JPH0459336B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a polyester film having a coating layer and thus having improved surface properties, and a method for producing the polyester film. [Problems to be improved by the prior art and the invention] Polyester film is used as a magnetic material, packaging material,
It is widely used in the fields of electrical/electronic materials and printing materials, and in these applications, coating layers, printing layers, or vapor deposition layers are provided for the purpose of imparting various functions or aesthetics to the film surface. It is being In practical use, it is important that the adhesion between the polyester film and the coating agent, ink, or metal vapor deposition film is ensured under the usage conditions of each application, and in order to improve the adhesion, polyurethane resin or polyester resin is usually used. An anchor coat layer and a primer layer coated with a solution or dispersion of acrylic resin or the like are provided. However, the current situation is that there is still no material that is satisfactory in all aspects of adhesiveness, water resistance, and weather resistance. Therefore, an object of the present invention is to provide a polyester film having a coating layer obtained by applying a coating agent with excellent performance, and an industrially advantageous manufacturing method thereof. [Means and effects for solving the problem] The present inventors have developed an aqueous resin dispersion obtained by emulsion polymerization of a polymerizable monomer in the presence of a reactive surfactant consisting of a polymer with a specific structure. , or a polyester film having a coating layer obtained by applying a coating agent containing the aqueous resin dispersion and polyvinyl alcohol can achieve the above object, and the coating agent can be applied by a stretching operation. The method of manufacturing a polyester film by applying it to an unfinished polyester film and then completing the stretching operation is industrially advantageous, and the method of manufacturing the polyester film is industrially advantageous, and the method of manufacturing the polyester film is more efficient than conventional coating agents. The present invention was achieved by discovering that the method has excellent adaptability. That is, the present invention has the general formula () on at least one side of the polyester film. (In the formula, R ₁ represents an alkyl group having 6 to 18 carbon atoms,
R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent hydrogen, a methyl group, a carboxyl group, a carboxymethyl group, or a salt thereof;
It represents an ammonium group, an amine base, an alkali metal or an alkaline earth metal, Y represents a hydrocarbon group having a polymerizable unsaturated group, and Z represents a nitrile group or a phenyl group which may have a substituent, an amide group or represents a carboxylic acid alkyl ester group, a is an integer of 1 to 500, b is 0 or an integer of 1 to 100, and c
is 0 or an integer from 1 to 250. ) and/or a salt thereof as an emulsifier, one or two of the polymerizable monomers.
Formed by a coating agent comprising an aqueous resin composition consisting of 100 parts by weight (solid content equivalent) of an aqueous resin dispersion obtained by emulsion polymerization of at least one seed in an aqueous medium and 0 to 50 parts by weight of polyvinyl alcohol. A polyester film characterized by having a coating layer of the general formula () (In the formula, R ₁ represents an alkyl group having 6 to 18 carbon atoms,
R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent hydrogen, a methyl group, a carboxyl group, a carboxymethyl group, or a salt thereof;
It represents an ammonium group, an amine base, an alkali metal or an alkaline earth metal, Y represents a hydrocarbon group having a polymerizable unsaturated group, and Z represents a nitrile group or a phenyl group which may have a substituent, an amide group or represents a carboxylic acid alkyl ester group, a is an integer of 1 to 500, b is 0 or an integer of 1 to 100, and c
is 0 or an integer from 1 to 250. ) and/or a salt thereof as an emulsifier, one or two of the polymerizable monomers.
Applying a coating agent comprising an aqueous resin composition consisting of 100 parts by weight (solid content equivalent) of an aqueous resin dispersion obtained by emulsion polymerizing seeds or more in an aqueous medium and 0 to 50 parts by weight of polyvinyl alcohol, The present invention relates to a method for producing a polyester film, which is characterized in that a stretching operation is then completed. The reactive surfactant used as an emulsifier in the present invention is a polymerizable monomer (A) having a carboxyl group.
