JPS61254637A - Slippery transparent film and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled film having high transparency and slipperiness, by coating the surface of an undrawn film, etc., with a dispersion liquid consisting of a water-insoluble polyester containing sulfonic acid metal salt group, a water-soluble organic compound, water and inert fine particles, and drawing the coated film. CONSTITUTION:At least one surface of an undrawn or uniaxially drawn thermoplastic resin film produced by melt textrusion process is coated with a dispersion liquid consisting of (A) a water-insoluble polyester copolymer derived from 0.5-15mol% dicarboxylic acid containing sulfonic acid metal salt group based on the whole dicarboxylic acid component and a polyhydric alcohol, (B) a water- soluble organic compound having a boiling point of 60-120 deg.C, (C) water and (D) inert particles having an average particle diameter of 0.01-10mu. The weight ratios of the above components are selected to satisfy the formulas I-III at the same time. After drying the applied dispersion liquid, the film is drawn at least uniaxially to obtain the objective film.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a thermoplastic resin film having both transparency and slipperiness, and a method for producing the same.

(Prior Art) Thermoplastic resin films, especially biaxially stretched polypropylene, polyethylene terephthalate films, etc., are used for packaging materials and metal vapor deposition due to their excellent properties such as dimensional stability, mechanical strength, and transparency. for photography, for drafting, for electricity,
It has been used in a wide variety of fields, including magnetic tape and other industrial applications. However, in all of these cases, the thermoplastic resin film does not satisfy all properties. In most applications, films are rarely used alone;
Some kind of secondary processing is performed. Therefore, in terms of workability during processing, product performance, and quality stability,
In particular, properties such as surface lubricity and transparency are considered important issues. For example, slipperiness not only significantly affects the efficiency of basic operations such as film unwinding, winding, slitting, cutting, and coating, which are essential steps for secondary processing for all purposes, but also In particular, winding becomes difficult, and the work efficiency of the user of the resulting film, for example, the efficiency of an automatic packaging machine when used for packaging, and the uniformity of the film when used for cutting for office work, drafting, etc. , work efficiency such as p transportability is greatly affected. For this reason, for the purpose of improving the slipperiness of the optical surface of the film, waxes, fatty acid amides, higher fatty acid compounds such as fatty acid metal salts, organic polysiloxanes, or
By dispersing so-called lubricants such as titanium dioxide, calcium carbonate, talc, kaolin, barium sulfate, albanium oxide, silicon dioxide, and various other inert inorganic compound particles into the synthetic resin for film, the improvement can be greatly improved. It was rice.

In addition, especially in the case of polyester films, lubricants other than those mentioned above may be used, such as metal compound catalysts used during polyester production, methods of forming fine particles with alkali metal compounds, alkaline earth metal compounds, etc. Examples include a so-called internal particle method in which particles are generated from a salt of terephthalic acid and a metal such as calcium or lithium, and a method in which these compound particles are synthesized in advance and added to the polyester production system. However, no matter which method is used, these conventional methods of adding a lubricant have the disadvantage that while the slipperiness improves, the transparency necessarily decreases. It has been considered impossible to fully satisfy both transparency and transparency, and some compromise has always been forced. In other words, there has never been a film that has almost the same transparency as an unmarked film and has a significantly lower coefficient of friction.

Furthermore, there is a method in which morphological processing such as knurl processing is performed before winding, but conventional manufacturing methods do not work, as the knurled part is tri-hung due to slits in secondary processing, or exists only on one side. The following has various problems.

(Problems to be Solved by the Invention) As a result of intensive research in order to solve the above problems, the present inventors have found that a film obtained from a thermoplastic resin containing a lubricant amount of less than a specific amount has a specific lubricant that is insoluble in water. The film can be reused by laminating a coating agent containing a polyester copolymer, a water-soluble organic compound, water, inert particles, and other additives if necessary, and the coating process The present invention provides a transparent coating film with good explosion-proof stability, improved slipperiness, and a method for producing the same.

(Means for Solving the Problems) The first aspect of the present invention is that at least one side of a thermoplastic resin film (A) contains 0.5 to 15 mol of sulfonic acid metal base-containing dicarboxylic acid Ti1 based on 9 of the total dicarboxylic acid components; A water-soluble polyester copolymer consisting of alcohols, (B
) A water-soluble organic compound with a boiling point of 60 to 200°C, (
In a thermoplastic resin film coated with an aqueous polyester resin dispersion comprising C) water and (D) inert fine particles having an average particle size of 0.01 to 10 μm, the water-soluble organic compound (part of El and A portion of water (C) is mixed in advance, a required amount of inert fine particles (D) are added to the Ryoki solution, and after sufficient dispersion pretreatment is performed, the required amount of water is added to the dispersion. A resin dispersion consisting of the insoluble polyester resin (A) and the remaining water-soluble organic compound (BJ and water (C1) is added, and the mixing ratio of each is expressed by the following formulas (1) and (2) in weight ratio.
, (31).

