-methyl-
2-dimethylaminomethyl-1,3-propanol, 2-methyl-2-dimethylamino-1,3-
Nitrogen-containing alcohols such as propanediol and their derivatives. (3) (R ₁ has the same meaning as above) picolinic acid, dipicolinic acid, aminopyridine,
Pyridine ring-containing compounds and derivatives thereof, such as diaminopyridine, hydroxypyridine, dihydroxypyridine, aminohydroxypyridine, pyridinylmethanol, pyridinylpropanediol, and pyridinylethanol. (4) _-SO3M (M has the same meaning as above) Polycarboxylic acids such as 5-sodium sulfoisophthalic acid, sulfoisophthalic acid, sodium sulfosuccinic acid, and derivatives thereof; sodium sulfohydroquinone and its alkylene oxide addition substances; sodium sulfobisphenol A and its alkylene oxide adducts, etc. (5) Phosphorus-containing hydrophilic group [R ₄ is a trivalent hydrocarbon group having 3 to 10 carbon atoms; R ₅
is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, an alkoxy group having 1 to 12 carbon atoms,
It is a cycloalkoxy group or an aryloxy group [The aryl group and the aryloxy group are a halogen atom, a hydroxy group, -OM ₂ (M ₂
represents an alkali metal) or an amino group]; R ₆ and R ₇ are each an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group,
An arylene group or a group represented by the formula --(CH ₂ OR ₆ ) _r -- (R ₈ represents an alkylene group having 1 to 12 carbon atoms,
represents a cycloalkylene group or an arylene group,
r is 1 to 4); and M ₁ represents an alkali metal atom, hydrogen, a monovalent hydrocarbon group, or an amino group] Examples of compounds represented by formula ()-1 Examples of compounds represented by formula ()-2 Examples of compounds represented by formula ()-3 Example of compound represented by formula ()-4 Examples of compounds represented by formula ()-5 Using the above carboxylic acid component, glycol component and optionally the above monomer having a hydrophilic group,
Polyesters are usually prepared by a melt polycondensation method. For example, a direct esterification method in which each of the above components is directly reacted, water is distilled off, esterified, and polycondensation is performed; or methyl alcohol is distilled out by reacting the dimethyl ester of the dicarboxylic acid component with the glycol component. It is prepared by a transesterification method that involves transesterification and polycondensation. In addition to the melt polymerization method, a solution polycondensation method, an interfacial polycondensation method, etc. may also be employed. Among the resins contained in the composition used in the film of the present invention, polyurethane can be obtained by, for example, chain-extending polyalkylene glycol or the like with polyisocyanate; or by polyester polyol (polycondensation of a carboxylic acid component and a glycol component). It is prepared by chain-extending the polyisocyanate obtained by As the polyalkylene glycol, polyethylene glycol, polybutylene glycol, polypropylene glycol, etc. are used. As the carboxylic acid component and glycol component serving as raw materials for the polyester polyol, any of the carboxylic acid components and glycol components listed in the section for polyester preparation can be used.
The above polyisocyanate includes 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate,
biphenylmethane diisocyanate, m-phenylene diisocyanate, xamethylene diisocyanate, tetramethylene diisocyanate, 3,
3'-Dimethoxy-4,4'-biphenylene diisocyanate, 2,4-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 4,4'-diphenylene diisocyanate, 4 , 4'-Diisocyanate-diphenyl ether, 1,5'-naphthalene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 1,3-diisocyanatemethylcyclohexane, 1,4-diisocyanatemethylcyclohexane, 4,4' There are diisocyanate compounds such as -diisocyanate dicyclohexane, 4,4'-diisocyanate cyclohexylmethane, and isophorone diisocyanate. These polyisocyanates include 2,4-
Triisocyanate compounds such as tolylene diisocyanate trimer and hexamethylene diisocyanate trimer account for 7 of the total isocyanate groups.
