JPH0684064B2 - Polyester vapor deposition film - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a vapor-deposited polyester film, and more particularly to a polyester vapor film having an excellent interlayer resistance with excellent water resistance.

(Prior Art) A film laminate obtained by laminating a polyolefin layer as an easy heat seal material on a polyester film vapor-deposited with a metal or the like, particularly a polyethylene terephthalate film, is excellent in applications such as food packaging, industrial part packaging, and protective coating. It is widely used because of its oxygen-preventing property, water-preventing property, and light-shielding property against visible light, ultraviolet rays, and the like. However, these vapor-deposited polyester film laminates are not always satisfied, and various problems remain in each application, and new demands are increasing.

For example, in the field of food packaging, there is a drawback that peeling occurs easily by a hot water treatment such as a boiling treatment which is performed for the purpose of sterilizing foods to be contained. Particularly, these peeling phenomena often cause problems due to lack of water-resistant adhesive strength at the interface between the polyester film as the base material and the vapor deposition layer.

As a method for improving the adhesion between the substrate polyester film and the vapor-deposited layer of a metal or the like, various methods such as a method by heating the film described in British Patent No. 1370893 have been proposed, but all of them are still sufficient. It was not present, and especially the water-proof adhesive strength was insufficient. On the other hand, polyester film printing inks, photographic emulsions, matting agents,
Various methods aimed at improving the adhesiveness to magnetic paints and other various paints have also been proposed. Especially in printing films, as a method for improving the peeling of the printing layer during hot water treatment, JP-B-55-4583. , A method of blending a specific copolyester as found in Japanese Examined Patent Publication No. Sho 55-12870 with a polyester raw material for film is proposed,
Even with such a method, when the target is a vapor-deposited layer of metal or the like, sufficient water-resistant adhesion has not been obtained yet. Further, a method of applying a so-called anchor coating agent such as an alkyl titanate type or a urethane type to the film surface is used according to each coating application. However, in general, these are not only insufficient in their performance, but also have poor versatility such that they are effective in some cases but have no effect in other cases, and particularly metal At present, it is difficult to exert the effect on the vapor deposition layer such as. Moreover, many of them are very unstable in terms of hydrolysis, storability and the like. Further, all of them are expensive, and since they are generally used in an organic solvent system, they are highly inflammable and toxic, and are very inconvenient from the standpoint of workability, pollution, energy saving, and the like. Further, recently, as an undercoating agent having good adhesiveness to polyester instead of these anchor coating agents, a polyester system, a polyether ester copolymer system and the like as shown in JP-A-48-37480 are proposed. Has been done. However, although these polymers generally have good adhesiveness to a polyester film, they may be insufficient in versatility because they may be insufficient as a topcoat agent during other secondary processing depending on the object. In particular, in many cases, the adhesiveness is insufficient with respect to a paint having a relatively high polarity component or a vapor deposition layer of metal or the like. Also,
Many of the solvents applicable to these processing agents are highly toxic and highly flammable, as seen in Japanese Patent Publication No. 54-16557.
Many attempts have been made to change the composition of the processing agent to make it water-soluble, but in this case, of course, the water resistance of the obtained undercoating film is poor, and the vapor-deposited film such as a metal comes into contact with moisture. In the final application, peeling defects are likely to occur. On the other hand, apart from these methods, for plastic films centered on polyolefin films,
Acrylic acid ester or methacrylic acid ester and acrylic acid or methacrylic acid, methylol acrylamide, acrylamide or methacrylamide as an anchor coating agent when applying vinylidene chloride resin for the purpose of imparting heat sealing property, gas barrier property, etc. A water-soluble acrylic polymer (Japanese Patent Application Laid-Open No. 48-80127), which is an acrylic anchor coating agent, is proposed. However, in this case, since it is water-soluble, as a matter of course, problems are likely to occur in applications requiring water resistance. At the same time, in the case of a complete aqueous solution system, it is difficult to obtain a uniform coating film due to poor leakage to the hydrophobic film substrate. Further, a method of performing emulsion polymerization of these acrylic compounds in a system containing a surfactant as an emulsifier to apply a particulate emulsion (JP-A-52-155633) and the like have also been proposed. Due to the activator, water resistance is still a problem, and a vapor-deposited polyester film such as metal having good water-resistant interlayer adhesion has not been obtained.

(Problems to be Solved by the Invention) In view of the above-mentioned problems of the prior art, the inventors of the present invention have a polyester-based vapor deposition film having excellent interlayer resistance that is particularly excellent in water resistance in a polyester-based film vapor-deposited with a metal or the like. Is to provide.

