JPH064710B2 - Polyester laminated film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention relates to a thermoplastic resin laminated film having excellent adhesiveness,
In particular, the present invention relates to a thermoplastic resin laminated film having good adhesiveness to any of hydrophilic polymers, hydrophobic polymers and inorganic substances.

(Prior Art) Thermoplastic resin films of polyester, polyamide, polypropylene, etc. (especially polyester films such as polyethylene terephthalate) have excellent mechanical strength, heat resistance, chemical resistance, transparency, dimensional stability, and magnetic properties. Widely used in applications such as tape base films, insulating tapes, photographic films, tracing films, and food packaging films. However, these thermoplastic resin films usually lack adhesion to hydrophilic polymers, hydrophobic polymers and inorganic substances. Therefore, when laminating a magnetic material, a photosensitizer, a matting agent, etc. on this film, it is necessary to provide the anchor coat layer after corona discharge treatment on the film surface. Even if this film is used as a food packaging film and a printing layer or a heat seal layer is provided, the adhesiveness between these layers and the thermoplastic resin film is weak, and the heat seal strength may be reduced.

In order to improve the adhesiveness of the thermoplastic resin film, in addition to corona discharge treatment, ultraviolet irradiation treatment,
Methods for performing physical treatments such as plasma discharge treatment, flame treatment, and corona discharge treatment in a nitrogen atmosphere have been proposed. Chemical treatment methods such as alkali treatment and primer treatment, and a combination of these and physical treatment methods are also used. However, the adhesiveness of the thermoplastic resin film is not sufficiently improved by either method. In particular, the adhesion between the hydrophilic polymer or the hydrophobic polymer and the film is insufficient.

(Problems to be Solved by the Invention) The present invention is to solve the above-mentioned conventional problems, and an object thereof is to provide a thermoplastic resin having good adhesiveness with any of hydrophilic polymers, hydrophobic polymers and inorganic substances. It is to provide a resin laminated film.

(Means for Solving the Problem) The present invention provides a composition containing, on the surface of a thermoplastic resin film, at least one of a water-soluble resin, a water-emulsifiable resin and a water-dispersible resin, and an inorganic boron compound as main components. It was completed based on the inventor's knowledge that the adhesiveness between a hydrophilic polymer, a hydrophobic polymer or an inorganic substance and a thermoplastic resin film can be remarkably improved by laminating.

The thermoplastic resin laminated film of the present invention comprises a composition comprising at least one of a water-soluble resin, a water-emulsifiable resin and a water-dispersible resin and an inorganic boron compound as a main component laminated on at least one surface of the thermoplastic resin film. The thermoplastic resin laminated film thus obtained achieves the above object.

Inorganic boron compounds used in the thermoplastic resin laminated film of the present invention include boric acid, boric acid analogs, borate salts and boric acid derivatives. Examples of boric acid analogs include metaboric acid, tetraboric acid, pentaboric acid, perboric acid and the like. As borate, sodium borate, potassium borate, ammonium borate, zinc borate, barium borate, lithium borate, magnesium borate,
Examples include copper borate, aluminum borate, manganese borate, lead borate, cobalt borate, iron borate, nickel borate, lithium borate, cesium borate, sodium fluoroborate, and potassium fluoroborate. Of these, boric acid and sodium borate are preferable.

Among the resins contained in the composition used for the film of the present invention, as the water-soluble resin, any of a natural polymer compound, a semi-synthetic polymer compound and a synthetic polymer compound can be used. Examples of natural polymer compounds include starches, sodium alginate, and proteins (gelatin etc.). Examples of the semi-synthetic polymer compound include cellulosic resins such as carboxycellulose and starch resins such as soluble starch. Examples of the synthetic polymer compound include polyvinyl alcohol, partially saponified polyvinyl acetate, poly (meth) acrylic acid salt, poly (meth) acrylic acid salt-containing copolymer, polyethylene oxide, and modified polymers of the above polymers. is there. Furthermore, as synthetic polymer compounds, epoxy resins prepared using polyhydric alcohols such as ethylene glycol and pentaerythritol; acrylic resins containing a high content of hydrophilic groups such as sulfonate groups, phosphinate groups, and ammonium bases. Resin, polyester resin, polyurethane resin,
Examples include polyamide resins.