A polymer obtained by radical polymerization of and, if necessary, other polymerizable monomers (B) in the presence of an alkyl mercaptan, or, if necessary, a polymerizable polymer having a group that is reactive with the polymer and a carboxyl group. It consists of a product obtained by reacting with monomer (C) and/or a salt thereof. Examples of the polymerizable monomer (A) having a carboxyl group include (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid or monoesters of maleic acid or fumaric acid, and ammonium salts thereof; Examples include organic amine salts and alkali metal salts, and one or two of these
Mixtures of more than one species can be used. The amount of the polymerizable monomer (A) to be used is in the range of 1 to 500 monomers per molecule of the polymer represented by the above general formula (), but it is more preferable that the polymerizable monomer (A) is It is preferable to use the amount such that the acid value of the polymer is 200 or more. In addition, other polymerizable monomers (B) include styrene, α-methylstyrene, chlorostyrene, methylstyrene, chloromethylstyrene, styrene derivatives such as styrene sulfonic acid or its salts;
(meth)acrylamide, methylolated (meth)
Acrylamide, alkoxymethylolated (meth)acrylamide having 1 to 4 carbon atoms, N,N-dimethylaminoethyl (meth)acrylamide,
Amide group-containing polymerizable monomers such as N,N-dimethylaminopropyl (meth)acrylamide; (meth)acrylic acid esters having an alkyl chain of 1 to 18 carbon atoms, 2-hydroxyethyl methacrylate, ( Hydroxypropyl meth)acrylate,
(meth)acrylic acid ester derivatives such as 2-N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate; nitrile group-containing polymerizable properties such as (meth)acrylonitrile Examples include monomers, and these monomers can be used alone or in a mixture of two or more. The alkyl mercaptan used in the present invention has 6 to 18 carbon atoms, and examples thereof include n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, cetyl mercaptan, and stearyl mercaptan. Among these, 1
It can be used as a species or as a mixture of two or more species. The conditions for polymerizing the polymerizable monomer (A) or the polymerizable monomer (A) and the polymerizable monomer (B) are not particularly limited. For example, alkyl mercaptan and the polymerizable monomer (A) and the necessary It can be obtained by polymerizing the polymerizable monomer (B) using a general radical polymerization initiator as it is or diluting it with a solvent if necessary, depending on the radical polymerization initiator used. is preferably 1/10 mole or less of the alkyl mercaptan, and the solvent used as necessary is one that can dissolve the polymerizable monomers (A), (B) and the alkyl mercaptan, And it is preferable that it is inert to these. In the present invention, the polymerizable monomer (A) or the polymerizable monomer (B) is added to the polymerizable monomer (A) as needed, and the polymerizable monomer (B) is polymerized as described above. Reactive surfactants consisting of polymers and/or salts thereof can be used as emulsifiers to obtain favorable results, but if the polymers and/or salts thereof contain polymerizable monomers,
When a reactive surfactant consisting of a polymer and/or a salt thereof into which a polymerizable unsaturated group is introduced by reacting (C) is used as an emulsifier, the emulsifier and the polymer obtained by emulsion polymerization are integrated and become waterproof. This is preferred because an aqueous resin dispersion with better properties and adhesion can be obtained. The polymerizable monomer (C) is a compound containing a polymerizable unsaturated group and a group reactive with a carboxyl group, such as an epoxy group-containing polymerizable monomer such as glycidyl (meth)acrylate or allyl glycidyl ether. Oxazoline group-containing polymerizable monomers such as 2-isopropenyl-2-oxazoline and 2-vinyl-2-oxazoline; such as 2-aziridinylethyl methacrylate and (meth)acryloylaziridine Aziridine group-containing polymerizable monomers; 2-hydroxyethyl (meth)acrylate,
Hydroxypropyl (meth)acrylate, (meth)
Examples include hydroxyl group-containing polymerizable monomers such as allyl alcohol and monoester compounds of (meth)acrylic acid and polypropylene glycol or polyethylene glycol. These can be used alone or in a mixture of two or more. When the polymerizable monomer (C) is used, the amount used is in the range of 1 to 100 molecules per molecule of the polymer,
