JPH01203438A - Polyester film and production thereof - Google Patents

Abstract

PURPOSE:To obtain the present film, excellent in adhesiveness to ink, vacuum deposited metallic films, etc., and suitable as magnetic recording, packing materials, etc., by coating the surface of a film with a composition of a specific aqueous resin dispersion and polyvinyl alcohol. CONSTITUTION:The aimed film obtained by carrying out emulsion polymerization of (B) a polymerizable monomer (e.g., allyl glycidyl ether) using (A) an emulsifying agent, prepared by radically polymerizing (i) a polymerizable monomer, such as (meth)acrylic acid, and (ii) an alkyl mercaptan and expressed by the formula [R1 is 6-18C alkyl; R2-R6 are H, methyl, etc.; X is H, ammonium, etc.; Y is hydrocarbon having polymerizable unsaturated group; Z is nitrile, etc.; (a) is 1-500; (b) is 0-100; (c) is 0-250] to provide an aqueous resin dispersion, coating (D) a polyester film with a blend of 100pts.wt. resultant aqueous resin dispersion with (C) 0-50pts.wt. polyvinyl alcohol and drawing the obtained film.

Description

[Detailed description of the invention] [Industrial application field].

The present invention relates to a polyester film having an entire coating layer and thus having improved surface properties, and a method for producing the polyester film.

[Prior art and problems to be improved by the invention] Polyester films are widely used in the fields of magnetic materials, packaging materials, electrical/electronic materials, and printing materials. We have added features such as
A coating layer, a printed layer, or a vapor deposited layer is provided for the purpose of imparting an aesthetic appearance. In practical use, it is important that the adhesion between the polyester film and the coating agent, ink, or metal vapor deposition film is maintained under the usage conditions of each application. An anchor coat layer and a brimer layer coated with a solution or dispersion of urethane resin, I-reester resin, acrylic resin, etc. 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.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a fixed 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 made 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 all of the above objects, and the coating agent is subjected to a stretching operation. incomplete, j? The method of producing a polyester film by coating it on a polyester film and then completing a stretching operation is industrially advantageous; We have discovered that this material has excellent properties and have arrived at the present invention.

That is, the present invention provides, on at least one side of a polyester film, a compound having the general formula (I) % formula % (wherein R1 represents an alkyl group having 6 to 18 carbon atoms, and R
2+ R5# Ra + R5 and R6 each independently represent hydrogen, a methyl group, a carboxyl group, a carboxymethyl group, or a salt thereof, and X represents hydrogen, an ammonium group, an amine base, an alkali metal or an alkaline earth metal. , Y represents a hydrocarbon group having a polymerizable unsaturated group, 2 represents a nitrile group, and represents a phenyl group, an amide group, or a cargenic acid alkyl ester group which may contain a substituent, and a represents 1 to 500%. b is O or 1 to lOO
is an integer of e td O or an integer of 1 to 250. ) Aqueous resin dispersion 100 obtained by emulsion polymerization of one or more polymerizable monomers in an aqueous medium using a reactive surfactant consisting of a polymer represented by and/or a salt thereof as an emulsifier. A polyester film characterized in that it has a coating layer formed by a coating agent entirely containing an aqueous resin composition consisting of 0 to 50 parts by weight (in terms of solid content) of toposavinyl alcohol, and a stretching operation. It is incomplete. jf At least one side of the IJ ester film has the general formula (I) (wherein R1 represents an alkyl group having 6 to 18 carbon atoms, R
2+ R3+ R4+ Rs and R6 each independently represent hydrogen, a methyl group, a carboxyl group, a carboxymethyl group, or a salt thereof, X represents hydrogen, an ammonium group, an amine base, an alkali metal or an alkaline earth metal, Y represents a hydrocarbon group containing a polymerizable unsaturated group, Z represents a nitrile group or a phenyl group which may have a substituent, amide group represents a cargenic acid alkyl ester group, a is 1 to 500%b is O or an integer from 1 to 100, and C is O or an integer from 1 to 2.50.

