JPH0149114B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a thermoplastic resin film laminate that is transparent, has excellent antistatic properties and easy adhesion, and a method for producing the same. (Prior Art) As is well known, thermoplastic resin films, such as polyester, polyamide, polypropylene, etc., especially polyester films, and especially polyethylene terephthalate films, have high crystallinity, excellent transparent gloss, mechanical properties, chemical resistance, heat resistance, etc. Because of this, it is rapidly being used in a wide range of applications year by year. However, thermoplastic resin films, especially polyester films, and especially polyethylene terephthalate films have a high degree of electrical insulation.
It has the disadvantage that static electricity is likely to be generated and accumulated, causing various troubles due to static electricity interference. For example, film forming process, printing, adhesion, bag making,
In packaging and other secondary processing processes, causes of reduced work efficiency such as wrapping around rolls, electric shock to the human body, and difficulty in handling, as well as reduced product value such as the occurrence of printing scratches and dirt on the film surface. becomes. As methods for preventing such electrostatic damage, there are generally two methods: kneading an antistatic agent into a resin to form a film, and coating the surface of a film with an antistatic agent. Regarding polyester films, this so-called kneading-type antistatic treatment method exhibits an antistatic effect by oozing the antistatic agent from inside the film to the surface, but due to the high secondary transition temperature of polyester resin, After film formation, the antistatic agent does not seep into the film at temperatures around room temperature.On the other hand, due to the high film forming temperature conditions and the high reactivity of the polar groups of the polyester itself, the antistatic agent is This has been difficult due to problems such as deterioration of the polymer during film formation, coloring, and deterioration of physical properties depending on the formulation. In particular, in the case of biaxially stretched polyester films, the antistatic agent on the surface of the film escapes and disappears during the stretching process, often resulting in no antistatic effect at all.Furthermore, many of the antistatic agents are compounded in polyester films. This extremely reduces the transparency of the film, making it difficult to put it to practical use. In addition, the usual method of applying antistatic agents to the film surface requires extra processing steps.
Economically disadvantageous. Furthermore, it is extremely rare to use a polyester biaxially stretched film alone for various purposes; for example, when used as a photographic film base, the adhesion between the gelatin layers and the magnetic layer when used as a magnetic tape base are important. In the case of a drafting base, the adhesion with the matting agent layer, in the case of metal vapor deposition, the adhesion with the vapor-deposited metal, and in the case of packaging, the adhesion with ink mainly based on nitrocellulose binder and heat seaming agent. At present, films are usually subjected to appropriate surface treatments to improve their properties depending on their use. However, in general, undercoating agents that have an affinity for the surface of a polyester biaxially stretched film have poor adhesion to the surface layer agent, and those that have an affinity for the surface layer agent generally have poor adhesion to the surface of the polyester biaxially stretched film. There is a drawback. Furthermore, as is well known in the art, if the coefficient of friction of polyester film is large, the films will not slide against each other, and if it is extremely bad, blocking will occur, making it difficult not only to handle the film but also to make it difficult to wind it up.
Conventionally, this objective has been achieved by adding inorganic or organic substances to the film, either singly or in combination, in order to lower the coefficient of friction of the film. However, if a small amount is added to such a film, the effect will be small, and if a large amount is added, the transparency of the film will drop sharply. In other words, there has never been a film in which the transparency is almost the same as that without additives and the coefficient of friction is significantly lowered. Furthermore, even if the same amount of the same additive is added to polyester, the rate of decrease in the coefficient of friction largely depends on the heat treatment conditions, and the greater the heat coverage history, the greater the rate of decrease. On the other hand, a method has been proposed to obtain a film with excellent lubricity and transparency by adding polyorganosiloxane or the like to a polyester film, but as the amount of polyorganosiloxane added increases, the lubricity increases, but vice versa. However, there is a tendency for the transparency of the film to deteriorate, and the mechanical properties such as dimensional stability and Young's modulus also tend to deteriorate.Furthermore, there is a method of knurling the film before winding it up, Conventional manufacturing methods have had various problems, such as the processed