More preferably 1 to 10 molecules. However, when a hydroxyl group-containing polymerizable monomer is used as the polymerizable monomer (B), a hydroxyl group-containing polymerizable monomer cannot be used as the polymerizable monomer (C). Reaction of polymerizable monomer (A) or a polymer obtained by polymerizing polymerizable monomer (A) and polymerizable monomer (B) and/or a salt thereof and polymerizable monomer (C) There are no particular restrictions on the conditions, and the polymerizable monomer (C) containing a group that is reactive with the polymer and carboxyl group is used as it is or diluted with a solvent as necessary, preferably at room temperature to 200°C. The reaction may be carried out under temperature conditions, more preferably 50 to 150°C, and an appropriate catalyst may be used if necessary. The polymer thus obtained can further have a base added thereto to increase the degree of dissociation of carboxyl groups and improve its solubility in water. Bases that can be blended include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia; organic bases such as trimethylamine and triethylamine; one type or a mixture of two or more of these can be used. can do. The molecular weight of the reactive surfactant thus obtained is preferably 400 to 10,000, more preferably
400-5000. The polymerizable monomers used in the emulsion polymerization of the present invention are not particularly limited as long as they are polymerizable, but one type or a combination of two or more types thereof can be used depending on the purpose and use. Examples of these polymerizable monomers include epoxy group-containing polymerizable monomers such as glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and allylglycidyl ether; (meth)acryloyl aziridine; Aziridinyl group-containing polymerizable monomers such as 2-aziridinylethyl (meth)acrylate; 2-isopropenyl-2-oxazoline, 2
- Oxazoline group-containing polymerizable monomers such as vinyl-2-oxazoline; Styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, chloromethylstyrene, styrenesulfonic acid and its salts; (meth)acrylamide, N - (meth)acrylamide derivatives such as monomethyl (meth)acrylamide, N-monoethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide; methyl (meth)acrylate, (meth)acrylamide;
(Meth)acrylic acid esters synthesized by esterification of (meth)acrylic acid such as ethyl acrylate and butyl (meth)acrylate with a _C1 to _C18 alcohol; 2-hydroxyethyl (meth)acrylate; Hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxypropyl (meth)acrylate and monoesters of (meth)acrylic acid and polypropylene glycol or polyethylene glycol; ethyl (meth)acrylic acid 2-sulfonate and its salts, vinyl sulfonic acid and its salts, vinyl acetate, (meth)acrylonitrile, etc., dimethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, vinylpyridine, vinylimidazole, Basic polymerizable monomers such as vinylpyrrolidone; (meth)acrylic acid and ethylene glycol,
1,3-butylene glycol, diethylene glycol, 1,6-hexane glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane,
Polyfunctional (meth)acrylic acid esters having two or more polymerizable unsaturated groups in the molecule, such as esters with polyhydric alcohols such as pentaerythritol and dipentaerythritol; N-methylol (meth)acrylamide, N-butoxy (Meth)acrylamides such as methyl (meth)acrylamide; vinyltrimethoxysilane, γ-(meth)
Organosilicon group-containing polymerizable monomers such as acryloxypropyltrimethoxysilane, allyltriethoxysilane, trimethoxysilylpropylallylamine; and vinyl fluoride, vinylidene fluoride, vinyl chloride, vinylidene chloride, divinylbenzene,
Examples include diallyl phthalate. In order to further improve the adhesion and water resistance of the coating agent of the present invention, at least one of the polymerizable monomers is required.
It is preferable that the species is a polymerizable monomer having a functional group capable of reacting with a carboxyl group and/or an organosilicon monomer having a polymerizable unsaturated group and a hydrolyzable group directly bonded to a silicon atom in the molecule. . Examples of the polymerizable monomer having a functional group capable of reacting with a carboxyl group include epoxy group-containing polymerizable monomers and aziridinyl group-containing polymerizable monomers among the above-mentioned polymerizable monomers for emulsion polymerization. oxazoline group-containing polymerizable monomers can be used, and as organosilicon monomers having a polymerizable unsaturated group and a hydrolyzable group directly bonded to a silicon atom in the molecule, organosilicon group-containing polymerizable monomers can be used. Polymerizable monomers can be used. As for the emulsion polymerization method, any conventionally known emulsion polymerization method can be applied. For example, polymerization catalyst, water,
The aqueous resin dispersion of the present invention can be synthesized by a method in which a reactive surfactant and a polymerizable monomer are mixed together and polymerized, or by a method such as a so-called monomer dropping method or a pre-emulsion method. The polymerization temperature is 0~100℃, preferably 50~
The temperature is 80°C and the polymerization time is 1 to 10 hours. During emulsion polymerization, it is possible to add a hydrophilic solvent and other known emulsifiers and additives as long as the physical properties of the film are not adversely affected. The amount of the reactive surfactant used is not particularly limited, but is preferably 0.5 to 200 parts by weight, more preferably 1 to 200 parts by weight per 100 parts by weight of the polymerizable monomer component.