) Aqueous resin dispersion 100 obtained by emulsion polymerization of one or more polymerizable monomers in an entirely aqueous medium using a reactive surfactant consisting of a polymer represented by and/or a salt thereof as an emulsifier. Parts by weight (in terms of solid content) and 0 to 50 parts by weight of jf divinyl alcohol. It is something.

The reactive surfactant used as an emulsifier in the present invention is obtained by radical polymerization of a polymerizable monomer (A) having a carboxyl group and, if necessary, other polymerizable monomers (CB) in the presence of t-alkylmercagutan. A product obtained by total reaction with a polymer or, if necessary, a polymerizable monomer (C) having a group reactive with the polymer and a carboxyl group, and/or a salt thereof. It is something.

The polymerizable monomer (A) having a carboxyl group is (
meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid 4L<i! Examples include monoesters of maleic acid or fumaric acid, ammonium salts, organic amine salts, and alkali metal salts thereof, and one type or a mixture of 2 m or more of these can be used. The amount of polymerizable monomer (A) used is based on the above general formula (I).
The amount is in the range of 1 to 500 per molecule of the polymer represented by the general formula (I), but it is more preferably used in an amount such that the acid value of the polymer represented by the general formula (I) is 200 or more. good.

In addition, other polymerizable monomers (B) include styrene,
Styrene derivatives such as α-methylstyrene, chlorstyrene, methylstyrene, chloromethylstyrene, styrenesulfonic 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-dimethylaminoethyl (meth)acrylamide; carbon number 1-1
(meth)acrylic ester having 8 alkyl chains, 2-hydroxyethyl methacrylate, hydroxyglovir (meth)acrylate, 2-(meth)acrylate
N, N-dimethylaminoethyl, (meth)acrylic acid N
, (meth)acrylic acid ester derivatives such as N-dimethylaminoglopyl; nitrile group-containing polymerizable monomers such as (meth)acrylonitrile, etc., and these may be used alone or in a mixture of two or more. can do.

The alkyl mercaptan used in the present invention has 6 to 18 carbon atoms, such as n-hexylmercaptan, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, cetylmercaptan, Examples include stearylmercagutan, among which IS makufi2. It can be used in a mixture of fl1 or more.

The conditions for polymerizing the polymerizable monomer (A) or the polymerizable monomer and the polymerizable monomer (B) are not particularly limited. For example, alkyl mercaptan and the polymerizable monomer (A) and, if necessary, The polymerizable monomer (B)' can be obtained by polymerizing the polymerizable monomer (B)' using a general radical polymerization initiator as it is or by diluting it with a solvent if necessary. At this time, the radical polymerization initiator used is an alkyl mercaptan. one-tenth of
It is preferable that the amount is mol or less, and the solvent used if necessary is one that can dissolve the polymerizable monomers (A), (B) and the alkyl mercaptan, and is inert to them. It is preferable that there be.

In the present invention, the polymerizable monomer (A) or the polymerizable monomer (B) is added to the polymerizable monomer (A) as necessary, and the polymerizable monomer is obtained by polymerizing as described above. Favorable results can be obtained by using a reactive surfactant consisting of a polymer and/or a salt thereof as an emulsifier; When a reactive surfactant consisting of an FC polymer and/or its salt is used as an emulsifier by introducing a polymerizable unsaturated group, the emulsifier and the polymer obtained by emulsion polymerization are integrated, resulting in better water resistance and adhesion. This is preferred because a nonaqueous resin dispersion can be obtained.

The polymerizable monomer (C) is a compound containing a polymerizable unsaturated group and a group reactive with a carboxyl group. Monomer a; Oxazoline group-containing polymerizable monomers such as 2-ingropenyl-2-oxazoline and 2-vinyl-2-oxazoline; such as 2-aziridinylethyl methacrylate and (meth)acryloylaziridine Aziridine group-containing polymerizable monomers: (meth)acrylic acid 2-hydrothousand diethyl, (meth)
Examples include hydroxyl group-containing polymerizable monomers such as hydroxyglobyl acrylate, (meth)allyl alcohol, and monoesterified products of (meth)acrylic acid and polypropylene glycol or polyethylene glycol. One of these can be used as a mixture of two or more. Polymerizable monomer (C) t- When 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).