Materials for water-emulsifying resins and water-dispersible resins include rubber resins such as polyisoprene, polybutadiene, poly- (styrene-butadiene), poly (acrylonitrile-butadiene); polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride. And vinyl resins such as copolymers thereof; acrylic resins prepared by using acrylic acid, methyl methacrylate, hydroxymethyl acrylate, styrene, glycidyl methacrylate, methyl acrylate, ethyl acrylate, etc .; isophthalic acid, adipic acid, sebacic acid , A polyester resin prepared by using ethylene glycol, diethylene glycol, neopentyl glycol, polyethylene glycol, polytetramethylene glycol, etc .; and the above glycols and diisocyanate And the like polyurethane resins prepared by the class.

In addition to these, water-emulsifiable resins and water-dispersible resins have a hydrophilic group in the molecule and thus exhibit dispersibility in an aqueous solvent, or have a hydrophilic group in the molecule to disperse a small amount of a dispersion aid. A polymer compound which exhibits dispersibility in an aqueous solvent by addition is included. Examples of the hydrophilic group include a phosphonic acid group, a phosphinic acid group, a sulfonic acid group,
Examples thereof include ammonium group and carboxyl group. Examples of the resin having such a hydrophilic group include polyester, polyurethane, polyamide, acrylic resin, epoxy resin, and polyolefin resin.

The water-emulsifiable resin or water-dispersible resin is advantageously prepared by, for example, an emulsion polymerization method in which a monomer is polymerized in an emulsified state. It is of course possible to prepare it by any other ordinary method. In the case of a composition, the polymer obtained is dispersed in water using a surfactant or an organic solvent in an emulsified state to prepare a film described below. Can be used conveniently.

Of the above-mentioned water-soluble resins, water-emulsifiable resins and water-dispersible resins, polyester, polyurethane and acrylic resins are particularly preferable. These will be described in more detail below.

Of the carboxylic acid components and diol components that compose the polyester, carboxylic acid components include terephthalic acid,
Aromatic dicarboxylic acids such as isophthalic acid, orthophthalic acid, and 1,5-naphthalic acid; aromatic oxycarboxylic acids such as p-oxybenzoic acid and p- (hydroxyethoxy) benzoic acid; succinic acid, adipic acid, azelaic acid, Resin group dicarboxylic acids such as sebacic acid and dodecanedicarboxylic acid;
Unsaturated aliphatic dicarboxylic acids such as fumaric acid, maleic acid and itaconic acid; alicyclic dicarboxylic acids such as tetrahydrophthalic acid and hexahydrophthalic acid; trimellitic acid,
Examples include tri- and tetracarboxylic acids such as trimesic acid and pyromellitic acid.

The glycol component constituting the polyester includes ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol and diethylene glycol. Propylene glycol,
2,2,4-trimethyl-1,3-pentadiol, 1,4-cyclohexanedimethanol, styrene-adduct of bisphenol A, propylene oxide of bisphenol A, ethylene oxide adduct of hydrogenated bisphenol A, There are propylene oxide adducts of hydrogenated bisphenol A, diols such as 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, examples of relatively high molecular weight diols include polyester polyols, including lactone polyester diols obtained by ring-opening polymerization of lactones such as ε-caprolactone.

The resin contained in the composition used for the film of the present invention, such as polyester and the following polyurethane-based resin and acrylic resin, may have a hydrophilic group as described above. For example, hydrophilic groups suitable for polyester and polyurethane resins, and compounds containing these groups (single polymer)
Is exemplified below.

(1) -COOM (M represents hydrogen atom, alkali metal, tetraalkylammonium or tetraalkylsulfonium) Polycarboxylic acid, glyceric acid, dimethylolpropionic acid, N, N-diethanolglycine, hydroxyethyloxybenzoic acid, etc. Oxycarboxylic acids; aminocarboxylic acids such as diaminopropionic acid and diaminobenzoic acid and their derivatives.