15 parts by weight. As the polymerization catalyst, any conventionally known catalyst can be used. However, in order to obtain an aqueous resin dispersion that provides a film with even better water resistance, hydrogen peroxide, di-t-butyl peroxide, peracetic acid, 2,2'-azobis(2-amidinopropane) dihydrochloric acid, It is preferred to use one or a mixture of two or more of polymerization catalysts that do not leave sulfate groups, such as salts, 4,4'-azobis(4-cyanopentanoic acid), etc. In addition, if at least one of the polymerizable monomers has a functional group that can react with a carboxyl group, the molecule may contain an amidino group, a carboxyl group, etc. that have high reactivity with these reactive groups. It is more preferable to use 2,2'-azobis(2-amidinopropane) dihydrochloride, 4,4'-azobis(4-cyanopentanoic acid), and the like. The amount of the polymerization catalyst used is usually in the range of 0.01 to 5 parts by weight per 100 parts by weight of the polymerizable monomer component. In addition, when at least one of the polymerizable monomers is a polymerizable monomer and/or an organosilicon monomer having a functional group that can react with a carboxyl group, the polymerizable monomer can be reacted with a carboxyl group. The adhesion, water resistance, and Solvent properties, strength, etc. may be significantly improved. The polyvinyl alcohol used as necessary in the present invention is a partially saponified product or a completely saponified product of polyvinyl acetate, and there are no particular restrictions on the degree of polymerization or saponification.
Those having a saponification degree of 70 to 100 mol% can be preferably used. In the present invention, polyvinyl alcohol has the effect of significantly improving the wettability of the coating agent to the polyester film. When using polyvinyl alcohol, the amount used is
The amount is 50 parts by weight or less, preferably 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the solid content of the aqueous resin dispersion. If the amount of polyvinyl alcohol used is more than 50 parts by weight, the water resistance of the resulting coating layer will decrease, which is not preferable. An aqueous resin composition consisting of an aqueous resin dispersion and polyvinyl alcohol can be prepared using the following methods: 1. Method of stirring and mixing the aqueous resin dispersion and polyvinyl alcohol at room temperature and under heating 2. Aqueous resin dispersion, polyvinyl alcohol, and peroxide or azo Method 3 of heating a compound that can generate radicals by heating to a temperature higher than the decomposition temperature of peroxides and azo compounds.Production of an aqueous resin dispersion (i.e., emulsion polymerization) in the presence of polyvinyl alcohol. It can be preferably produced by any of the methods. The aqueous resin dispersion obtained as described above can be used as it is as a coating agent of the present invention, but if necessary, other known substances capable of controlling light absorption/transmission, lubricants, antistatic agents, etc. , water repellent, crosslinking agent, PH regulator, wetting agent, viscosity regulator, solvent, etc. can be added. It can also be diluted as appropriate. The polyester resin serving as the base material of the polyester film of the present invention includes dihydric alcohols and aromatic dibasic acids or esters thereof such as polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate, etc. It is possible to use thermoplastic polyester resins obtained from. There are no particular limitations on the method for producing the polyester film having the coating layer of the present invention, and a film that has been melt-extruded and stretched by a conventional method may be coated using a roll coater, gravure coater, spray, air knife coater, curtain coater, etc. It can be manufactured by applying a coating agent to a predetermined thickness using a device and drying it. However, in order to prevent dust from adhering to the polyester film that serves as the base material and to form the minimum necessary thin film to exhibit performance, it is necessary to apply a coating agent to the polyester film that has been melt-extruded and has not yet been stretched. It is advantageous to manufacture by a method of coating and then completing stretching to a predetermined magnification (in-line coating method). Here, polyester film that has not been completely stretched refers to unstretched film,
This includes a uniaxially stretched film that is stretched only in one direction, a low-magnification stretched film that is stretched at a lower magnification than a predetermined magnification, and the like. A particularly preferred manufacturing method in terms of economy and quality of the coating layer is to stretch a melt-extruded polyester resin in the vertical direction to a predetermined magnification, apply the coating agent of the present invention, and then stretch it in the horizontal direction to a predetermined magnification. This is a method of heat fixing. When producing the film of the present invention by an in-line coating method, it is particularly preferable to use a coating agent containing polyvinyl alcohol. That is, the coating layer of the film produced in this process is usually
It is extremely thin, less than 0.1 μm, and the coating agent is diluted to a few percent concentration before use. When coating a thin layer with a coating agent diluted in this manner, conventional coating agents have poor wettability to polyester films, causing repellency and the like, making it difficult to obtain a smooth coating layer. To improve this point, it is common to add wettability improvers such as surfactants.