A polymer obtained by polymerizing the polymerizable monomer (A) or the polymerizable monomer (A) and the polymerizable monomer (B)' and/or a salt thereof and the polymerizable monomer (C). There are no particular restrictions on the reaction conditions, and the polymerizable monomer (C) ffi containing a group that is reactive with the polymer and carboxyl group may be used as it is or diluted with a solvent if necessary, preferably at room temperature to 2.
The reaction may be carried out at a temperature of 00°C, more preferably 50 to 150°C, and an appropriate catalyst may be used if necessary.

The specific polymer thus obtained can further have a base added thereto to increase the total dissociation degree of carboxyl groups and improve its solubility in water. Examples of 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; among these, ls or a mixture of two or more are used. be able to.

The molecular weight of the reactive surfactant thus obtained is preferably 400 to 10,000, more preferably 400.
~s, o o o.

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; Oxazoline group-containing polymerizable monomers such as 2-isobroynyl-2-oxazoline and 2-vinyl-2-oxazoline: styrene , vinyltoluene, α-methylstyrene, chloromethylstyrene, styrene sulfonic acid and its salts; (meth)acrylamide, N-monomethyl (meth)acrylamide, N-monoethyl (meth)acrylamide, N,N- (meth)acrylamide derivatives such as dimethyl (meth)acrylamide; methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylate;
(meth)acrylic acid such as butyl acrylate and C4-C
(Meth)acrylic acid esters synthesized by esterification of alcohols in No. 48; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid and polyethylene glycol esters; Hydroxyl group-containing (meth)acrylic acid esters such as monoesters with 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, dimethylamine propyl Basic polymerizable monomers such as (meth)acrylamide, vinylpyridine, vinylimidazole, and vinylpyrrolidone; (meth)acrylic acid triethylene glycol, 1,3-butylene glycol,
diethylene glycol, 1,6-hexane glycol,
Polyfunctional (meth)acrylic acids having two or more polymerizable unsaturated groups in the molecule, such as esters with polyhydric alcohols such as neopentyl glycol, polyethylene glycol, polyethylene glycol, trimethylolglopane, pentaerythritol, and dipentaerythritol. Esters; (meth)acrylamides such as N-methylol (meth)acrylamide and N-butoxymethyl (meth)acrylamide; vinyltrimethoxysilane, r-(meth)acrylamide;
Organosilicon group-containing polymerizable monomers such as acryloxyglobyltrimethoxysilane, allyltriethoxysilane, trimethoxysilylglopyllylamine; and vinyl fluoride, vinylidene fluoride, vinyl chloride, vinylidene chloride, divinyl Examples include benzene and 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 has a functional group capable of reacting with a calgexic group and/or is polymerized within the molecule. An organic silicon monomer containing a sexually unsaturated group and a hydrolyzable group directly bonded to a silicon atom is preferable.

Examples of the polymerizable monomer having a functional group capable of reacting with a carmexyl group include epoxy group-containing polymerizable monomers and aziridinyl group-containing polymerizable monomers among the above-mentioned polymerizable monomers for emulsion polymerization. and oxazoline group-containing polymerizable monomers can be used. As organosilicon monomers having a polymerizable unsaturated group and a hydrolyzable group directly bonded to a silicon atom in one molecule, organosilicon monomers containing an organosilicon group 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, the aqueous resin dispersion of the present invention may be prepared by a method of actively mixing a polymerization catalyst, water, a reactive surfactant, and a polymerizable monomer gold, or by a method such as the so-called seven-summer dropping method or pre-emulsion method. Can be synthesized.

The polymerization temperature is 0 to 100°C, preferably 50 to 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 100 polymerized parts of the polymerizable monomer component.
The amount is 200 parts by weight, more preferably 1 to 15 parts by weight.