(A) / (B) = 100/20~50000
・・・・・・(1) CB+ / (cl = t 0
0150~10000...(2)(A)/
(Dl= 10000015~3000...
...(3) The second aspect of the present invention is that at least one side of an unstretched or uniaxially stretched thermoplastic resin film obtained by a melt extrusion method is coated with (4) 0°5 to 0.5° with respect to all dicarboxylic acid components. A water-soluble polyester copolymer consisting of a dicarboxylic acid containing 15 moles of sulfonic acid base and a polyhydric alcohol, a water-soluble organic compound having a boiling point of 60 to 200°C, (C1 water, (D) average Particle size is 0.0
A predetermined amount of inert fine particles (D) is added to an aqueous solution in which a part of the water-soluble organic compound Φ) and a part of water tc) are mixed in advance with a water-based polyester resin dispersion consisting of inert fine particles of 1 to 10 μm. After sufficient dispersion treatment, a resin dispersion consisting of a portion of the water-insoluble polyester resin (4), the remaining water-soluble organic compound (B) and water (C) is added to the dispersion. It is characterized in that it is produced by a mixing method such that the mixing ratio of each satisfies the following formulas (1), (2), and (3) at the same time in terms of weight ratio, and that after coating and drying, it is stretched in at least one axis direction. This is a method for producing a transparent film that is easily slippery.

A preferred embodiment (1) of the first invention is that the thermoplastic resin film has a lubricant content of 0.0.
The film is made of polyester with a content of 51 t% or less.

A preferred embodiment (2) of the second invention is that the thermoplastic resin film has a lubricant content of 0.0.
This is a manufacturing method made of polyester having a diameter of 55 cm or less. Another preferred embodiment or embodiment (2) of the above-mentioned second invention
A more preferred embodiment (3) is a manufacturing method in which the dispersion pretreatment is ultrasonic dispersion treatment in the second invention or embodiment (2).

The polyester copolymer (A) contained in the aqueous dispersion of the present invention is a dicarboxylic acid containing sulfonic acid metal base.
This is a substantially water-insoluble polyester copolymer obtained by reacting a mixed dicarboxylic acid of 5 to 15 moles of dicarboxylic acid and 85 to 99.5 moles of dicarboxylic acid that does not contain a sulfonic acid maple base with a glycol component. Substantially water-insoluble means that the polyester copolymer does not dissipate in hot water even if the polyester copolymer is stirred in hot water at 80"C. Specifically, the polyester copolymer does not dissipate in hot water. excessive 80
The weight loss of the polyester copolymer after being stirred in hot water at °C for 24 hours is less than 5 cm.

The above-mentioned sulfonic acid metal base-containing dicarboxylic acids include:
Metal salts such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoheptalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5(4-sulfophenoxytiisophthalic acid) are particularly preferred; 5-sodium sulfoisophthalic acid, sodium sulfoterephthalic acid.These sulfonic acid metal base-containing dicarboxylic components account for 0.5 to 15 molti relative to the total dicarboxylic acid components, and if it exceeds 15 molti, it will be difficult to disperse in water. The water resistance of the polyester copolymer is improved, but the water resistance of the polyester copolymer is significantly reduced, and if it is less than 0.5 molar, the dispersibility in water is significantly reduced. The amount of the sulfonic acid metal base-containing dicarboxylic acid is preferably small, as long as the dispersibility under water pressure is not impaired, although the amount varies depending on the type of organic compound and the blending ratio.

As the dicarboxylic acid that does not contain a sulfonic acid metal group, 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 account for 4 of the total dicarboxylic acid components.
It is preferable that the amount is 0 molti or more, and if it is less than 40 molti, the mechanical strength and water resistance of the polyester copolymer will decrease. Aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, 1,3-cyclopentanedicarboxylic acid, and 1,2-cyclohexanedicarboxylic acid.
, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like. Addition of these non-aromatic dicarboxylic acid components may improve 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, and specifically, ethylene glycol, 1,2-propylene glycol, 1
, 3-propanediol, 1.4-7” tanediol,
Neopentyl glycol, 1,6-hexanediol,
These include l,2-cyclohexane dimetatool, 1,3-cyclohexane dimetatool, l,4-cyclohexane dimetatool, p-xylylene glycol, diethylene glycol, triethylene glycol, and the like. Examples of polyethers include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

Polyester copolymers are obtained and produced by conventional melt polycondensation. In other words, there is a direct esterification method in which the above dicarboxylic acid component and glycol component are directly reacted, water is distilled off and esterified, and then polycondensation is performed, or the dimethyl ester of the above dicarboxylic acid component and the glycol component are reacted to form methyl alcohol. It can be obtained by a transesterification method, etc., which involves distilling off, transesterifying, and then polycondensing it. In addition, solution polycondensation, interfacial polycondensation, etc. are also used, and the polyester copolymer of the present invention is not satisfied by the polycondensation method.