(Means for Solving the Problems) That is, the present invention comprises, on at least one side, (A) dicarboxylic acids in which 0.5 to 4 mol% of all dicarboxylic acid components are metal sulfonate-containing dicarboxylic acids and polyhydric alcohols. Water-insoluble polyester copolymer consisting of (B)
A water-resistant organic compound having a temperature of 60 to 200 ° C., and a water-based resin dispersion comprising (C) water are coated on the coated surface of a polyester film to form a vapor deposition layer of metal or the like on the water resistant adhesive strength. Excellent polyester vapor deposition film.

The water-insoluble polyester copolymer (A) used in the present invention has a sulfonic acid metal group-containing dicarboxylic acid of 0.5 to
It is a substantially water-insoluble polyester copolymer obtained by reacting a mixed dicarboxylic acid of 4 mol% and 96-99.5 mol% of a dicarboxylic acid containing no metal sulfonate with a glycol component. Substantially water-insoluble means that even if the polyester copolymer is stirred in hot water at 80 ° C, the polyester copolymer does not dissipate in the hot water. Specifically, excess polyester copolymer is used. The weight loss of the polyester copolymer after the stirring treatment in 80 ° C. hot water for 24 hours is 5% by weight or less.

The above-mentioned dicarboxylic acid containing sulfone powder metal base,
Sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5
Examples thereof include metal salts such as [4-sulfophenoxy] isophthalic acid, and particularly preferred are 5-sodiumsulfoisophthalic acid and sodium sulfoterephthalic acid. These sulfonic acid metal group-containing dicarboxylic acid components are 0.5 to 4 mol% with respect to the total dicarboxylic acid components, and if the amount exceeds 4 mol%, the water resistance in interlayer adhesion to a vapor-deposited layer of metal or the like is significantly reduced. So it's especially important. If it is less than 0.5 mol%, the dispersibility in water will decrease.

The dispersibility of the polyester copolymer in water varies depending on the copolymerization composition, the type of water-soluble organic compound, the compounding ratio, and the like. Is preferred.

As the dicarboxylic acid containing no metal sulfonate base,
Aromatic, aliphatic and alicyclic dicarboxylic acids can be used.
Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid. These aromatic dicarboxylic acids preferably account for 40 mol% or more of the total dicarboxylic acid components. If it is less than 40 mol%, the mechanical strength and water resistance of the polyester copolymer will decrease. Aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, and 1,3-
Examples thereof include cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Addition of these non-aromatic dicarboxylic acid components enhances the adhesive performance in some cases, but generally reduces the mechanical strength and water resistance of the polyester copolymer.

The glycol component to be reacted with the mixed dicarboxylic acid is an aliphatic glycol having 2 to 8 carbon atoms or an alicyclic glycol having 6 to 12 carbon atoms, specifically, ethylene glycol, 1,2-propylene. Glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-
Cyclohexanedimethanol, p-xylylene glycol, diethylene glycol, triethylene glycol and the like can be mentioned.

The polyester copolymer is obtained by usual melt polycondensation. That is, the above-mentioned dicarboxylic acid component and glycol component are directly reacted to distill off water to effect esterification, and then a direct esterification method in which polycondensation is performed, or a dimethyl ester of the dicarboxylic acid component and a glycol component are reacted to produce methyl. It is obtained by a transesterification method in which alcohol is distilled off and transesterification is carried out, followed by polycondensation. In addition, solution polycondensation, interfacial polycondensation, etc. are also used, and the polyester copolymer of the present invention is not limited by the polycondensation method.

As described in JP-A-60-198240, dispersion of a polyester in which 5 mol% or more of a dicarboxylic acid containing a metal sulfonate group is copolymerized can be carried out by vigorous stirring in hot water. In order to obtain an aqueous dispersion, it cannot be dispersed unless it is dispersed in water together with the water-soluble organic compound. For example, in the case of dispersion, the polyester copolymer and the water-soluble organic compound are premixed at 50 to 200 ° C., and water is added to this mixture and stirred to disperse, or conversely, the mixture is added to water and stirred. And a method in which the polyester copolymer, the water-soluble organic compound and water are allowed to coexist and stirred at 40 to 120 ° C.

The water-soluble organic compound is an organic compound having a solubility in water of 1 at 20 ° C. of 20 g or more, and is specifically an aliphatic or alicyclic alcohol, ether, ester, or ketone compound, such as methanol, ethanol, or the like. Monohydric alcohols such as isopropanol and n-butanol, glycols such as ethylene glycol and propylene glycol,
Examples are glycol derivatives such as methyl cellosolve, ethyl cellosolve and n-butyl cellosolve, ethers such as dioxane and tetrahydrofuran, esters such as ethyl acetate, and ketones such as methyl ethyl ketone. These water-soluble organic compounds may be used alone or in combination of two or more. Of the above compounds, butyl cellosolve and ethyl cellosolve are preferable in view of dispersibility in water and coatability on a film.