It may be contained in a proportion of mol% or less. Polyurethane is prepared by a conventional method using each of the above components. It is also possible to use monomers with hydrophilic groups as described in the section on polyester preparation and to incorporate these into the polyurethane backbone. The acrylic resin is obtained by polymerizing acrylic acid or a derivative thereof, and, if necessary, a monomer other than acrylic acid (derivative) having a vinyl group. The monomers used include the following compounds. R ₉ is H or an alkyl group having 1 to 4 carbon atoms;
R ₁₆ is an alkyl group having 1 to 8 carbon atoms. R ₁₁ is H or an alkyl group having 1 to 4 carbon atoms;
R ₁₂ and R ₁₃ are each independently H or an alkyl group having 1 to 8 carbon atoms. R ₁₄ is H or an alkyl group having 1 to 4 carbon atoms;
R ₁₅ is H, −(CH ₂ ) _s −OH, −(CH ₂ ) _s −RO ₁₆ , −
{(CH ₂ ) _s −O−} _t −R ₁₇ or

s and t are each independently an integer of 1 to 3; and R ₁₆ and R ₁₇ are each independently an alkyl group having 1 to 4 carbon atoms. R ₁₈ is H or an alkyl group having 1 to 4 carbon atoms;
R ₁₉ and R ₂₀ are each independently Cl, -OH or an alkoxy group having 1 to 8 carbon atoms. R ₂₁ is H or an alkyl group having 1 to 4 carbon atoms;
_M3 is H, an alkali metal or _-NH4 . R ₂₂ is H or an alkyl group having 1 to 4 carbon atoms, and M ₃ has the same meaning as above. CH ₂ =CHSO ₃ R ₂₃ ()-5-3 R ₂₃ is H or an alkyl group having 1 to 8 carbon atoms. R ₂₄ and R ₂₅ are each independently H or an alkyl group having 1 to 4 carbon atoms. _R26 is H or an alkyl group having 1 to 4 carbon atoms. Among these, the compounds represented by the formula ()-1 include acrylic acid and methacrylic acid (hereinafter referred to as acrylic acid and/or methacrylic acid).
acrylic acid), lower alkyl esters of (meth)acrylic acid (eg, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, 2-ethylhexyl ester), and the like. Compounds represented by the formula ()-2 (including analogs thereof) include styrene; p-monoalkylstyrene; 2,4
-(or 2,5-,2,6-,3,4-,3,
5-) Dialkylstyrene; 2,4,5-(or 2,4,6-)trialkylstyrene; 2,
3,4,5-tetraalkylstyrene; α-methyl substituted products of these styrenes and derivatives thereof, and the like. As a compound represented by the formula ()-3,
Examples include hydroxyalkyl esters, alkoxyalkyl esters, alkylalkylene glycol esters, and glycidyl esters of (meth)acrylic acid. Compounds represented by ()-4 (including analogs thereof) include o-(or m-, p-)
Monochlorostyrene, 2,3-(or 2,4-,
2,5-,2,6-,3,4-,3,5-)dichlorostyrene, 2,3,4-(or 2,4,5-)
-) Halogen-substituted styrenes such as trichlorostyrene, tetrachlorostyrene, and pentachlorstyrene; 2-chloro-5-methylstyrene, 4-
Halogen-alkyl substituted styrenes such as chloro-3-methylstyrene, p-chloromethylstyrene; o-(or m-, p-) hydroxystyrene, o-(or m-, p-) methoxystyrene;
o-(or m-, p-)ethoxystyrene, 3
-methoxy-4-hydroxystyrene and other hydroxy or alkoxystyrene derivatives. Examples of the compounds represented by ()-5-1 to ()-5-4 include ethylene sulfonic acid, alkali metal ethylene sulfonate salts (e.g., sodium salt, potassium salt); vinylmethylsulfonine, vinylethylsulfone, vinyl Vinyl alkyl sulfonic acids such as butyl sulfone; vinyl sulfonamides such as vinyl sulfonamide, vinyl sulfonanilide, and vinyl sulfone methyl anilide; styrene sulfonic acid, alkali metal salts of styrene sulfonate (e.g., sodium salts, potassium salts); mono( Examples include 2-methacryloyloxyethyl) acid phosphate and mono(2-acryloyloxyethyl) acid phosphate. Among the compounds listed in ()-1 to ()-5, (meth)acrylic acid, glycidyl (meth)acrylate, mono(2-(meth)acryloyloxyethyl)acid phosphate, hydroxy Ethyl (meth)acrylate and the like are suitable. The acrylic resin can be prepared by a conventional method using the above monomers. For example, it is prepared by a method in which the above monomers are reacted in an aqueous medium in the presence of a water-soluble polymerization initiator (suspension polymerization method). As the polymerization initiator, ceric ammonium nitrate, ceric ammonium sulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, etc. are used. The polymerization reaction is normally carried out at a temperature of 0 to 100°C, preferably 5 to 80°C. 0℃
