JPH0557293B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a thermoplastic resin laminated film with excellent adhesiveness, and particularly to a thermoplastic resin laminated film with good adhesiveness to any of hydrophilic polymers, hydrophobic polymers, and inorganic materials. (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. (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. (Means for Solving the Problems) The present invention provides a thermoplastic resin film containing at least one of a water-soluble resin, a water-emulsifiable resin, and a water-dispersible resin as main components and a specific organic boron polymer compound on the surface of a thermoplastic resin film. This invention was completed based on the inventor's knowledge that the adhesion between a hydrophilic polymer, a hydrophobic polymer, or an inorganic substance and a thermoplastic resin film can be significantly improved by laminating the composition. The thermoplastic resin film of the present invention mainly contains at least one of a water-soluble resin, a water-emulsifiable resin, and a water-dispersible resin, and an organic boron polymer compound represented by the following formula on at least one side of the thermoplastic resin film. This is a thermoplastic resin laminated film laminated with a composition that achieves the above objects: 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 with 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 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 polyether 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, for di(glycerol)borate or a diol having the above di(glycerol)borate residue, a dicarboxylic acid having 3 to 36 carbon atoms; (ester of a lower alcohol having 4 or less carbon atoms and the above dicarboxylic acid; A dicarboxylic 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: 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 polyvinyl alcohol, partially saponified polyvinyl acetate, poly(meth)acrylate, poly(meth)acrylate-containing copolymers, polyethylene oxide, and modified products of the above polymers. be. 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 hydrogen atom, 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, pyridinyldimethanol, 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 ₈ ) _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 melt polycondensation. For example, a direct esterification method in which each of the above components is directly reacted to distill water and esterify, and polycondensation is also performed; or a method in which the dimethyl ester of the dicarboxylic acid component and the glycol component are reacted and methyl alcohol is distilled off. 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 styrene such as trichlorostyrene, tetrachlorostyrene, pentachlor, styrene; 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 has at least one of the above-mentioned water-soluble resin, water-emulsifiable resin, and water-dispersible resin (collectively referred to as water-based resin) and the above-mentioned organoboron polymer compound as main components. do. The content ratio of aqueous resin and organic boron polymer compound is
95/5~5/95 (w/w), preferably 80/20~
It is 20/80 (w/w). When the content of the aqueous resin is less than 5% by weight, the adhesion between the resulting film and the hydrophilic polymer is somewhat poor. On the other hand, if the amount of the organic boron polymer compound is less than 5% by weight, the adhesion between the resulting film and the hydrophilic polymer will be somewhat poor. The composition further contains a colorant, an antistatic agent,
Crosslinking agents, anti-blocking agents, lubricants using particles of inorganic or organic materials, other polymers, ultraviolet absorbers, deterioration inhibitors, etc. are contained in proportions that do not impair the properties of the resulting film. It's okay. 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 properties 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. From the viewpoint of the adhesion between the base film and the composition, the durability of the obtained film, etc., the method of applying the composition to an unstretched or uniaxially stretched base film and further stretching it as necessary is More preferred. 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 carried out, for example, by adding an organic boron polymer compound to the latex; or by adding water or an aqueous solvent while kneading the resin and the organic boron polymer compound in a molten state. The above-mentioned aqueous solvent is, for example, 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 fluid catching fire or exploding. For the purpose of improving coating properties, fluorocarbon resins, silicone resins,
It is also recommended to include a surfactant or the like.
The coating solution containing this composition is applied onto the surface of the base film at a concentration of usually 0.01 to 5 g/m ² , preferably 0.02 to 5 g/m 2 .