As the polymerization catalyst, any conventionally known catalyst can be used. As a precaution, in order to obtain an aqueous resin dispersion that has excellent water resistance and provides a solid coating, hydrogen peroxide, di-
t-Butyl peroxide, peracetic acid, 2.2'-azobis(2-amidinoglopane) dihydrochloride, 4.4'-
It is preferred to use one or a mixture of two or more polymerization catalysts that leave sulfate groups, such as azobis (4-cyanointanoic acid). (9) When at least one of the polymerizable monomers has all functional groups that can react with carmexyl groups, the molecule contains amidino groups, carzaxyl groups, etc. that have high reactivity with these reactive groups. 2,2'-
Azobis(2-abadinoglobin) dihydrochloride, 4.4
It is more preferable to use '-azobis(4-cyatintanoic acid) or 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 1 m of the polymerizable monomer is a polymerizable monomer and/or an organosilicon monomer having a functional group that can react with a carboxyl group, the entire carboxyl group of the polymerizable monomer is The adhesion, water resistance, and Solvent resistance, 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; Saponification degree 70-100
Morchi 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 polyvinyl alcohol is used, the amount used is 100% of the solid content of the aqueous resin dispersion! 50 against Keibu
It is preferably in the range of 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight.

, 1 +7 If the amount of vinyl alcohol used is greater than t-50 parts by weight, the water resistance of the resulting coating layer will decrease, which is not preferred.

An aqueous resin composition consisting of an aqueous resin dispersion and polyvinyl alcohol is composed of: 1. an aqueous resin dispersion, and 3. Method 2: Stirring and mixing 1J vinyl alcohol at room temperature and under heating. Method 2: Aqueous resin dispersion, polyvinyl alcohol, and compounds that can generate radicals when heated, such as peroxides and azo compounds. Decomposition of peroxides and azo compounds It can be preferably produced by any of the following methods: method 33, which involves heating to a temperature higher than the above temperature, and method 3, which involves producing an aqueous resin dispersion in the presence of vinyl alcohol (ie, emulsion polymerization).

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, in addition, known substances that can completely control light absorption and transmission - 1 lubricant and antistatic agent.

Water repellents, crosslinking agents, moderators, wetting agents, viscosity control agents, solvents, etc. can be added. By the way, you can dilute it as appropriate.

The polyester resin serving as the base material of the polyester film of the present invention includes a dihydric alcohol and an aromatic tribasic acid or an ester thereof, such as polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalenedicarugexylate, etc. Thermoplastic polyester resins obtained from the following can be used.

There is no particular limitation on the method for producing the polyester film having the coating layer of the present invention, and the film is melt-extruded and stretched by a conventional method, and then coated with a known coating device such as a roll coater, gravure coater, spray, air knife coater, curtain coater, etc. The coating agent is applied to a specified film thickness using a Apply the coating agent to the polyester film.

It is advantageous to manufacture the film by a method (in-line coating method) in which stretching is then completed to a predetermined magnification. This includes preester films that have not been completely stretched, unstretched films, uniaxially stretched films that have been stretched only in one direction, and low-stretched films that have been stretched at a lower ratio than a predetermined ratio. . A particularly preferred manufacturing method in terms of economy and quality of the coating layer is to melt-extrude a polyester resin, stretch it in all vertical directions 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 method involves heat setting.

When producing the film of the present invention by an in-line coating method, it is particularly preferable that the coating agent used is one containing polyvinyl alcohol. That is, the coating layer of the film produced in this process is usually very thin, 0.1 μm or less, and the coating agent is diluted to a concentration of several ml before use. When coating a thin film with a coating agent diluted in this manner, conventional coating agents have poor wettability to polyester films, causing flaking and the like, making it difficult to obtain a smooth coating layer.

In order to improve this point, it is common to add a wettability improver such as a surfactant.