If the temperature is below 100°C, the polymerization rate will be slow, and if it exceeds 100°C, the polymerization initiator will decompose and the stability of the polymerization system will decrease, making it easier to gel. In addition to the above suspension polymerization method,
It can also be prepared using a solution polymerization method or a bulk polymerization method. The resin composition used in the present invention includes at least one of the above-mentioned water-soluble resin, water-emulsifiable resin, and water-dispersible resin (these are collectively referred to as aqueous resin), the above-mentioned organoboron polymer compound (), and polyvinyl alcohol. The main component is a complex with. The content ratio of the aqueous resin and the above composite is 95/5 to 5/95
(w/w), preferably 80/20 to 20/80 (w/w)
It is. When the aqueous resin content is less than 5% by weight, the adhesion between the resulting film and the hydrophobic polymer is somewhat poor. Conversely, if the amount of the composite is less than 5% by weight, the adhesion between the resulting film and the hydrophilic polymer will be somewhat poor. The composition may further contain a coloring agent, an antistatic agent, a crosslinking agent, an anti-blocking agent, a lubricant using particles of inorganic or organic materials, other polymers, an ultraviolet absorber, and an anti-deterioration agent, if necessary. drugs, etc.
It may be contained in a proportion that does not impair the properties of the resulting film. The thermoplastic resin film (base film) on which the above composition is laminated includes polyester film, polyamide film, polycarbonate film, polyphenylene sulfide film,
Examples include polyetherimide film, polyether sulfone film, polyolefin film, cellulose film, PVA film, acrylic film, vinyl chloride film, etc. Applications and required characteristics of the final laminated film. The most suitable material is selected according to the The most commonly used materials include polyester film, polyamide film, polycarbonate film, and cellulose film. The base film is usually obtained by melting and extruding the thermoplastic resin that is its raw material, or by dissolving the resin in a solvent and casting it. After such an unstretched film is uniaxially or biaxially stretched as required, the above-mentioned composition is applied (coated) to the surface thereof by the method described below. A method of applying a composition to an unstretched or uniaxially stretched base film and further stretching it as necessary improves the adhesion between the base film and the composition, imparts slipperiness, and improves the durability of the obtained film. It is more preferable from the following points. Biaxially stretched base film has a wide film width, and in order to coat the composition thinly on this base film, it is necessary to increase the running speed of the film, so it is somewhat difficult to coat uniformly. . The thermoplastic resin laminate film of the present invention is prepared, for example, by the following method. First, the above composition is dissolved, dispersed or emulsified in water or an aqueous solvent. This can be done, for example, by adding a complex of an organoboron polymer compound and polyvinyl alcohol to the latex; or by adding water or an aqueous solvent while kneading the resin and the complex in a molten state. . The above aqueous solvent is
For example, it is a solvent containing an organic solvent such as alcohol (eg, methyl alcohol, ethyl alcohol, isopropyl alcohol) in a proportion of 50% by weight or less in addition to water. The organic solvent is added for the purpose of improving the coating properties of the coating liquid on the base film and also for the purpose of improving the drying properties after coating. If the content of organic solvent is 50% by weight or less, there is no risk of the coating solution catching fire or exploding. For the purpose of improving coating properties, it is also recommended that the composition contain additives such as fluorine-based resins, silicone-based resins, and surfactants. The coating solution containing this composition is usually applied to the surface of the base film at a concentration of 0.003 to 5 g/m ² ,
It is preferably applied at a rate of 0.01 to 3 g/m ² .