portion being trimmed or existing only on one side. (Problems to be Solved by the Invention) The present inventors have made extensive research and efforts to solve the problems in the conventional technology, namely the difficulty of imparting transparency, antistatic properties, and easy adhesion at the same time. As a result, the present invention has been completed. (Means for Solving the Problems) That is, the present invention provides (A) a mixed dicarboxylic acid component containing a dicarboxylic acid containing sulfonic acid metal base in an amount of 0.5 to 15 mol % in the total dicarboxylic acid component, and a glycol component; Water-insoluble polyester copolymer (B) Inert particles (C) Polyethylene glycol or its derivative or/and (D) Anionic antistatic agent and (E) Phosphate (A)/(B) = 100000/0.5~ 3000, (A)/(C)=
100/1~20, (A)/(D)=100/0.1~10, (A/E)
A thermoplastic resin film laminate, a melt-extruded unstretched thermoplastic resin film, or a uniaxially stretched thermoplastic resin film, characterized in that a polyester resin composition blended at a weight ratio of =100/1 to 15 is laminated on at least one side. On at least one side of the thermoplastic resin film, (A) a water-insoluble polyester copolymer formed from a mixed dicarboxylic acid component containing 0.5 to 15 mol % of a dicarboxylic acid containing a sulfonic acid metal base to the total dicarboxylic acid component and a glycol component; (B) Inert particles and (C) polyethylene glycol or its derivatives or/and (D) anionic antistatic agent and (E) phosphate (F) a water-soluble organic compound with a boiling point of 60 to 200°C (G) water (A)/(B)=100000/0.5~3000, (A)/(C)=100/1
~20, (A)/(D)=100/0.1~10, (A)/(E)=100/1
~15, (A)/(F)=100/20~5000, (F)/(G)=100/50
This is a method for producing a thermoplastic resin film laminate, which is characterized in that a polyester resin composition blended at a weight ratio of ~10,000 is further subjected to biaxial stretching or uniaxial stretching after coating. The polyester copolymer (A) of the present invention contains 0.5 to 15 mol% of a sulfonic acid metal group-containing dicarboxylic acid,
Dicarboxylic acids without sulfonic acid metal bases 85
It is a substantially water-insoluble polyester copolymer obtained by reacting ~99.5 mol% of a mixed dicarboxylic acid 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, and specifically, the polyester copolymer does not dissipate in hot water. The weight loss of the polyester copolymer after being stirred in 80°C hot water for 24 hours is 5% by weight or less. Examples of the above-mentioned dicarboxylic acids containing sulfonic acid metal groups include metals such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5[4-sulfophenoxy]isophthalic acid. salt was given,
Particularly preferred are 5-sodium sulfoisophthalic acid and sodium sulfoterephthalic acid. These sulfonic acid metal base-containing dicarboxylic acid components are 0.5 to 15 mol% of the total dicarboxylic acid components.
If it exceeds 15 mol%, the water resistance of the polyester copolymer will be significantly reduced, and if it is less than 0.5 mol%, the dispersibility with respect to inert particles will be significantly reduced. As the dicarboxylic acid containing no sulfonic acid metal base, aromatic, aliphatic, and alicyclic dicarboxylic acids can be used. Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid,
Examples include 2,6-naphthalene dicarboxylic acid. These aromatic dicarboxylic acids preferably account for 40 mol% or more of the total dicarboxylic acid components. If it is less than 40 mol%, the mechanical strength and water resistance of the polyester copolymer will decrease. Aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, 1,3-cyclobentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid,
1,3-cyclohexanedicarboxylic acid, 1,4-
Examples include cyclohexanedicarboxylic acid.
When these non-aromatic dicarboxylic acid components are added,
Although adhesive performance may be improved in some cases, it 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-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol These include methanol, p-xylylene glycol, diethylene glycol, triethylene glycol, and the like. Further, examples of the polyether include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like. Polyester copolymers are obtained 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. may also be used, and the polyester copolymer of the present invention is not limited by the polycondensation method. When the polyester copolymer is laminated onto a film, the polyester copolymer and the raw material resin for the film are simultaneously coextruded from separate extrusion ports of an extruder, or a molten sheet of the polyester copolymer is placed on the film. There are a method of extrusion lamination, a method of coating a film with an aqueous dispersion of the polyester copolymer, and any of these methods may be used. It is more preferable in terms of ease of slippage and transparency. In order to obtain an aqueous dispersion of the polyester copolymer, it is necessary to disperse it in water together with a water-soluble organic compound. 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, the mixture is added to water and dispersed by stirring. method, or by coexisting a polyester copolymer, a water-soluble organic compound, and water.