When blending a wettability improver, it is necessary to select and blend the wettability improver, and since the wettability improver remains in the coating layer,
There was also the problem of decreased water resistance and adhesion. on the other hand,
Since the coating agent containing polyvinyl alcohol used in the present invention has good wettability to polyester, there is no need to add a wettability improver when applying it to the above process, and it also has good water resistance and adhesion. Because of its excellent properties, it can form an excellent coating layer without the drawbacks of conventional coating agents. [Effects of the Invention] The polyester film of the present invention is coated with a coating agent containing an aqueous resin dispersion obtained by using a reactive surfactant with a specific structure as an emulsifier and, if necessary, polyvinyl alcohol. Because it has a coating layer obtained by manufacturing, it has excellent adhesion to various coating agents, inks, and metal vapor deposition films, and is suitable for magnetic recording materials, packaging materials, electrical and electronic related materials, plate-making and printing materials, and photographic films. It can be widely and effectively used as a material. Furthermore, since the coating agent used in the present invention is water-based, there is no fear of fire or environmental pollution. In particular, films manufactured through the process of applying a coating agent to a film that has not yet been stretched and then completing the stretching have fewer defects in the coating layer, and have a thin coating layer that fully has the characteristics of the coating agent of the present invention. Therefore, it is particularly excellent in terms of economy and quality. [Examples] The present invention will be explained in detail with reference to Examples below, but the scope of the present invention is not limited only to these Examples. In the examples, unless otherwise specified, % means % by weight, and parts represent parts by weight. Reference Example 1 Put 180 parts of isopropyl alcohol into a flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, and heat to 81°C while blowing nitrogen.
The isopropyl alcohol was refluxed for 10 minutes. Next, I prepared in advance,
174 parts of acrylic acid, 36 parts of n-dodecyl mercaptan
and 0.42 parts of 2,2'-azobisisobutyronitrile (AIBN) were added dropwise over 1 hour to polymerize. After the dropwise addition was completed, thermal aging was performed for 1 hour under reflux to obtain a solution of polymer (1) with a solid content of 53.9%. The polymer (1) was a white powder with an acid value of 645 and a number average molecular weight of 1200, having a structure represented by the following general formula. Reference Example 2 Into a flask similar to Reference Example 1, 180 parts of isopropyl alcohol was charged, and while blowing nitrogen,
The internal temperature was raised to 81°C, and the isopropyl alcohol was refluxed for 10 minutes. Next, a polymerizable monomer mixture prepared in advance consisting of 86 parts of acrylic acid, 139 parts of 2-hydroxyethyl acrylate, 36 parts of n-dodecyl mercaptan, 30 parts of isopropyl alcohol, and 0.30 parts of AIBN was added over 1 hour. was added dropwise to polymerize. After completion of the dropwise addition, the solution was aged under reflux for 1 hour to obtain a solution of polymer (2) with a solid content of 55.4%. the polymer
(2) was a white viscous substance with an acid value of 256 and a number average molecular weight of 1500, having a structure represented by the following general formula. Reference Example 3 Put 180 parts of isopropyl alcohol into the same flask as in Reference Example 1, and add it while blowing nitrogen.
Heated to 80°C. A polymerizable monomer mixture consisting of 148 parts of acrylic acid, 31 parts of itaconic acid, 18 parts of lauryl acrylate, 24 parts of n-octylmercaptan, and 0.41 parts of AIBN was added dropwise thereto over 2.0 hours.
After the dropwise addition was completed, the mixture was stirred under reflux for 1 hour for aging to obtain a solution of polymer (3) with a solid content of 54.2%. polymer
(3) has a structure represented by the general formula below, and has an acid value
420, and the number average molecular weight was 2000. Reference Example 4 193.5 parts of ion-exchanged water was placed in a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer, and a condenser.