To obtain the aqueous dispersion of the above polyester copolymer,
It is necessary to disperse it in water together with water-soluble organic compounds. For example, the above polyester copolymer and a water-soluble organic compound are mixed in advance at 50 to 200°C, and water is added to this mixture and dispersed by stirring, or conversely,
There is a method in which a mixture is added to water and stirred to disperse it, or a method in which a polyester copolymer, a water-soluble organic compound, and water are made to coexist and stirred at 40 to 120''C.

The above-mentioned water-soluble organic compound is an organic compound having a solubility in water of 1/209 or more at 20°C, and specifically includes aliphatic and alicyclic alcohols, ethers, esters, and ketone compounds, such as methanol, Monohydric alcohols such as ethanol, isoglopanol, n-butanol, glycols such as ethylene glycol and propylene glycol, methyl cellosolve, ethyl cellosolve, n-
Glycol derivatives such as butyl cellosolve, dioxane,
These include ethers such as tetrahydrofuran, esters such as ethyl acetate, and ketones such as methyl ethyl ketone. These water-soluble organic compounds can be used alone or in combination of two or more. Among the above compounds, butyl cellosolve and ethyl cellosolve are preferred in terms of dispersibility in water and coatability on films.

The weight ratio of cA) polyester copolymer, (B) water-soluble organic compound, and (C) water is (A)/(B).
= 100/20~5000(B)/(Cri=100
150 to 10,000 is superposition. Contains fewer water-soluble organic compounds than polyester copolymers
(A) / (When Bl exceeds 100/20, the dispersibility of the aqueous dispersion decreases. In this case, the dispersibility can be assisted by adding a surfactant, but the surfactant If the amount of the agent is too large, the adhesiveness and water resistance will decrease.On the other hand, if (A) / (B) is less than 10015000 or (B) / (C) exceeds 10015 Q, the aqueous dispersion The amount of water-soluble organic compounds in the coating increases, creating a risk of explosion due to the solvent during coating.For this reason, explosion-proof measures must be taken, and furthermore, environmental pollution and high costs will occur, so recovery of the compounds must be considered. .

old) / (If C is less than 100/10000,
If the surface tension of the aqueous dispersion is high, the wettability to the film will be reduced and coating spots will likely occur. In this case, the wettability can be improved by adding a surfactant, but
If the amount of surfactant is too large, the adhesiveness and water resistance will decrease as described above.

Further, add to this dispersion (DJ inert particles include white powder, semi-yoke, heavy charcoal, light charcoal, ultrafine charcoal, basic magnesium carbonate, dolomite, special calcium carbonate, kaolin, calcined Riley, pyrophyllite, bentonite, serisalite, zeolite, nephelin, sinite, talc, attapuljanite, synthetic alba silicate, synthetic calcium silicate, diatomaceous earth, silica powder, hydrous fine silicic acid, anhydrous fine silicic acid, aluminum hydroxide, oxidation Aluminum, pallite, precipitated barium sulfate, natural gypsum, gypsum, calcium sulfite, spherical glass fine particles, hollow glass sphere imitation particles, and various other inorganic or organic particles such as benzoguanamine resin, polystyrene resin, acrylic resin Examples include crosslinked resins, etc. Any of these may be used in relation to transparency and slipperiness, but particularly preferred are fine particles of silicic acid, white titanium oxide, and black carbon. Particles such as black are not preferred because they significantly reduce transparency.

The particle size to be used is preferably 0.01 to 10 microns, more preferably 0.015 to 5 microns.

Particles with a particle size of 0.01μ or less must be used in large quantities, and particles with a diameter of 10μ or more result in coarse protrusions, which is undesirable for applications that require surface smoothness, and conversely because the protrusion density decreases. The slipperiness may become worse.

For (A), the weight ratio of 1t used for Dl is (4)/
The ratio of Φ) = 10000015 to 3000 is good, preferably cA) / (DJ = toooooo / 20 to 5
00 T6 le.

If (4)/(D) exceeds 10000015, the effect of improving slipperiness cannot be obtained;
If it is less than this, transparency will deteriorate, which is not preferable.