The blending weight ratios of the above (A) polyester copolymer, (B) water-soluble organic compound and (C) water are (A) / (B) = 100/20 to 100/5000 (B) / (C) = It is important to satisfy 100/5 to 100/10000. Less water-soluble organic compounds than polyester copolymer (A) / (B) 100 /
If it exceeds 20, the dispersibility of the aqueous dispersion will decrease. In this case, the dispersibility can be assisted by adding a surfactant, but if the amount of the surfactant is too large, the adhesiveness and the water resistance decrease. Conversely, (A) / (B) is 100 /
When it is less than 5,000 or when (B) / (C) exceeds 100/50, the amount of the water-soluble organic compound in the aqueous dispersion is large and the risk of solvent residue after coating tends to occur. Since the cost will be higher, it is necessary to consider the compound recovery.
When (B) / (C) is less than 100/10000, the surface tension of the aqueous dispersion becomes large, the leak property to the film is lowered, and coating spots are likely to occur. In this case, the leakage property can be improved by adding a surfactant, but if the amount of the surfactant is too large, the adhesiveness and the water resistance are reduced at the same time as described above.

In the above aqueous polyester copolymer resin dispersion,
Various kinds of inorganic particles such as silica, calcium carbonate, kaolinite, alumina, talc, barium sulfate, and organic type such as benzoguanamine resin and polystyrene resin.
In addition, slipperiness and blocking resistance may be improved by adding an inert particle of about 01 μ to 10 μ.
If necessary, mixing an organic or inorganic antistatic agent and other additives is an additive, unless the water resistance of the interlayer adhesive strength with the vapor deposition layer of the metal or the like which is the original purpose is greatly impaired. There is no limitation on the amount added.

The method for applying the coating dispersion composition in the present invention can be carried out by an ordinary method, but in particular, an unstretched film after the thermoplastic resin has been melt extruded, or uniaxially in the longitudinal or transverse direction. Adhesion of the coated film is a method of obtaining a biaxially oriented coat film by applying the stretched film, then biaxially or uniaxially stretching and then performing heat treatment.
It is preferable from the viewpoint of transparency and economy. In particular, in consideration of the drying property and workability of the coating film, it is preferable to apply the film after stretching it in a uniaxial direction, and then apply it after uniaxially stretching it in the longitudinal direction and then stretch it in the transverse direction. Is particularly preferred. The coating amount to be applied is 0.005 to 5 g / m ² as the amount present on the film after biaxial stretching.
Is preferred and 0.01-3 g / m ² is particularly preferred. Coating amount is 0.005
If it is less than g / m ² , the desired effect cannot be obtained, and if it exceeds 5 g / m ² , adverse effects such as blocking are likely to occur.

If necessary, a physical or chemical surface activation treatment such as corona treatment may be performed before or after the coating step.

In the present invention, it is preferable that the main component of the base polyester film to be coated with the aqueous resin dispersion is polyethylene terephthalate, and 80% or more thereof is polyethylene terephthalate. The remaining 20% or less of the polyester component can be an aromatic, aliphatic, or alicyclic dicarboxylic acid as the dicarboxylic acid component. As the aromatic dicarboxylic acid, isophthalic acid, orthophthalic acid,
Examples of aliphatic and alicyclic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid include succinic acid, adipic acid, sebacic acid, oxalic acid, 1,3-cyclopentanedicarboxylic acid and 1,2-
Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc. and a part of oxyacid such as p-hydroxybenzoic acid, etc., and an aliphatic glycol having 2 to 8 carbon atoms as a glycol component or An alicyclic glycol having 6 to 12 carbon atoms, specifically, ethylene glycol, 1,2-propylene glycol,
1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, p -An ester of xylylene glycol, diethylene glycol, triethylene glycol, etc., and a polyether such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. may be contained.

These components other than polyethylene terephthalate may be contained by any method of copolymerization and mixing of polymers.

The metal deposited on the surface of the film is gold,
Silver, aluminum, zinc, tin, copper, nickel, iron, cobalt, chromium, manganese, palladium, indium,
Examples thereof include titanium and the like alone or two or more kinds of metals and oxides thereof, and aluminum is particularly frequently used and effective. In addition, the effectiveness is recognized for silicon oxide compounds.