There is a method of stirring at °C. The above-mentioned water-soluble organic compound is an organic compound having a solubility in water of 20 g or more at 20°C, and specifically includes aliphatic and alicyclic alcohols, ethers, esters, and ketone compounds, such as methanol, ethanol, Monohydric alcohols such as isopropanol and n-butanol, glycols such as ethylene glycol and propylene glycol,
These include glycol derivatives such as methyl cellosolve, ethyl cellosolve, and n-butyl cellosolve, ethers such as dioxane and tetrahydrofuran, esters such as ethyl acetate, and ketones such as methyl ethyl ketone. These water-soluble organic compounds 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 the above (A) polyester copolymer, (F) water-soluble organic compound, and (G) water is (A)/(F) = 100/20 to 5000 (F)/(G) = 100/ It is important to satisfy the range of 50 to 10,000. Compared to polyester copolymers, (A)/(F) contains fewer water-soluble organic compounds.
When the ratio exceeds 100/20, the dispersibility of the aqueous dispersion decreases. In this case, dispersibility can be assisted by adding a surfactant, but
If the amount of surfactant is too large, adhesiveness and water resistance will decrease. On the other hand, if (A)/(F) is less than 100/5000 or (F)/'' exceeds 100/50, the amount of water-soluble organic compounds in the aqueous dispersion will increase and the solvent will remain after coating. In addition, it is necessary to consider recovery of the compound as it increases the cost.
When (F)/(G) is less than 100/10,000, the surface tension of the aqueous dispersion increases, the wettability to the film decreases, and coating spots are likely to occur. In this case, the wettability can be improved by adding a surfactant, but if the amount of the surfactant is too large, the adhesiveness and water resistance decrease as described above. Furthermore, as inert particles added to the polyester copolymer or the aqueous dispersion of the polyester copolymer, examples of the inert particles include chalk, chiyolk, heavy carbon, light carbon, ultrafine carbon, basic magnesium carbonate, and dolomite. , special calcium carbonate, kaolin, calcined clay, birofluorite, bentonite, serisalite, zeolite, nephelin, sinite, talc, attabuldianite, synthetic aluminum silicate, synthetic calcium silicate, diatomaceous earth, silica powder,
Contains inorganic particles such as fine silicic acid, anhydrous fine silicic acid, aluminum hydroxide, barite, precipitated barium sulfate, natural gypsum, gypsum, and calcium sulfite, and organic particles such as crosslinked benzoguanamine resin. Although any may be used in this connection, natural and synthetic silicic acids are particularly preferred. It is preferable to use particles with a particle size of 0.01μ to 10μ. If the particle size is 0.01 μm or less, a large amount must be used, and if the particle size is 10 μm or more, coarse protuberances will occur and the slipperiness will deteriorate. The amount of (B) used for (A) is (A)/(B)=100000/
A ratio of 0.5 to 3000 is good, preferably (A)/(B)=
100000/20~1000. A further feature of the present invention is that by using polyethylene glycol or a derivative thereof and/or an anionic antistatic agent in combination, adhesiveness and antistatic properties can be imparted without impairing transparency and slipperiness. Polyethylene glycol or its derivatives usually have a molecular weight of 1,000 to 50,000, and those represented by the following general formula are typical, but are not limited thereto. R, R′: Hydrogen, C _1-20 hydrocarbon group, epoxy group or -COR group (R is C _1-20 hydrocarbon group) R″: C _1-20 hydrocarbon group m, n: 3 -100 In addition, all of the above _C1-20 hydrocarbon groups are preferably _C1-20 alkyl groups and alkylaryl groups. Examples of commonly used polyethylene glycol derivatives include the following: can.

[Table] Polyethylene glycol or its derivatives are used in an amount of 1 to 20% based on the water-insoluble polyester copolymer. If it is less than 1%, there is no antistatic property, and if it is more than 20%, haze, blocking and slipping properties are poor. In addition, anionic antistatic agents include higher alcohols, phosphoric acid ester salts of alkylphenol ethylene oxide adducts, various other phosphoric acid derivatives such as phosphonic acid, phofuic acid, and phosphite esters, Na salts of higher alcohol sulfuric esters,
Organic amine salts, sulfuric acid ester salts of alkylphenol ethylene oxide adducts, alkyl sulfonates, sulfuric acid derivatives such as alkylaryl sulfonic acids, sodium salts of sarcosinate stearate, and carboxylic acid derivatives such as triethanolamine salts of sebacic acid. Preferred examples include those containing a sulfonic group, such as Na salt of dodecylbenzenesulfonate, potassium salt of octyl sulfonate, sodium salt of oligostyrene sulfonate, sodium salt of dibutylnaphthalene sulfonate, and sodium salt of lauryl sulfosuccinate. If the antistatic agent is less than 0.1%, the antistatic properties will be poor.