In addition, additives other than Dl, which may be mixed if necessary, include organic and inorganic electrophoretic agents, adhesion improvers, mold release improvers, and other functional agents. Basically, there are no restrictions on the additives or the amounts added, as long as they do not significantly impair both transparency and slipperiness, which are the gist of the present invention.

The mixing procedure for coating a synthetic resin film with the above water-based resin dispersion composition includes a part of the water-soluble organic compound (B), preferably 98 to 98% of the total amount of (B). 50% by weight and a portion of water (C), preferably (C
) and 85 to 30″M#L of the total required amount are mixed in advance to prepare an aqueous solution of the water-soluble organic compound (B), and the required amount of inert particles Φ) is added to the aqueous solution to ensure sufficient dispersion. A particle dispersion liquid (1) containing no secondary agglomerated particles is prepared by reproducing the primary particle diameter of the inert particles as much as possible. Typical examples include high-speed impeller stirring type dispersion machines, mill type dispersion machines that use stainless steel, glass, and other balls or beads for stirring, high-pressure homogeneous dispersion machines that utilize ejection force based on high pressure differentials, and super It is possible to use an ultrasonic molecule f!1. @ various other types of dispersion machines that utilize minute vibration energy due to sonic oscillation, and all of them are effective, but in particular, as in the present invention, it is possible to use As a dispersion method for a dilute concentration system in which the amount of dispersed particles is relatively small, the present inventors have conducted intensive studies and found that it is suitable to use an ultrasonic dispersion machine.The reasons for this are as follows.
Dispersion methods under particle collisions and high shear forces, such as high-speed impeller agitation type, ball mill method, and high pressure type, are effective only in high-concentration systems with a high probability of particle side collisions, but they are only effective in high-concentration systems where the probability of particle side collision is high. In the 1 degree system, it is thought that the ultrasonic dispersion method, in which impact imaging is applied directly to the particles, works advantageously, regardless of the particle size. Of course, to the extent that the effects of the present invention are not impaired, there is no problem in using the above-mentioned other dispersion methods together with the ultrasonic dispersion treatment temporarily or after the treatment.

To the thus obtained particle dispersion (1), add the water-insoluble copolymer particles prepolymerized by the above-described method and the remaining water-soluble organic compound (B), preferably a total of 1
! By a method of adding and mixing 2 to 50% by weight of the polyester copolymer resin aqueous dispersion 1) obtained from the remaining water (C), preferably 15 to 70% of the total required amount, A dispersion composition suitable for coating thermoplastic resin films, particularly polyester films, can be obtained.

One of the features of the present invention is that the water-soluble organic compound (B) and water (C) are each divided into a particle dispersion liquid (I) and a polyester copolymer resin aqueous dispersion several times. In order to obtain a dispersion composition for coating later as a uniform mixture, undispersed inert particles (D) before being subjected to ultrasonic dispersion
However, avoid contact with the concentrated polyester copolymer resin dispersion liquid, and after fully dispersing the inert particles Φ) into a particle state by ultrasonic dispersion treatment, contact with the diluted polyester copolymer resin. We found that it was possible to obtain a liquid with extremely finely dispersed particles, which was impossible to achieve in the past, only when the method was carried out.

Although this coating composition can be applied to thermoplastic resin films in general, it is effectively used for films made of polypropylene, polyester, polyamide, etc., which have been subjected to stretching treatment, and is especially suitable for use with polyester yarn-oriented films mainly made of polyethylene terephthalate. In films, it exhibits good effects in terms of adhesion and other aspects.

9. Features of the present invention - In order to exhibit it most effectively,
From the viewpoint of transparency, it is preferable that the amount of lubricant contained in the oriented polyester film is 0.05 parts by weight or less.

The coating dispersion composition of the present invention can be applied by a conventional method, but in particular, it can be applied to an unstretched film after the thermoplastic resin has been melt-extruded, or uniaxially in the vertical or horizontal direction. The method of obtaining a biaxially oriented coated film by coating the film after it has been stretched in 2S or uniaxial directions, and then heat-treating it is a method that improves the dense layer properties of the coated film.
Preferable from the viewpoint of transparency and economy. In particular, if the drying properties, workability, etc. of the coating film are *mL, it is preferable to apply after stretching in the -axial direction. Particularly preferred are methods for obtaining axially oriented films. The surface to be coated and the amount to be coated vary depending on the purpose and use of the resulting film, but it is possible to coat either one side or both sides.
oos to 59/lri is preferred, and 0.01 to 39/lri is particularly preferred. When the coating amount is less than 0.0059/lIt, the desired effect cannot be obtained, and when it exceeds 52/-, problems such as blocking are likely to occur.

Furthermore, by subjecting the polyester film to a corona discharge treatment before applying the aqueous dispersion 1.1 of the above-mentioned polyester copolymer, the coating properties of the aqueous dispersion are improved, and the coating of the polyester film and polyester copolymer is improved. The adhesive strength between the membrane and the membrane is improved.