Incorporating all wettability improvers requires time and effort to select and blend all wettability improvers, and the wettability improvers remain in the coating layer, resulting in poor water resistance and adhesion. The place is also next. On the other hand, since the coating agent containing all 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 Since it has excellent adhesion, it can form an excellent coating layer without the drawbacks of conventional coating agents.

〔Effect of the invention〕

The polyester film of the present invention is a coating layer obtained by applying 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. It has excellent adhesion to various coating agents, inks, and metal vapor deposition films, making it widely effective as magnetic recording materials, packaging materials, electrical and electronic related materials, plate-making and printing materials, and photographic film materials. It can be used for. 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 entire process of applying a coating agent to a film that has not yet been stretched and then completing the stretching process have fewer defects in the coating layer. Therefore, it is particularly excellent in terms of economy and quality.

〔Example〕

The present invention will be described in detail below with reference to Examples, but the scope of the present invention is not limited only to these Examples.

In addition, unless otherwise specified in the examples, Q is weight% gold,
Parts shall indicate all parts by weight.

Reference Example 1 A flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer and a dropping funnel was charged with 180 parts of Inglobil alcohol, and nitrogen was blown into the flask and the internal temperature was raised to 81°C to produce isonorobil alcohol. It was refluxed for 210 minutes.

Next, 1 part of a polymerizable monomer mixture prepared in advance, consisting of 174 parts of acrylic acid, 36 parts of n-dodecylmercaptan, and 0.42 parts of 2,2'-azobisisobutyronitrile (ATBN), was added. It takes time to drip and polymerize. After the dropwise addition, it was aged for 1 hour under reflux, and the solid content was 53.9.
% of polymer (I) solution. The polymer (I) was a white powder having an acid value of 645 and a number average molecular weight of 1,200, having a structure represented by the following general formula.

Reference Example 2 In 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 inglobyl alcohol was refluxed for 10 minutes. Oita acrylic acid 86 cities,
A polymerizable monomer mixture consisting of 139N 2-hydroxyethyl acrylate, 36 parts of n-dodecyl mercaptan, 30 parts of Improvil alcohol, and 130 parts of All0 was added to 1
It was added dropwise and polymerized over time. After finishing dropping, 1 hour under reflux.
A solution of polymer (2) with a solid content of 55.41 was obtained by aging for a period of time. The polymer (2) is a white viscous substance having an acid value of 256 and a number average molecular weight of 1,500 and having a structure represented by the following general formula.

Reference Example 3 In a flask similar to Reference Example 1, 180 parts of Improvil alcohol was charged and heated to 80°C while blowing nitrogen. Add 148 parts of acrylic acid to it.

A polymerizable monomer mixture consisting of 31 parts of itaconic acid, 18 parts of lauryl acrylate, 24 parts of n-octylmercaptan, and 0.41 parts of AIBN was added dropwise 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 54.21. Polymer (
3) has a structure represented by the general formula below, and has an acid value of 42
0, and the number average molecular weight was 2,000.

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 cooler, Reference Example 1
4 parts of the solution of polymer (I) obtained in step 1 and 1.6 parts of 28 thiammonium water were charged and heated to 65° C. while slowly flowing nitrogen gas. There, 2.2′-azobis(2
- All 4 parts of a 5% aqueous solution of abadinopro/4' dihydrochloride were injected, and then 55 parts of methyl methacrylate and 45 parts of butyl acrylate, which had been prepared in advance, were poured into the dropping funnel.
A polymerizable monomer mixture consisting of 50% was added dropwise over 2 hours. After the dropwise addition was completed, the temperature was maintained at 65° C. and stirring was continued for 1 hour, followed by cooling to obtain an aqueous resin dispersion [1] with a nonvolatile content of 33.5%. This is referred to as coating agent (I).

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 exactly as shown in Table 1. Aqueous resin dispersion [2]
~ [6] was obtained. Coating agents (II) to (
It will be VD.