Below 0.003g/ ^m2 , the obtained film and
Poor adhesion with other resins intended for adhesion, 5
If it exceeds g/m ² , the resulting film will have poor slipperiness and anti-blocking properties. In addition to the coating method in which the above-mentioned coating solution is prepared and applied to the base film, for example, a coextrusion coating method, an extrusion lamination method, a dry lamination method, a hot melt adhesion method, etc. may be employed. Before or after laminating the resin composition by a method such as coating, the surface of the base film may be subjected to corona discharge treatment or ultraviolet irradiation treatment in an air or nitrogen atmosphere. These treatments further improve the adhesion between the base film and the resin composition, or the adhesion between the obtained film and other resins. The composition used for the film of the present invention contains a complex of an organoboron polymer compound having a specific structure and polyvinyl alcohol, and an aqueous resin. It has good adhesion to both natural polymers and inorganic materials. Therefore, the thermoplastic resin laminate film of the present invention provided with this resin composition layer exhibits good adhesion to both hydrophobic polymers and hydrophilic polymers. Furthermore, the resin composition film containing the above composite and the aqueous resin has fine irregularities formed on its surface. Therefore, the film of the present invention also has good slip properties. Such films are used as base films for printing, base films for magnetic tapes, base films for label stickers, base films for chemical mats, films for overhead projectors, films for food packaging, and the like. (Example) The present invention will be described below with reference to Examples. Example 1 (A) Preparation of thermoplastic resin laminated film The dicarboxylic acid units were 50 mol% of terephthalic acid,
A sulfonic acid-modified polyester (molecular weight approx. 2
10,000) were synthesized. This polyester was dispersed in water at a proportion of 10% by weight. Separately, an organic boron polymer compound ()-1 (P ₁ = 1000) was added to an aqueous solution of polyvinyl alcohol with a degree of saponification of 88% and a degree of polymerization of 500.
The weight ratio of PVA and organic boron polymer compound is 1:
4 and stirred at 40 to 50°C for 30 minutes to obtain a complex aqueous solution. This composite aqueous solution was added to the polyester aqueous solution in such a proportion that the composite was 50% by weight in terms of solid content based on the polyester to prepare a coating solution. On the other hand, polyethylene terephthalate is 280-300
The film was melt-extruded at 15°C and cooled with a cooling roll at 15°C to obtain an unstretched film with a thickness of 150 μm. This unstretched film was stretched 3.5 times in the longitudinal direction through a pair of rolls at different circumferential speeds of 85°C. The above coating liquid was applied to the surface of this film using an air knife method and dried with hot air at 70°C to form a resin composition layer. This film was stretched 3.5 times in the transverse direction at 98℃ using a tenter, and then heat-set at 200-210℃ to a thickness of 12μm.
A biaxially stretched coated polyester film (resin composition layer 0.15 μm) was obtained. (B) Evaluation of thermoplastic resin laminated film (1) Adhesion A 10% aqueous solution of polyvinyl alcohol (PVA, a hydrophilic polymer) and a 10% DMF (dimethylformamide) solution of polyvinyl chloride (PVC, a hydrophobic polymer) were used. Prepared. Each solution was colored with a red dye, and a coating amount of 2
g/m ² and were printed separately. Incisions were made in the resulting printed layer in a grid pattern at 1 mm intervals using a cutter knife to form 100 grids. On each printing surface of this thermoplastic resin laminated film,
After uniformly applying cellophane tape (L Pack, manufactured by Nichiban Co., Ltd.), this tape was quickly peeled off in a 180 degree direction. After repeating the peel test three times, the number of remaining eyelets was counted on the printed surface.