(2) (R _{1 to} R ₃ are each independently a hydrogen atom and a carbon number of 1 to 8
Of alkyl group, aryl group and aralkyl group of N-methyldiethanolamine, 2-methyl-2-dimethylaminomethyl-1,3-propanol, 2-methyl-
Nitrogen-containing alcohol such as 2-dimethylamino-1,3-propanediol and its derivatives.

(3) (R ₁ has the same meaning as above) such as picolinic acid, dipicolinic acid, aminopyridine, diaminopyridine, hydroxypyridine, dihydroxypyridine, aminohydroxypyridine, pyridinyl dimethanol, pyridinyl propanediol, and pyridinyl ethanol. Pyridine ring-containing compounds and their derivatives.

(4) -SO ₃ M (M has the same meaning as above) 5-sodium sulfoisophthalic acid, 5-tetrabutylsulfonium, sulfoisophthalic acid, polycarboxylic acids such as sodium sulfosuccinic acid, and derivatives thereof;
Sodium sulfohydroquinone and alkylene oxide adduct; sodium sulfobisphenol A and its alkylene oxide adduct and the like.

(5) Phosphorus-containing hydrophilic group An example (general formula) of a compound having a phosphorus-containing hydrophilic group is shown below: [X and Y are each an ester-forming functional group; R ₄ is a trivalent hydrocarbon group having 3 to 10 carbon atoms; R ₅ is an alkyl group, cycloalkyl group, aryl group, or 1 carbon atom having 1 to 12 carbon atoms. ~ 12
An alkoxy group, a cycloalkoxy group or an aryloxy group of [wherein the aryl group and the aryloxy group are substituted with a halogen atom, a hydroxy group, -OM ₂ (M ₂ represents an alkali metal) or an amino group, respectively. R ₆ and R ₇ are each an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an arylene group or a formula A group represented by (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 (III) -1 Examples of compounds represented by formula (III) -2 Examples of compounds represented by formula (III) -3 Examples of compounds represented by formula (III) -4 Examples of compounds represented by formula (III) -5 A polyester is usually prepared by a melt polycondensation method using the carboxylic acid component, the glycol component and optionally the monomer having the hydrophilic group. For example, a direct esterification method in which each of the above components is directly reacted to distill off water for esterification and polycondensation is performed; or a dimethyl ester of the dicarboxylic acid component is reacted with a glycol component to distill methyl alcohol. It is prepared by a transesterification method or the like in which transesterification and polycondensation are performed. In addition to the melt polymerization method, a solution polycondensation method, an interfacial polycondensation method, etc. can be adopted.

Among the resins contained in the composition used for the film of the present invention, polyurethane can be obtained, for example, by chain-extending polyalkylene glycol with polyisocyanate; or polyester polyol (polycondensation of carboxylic acid component and glycol component). (Obtained by the method) is chain-extended with polyisocyanate.

As the polyalkylene glycol, polyethylene glycol, polybutylene glycol, polypropylene glycol or the like is used. As the carboxylic acid component and the glycol component which are raw materials of the polyester polyol, any of the carboxylic acid component and the glycol component described in the section of the polyester preparation can be used.
Examples of the polyisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-
Phenylene diisocyanate, biphenyl methane diisocyanate, m-phenylene diisocyanate, hexamethylene 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-diisocyanate methylcyclohexane, 1,4-diisocyanate methylcyclohexane, 4,4'-diisocyanate dicyclohexane, 4,4'-diisocyanate cyclohexylmethane, and isophorone diisocyanate. These polyisocyanates include triisocyanate compounds such as trimers of 2,4-tolylene diisocyanate and trimers of hexamethylene diisocyanate, which account for 7 mol% of all isocyanate groups.
It may be contained in the following proportions.

Polyurethane is prepared by the usual method using the above components. It is also possible to use the monomers having hydrophilic groups described in the section of polyester preparation and to incorporate these into the polyurethane main chain.

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. Examples of the monomer used include the following compounds.