4 parts and 28% solution of polymer (1) obtained in Reference Example 1
1.6 parts of aqueous ammonia was added and heated to 65°C while slowly flowing nitrogen gas. There 2,2'-
Azobis(2-amidinopropane) dihydrochloride 5
% aqueous solution was injected, and then a polymerizable monomer mixture consisting of 55 parts of methyl methacrylate and 45 parts of butyl acrylate, which had been prepared in advance, was added dropwise from the dropping funnel over a period of 2 hours. After the dropwise addition was completed, the temperature was kept at 65°C and stirring was continued for 1 hour, followed by cooling to obtain an aqueous resin dispersion [1] with a non-volatile content of 33.5%. This is referred to as a coating agent (). Reference Examples 5 to 9 In Reference Example 4, the same operations as in Reference Example 4 were repeated except that the amount and type of polymer solution and the composition of the polymerizable monomer mixture were as shown in Table 1. Aqueous resin dispersions [2] to [6] were obtained. These are referred to as coating agents () to ().

[Table] Reference example 10 Add ion-exchanged water to the same flask as in reference example 4.
193.5 parts, solution 7.4 of polymer (1) obtained in Reference Example 1
1 part and 1.6 parts of 28% ammonia water were added, and the temperature was raised to 65°C while slowly flowing nitrogen gas. 4 parts of a 5% aqueous solution of 2,2'-azobis(2-amidinopropane) dihydrochloride was injected therein, and then 39 parts of methyl methacrylate, which had been prepared in advance,
A first polymerizable monomer mixture consisting of 8 parts of butyl acrylate and 3 parts of glycidyl methacrylate was added dropwise over 1 hour. After stirring for 30 minutes,
A second component consisting of 29 parts of methyl methacrylate, 18 parts of butyl acrylate, and 3 parts of vinyltrimethoxysilane.
A mixture of polymerizable monomers was added dropwise over 1 hour. After continuing stirring for an additional hour, the mixture was cooled to obtain an aqueous resin dispersion [7] with a nonvolatile content of 33.8%. This is referred to as a coating agent (). Reference Example 11 100 parts of each of the aqueous resin dispersions [2], [3], [6] and [7] obtained in Reference Examples 5, 6, 9 and 10 were mixed with the types and amounts shown in Table 2. A 5% aqueous solution of polyvinyl alcohol was added and stirred at room temperature for 30 minutes to obtain coating agents () to (XI).

[Table] Reference Example 12 Add 6.8 parts of a 5% aqueous solution of Kuraray Poval 117 and 0.3 parts of potassium persulfate to 100 parts of the aqueous resin dispersion [2] obtained in Reference Example 5 in a flask similar to that used in Reference Example 4. Add and heat and stir at 80℃ for 2 hours.
A coating agent (XII) was obtained. Reference Example 13 In a flask similar to that used in Reference Example 4, add 112.5 parts of ion-exchanged water and the polymer (1) obtained in Reference Example 1.
5 parts of a solution of, 40 parts of a 5% aqueous solution of Kuraray Poval 205
1 part and 2 parts of 28% ammonia water were added, and the mixture was heated to 65°C while slowly flowing nitrogen gas. 4 parts of a 5% aqueous solution of 2,2'-azobis(2-amidinopropane) dihydrochloride were added thereto, and then 50 parts of methyl methacrylate, 45 parts of butyl acrylate, and vinyl A polymerizable monomer mixture consisting of 5 parts of trimethoxysilane was added dropwise over 2 hours. Keep the temperature at 65% even after the dripping is complete.
After stirring was continued for 1 hour while maintaining the temperature at °C, the mixture was cooled to obtain a coating agent (2) with a nonvolatile content of 34.5%. Comparative Reference Example 1 In Reference Example 4, the same operation as in Reference Example 4 was repeated except that 2 parts of sodium dodecylbenzenesulfonate, which is a known emulsifier, was used instead of the solution of polymer (1), and the nonvolatile content was 33.9%. A comparative aqueous resin dispersion [1'] was obtained. This is used as a comparative coating agent (). Example 1 Coating agent obtained in Reference Examples 4 to 13 ()
～() and the comparative coating agent () obtained in Comparative Reference Example 1 were biaxially stretched at the same concentration as the undiluted solution to a thickness of 10μ with no surface treatment (no coating layer).
polyethylene terephthalate film (PET)
film) using a bar coater to a dry film thickness of 2μ
m, heated at 110℃ for 1 minute,
A PET film with a coating layer was obtained.
Since repellency occurred partially in the samples using coating agents () to () and comparative coating agent (), the areas without repellency were used in the following tests. No repellency occurred in the samples using coating agents () to (). Nitrocellulose lacquer (non-volatile content: 40%) was applied to the PET film with the obtained coating layer and the untreated PET film using a bar coater to a dry film thickness of 5 μm, dried at 110°C for 1 minute, and used for testing. I got the film. Regarding the obtained test film, adhesion,
A hot water resistance test was conducted. The results are shown in Table 3.