In addition, by subjecting the polyester copolymer layer after inline coating or biaxial stretching to corona discharge treatment, corona discharge treatment under a nitrogen atmosphere, ultraviolet irradiation treatment, etc., the wettability and fitability within the film bag are improved. can be done.

(Example) The present invention will be explained below with reference to Examples. In the examples, parts and parts all refer to the Xt standard unless otherwise specified.

Example 1 (1) Production of transparent polyethylene terephthalate Lead hydroxide pbo-pb (OH
) 22.2 f (pb O, 95X 10-2 mol) was dissolved, and in this solution GeO22,
A transparent Wr solution was obtained in about 30 minutes by adding G-2 moles) and heating under reflux at the boiling point of ethylene glycol of 197"O. Next, polyethylene terephthalate was produced using this solution as a polycondensation catalyst. 480 parts of dimethyl terephthalate azolL ethylene glycol, Zn acetate (OA(RI, 22120) as a transesterification catalyst)
0.036 part was placed in a transesterification reactor, and the transesterification reaction was carried out while gradually raising the temperature from 150°C to 230°C, and the distillation of methanol was completed after 120 minutes. Next, the contents were transferred to a 'fr polycondensation apparatus, 2.7 parts of the above M medium solution was added as a polycondensation catalyst, the temperature was gradually raised and the pressure was reduced, and the temperature was raised to 280'C and 0.51EIII'
The polymer obtained by carrying out the polycondensation reaction under the high vacuum of IP for 25 minutes had an intrinsic viscosity of 0.63 and a melting point of 262°C.

(2) Production of polyester copolymer 117 parts of dimethyl terephthalate (49 moles);
3i (50 mol%), diethylene glycol 58 parts (5
0 mol%), 0.08 parts of zinc acetate, 0.08 parts of antimony dioxide.
08 parts was heated to 40 to 220°C in a reaction vessel and 3
The esterification reaction was carried out for an hour, and then 9 parts (2 mol) of sodium 5-sulfoiphthalate was added to give 220 to 2
The esterification reaction was carried out at 60°C for 1 hour, and then the polycondensation reaction was carried out under reduced pressure (10 to 0.2 ff H gun for 2 hours).
The average molecular weight is 18,000. A polyester copolymer having a soft point of 140°C was obtained.

(3) Production of polyester copolymer aqueous dispersion 300 parts of the polyester copolymer obtained above (27K) and 140 s of n-butylseron lube were mixed in a container at 150 to 1
Stir at 70°C for about 3 hours to make it uniform and viscous.
560 parts of water was gradually added to this melt to give about 1 g.
After a period of time, a homogeneous pale white stable aqueous dispersion with a solid content concentration of 30% was obtained.

(43* Preparation of useful dispersion 10 parts of n-butyl cellosolve, 45 parts of isopropyl alcohol, and 45 parts of ion-exchanged water were mixed to prepare an aqueous mixed solvent, and this was mixed with 0.5 parts of silicic anhydride having an average particle size of 2.5 μm. After adding 0.015 parts, high frequency output was 600 W using an ultrasonic dispersion machine (manufactured by Nippon Seiki ■).

A dispersion treatment was performed for 15 minutes at an oscillation frequency of ZOXN8 to obtain a sufficiently dispersed silicic acid anhydride particle dispersion. Next, 20 parts of the aqueous polyester copolymer dispersion obtained in step (3) above was mixed with the particle dispersion 8086, and the mixture was thoroughly stirred until uniform, thereby preparing a coating solution. The ratio of copolymerized polyester resin/silicic anhydride particles in the coating liquid is 100000/200
Oh my friend.

(5) Production of coated film The polyethylene terephthalate produced in (1) was
The unstretched film was melt extruded at ~300°C and cooled with a cooling roll at 15°C to obtain an unstretched film with a thickness of 1000ξcm, and this unstretched film was stretched in the longitudinal direction between a pair of rolls at different circumferential speeds at 85°C. It was stretched 3.5 times. Next, the coating solution of 11J was applied using a roll coater, dried with hot air at 70°C, and then coated horizontally at 98°C with a tenter for 3.5 minutes.
Stretched twice and further heat-set at 200-210"G to a thickness of 1
A biaxially stretched coated polyester film of 0.00 microns was obtained. The amount of coating agent applied was 0.06 l/d.

The evaluation results of the obtained film are shown in Table-1.

Example 2 Biaxial stretching was carried out in exactly the same manner as in Example, except that the amount of sodium 5-sulfoisophthalate in the polyester copolymer for dispersion was changed to 10 moles, the total amount of dimethyl terephthalate was changed to 45 moles, and the amount of dimethyl ino-7 tallate was changed to 45 moles. A coated polyester film was obtained.