Reference Example 10 Into a flask similar to Reference Example 4, 193.5 parts of ion-exchanged water, 7.4 parts of the solution of polymer (I) obtained in Reference Example 1, and 1.6 parts of 28% ammonia water were added, and the mixture was slowly heated. The temperature was raised to 65°C while flowing nitrogen gas 'Jk. There 2, 2
5% of '-azobis(2-amidinopropane) dihydrochloride
4 parts of an aqueous solution was injected, and then a first polymerizable monomer mixture prepared in advance consisting of 39 parts of methyl methacrylate, 8 parts of butyl acrylate, and 3 parts of glycidyl methacrylate was added for 1 hour. dripped. After continued stirring for 30 minutes, a second polymerizable monomer mixture consisting of 29 parts of methyl methacrylate, 18 parts of butyl acrylate, and 3 parts of vinyltrimethoxysilane was added dropwise over 1 hour. After stirring for another 1 hour, it was cooled and the non-volatile content was reduced to 3.
A 3.8% aqueous resin dispersion [7] was obtained.

This is used as a coating agent (■).

Reference Example 11 Aqueous resin dispersions obtained in Reference Examples 5.6.9 and 10 (
2), (3:]! 1 each of (6:] and [7]
A 5% aqueous solution of z IJ vinyl alcohol of nine types and amounts as shown in Table 2 was added to 00 parts and stirred at room temperature for 30 minutes to obtain coating agents (■) to (XI).

Table 2 Reference Example 12 Into 100 parts of the aqueous resin dispersion obtained in Reference Example 5 [2] in a flask similar to that used in Reference Example 4, 6.8 parts of a 5-ti aqueous solution of Clarezi Pearl 117 and 0.0 parts of potassium persulfate were added. ．．
3 parts were added and heated and stirred at 80°C for 2 hours to obtain a coating agent (Xll)'.

Reference Example 13 In a flask similar to that used in Reference Example 4, 112.5 parts of ion-exchanged water, 5 parts of the solution of the polymer (I) obtained in Reference Example 1, 40 parts of a 5-ti aqueous solution of Kuraray Bhopal 205, and 2
Add 2 parts of 8% ammonia water and heat to 65°C while slowly blowing nitrogen gas. There, 5% aqueous solution of 2,2'-azobime(2-amidinoglomeran) dihydrochloride 4
50 parts of methyl methacrylate and 4 parts of butyl acrylate prepared in advance from the dropping funnel.
Part 5.

A polymerizable monomer mixture consisting of 5 parts of vinyltrimethoxysilane was added dropwise over 2 hours. The temperature remains t- even after the dropping is completed.
The mixture was kept at 65°C and stirred for 1 hour, then cooled to obtain a coating agent (X[[[)] with a non-volatile content of 34.5'l.

Comparative Reference Example 1 In Reference Example 4, a known emulsifier was used instead of the solution of polymer (I). Sodium dodecylbenzenesulfonate 2
The same operation as in Reference Example 4 was repeated except that the same procedure as in Reference Example 4 was used, except that a comparative aqueous resin dispersion having a non-volatile content of 33.9% was obtained.

This is designated as comparative coating agent (I).

Example 1 Coating agents (I) to (X
A percoater was used on a polyethylene terephthalate film (PET film) with a thickness of 10 μm and no surface treatment (no coating layer), which was biaxially stretched with the concentration of the comparative coating agent mt stock solution obtained in [I[] and Comparative Reference Example 1. It was applied to a dry film thickness of 2 μm at 110°C.
Heating for a minute to obtain a PET film with a coating layer. When using coating agents (I) to (to) and comparative coating agent (I) t-, repellency occurred partially in the following samples, so in the following tests, I was careful to use areas without repellency. No repellency occurred when coating agents (■) to (XI[l) were used.

The resulting PET film with nine coating layers and the untreated ET film were coated with nitrocellulose lacquer (
Non-volatile content: 40%) Dry film thickness: 5μ using a wafer coater
The film was coated on a test film and dried at 110° C. for 1 minute to obtain a test film.

Adhesion of the obtained test film.