It is applied at a rate of 3 g/m ² . If it is less than 0.01 g/m ² , the adhesiveness between the obtained film and other resin for adhesion will be poor, and if it exceeds 5 g/m ² , the obtained film will have poor slipperiness and anti-blocking properties. inferior to sex. 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 layer, or the adhesion between the obtained film and other resins. Since the composition used for the film of the present invention contains an organic boron polymer compound having a specific structure and an aqueous resin, the composition is free from any of hydrophobic polymers, hydrophilic polymers, and inorganic substances. Good adhesion. 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. Such films include base films for printing, base films for magnetic tapes, base films for label stickers,
Used in base films for chemical mats, films for overhead projectors, films for food packaging, etc. (Example) The present invention will be described below with reference to Examples. Example 1 (1) Preparation of thermoplastic resin laminated film The dicarboxylic acid units were 50 mol% of terephthalic acid,
A sulfonic acid-modified polyester was synthesized, which was composed of 30 mol% of isophthalic acid and 5 mol% of 5-sodium sulfoisophthalic acid, and whose glycol units were composed of 80 mol% of ethylene glycol and 20% of neopentyl glycol. This polyester was dispersed in water at a ratio of 10% by weight, and an organic boron polymer compound ()-1 (P ₁ = 1000) was added to it.
was added in a proportion of 30% by weight based on the polyester to prepare a coating solution. Separately, polyethylene terephthalate 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 1000 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 solution was applied to the surface of this film using an air knife method, and the film was heated to 70°C.
It was dried with hot air to form a resin composition layer. This film was stretched 3.5 times in the transverse direction at 98°C using a tenter, and then heat-set at 200-210°C.
A biaxially stretched coated polyester film of 0.00 μm (resin composition layer 0.15 μm) was obtained. (2) Evaluation of thermoplastic resin laminated film 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 prepared. Each solution was colored with a red dye, and a coating amount of 2
g/m ² and printed separately. On each printing surface of this thermoplastic resin laminated film,
After applying cellophane tape (L Pack, manufactured by Nichiban Co., Ltd.) evenly, apply this tape in a 180 degree direction and
It was quickly peeled off in a 360 degree direction. On the printed surface after peeling, the ratio of the area of the residual ink to the total area was visually determined, and the adhesion was evaluated according to the following criteria. If the ratio of residual ink area to the total area is 95% or more, it is A grade, and if it is 50 to 95%, it is B grade.
10% to 50% were classified as C class, and 10% or less were designated as D class. The evaluation of the film of this example was A grade.
Adhesion evaluations in Examples 2 to 5 and Comparative Examples 1 to 2, which will be described later, were also conducted in the same manner as in this example. Examples 2 to 3 The same as Example 1 except that the type of organic boron polymer compound was changed as shown in Table 1. Table 1 shows the results of adhesive evaluation of the obtained thermoplastic resin laminated film. Table 1 shows the results of Examples 4 and 5 and Comparative Examples 1 and 2, which will be described later. Examples 4 to 5 The same as Example 1 except that the ratio of the organic boron polymer compound to the polyester was changed. Comparative Example 1 The same as Example 1 except that the coating solution containing polyester and organic boron polymer compound was not coated. Comparative Example 2 Same as Example 1 except that the organoboron polymer compound was not used.

【table】

[Table] *1 Content against polyester From Table 1, it is clear that the thermoplastic resin laminated film of the present invention exhibits good adhesion to both PVA, which is a hydrophilic resin, and PVC, which is a hydrophobic resin. . If the content of the organoboron polymer compound in the resin composition is very high or low, the adhesion will be slightly inferior, but it will be much better than the film without the resin composition layer (Comparative Example 1). Highly sexual. It can be seen that the film containing no organic boron polymer compound in the resin composition (Comparative Example 2) has poor adhesion to hydrophilic resins. Example 6 (1) Preparation of thermoplastic resin laminated film 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. To this, _an organic boron polymer compound (( ₎ -2; Using this, a thermoplastic resin laminated film was prepared in the same manner as in Example 1. (2) Evaluation of thermoplastic resin laminated film Cellulose acetate butyrate colored with red dye (usually used in photosensitizers, etc.) was added to the resin composition layer side of the thermoplastic resin laminated film obtained in section (1). 2 g/m ² of 10% methyl cellosolve solution