The bond value of the obtained film is shown in Table 1.

Comparative Example 1 Sodium 5-sulfoiphthalate in a polyester copolymer for dispersion was t-o,z molar, and dimethyl terephthalate and dimethyl isophthalate were each 49.
A polyester copolymer was obtained in the same manner as in the example except that the amount was 9 mol. An attempt was made to produce an aqueous dispersion of the obtained 9-polyester copolymer in the same manner as in Example 1, but the dispersibility in water was extremely poor and a stable aqueous dispersion could not be obtained.

Comparative Example 2 Biaxial stretching was carried out in exactly the same manner as in Example 1, except that 20 moles of sodium 5-sulfoiphthalate and 40 moles of dimethyl terephthalate and dimethyl isophthalate were used in the polyester copolymer for dispersion. A coated polyester film was obtained. The evaluation results of the obtained film are shown in Table-1.

Example 3 This is exactly the same as Example 1, except that the average particle size of the silicic anhydride particles used is 0.04μ, the additive is 0.03 parts, and the ratio of copolyester/silicic anhydride particles is 100,000/400. A similar method was used to obtain the following biaxially oriented coated polyester film. The evaluation results of the obtained 7t film are shown in Cloth-1.

Comparative Example 3 Except that the average particle size of the silicic anhydride particles used was 20μ,
A biaxially stretched coated polyester film was obtained in exactly the same manner as in Example 1.

The evaluation results of the obtained film are shown in 2-1.

Comparative Example 4 A biaxially stretched coated polyester film was obtained in exactly the same manner as in Example 1, except that the average particle size of the silicic anhydride particles used was 0.007 μm.

Evaluation of the obtained film 1'dfl binding is shown in Table II/c.

Example 4 Dispersion was carried out in exactly the same manner as in Example 1, except that the dispersion treatment using an ultrasonic dispersion machine was changed to a dispersion treatment using a homovaxer (Tokushu Kika Kogyo@H) ILCYF) at 3600 rpm for 15 minutes. An axially stretched coated polyester film was obtained. The evaluation results of the obtained fL7'c film are shown in Table-1.

Comparative Example 5 Exactly the same method as in Example 1 except that silicic anhydride particles were added to an aqueous mixed solvent consisting of n-7"f lucerosolp, iso7° lobil alcohol, and ion-exchanged water, and then no dispersion treatment was performed. A biaxially stretched coated polyester film was obtained.Evaluation results of the obtained film are shown in Table 1.

Comparative Example 6 The procedure for preparing a coating dispersion was as follows: 0.015 parts of 2.5μ silicic anhydride particles were directly added to 20 parts of an aqueous polyester copolymer dispersion, followed by ultrasonic dispersion treatment, and then n-
A biaxially stretched coated polyester film was obtained in exactly the same manner as in Example 1, except for mixing with 80 parts of an aqueous mixed solvent consisting of butyl cellosolve, isopropyl alcohol, and water. The evaluation results of the obtained film are shown in Table-1.

Comparative Example 7 The procedure for preparing a dispersion for coating was as follows: After mixing 20 parts of a polyester copolymer aqueous dispersion and 80 parts of an aqueous mixed solvent consisting of n-butyl cellosolve, isopropyl alcohol, and water, 2.5μ silicic anhydride particles were mixed. A biaxially stretched coated polyester film was obtained in exactly the same manner as in Example 1, except for adding the following: and then performing an ultrasonic dispersion treatment.

The evaluation results of the obtained film are shown in Table-1.

Comparative Example 8 The procedure for preparing a coating dispersion was as follows: 2.5μ of silicic anhydride was added to 80 parts of an aqueous mixed solvent consisting of n-butyl cellosolve, isopropyl alcohol, and water, and then 20 parts of a polyester copolymer aqueous dispersion was mixed. A biaxially stretched coated film was obtained in exactly the same manner as in Example 1, except that the method was changed to a method in which the film was then subjected to an ultrasonic dispersion treatment. The evaluation results of the obtained film are shown in Table-1.

In the table, TPAd is equivalent to terephthalic acid, and IPA is equivalent to isophthalic acid.

The haze in the table was measured using a haze meter manufactured by Nippon Seimitsu Kogaku Co., Ltd. according to J-Ko8 [6714].

The friction coefficient is a value measured on both coated and uncoated surfaces using Tensilon manufactured by Toyo Seiki Co., Ltd. in accordance with ABTM-1894.