R ₉ is H or an alkyl group having 1 to 4 carbon atoms; R ₁₀ 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
Each R ₁₃ is 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-} tR 17 or A group; s and t are each independently an integer of 1 to 3; and R ₁₆ and R ₁₇ are each independently C 1
~ 4 alkyl groups.

R ₁₈ is H or an alkyl group having 1 to 4 carbon atoms; R ₁₉ , and R ₂₀ are each independently CI, —OH or 1 to 8 carbon atoms.
Is an alkoxy group.

R ₂₁ is H or an alkyl group having 1 to 4 carbon atoms; M ₃ is H,
Alkali metal or -NH ₄ .

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 (} VI) -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 having 1 to 1 carbon atoms.
4 is an alkyl group.

R ₂₆ is H or an alkyl group having 1 to 4 carbon atoms.

Among these, the compound represented by the formula (IV) -1 includes
Acrylic acid, methacrylic acid (hereinafter acrylic acid and / or methacrylic acid are referred to as (meth) acrylic acid),
Lower alkyl ester of (meth) acrylic acid (for example,
Methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, 2-ethylhexyl ester) and the like. Examples of the compound represented by the formula (IV) -2 (including analogs thereof) include styrene; o, m having a lower alkyl group (eg, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl or octyl group) ，
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; these styrenes and their Examples include α-methyl substituted derivatives. Examples of the compound represented by the formula (IV) -3 include (meth) acrylic acid hydroxyalkyl ester, alkoxyalkyl ester, alkylalkylene glycol ester, and glycidyl ester. Examples of the compound represented by (IV) -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, pentachlorostyrene; halogen-alkyl substituted styrenes such as 2-chloro-5-methylstyrene, 4-chloro-3-methylstyrene, p-chloromethylstyrene; o- ( Or m-, p-) hydroxystyrene, o- (or m-, p-) methoxystyrene, o- (or m-, p-) ethoxystyrene, 3-
There are hydroxy or alkoxy styrene derivatives such as methoxy-4-hydroxy styrene. (IV) -5
Examples of the compounds represented by -1- (IV) -5-4 include ethylene sulfonic acid, ethylene sulfonic acid alkali metal salt (for example, sodium salt, potassium salt); vinyl methyl sulfonin, vinyl ethyl sulfone, vinyl butyl sulfone, etc. Vinyl alkyl sulfones; vinyl sulfonamides, vinyl sulfonanilides, vinyl sulfone methylanilides and other vinyl sulfonamides; styrenesulfonic acid, styrenesulfonic acid alkali metal salts (for example, sodium salt, potassium salt); Examples include loyloxyethyl) acid phosphate and mono (2-acryloyloxyethyl) acid phosphate.
Among these compounds (IV) -1 to (IV) -5, particularly (meth) acrylic acid, glycidyl (meth) acrylate, mono (2- (meth) acryloyloxyethyl) acid phosphate, hydroxy Ethyl (meta)
Acrylate and the like are preferred.

The acrylic resin can be prepared by a conventional method using the above monomers. For example, it is prepared by a method (suspension polymerization method) of reacting the above monomer in an aqueous medium in the presence of a water-soluble polymerization initiator. As the above-mentioned polymerization initiator, ceric ammonium nitrate, cerium ammonium sulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide and the like are used. The polymerization reaction is usually carried out in the range of 0 to 100 ° C, preferably 5 to 80 ° C. If the temperature falls below 0 ° 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, so that gelation tends to occur. In addition to the suspension polymerization method, it can be prepared by using a solution polymerization method or a bulk polymerization method.

The resin composition used in the present invention contains at least one of the water-soluble resin, water-emulsifiable resin and water-dispersible resin (collectively referred to as water-based resin) and the above-mentioned inorganic boron compound as main components. The content ratio of the aqueous resin and the inorganic boron compound is 99.9 / 0.1 to 70:30 (w / w), preferably 98/2 to 80/2
It is 0 (w / w). When the amount of the water-based resin is less than 70% by weight, the adhesiveness between the obtained film and the hydrophobic polymer is poor. On the contrary, when the content of the inorganic boron compound is less than 0.1% by weight, the adhesiveness between the obtained film and the hydrophilic polymer is poor. If necessary, the composition may further include a colorant, an antistatic agent, a cross-linking agent, an anti-blocking agent, a lubricant using particles of an inorganic or organic material, other polymers, an ultraviolet absorber, and deterioration prevention. The agent or the like may be contained in such a proportion that the characteristics of the obtained film are not impaired.