It was printed as follows. Cellophane tape was attached to the printed surface of this thermoplastic resin laminated film in the same manner as in Example 1, and a peeling reagent was applied. As a result, the adhesiveness was grade A. Example 7 Polyester and organic boron polymer compound synthesized by the same method as Example 1 (()-3; x ₂ =
6, P ₃ =500) in a ratio of 3:1 (w/w) was coated on a 100 μm thick polyethylene terephthalate film so that the thickness after drying was 0.3 μm. PVA and PVC were printed on the coated surface of this thermoplastic resin laminated film in the same manner as in Example 1,
A peel-off test was conducted with Ceron tape attached. As a result, the adhesive properties were all grade A. Example 8 (1) 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, 485 parts by weight of neopentyl glycol, and tetrabutoxy were added. 0.68 parts by weight of titanate was 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. (2) Preparation of thermoplastic resin laminated film 300 parts by weight of the phosphorous-containing polyurethane obtained in section (1) 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. An organic boron polymer compound (()-
6; x ₅ = 200, P ₆ = 10) was added thereto, 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 polyester film using an air knife method and dried with hot air at 120°C to obtain a coated polyester film with a coating weight of 0.3 g/m ² . (3) Evaluation of thermoplastic resin laminated film The resin whose adhesion to the film is to be tested is applied with a solvent to the surface of the resin composition layer of the film obtained in section (2), dried, and a 3 μm thick film is coated with a solvent. A resin layer was formed.
The resins used were carboxymethyl cellulose, polyvinylidene chloride, polyvinyl acetate,
There are five types: gelatin and cellulose acetate butyrate, and each resin solution contains
A red dye having good compatibility with the resin was added. Incisions were made in the resulting resin layer in a grid pattern at 1 mm intervals using a cutter knife to form 100 grids.
Sellotape manufactured by Nichiban was applied so as to be in close contact with the grid, and peeled off at a peeling angle of 180°. As a result, the remaining number is 100 and 95.
100 pieces, 100 pieces, and 90 pieces, indicating good adhesion with both resins. Example 9 (1) 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 stream, and the remaining monomers and catalyst were gradually added at the same temperature over 1 hour and 30 minutes. The stirrer 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. (2) Preparation and evaluation of thermoplastic resin laminated film To 1000 parts by weight of this latex, 150 parts by weight of organic boron polymer compound ()-1; (P ₁ = 1000) was added.
Further water was added to make 3000 parts by weight. Using this coating liquid, a film was prepared in the same manner as in Example 1 and evaluated. Adhesion was grade A. Example 10 50 parts by weight of an organic boron polymer compound (()-4; P ₄ = 100) was added to 500 parts by weight of the milky white liquid acrylic latex obtained in Example 9, and water was further added to give a total volume of 1500 parts by weight. Department. This coating liquid,
A cellulose acetate film (thickness 75 μm) was coated with a solid content of 0.5 g/ ^m2 , and 80
Dry for 2 minutes at °C. The adhesiveness of this film was evaluated in the same manner as in Example 1, and as a result, it was grade A. Example 11 Aluminum was laminated (500 Å) on the biaxially stretched coated polyester film obtained in Example 1 (1) using a vacuum evaporation method, and cellophane tape was attached to the surface of the aluminum layer in the same manner as in Example 1. A peel test was conducted. As a result, it was grade A. A similar test was carried out using a layer of silicon dioxide (800 Å) deposited using a sputtering method instead of aluminum, and the result was Class A. (Effects of the Invention) The thermoplastic resin laminated film of the present invention is thus constructed by laminating a thermoplastic resin film with a composition containing a specific organoboron polymer compound and a resin, and therefore has a hydrophilic polymer. , has good adhesion to both hydrophobic polymers and inorganic materials. As a result, this thermoplastic resin laminated film can be used as a base film for magnetic tapes, insulating tapes,
Suitable for use in applications such as photographic film, tracing film, and food packaging film.

Claims (1)

[Claims] 1. On at least one side of the thermoplastic resin film,
A thermoplastic resin laminated film in which a composition containing as main components at least one of a water-soluble resin, a water-emulsifiable resin, and a water-dispersible resin and an organic boron polymer compound represented by the following formula () is laminated: 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.