Blocking property is 8 when the coated and uncoated surfaces are in close contact.
Cut into X12QII, sandwiched between T-2 silicone rubber sheets, further sandwiched between glass plates, apply an instant load from above the glass plates, and leave it in an atmosphere of 40 ° C 180 SRH for 24 hours, Thereafter, the films were removed and the blocking state between the films was visually determined, and the blocking area of 5 inches or less was indicated by Δ for 0.5 to 20 inches, and the blocking area of 20 inches or more was indicated by x. The condition of the coated surface was evaluated by visual inspection and differential interference microscopic photography of the surface of the obtained coating film, and the results were ranked as follows.

(Effects of the Invention) As shown in the Examples above, it can be seen that the films obtained by the method of the present invention have both excellent transparency and slipperiness, and are also excellent in uniformity and workability. Furthermore, if the amount of the sulfonic acid metal base-containing component in the carboxylic acid component of the water-insoluble polyester comonomer is too small, the dispersibility will be poor (Comparative Example 1), and if it is too large, the blocking property will be poor (Comparative Example 2). I understand. If the particle size of the inert particles to be added is too large, both transparency and slip properties will be insufficient, resulting in a large number of coarse protrusions on the coated surface (Comparative Example 3).If the particle size is too small, the slip properties will be insufficient. It can be seen that agglomeration is likely to occur (Comparative Example 4). In addition, when the preparation method of the coating dispersion is different from the method of the present invention (Comparative Examples 5 to 8, even if the composition is the same, the particle dispersibility is insufficient and it is difficult to obtain a good coated surface. I understand that.

Written amendment to the above procedures (voluntary) Manabu Shiga, Commissioner of the Patent Office, Patent application dated May 2, 1985 (2) i Name of the invention Easy-sliding transparent film and its manufacturing method & Relationship with the case of the person making the amendment Patent application 2-2-8 Dojimahama, Kita-ku, Osaka-shi Detailed explanation of the invention Contents of amendment (1) On page 7, line 9 of the specification, "aqueous polyester resin dispersion" was replaced with "aqueous polyester resin dispersion". Corrected to "resin dispersion".

(2) Page 22, bottom line 1'-Zn(OAo)s RE, OJ as "Zn(O
Ao), -2H, OJ.

, (8) p. 24, line 14 ``zaycm, correct J to ``goxnzJ.''

(4) On page 29, lines 19 and 20, "Isophthalic acid converted" is corrected to "Isophthalic acid converted."

(6)　Page 30, line 13 Correct “5% or less” to “5% or less as O, J.”

(6) Above the table on page 32 Add "Table 1".

(C) No. 33, line 10 "Transparency slip property" is corrected to "transparency 1゛ slip property".

(8) On the bottom line of page 33, under “or more”, “Patent applicant
Toyobo Co., Ltd." joins.

Proceedings Report May 17, 1985 Mr. Manabu Shiga, Commissioner of the Patent Office L. Indication of the case A. -07 Akuto June 2, 1985 Patent Application (2) 2 Name of the invention Easy-sliding transparent film and its manufacturing method a Relationship with the case of the person making the amendment Patent applicant 2-2 Dojimahama, Kita-ku, Osaka No. 8 (316) Scope of Claims and Detailed Description of the Invention Column a of Toyobo Co., Ltd. Specification Contents of Amendment (1) The scope of claims is amended as shown in the attached sheet.

(2) "Water-soluble polyester copolymer" on page 7, lines 6-7 of the specification is corrected to "water-insoluble polyester copolymer."

(8) Page 7, bottom line r(A)/(B)-100/20~l5OOOO”
” ”(1) J r (A)/(B)-loo/go~
5ooo---(2) Correct as J.

(4) On page 8, line 8, "water-soluble polyester copolymer" is corrected to "water-insoluble polyester copolymer."

(5) Add the following sentence between the bottom line 100 on page 8 and the first line on page 9.

r(A)/(B) -100/20~5000...
...(1)(B)/(0)-100150~10000
----- (2) (A) / (D) -100000
/ 5-3000...(8)'' (6) On page 25, line 4, ``thickness 1000 microns'' is corrected to ``thickness approximately 1000 microns''.

()) p. 25, line 18 "Example" is corrected to "Example 1."

Attachment Claim L: On at least one side of a thermoplastic resin film, (A) a water-insoluble polyester comprising 0.5 to 15 mol% of dicarboxylic acids containing sulfonic acid metal bases and polyhydric alcohols based on the total dicarboxylic acid components Copolymer, 03) Boiling point is 6
Water-soluble organic compound 1 (0) water 1 (D
In a thermoplastic resin film formed by applying an aqueous polyester resin dispersion comprising inert fine particles having an average particle size of 0.01 to 10 μm, part of the water-soluble organic compound (B) and water (0) A required amount of inert fine particles (Y) is added in advance to an aqueous solution in which a portion of A resin dispersion consisting of the remaining water-soluble organic compound (B) and water (0) is added so that the mixing ratio of each component simultaneously satisfies the following formulas (1), (2), and (8) in terms of weight ratio. An easily slippery transparent film characterized by being formulated as follows.