Materials for the polyester film (base film) on which the above composition is laminated include poly (ethylene terephthalate), poly (butylene terephthalate), and polyethylene naphthalate.

The base film is usually obtained by melting or extruding the thermoplastic resin as the material, or by dissolving the resin in a solvent and casting. Such an unstretched film is uniaxially or biaxially stretched as necessary, and then the composition is applied (coated) to the surface thereof by the method described below. The method of applying the composition to an unstretched or uniaxially stretched base film, and further stretching the composition if necessary is to improve the adhesion between the base film and the composition and the durability of the obtained film. , More preferable. The biaxially stretched base film has a wide film width, and it is somewhat difficult to apply the composition uniformly because it is necessary to increase the running speed of the film in order to apply the composition thinly on the base film. .

The thermoplastic resin laminated 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 performed, for example, by a method of adding an inorganic boron compound to the latex; a method of adding water or an aqueous solvent while kneading the resin and the inorganic boron 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) at a ratio of 50% by weight or less in addition to water. The organic solvent is added for the purpose of improving the coating property of the coating liquid containing the composition on the base film, and further for improving the drying property after coating. If the organic solvent content is 50% by weight or less, there is no danger of the coating liquid catching fire or exploding. For the purpose of improving the coating property, it is also recommended that the composition contain an additive such as a fluororesin, a silicone resin and a surfactant. The coating solution containing this composition is usually applied to the surface of the base film at a rate of 0.01 to 5 g / m ² . If it is less than 0.01 g / m ² , the adhesiveness between the obtained film and other resins for the purpose of adhesion is poor, and it is 5 g / m 2.
^When it exceeds ² , the slipperiness and blocking resistance of the obtained film are poor.

In addition to the coating method of preparing the above-mentioned coating liquid and coating it on the base film, for example, a coextrusion coating method, an extrusion laminating method, a dry laminating method, a hot melt adhesion method, etc. can be adopted.

Before laminating the above resin composition by a method such as coating,
Alternatively, after laminating, the surface of the base film may be subjected to corona discharge treatment or ultraviolet irradiation treatment under air or nitrogen atmosphere. By performing these treatments, the adhesion between the base film and the resin composition layer or the adhesion between the obtained film and another resin is further improved.

Since the composition used for the film of the present invention contains an inorganic boron polymer compound and an aqueous resin, the composition has good adhesiveness to any of hydrophobic polymer, hydrophilic polymer and inorganic material. Is. Therefore, the thermoplastic resin laminated film of the present invention provided with this resin composition layer,
It exhibits good adhesion with both hydrophobic and hydrophilic polymers. Such films are used for printing base films, magnetic tape base films, label sticker base films, chemical mat base films, overhead projector films, food packaging films, and the like.

(Examples) The present invention will be described below with reference to Examples.

Example 1 (A) Preparation of thermoplastic resin laminated film The dicarboxylic acid unit is composed of 50 mol% terephthalic acid, 45 mol% isophthalic acid and 5 mol% sodium 5-sulfoisophthalate, and the glycol unit is ethylene glycol. 80 mol% and neopentyl glycol
A sulfonic acid-modified polyester (molecular weight of about 20,000) composed of 20 mol% was synthesized. This polyester was dispersed in water at a ratio of 10% by weight, and boric acid was added to this in an amount of 5% by weight to the polyester to prepare a coating solution.