I went to the hot water resistance test. All results are shown in Table 3.

Third surface adhesion: After adhering a cellophane tube to the coating surface, it was peeled off at once in a 90° direction, and evaluated from 10 points (no peeling) to 1 point (full peeling) depending on the degree of peeling of the coating layer.

Hot water resistance: coated N PET film gold 90~
After being immersed in hot water at 95° C. for 30 minutes, the moisture on the surface was wiped off and an adhesion test was conducted in the same manner as above.

Example 2 The coating agent obtained in Example 1 (X
The film was deposited to a thickness of aluminum T-3001. The adhesion and water resistance of the obtained vapor-deposited film were tested. The results are shown in Table 4.

Table 4 Water resistance: After soaking overnight in tap water at room temperature.

Wipe off moisture from the surface to ensure good adhesion. Don't forget to test.

Example 3 A PET film kH having a coating layer was prepared by an in-line coating method using coating agents (■) to (X[0) and comparative coating agent (I) 'e.

In-line coating method: Polyethylene terephthalate is melt-extruded, cast onto a cooling rotating drum, stretched 3.5 times in the extrusion direction (vertical direction), diluted with water to a concentration of 3%, and carefully coated with each coating and coating agent. It was coated with a roll coater, then stretched 3.5 times laterally (horizontal direction) at 105°C, and heat-set at 200°C, resulting in a film thickness of approximately 12 μm and a coating layer thickness of approximately 0.05 μm.
Obtain a PET film with a coating layer of 9 μm.

PET films with nine coating layers obtained using coating agents (■) to (XI[I) can be coated uniformly over the entire surface of the PET film. However, when using this method, repellency occurred on the entire surface, and we were unable to obtain a film that could be used for the following tests.

A test piece (I5 x 20α) was cut out from the PET film having the obtained coating layer, and coated with nitrocellulose lacquer in the same manner as in Example 1 to prepare a film for testing, and tested for adhesion and hot water resistance. The results are shown in Table 5.

Claims (1)

[Claims] 1. On at least one side of the polyester film, there is a general formula (I) ▲mathematical formula, chemical formula, table, etc.▼ (wherein 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, X is hydrogen,
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 1-500, b is 0 or 1-1
c is an integer of 0 or 1 to 250. ) Aqueous resin dispersion 100 obtained by emulsion polymerization of one or more polymerizable monomers in an aqueous medium using a reactive surfactant consisting of a polymer represented by and/or a salt thereof as an emulsifier. 1. A polyester film comprising a coating layer formed of a coating agent comprising an aqueous resin composition consisting of parts by weight (in terms of solid content) and 0 to 50 parts by weight of polyvinyl alcohol. 2. The polyester film according to claim 1, wherein the amount of polyvinyl alcohol used is 0.01 to 20 parts by weight based on 100 parts by weight (in terms of solid content) of the aqueous resin dispersion. 3. At least one of the polymerizable monomers has a functional group capable of reacting with a carboxyl group and/or a polymerizable monomer having a polymerizable unsaturated group and a hydrolyzable group directly bonded to a silicon atom in the molecule. The polyester film according to claim 1 or 2, which is an organosilicon monomer having a polysilicon monomer. 4. The polyester film according to claims 1 and 3, wherein in the general formula (I), b is an integer of 1 to 100. 5. At least one side of the unstretched polyester film has the general formula (I) ▲mathematical formula, chemical formula, table, etc.▼ (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, X is hydrogen,
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 1-500, b is 0 or 1-1
c is an integer of 0 or 1 to 250. ) Aqueous resin dispersion 100 obtained by emulsion polymerization of one or more polymerizable monomers in an aqueous medium using a reactive surfactant consisting of a polymer represented by and/or a salt thereof as an emulsifier. 1. A method for producing a polyester film, which comprises applying a coating agent comprising an aqueous resin composition consisting of parts by weight (in terms of solid content) and 0 to 50 parts by weight of polyvinyl alcohol, and then completing a stretching operation.