Ck)/(B) Proverb 100/20~50oO・War-・+1
(1)(B)/(0)-100150~10000--
-- (2) (A)/(D) -10000015~30
00--- (8) & The film according to claim 1, wherein the thermoplastic resin film is made of polyester having a detergent content of 0.05% by weight or less.

& 5 (4) 0.5 to 15 mol % based on the total dicarboxylic acid component on at least one side of an unstretched or uniaxially stretched thermoplastic resin film obtained by melt extrusion.
Water-insoluble polyester copolymer 1 (B
) A water-soluble organic compound with a boiling point of 60 to 200°C) (0
) Water 1 (D) A water-based polyester resin dispersion consisting of inert fine particles with an average particle size of 0.01 to 10 μm 1 A part of the water-soluble organic compound (B) and a part of the water (0) are mixed in advance. Add inert fine particles (D) of a predetermined mackerel to the mixed aqueous solution.
After preliminary dispersion treatment, the required amount of water-insoluble polyester resin (A) and the remaining water-soluble organic compound C are added to the dispersion.
A resin dispersion consisting of B) and water (0) is added, and the mixing ratio of each is expressed by the following formula (1)% (Z)% by weight:
A method for producing an easily slippery transparent film, which is prepared by a compounding method that satisfies each of (Ill) at the same time, and is coated, dried, and then stretched in at least one direction.

The method according to claim 3, wherein the thermoplastic resin film is made of polyester having a lubricant content of 0.05% by weight or less.

(v) The manufacturing method according to any one of claims 3 to 4, wherein the pre-dispersion treatment is an ultrasonic dispersion treatment.

Claims (1)

[Scope of Claims] 1) On at least one side of the thermoplastic resin film, (A) a water-soluble material comprising 0.5 to 15 mol % of sulfonic acid metal base-containing dicarboxylic acids and polyhydric alcohols based on the total dicarboxylic acid components; Polyester copolymer, (B) boiling point is 60
~200°C water-soluble organic compound, (C) water, (D)
In a thermoplastic resin film coated with an aqueous polyester resin dispersion comprising inert fine particles having an average particle size of 0.01 to 10 μm, part of the water-soluble organic compound (B) and part of the water (C) are coated. A required amount of inert fine particles (D) is added in advance to an aqueous solution in which 1 part is mixed in advance, and after sufficient dispersion pretreatment is performed, the required amount of water-insoluble polyester resin (A) and the rest are added to the dispersion. A resin dispersion consisting of a water-soluble organic compound (B) and water (C) is added so that the mixing ratio of each satisfies the following formulas (1), (2), and (3) at the same time in terms of weight ratio. An easily slippery transparent film characterized by being formulated with: (A)/(B)=100/20~50000...
...(1)(B)/(C)=100/50~100
00・・・・・・・・・(2)(A)/(B)=100
000/5 to 3000 (3) 2) The film according to claim 1, wherein the thermoplastic resin film is made of polyester having a lubricant content of 0.05% by weight or less. 3) At least one side of the unstretched or uniaxially stretched thermoplastic resin film obtained by melt extrusion, (A) 0.5 to 15 mol % based on the total dicarboxylic acid component.
A water-soluble polyester copolymer comprising a sulfonic acid metal group-containing dicarboxylic acid and a polyhydric alcohol, (B)
A water-soluble organic compound having a boiling point of 60 to 200°C, (C)
A water-based polyester resin dispersion consisting of water and (D) inert fine particles with an average particle size of 0.01 to 10 μm is mixed in advance with a portion of the water-soluble organic compound (B) and a portion of the water (C). After adding a predetermined amount of inert fine particles (D) into the aqueous solution and sufficiently dispersing the dispersion, the required amount of water-insoluble polyester resin (A) and the remaining water-soluble organic compound (B) are added to the dispersion.
) and water (C), and the mixing ratio of each is expressed by the following formulas (1), (2), and (3) in terms of weight ratio.
1. A method for producing an easily slippery transparent film, which is produced by a compounding method that simultaneously satisfies each of the following, and after coating and drying, is subjected to a stretching treatment in at least one axis direction. 4) The manufacturing method according to claim 3, wherein the thermoplastic resin film is made of polyester having a lubricant content of 0.05% by weight or less. 5) The manufacturing method according to any one of claims 3 to 4, wherein the dispersion pretreatment is an ultrasonic dispersion treatment.