The polyester film of the present invention is excellent in water resistance, hot water resistance, and heat resistance, and the interlayer adhesive strength at the interface between the film and the vapor deposition layer is not reduced by the high temperature hot water treatment.

Polyethylene, polypropylene, ionomer, ethylene vinyl acetate copolymer, on the vapor deposition surface of the film of the present invention,
Sheets or films of ethylene / ethyl acrylate copolymer, polyester, polyamide and the like can be laminated and used.

(Example) Hereinafter, the present invention will be described with reference to an example. Part of the example,%
All means by weight unless otherwise specified.

Example 1-Production of Polyester Copolymer-Dimethyl terephthalate 117 parts (49 mol%), dimethyl isophthalate 117 parts (49 mol%), ethylene glycol 103 parts (50 mol%), diethylene glycol 58 parts (50
Mol%), 0.08 part of zinc acetate and 0.08 part of antimony trioxide are heated in a reaction vessel to 40 to 220 ° C. for a transesterification reaction for 3 hours, and then sodium 5-sulfoisophthalate 9
Part (2 mol%) is added to carry out an esterification reaction at 220 to 260 ° C. for 1 hour, and then polycondensation reaction is carried out under reduced pressure (10 to 0.2 mmHg) for 2 hours to obtain a polyester having an average molecular weight of 18,000 and a softening point of 140 ° C. A copolymer was obtained.

-Production of Polyester Copolymer Aqueous Dispersion- 300 parts of the polyester copolymer obtained above and 140 parts of n-butyl cellosolve are stirred in a container at 150 to 170 ° C for about 3 hours to make a uniform viscosity. Then, 560 parts of water was gradually added to the melt, and after about 1 hour, a stable pale white solid dispersion having a solid content concentration of 30% was obtained.

This aqueous dispersion was added to an equal amount mixed solvent of ion-exchanged water and isopropyl alcohol, and stirred sufficiently to prepare a uniform diluted solution having a resin solid content of 5%, which was used as a coating solution.

-Manufacture of coated film-Polyethylene terephthalate is melt extruded at 280 to 300 ° C and cooled with a cooling roll at 15 ° C to obtain an unstretched film having a thickness of about 150 microns. The unstretched film has different peripheral speeds. It was stretched 3.5 times in the machine direction between a pair of rolls at 85 ° C.

Then, the above coating solution is applied by a roll coater method,
Dry with hot air at ℃, then laterally at 98 ℃ in a tenter
The film was stretched 3.5 times and heat-set at 200 to 210 ° C. to obtain a biaxially stretched coated polyester film having a thickness of 12 μm.
The final coating amount of the coating agent was 0.06 g / m ² .

Then, aluminum was vapor-deposited on the coated surface of the obtained film by a conventional method to obtain a vapor-deposited polyester film. A 60 micron unstretched polyethylene sheet was laminated on the vapor-deposited surface of this aluminum vapor-deposited film by a usual dry lamination method, and then aging treatment was carried out for 24 hours to obtain an aluminum vapor-deposited film laminate. The obtained vapor-deposited film laminate was cut into a 15 mm-width single-piece form, and a T-type peel strength test was carried out with and without boiling water treatment to evaluate the interlayer adhesion.

The boiling water treatment was performed by immersing the sample in boiling water at 95 ° C or higher for 30 minutes. Further, the peeling test was carried out by using Tensilon manufactured by Toyo Baldwin Co., Ltd. in two types, that is, a method of performing a normal T-type peeling and a water-resistant peeling method in which a water drop was formed on the peeling interface. The obtained results are shown in Table-1.

Example 2 In the production of a polyester copolymer, dimethyl terephthalate was 49 mol%, dimethyl isophthalate was 47 mol%, neoperetyl glycol was used instead of diethyl glycol as 50% of the glycol component, and sodium 5-sulfoisophthalate was mixed with 4 mol. A vapor-deposited polyester film laminate was obtained in the same manner as in Example 1 except that the mol% was changed.
Table 1 shows the results of evaluation of the adhesive force between layers as in Example 1.

Example 3 In the production of a polyester copolymer, dimethylisophthalate was 48.5 mol%, cyclohexanedimethanol was used instead of dimethyleneglycol as 50 mol% of the glycol component, and sodium 5-sulfoisophthalate was 2.5 mol%.
A coated polyester film was obtained in the same manner as in Example 1, except that The coating amount of the coating agent is 0.11g / m ²
Met. Then, a vapor deposition film and a laminated body thereof were obtained in the same manner as in Example 1. Table 1 shows the evaluation results of the interlayer adhesion.