On the other hand, poly (ethylene terephthalate) is melt extruded at 280-300 ℃ and cooled with a cooling roll at 15 ℃ to obtain an unstretched film with a thickness of 1000μm.
It was stretched 3.5 times in the machine direction through a pair of rolls at 85 ° C. The coating liquid was applied to the surface of this film by an air knife method and dried with hot air at 70 ° C. to form a resin composition layer. This film is placed in a tenter at 3.5 ° C at 3.5 ° C.
Double stretching, heat setting at 200-210 ℃, thickness 100μm
A biaxially stretched coated polyester film having a resin composition amount of 0.1 g / m ² was obtained.

(B) Evaluation of thermoplastic resin laminated film (1) Adhesion 10% of polyvinyl alcohol (PVA, hydrophilic polymer)
An aqueous solution and a 10% DMF (dimethylformamide) solution of polyvinyl chloride (PVC, hydrophobic polymer) were prepared. Each solution was colored with a red dye and printed separately on the resin composition layer side of the two thermoplastic resin laminated films obtained in the item (A) so that the coating amount was 2 g / m ² .

Cellophane tape (L pack, manufactured by Nichiban Co., Ltd.) was evenly adhered to each printed surface of the thermoplastic resin laminated film, and then the tape was quickly peeled off in the 180 ° direction.
On the printed surface after peeling, the ratio of the area of the remaining portion of the ink to the total area was visually judged, and the adhesiveness was evaluated according to the following criteria. 95% or more of the area of the residual area of the ink to the total area is A class, 50 to 95% or more is B class, 10 to
50% was designated as C grade and 10% or less was designated as D grade. The results are shown in Table 1.

Example 2 The same as Example 1 except that sodium borate was used as the inorganic boron compound.

Example 3 The same as Example 1 except that potassium borate was used as the inorganic boron compound.

Comparative Example 1 The same as Example 1 except that the resin composition layer was not formed.

Comparative Example 2 The same as Example 1 except that no boric acid was added.

From Table 1, it can be seen that the thermoplastic resin film of the present invention has excellent adhesiveness to both PVA, which is a hydrophilic polymer, and PVC, which is a hydrophobic polymer. On the other hand, such an effect cannot be obtained in the film in which the layer of the composition containing neither the sulfonic acid modified polyester nor the inorganic boron compound is formed or in the film in which the resin composition is not formed.

Example 4 By the same method as in Example 1, the reaction time was shortened to prepare a 10% aqueous dispersion of a sulfonic acid-modified polyester having a molecular weight of 4000. After 100 parts by weight of this polyester was dissolved 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 stirred at 70-80 ° C for 3 hours. Reacted for hours. The solvent was evaporated to obtain an aqueous dispersion containing polyester polyurethane.

Sodium metaborate was added to this aqueous dispersion at a ratio of 6% by weight to the polyester polyurethane to obtain a coating liquid. Using this, a thermoplastic resin laminated film was prepared in the same manner as in Example 1. On the resin composition layer side of this film, a film of cellulose acetate butyrate (usually used as a photosensitizer) colored with a red dye
A 10% methyl cellosolve solution was printed at a coating amount of 2 g / m ² . Using this, evaluation was performed in the same manner as in Example 1. As a result, the adhesiveness with PVA and PVC was B grade in all cases.

Example 5 A coating solution containing polyester synthesized by the same method as in Example 1 and boric acid (3%) was prepared.
It was applied to a polyethylene naphthalate film having a thickness of 100 μm so that the thickness after drying would be 0.3 μm.

On the coated surface of this thermoplastic resin layer film, the following Example 1 was applied.
PVA and PVC were printed in the same manner as above, cellophane tape was attached, and a peeling test was performed. As a result, the adhesiveness was B grade for PVA and A grade for PVC.

Example 6 (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, 485 parts by weight of neopentyl glycol and tetra. 0.68 parts by weight of butoxy titanate was charged and heated at 150 to 230 ° C for 120 minutes for transesterification. Then, 50.1 parts by weight of the phosphorus-containing compound ((III) -2-2) described in the present specification was added, and the reaction was further carried out at 220 to 230 ° C. for 1 hour. The temperature of this reaction system was raised to 250 ° C. in 30 minutes, the pressure of the system was gradually reduced to 10 mHg 45 minutes later, and the reaction was continued for another 60 minutes under these conditions. The obtained polyester diol A has a molecular weight of 2500 and a phosphorus content of 1600.
It was ppm.