The results are shown in Table 1. (2) Slip property (friction coefficient) Using the film obtained in section (A), ASTM-
The friction coefficient was measured according to 1894. The results are shown in Table 1. Comparative Example 1 PVA (saponification degree 88%, polymerization degree
The procedure was the same as in Example 1 except that an aqueous solution of 500) was used. The results are shown in Table 1. Table 1 also shows the results of Comparative Examples 2 to 4, which will be described later. Comparative Example 2 This was the same as Example 1 except that the organoboron polymer compound used to prepare the complex was used instead of the aqueous solution containing the complex of PVA and the organoboron polymer compound. Comparative Example 3 The same as Example 1 except that the 10% by weight aqueous polyester dispersion obtained in Example (A) was used as the coating liquid. Comparative Example 4 Same as Example 1 except that no coating liquid was applied.

【table】

[Table] From Table 1, the thermoplastic resin film of the present invention is
It can be seen that it has excellent adhesion to both PVA, which is a hydrophilic polymer, and PVC, which is a hydrophobic polymer, and has good sliding properties. On the other hand, such an effect cannot be obtained in a film in which a layer of a composition not containing a composite of PVA and an organic boron polymer compound is formed, and in a film in which a resin composition is not formed. Example 2 A 10% aqueous dispersion of a sulfonic acid-modified polyester having a molecular weight of 4000 was prepared in the same manner as in Example 1 by shortening the reaction time. This polyester
After dissolving 100 parts by weight in 72 parts by weight of methyl ethyl ketone and 72 parts by weight of toluene, 21 parts by weight of 4,4'-diphenylmethane diisocyanate and 0.05 parts by weight of dibutyltin dilaurate were added to this solution, and the mixture was heated to 70 to 80°C. The mixture was allowed to react for 3 hours. The solvent was evaporated to obtain an aqueous dispersion containing polyester polyurethane. Separately, an organic boron polymer compound was added to an aqueous solution of PVA with a degree of saponification of 92% and a degree of polymerization of 650 so that the weight ratio of PVA and the organic boron polymer compound was 1:9, and the mixture was heated at 40 to 50°C. The mixture was stirred for 30 minutes to obtain an aqueous complex solution. As an organic boron polymer compound, ()-
8 (x ₆ +z ₃ =100; P ₈ =2) was used. This composite aqueous solution was added to the aqueous dispersion of the polyester polyurethane described above so that the solid content ratio was 100:50 (weight ratio) to obtain a coating liquid. Using this, a thermoplastic resin laminated film was prepared in the same manner as in Example 1. Using this film, the adhesiveness to polyvinyl alcohol and slipperiness were evaluated in the same manner as in Example 1. The results are shown in Table 2. Example 3 The same as Example 2 except that the compound ()-5 (x ₃ = 32, x ₄ = 2, P ₅ = 20) was used as the organoboron polymer compound. Example 4 The same as Example 2 except that the compound ()-2 (x ₁ =9, P ₂ =10) was used as the organoboron polymer compound.

[Table] Example 5 (A) Synthesis of phosphorus-containing polyurethane In an autoclave equipped with a thermometer and a stirrer, 485 parts by weight of dimethyl terephthalate, 485 parts by weight of dimethyl isophthalate, 409 parts by weight of ethylene glycol, and 485 parts by weight of neopentyl glycol. and 0.68 parts by weight of tetrabutoxy titanate were charged and heated at 150 to 230°C for 120 minutes to perform transesterification. Next, 50.1 parts by weight of the phosphorus-containing compound (()-2-2) described herein was added, and the mixture was heated at 220 to 230°C.
The reaction was continued for an additional hour. The temperature of this reaction system was still raised to 250°C in 30 minutes, and the pressure of the system was gradually reduced to 10 mmHg after 45 minutes, and the reaction was continued under these conditions for an additional 60 minutes. The obtained polyester diol A had a molecular weight of 2500 and a phosphorus content of 1600 ppm. Next, 100 parts by weight of the above polyester diol A was added to 72 parts by weight of toluene and 72 parts by weight of methyl ethyl ketone.
After dissolving in parts by weight, 21 parts by weight of 4,4'-diphenylmethane diisocyanate and 0.05 parts by weight of dibutyltin dilaurate were added, and the mixture was reacted at 70 to 80°C for 3 hours. (B) Preparation and evaluation of thermoplastic resin laminated film 300 parts by weight of the phosphorous-containing polyurethane obtained in section (A) and 140 parts by weight of n-butyl cellosolve were placed in a container.