[Table] Example 2 PET film with a coating layer obtained by applying the coating agent () obtained in Example 1 and the comparative coating agent () and an untreated PET film were coated with aluminum to a thickness of 300 mm. was deposited on. The adhesion and water resistance of the obtained vapor-deposited film were tested. The results are shown in Table 4.

[Table] Water resistance: After soaking in tap water overnight at room temperature,
Adhesion was tested by wiping off moisture from the surface.
Example 3 A PET film having a coating layer was manufactured by an in-line coating method using coating agents () to () and comparative coating agent (). In-line coating method: Polyethylene terephthalate is melt-extruded and cast onto a cooled rotating drum, then in the extrusion direction (vertical direction).
After stretching 3.5 times, each coating agent diluted with water to a concentration of 3% was applied using a roll coater, then stretched 3.5 times laterally (horizontal direction) at 105°C, and heat-set at 200°C. The film thickness is approximately 12μm, and the coating layer thickness is approximately 0.05μm.
A PET film with m coating layers was obtained. PET films with coating layers obtained using coating agents () to () were free from repelling and could be coated uniformly over the entire surface of the PET film, but those using comparative coating agent () were coated over the entire surface. Cracks occur in
No film was available for use in the following tests. A test piece (15 x 20 cm) was cut out from the PET film having the obtained coating layer, and a test film coated with nitrocellulose lacquer was prepared in the same manner as in Example 1, and adhesion and hot water resistance tests were conducted. Ivy. The results are shown in Table 5.

【table】

Claims (1)

[Claims] 1. On at least one side of the polyester film,
General formula () (In the formula, R ₁ represents an alkyl group having 6 to 18 carbon atoms,
R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent hydrogen, a methyl group, a carboxyl group, a carboxymethyl group, or a salt thereof;
It represents an ammonium group, an amine base, an alkali metal or an alkaline earth metal, Y represents a hydrocarbon group having a polymerizable unsaturated group, and Z represents a nitrile group or a phenyl group which may have a substituent, an amide group or represents a carboxylic acid alkyl ester group, a is an integer of 1 to 500, b is 0 or an integer of 1 to 100, and c
is 0 or an integer from 1 to 250. ) and/or a salt thereof as an emulsifier, one or two of the polymerizable monomers.
Formed by a coating agent comprising an aqueous resin composition consisting of 100 parts by weight (solid content equivalent) of an aqueous resin dispersion obtained by emulsion polymerization of at least one seed in an aqueous medium and 0 to 50 parts by weight of polyvinyl alcohol. A polyester film characterized by having a coating layer. 2 The amount of polyvinyl alcohol used is 0.01 to 100 parts by weight (solid content equivalent) of the aqueous resin dispersion.
2. The polyester film according to claim 1, wherein the amount is 20 parts by weight. 3. At least one of the polymerizable monomers has a functional group capable of reacting with a carboxyl group and/or has a polymerizable unsaturated group and a hydrolyzable group directly bonded to a silicon atom in the molecule. 3. The polyester film according to claim 1 or 2, which is an organic silicon monomer. 4. The polyester film according to claims 1 and 3, wherein in the general formula (), b is an integer of 1 to 100. 5 General formula () on at least one side of the unstretched polyester film (In the formula, R ₁ represents an alkyl group having 6 to 18 carbon atoms,
R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent hydrogen, a methyl group, a carboxyl group, a carboxymethyl group, or a salt thereof;
It represents an ammonium group, an amine base, an alkali metal or an alkaline earth metal, Y represents a hydrocarbon group having a polymerizable unsaturated group, and Z represents a nitrile group or a phenyl group which may have a substituent, an amide group or represents a carboxylic acid alkyl ester group, a is an integer of 1 to 500, b is 0 or an integer of 1 to 100, and c
is 0 or an integer from 1 to 250. ) and/or a salt thereof as an emulsifier, one or two of the polymerizable monomers.
Applying a coating agent comprising an aqueous resin composition consisting of 100 parts by weight (solid content equivalent) of an aqueous resin dispersion obtained by emulsion polymerizing seeds or more in an aqueous medium and 0 to 50 parts by weight of polyvinyl alcohol, A method for producing a polyester film, characterized in that a stretching operation is then completed.