Next, 100 parts by weight of the polyester diol A was dissolved in 72 parts by weight of toluene and 72 parts by weight of methyl ethyl ketone, and then 21 parts by weight of 4,4'-diphenylmethane diisocyanate and 0.05 part by weight of dibutyltin dilaurate were added to give 70 parts by weight.
The reaction was carried out at -80 ° C for 3 hours.

(B) Preparation and evaluation of thermoplastic resin laminated film 300 parts by weight of polyurethane containing the phosphorus obtained in (A) and n-
140 parts by weight of butyl cellosolve were stirred in a container 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 uniform pale white aqueous dispersion (solid content concentration 30%) was obtained.

Dilute with 15 parts by weight of zinc borate (based on 100 parts by weight of polymer), water and ethyl alcohol (water: ethyl alcohol = 1: 1) to obtain a solid concentration of 4.5.
% Coating solution was obtained. This coating liquid is air knife type,
It was applied to a polyester film and dried with hot air at 120 ° C to obtain a coated polyester film with a coating amount of 0.3 g / m ² .

Separately, the amount of zinc borate added was 10 parts by weight, and this was diluted with water to obtain a coating liquid having a solid content of 10%. The coating solution has a thickness of 0.
It was coated so as to have a thickness of 5 μ / m and dried.

The surface of each of these laminated films was coated with a resin solution containing a red dye according to Example 1. As a resin,
Carboxymethyl cellulose, polyvinylitene chloride,
Each of polyvinyl acetate, gelatin, and cellulose acetate butyrate was used so that the resin layer (printing layer) had a thickness of 3 μm. These print layers were cut with a cutter knife at intervals of 1 mm in a grid pattern to form 100 squares. Cellophane tape (L pack, manufactured by Nichiban Co., Ltd.) was evenly attached to each printed surface of this thermoplastic resin laminated film, and then this tape was applied.
It was quickly peeled off in the 180 degree direction. The number of cells remaining on the printed surface after the peeling test was counted. The results are shown in Table 2.

Example 6 650 g of water in a two-necked four-necked flask equipped with a reflux condenser, of the monomers shown in the above table (total amount of 350 g), the total amount of sodium vinyl sulfonate, and one-fifth amount of each of the other monomers. , 0.85 g of dodecyl mercaptan and 1/4 of potassium persulfate (catalyst; total amount 0.2 g) were 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. Stirring was continued for another 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 To 1000 parts by weight of the latex obtained in (A), 150 parts by weight of boric acid was added, and further water was added to make 3000 parts by weight. When this coating solution was used and evaluated in the same manner as in Example 1, the adhesiveness to PVA and PVC was both Class A.

(Effect of the invention) Since the thermoplastic resin laminated film of the present invention is formed by laminating the composition containing the inorganic boron compound and the aqueous resin on the thermoplastic resin film as described above, the hydrophilic polymer, the hydrophobic polymer Good adhesion to both polymers and inorganics. Therefore, this thermoplastic resin laminated film is suitably used for applications such as magnetic tape base films, insulating tapes, photographic films, tracing films, and food packaging films.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-60-111192 (JP, A) JP-A-59-192564 (JP, A) JP-A-61-72074 (JP, A) JP-A-63- 45051 (JP, A) JP 60-112875 (JP, A) Actually developed 60-109099 (JP, U)

Claims (1)

[Claims] 1. A polyester film comprising, on at least one surface thereof, at least one of a water-soluble resin, a water-emulsifiable resin and a water-dispersible resin, and at least one inorganic boron compound selected from boric acid, a borate salt and a boric acid analogue. A polyester laminated film in which the composition is laminated; wherein the water-soluble resin, water-emulsifiable resin and water-dispersible resin are selected from acrylic resin, polyester resin, and polyurethane resin, and the water-soluble resin, water The content ratio of the emulsifying resin and the water dispersible resin to the inorganic boron compound is 9 by weight.
It is 8: 2 to 80:20.