The mixture was stirred at 150 to 170°C for about 3 hours to obtain a uniform and viscous melt. 560 parts by weight of water was gradually added to this melt, and after about 1 hour, a homogeneous pale white aqueous dispersion (solid content concentration 30%) was obtained. Separately, an organic boron polymer compound (()-6; x ₅ = 200,
_P6 = 10) was added so that the weight ratio of PVA and the organoboron polymer compound was 3:7, and the mixture was heated at 40 to 50℃ for 30 minutes.
The mixture was stirred for a minute to obtain a complex aqueous solution. This composite aqueous solution was added to the above aqueous dispersion so that the solid content ratio was 100:150 (weight ratio), and ethyl alcohol was further added to dilute it to obtain a coating liquid with a solid content concentration of 4.5%. This coating solution was applied to a cellulose acetate film using an air knife method and dried with hot air at 100°C to obtain a coated cellulose acetate film with a coating weight of 0.3 g/m ² . The obtained film was evaluated for adhesion and slipperiness with polyvinyl alcohol in the same manner as in Example 2.
In all cases, almost the same results as in Example 2 were obtained. Example 6 (A) Synthesis of acrylic resin

[Table] Add water to 2 four-necked flasks equipped with a reflux condenser.
650 g, of the monomers shown in the table above (total amount 350 g), the total amount of sodium vinyl sulfonate, one-fifth amount of each of the other monomers, 0.85 g of dodecyl mercaptan and potassium persulfate (catalyst; total amount)
0.2g) was charged. The temperature was raised to 80° C. with stirring under a nitrogen flow, and at the same temperature, the remaining monomers and catalyst were gradually added over 1 hour and 30 minutes. Stirring was continued for an additional hour at the same temperature to complete the reaction. A milky white liquid, uniform and stable emulsifier-free latex was obtained. (B) Preparation and evaluation of thermoplastic resin laminated film Organic boron polymer compound ()-1; (P ₁ = 1000) in a PVA aqueous solution with a degree of saponification of 80% and a degree of polymerization of 1000.
was added so that the weight ratio of PVA and the organic boron polymer compound was 1:9, and the mixture was stirred at 40 to 50°C for 30 minutes to obtain an aqueous composite solution. Latex 1000 above
This aqueous solution was added to parts by weight so that the solid content ratio was 2:1, and water was further added to make 3000 parts by weight.
This coating solution was coated on a polyethylene naphthalate film, dried at 100℃, and then heated to 150℃ under tension.
heat treated with When this film was evaluated for adhesion and slipperiness to polyvinyl alcohol in the same manner as in Example 2, almost the same results as in Example 2 were obtained. (Effects of the Invention) The thermoplastic resin laminated film of the present invention has a composite of a specific organic boron polymer compound and polyvinyl alcohol in the thermoplastic resin film,
Since it is constructed by laminating a composition containing a resin and a resin, it has good adhesion to all hydrophilic polymers, hydrophobic polymers, and inorganic materials, and has extremely good slipperiness. Therefore, this thermoplastic resin laminated film is suitably used for applications such as base films for magnetic tapes, insulating tapes, photographic films, tracing films, and films for food packaging. It has excellent workability without causing blocking even during film processing.

Claims (1)

[Claims] 1. On at least one side of the thermoplastic resin film,
A thermoplastic material in which a composition mainly composed of at least one of a water-soluble resin, a water-emulsifiable resin, and a water-dispersible resin, and a composite of an organic boron polymer compound and polyvinyl alcohol represented by the following formula () is laminated. Resin laminated film: Here, p is 10 to 10000; q is 0 or 1; when q is 1, A is -(X) _l -(Y) _n -(Z) _o -, and X and Z are one An oxygen-containing hydrocarbon group having a terminal ether residue and a total number of carbon atoms of 100 or less, Y is a [formula] group (however, R is a hydrocarbon group having 1 to 34 carbon atoms) or a [formula] group (however, , R' is a hydrocarbon group having 2 to 13 carbon atoms), and l, m and n are each independently 0 or 1.