Comparative Example 1 Polyethylene terephthalate was melt extruded at 280 to 300 ° C. and cooled by a cooling roll at 15 ° C. to obtain an unstretched film having a thickness of about 150 μm. The unstretched film was formed into a pair of 85 ° C. having different peripheral speeds. It was stretched 3.5 times in the machine direction between the rolls. Then, draw it 3.5 times in the transverse direction at 98 ° C with a tenter, then 200-
It was heat set at 210 ° C. to obtain a biaxially stretched polyester film having a thickness of 12 μm. Then, aluminum was vapor-deposited on one surface of the obtained film by a conventional method to obtain a vapor-deposited polyester film. On the vapor deposition surface of this aluminum vapor deposition film
A 60 micron unstretched polyethylene sheet was laminated by a usual dry laminating method and then subjected to an aging treatment for 24 hours to obtain an aluminum vapor deposition film laminate. The interlayer adhesion of the obtained vapor deposition film laminate was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 The polyester copolymer obtained in Example 1 was chip-blended at a ratio of 10 parts to 90 parts of polyethylene terephthalate, and a biaxially stretched polyester film and a vapor-deposited film laminate were obtained in the same manner as in Comparative Example 1. It was The interlayer adhesion of the obtained vapor deposition film laminate was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3 47 mol% of dimethyl terephthalate, 46 mol% of dimethyl isophthalate in the production of a polyester copolymer, and
Example 1 except that the amount of 5-sulfoisophthalic acid was 7 mol%.
A vapor-deposited polyester film laminate was obtained in exactly the same manner as in. Table 1 shows the evaluation results of the interlayer adhesion.

Comparative Example 4 In the production of a polyester copolymer, 50 mol% of dimethyl terephthalate and 49.7 mol% of dimethyl isophthalate
And sodium 5-sulfoisophthalate 0.3 mol%, ethylene glycol 50 mol%, neopentyl glycol 50
A polyester copolymer was obtained in exactly the same manner as in Example 1 except that mol% was used. An aqueous dispersion of the obtained polyester copolymer was prepared in the same manner as in Example 1. However, the obtained dispersion was unstable and a coating solution prepared by dilution as in Example 1 was not prepared. It was uniform.

Comparative Example 5 300 parts of the polyester copolymer obtained in Example 1 and 140 parts of water
Parts in a container at 90 to 95 ° C for about 3 hours and then water.
An aqueous dispersion was prepared by gradually adding 560 parts, but it was difficult to obtain a uniform and stable aqueous dispersion.

Comparative Example 6 In the production of a polyester copolymer, 95 mol% of dimethyl isophthalate and 5 sodium 5-sulfoisophthalate were used.
A vapor-deposited polyester film laminate was obtained in the same manner as in Example 1 except that mol% and diethylene glycol (100 mol%) were used as the glycol component. Table 1 shows the results of evaluation of the interlayer adhesive strength.

The polyester copolymer obtained here was 80
It is soluble in hot water at ℃ and does not correspond to the practically water-insoluble polyester copolymer defined in the text.

(Effects of the Invention) As shown in the above examples, the vapor-deposited polyester film of the present invention is found to have particularly excellent interlayer adhesion between the vapor-deposited layer of a metal or the like and the polyester film, particularly water resistance and hot water resistance. It Further, even if the same water-insoluble copolymer polyester used in the method of the present invention is not the method of the present invention but the method of blending into the base polyester, the desired effect cannot be obtained (comparison In Example 2), when the sulfonic acid metal group-containing dicarboxylic acid as a dicarboxylic acid component is more than the range of the present invention (Comparative Example 3) and less (Comparative Example 4), sufficient water resistance cannot be obtained. Alternatively, when the dispersibility is insufficient, or when the water-soluble organic compound of the present invention is not used (Comparative Example 5) or when the copolyester (A) is water-soluble (Comparative Example 6), the polyester (A) is used. It can be seen that sufficient effects cannot be obtained even if the copolymer composition of is within the range of the invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location C23C 14/20 9271-4K Judge's collegial body Referee Chief Yukiyuki Yamada Referee Ebisawa Yumiko Niki (56 ) References JP-A-60-198240 (JP, A)

Claims (1)

[Claims] 1. A water-insoluble polyester copolymer composed of polycarboxylic alcohols and dicarboxylic acids in which 0.5 to 4 mol% of the total dicarboxylic acid component (A) contains a sulfonic acid metal salt on at least one side. , (B) Boiling point is 60 to 200
A water-soluble organic compound (° C.) and a water-based resin dispersion liquid (C), which is applied, and a vapor deposition layer is provided on the applied surface of a polyester film whose main component is polyethylene terephthalate. Polyester vapor deposition film that does.