If the amount of antistatic agent exceeds 10%, haze, blocking properties, and adhesion properties will be poor. Furthermore, a feature of the present invention is that the antistatic property is improved by using a phosphate in combination. Examples of added phosphates are monosodium phosphate,
Triammonium phosphate, dipotassium phosphate, sodium phosphite, sodium hypophosphite, ammonium hypophosphite, aluminum phosphate, magnesium phosphate, potassium pyrophosphate, sodium pyrophosphate, potassium hexametaphosphate, sodium tripolyphosphate , potassium tripolyphosphate, etc., but are not limited to these. However, if it is less than 1%, antistatic properties are poor and if it is more than 15%, haze and blocking resistance are poor. The aqueous dispersion of the polyester copolymer obtained in this manner may be applied to a polyester film by a coating method, either on an unstretched film obtained by melt-extruding the polyester film, or on a uniaxially stretched film or a biaxially stretched film. but,
When coating biaxially stretched film, it is difficult to coat it uniformly because the film is wide and the film travels at a high speed. is more preferable. The amount of the aqueous dispersion applied to the polyester film by the coating method is the amount present on the film after biaxial stretching as the polyester copolymer.
It is 0.01-5 g/ ^m2 . If the coating amount is less than 0.01 g/m ² , the ability to fix inert particles etc. will be weak and the durability will be poor. If you apply ^more than 5.0g/m2, the slipperiness will worsen. In addition, by subjecting the polyester film to corona discharge treatment before applying the aqueous dispersion of the polyester copolymer described above, the coating properties of the aqueous dispersion can be improved, and the coating of the polyester film and polyester copolymer can be improved. The adhesive strength between the two is improved. In addition, the wettability and adhesion of the film surface can be improved by subjecting the polyester copolymer layer after coating or biaxial stretching to corona discharge treatment, corona discharge treatment under a nitrogen atmosphere, ultraviolet irradiation treatment, etc. be able to. Further, in the present invention, it is preferable to use a polyester film, particularly a polyethylene terephthalate film, as the thermoplastic resin film, since film waste generated during lamination and film forming processes can be recovered and reused. In addition, for polyester, it is preferable that the amount of lubricant is as small as possible from the viewpoint of transparency, and preferably
300ppm or less. The coated polyester film produced by the above method is used as a base film for magnetic tapes, a base film for label stickers, a base film for chemical mats, a film for overhead projectors, a film for food packaging, and other uses. can do. (Example) Examples of the present invention will be described below. In the middle part of the example, percentages are based on weight. Example 1 (1) Production of polyethylene terephthalate Lead hydroxide in 200ml of ethylene glycol
pbO・pb(OH) ₂ 2・2g (pb0.95×10 ^-2 mol)
2.0 g (1.9×10 ⁻² mol) of GeO ₂ was added to this solution and heated under reflux at the boiling point of ethylene glycol at 197° C., and a transparent solution was obtained in about 30 minutes. Next, polyethylene terephthalate was produced using this solution as a polycondensation catalyst. 620 parts of dimethyl terephthalate, 480 parts of ethylene glycol, zinc acetate as transesterification catalyst
Zn(OAc) ₂ and 0.036 parts of 2H ₂ O are placed in a transesterification reactor, and the transesterification reaction is carried out at 230°C from 150°C.
It took 120 minutes to complete the distillation of methanol. Next, the contents were transferred to a polycondensation apparatus, and the above catalyst solution was added as a polycondensation catalyst.
Add 2.7 parts, gradually raise the temperature and reduce the pressure,
The polycondensation reaction was carried out for 25 minutes at 280°C under a high vacuum of 0.5 mmHg, and the resulting polymer had an intrinsic viscosity of 0.63 and a melting point of 262°C. (2) Production of aqueous dispersion of polyester copolymer 117 parts of dimethyl terephthalate (49 mol%),
Dimethyl isophthalate 117 parts (49 mol%), ethylene glycol 103 parts (50 mol%), diethylene glycol 58 parts (50 mol%), zinc acetate 0.08
40 parts and 0.08 parts of antimony trioxide in a reaction vessel.
The temperature was raised to ~220°C to carry out the transesterification reaction for 3 hours, and then 9 parts (2 mol%) of 5-sodium sulfoisophthalic acid was added and the mixture was heated at 220 to 260°C for 1 hour.
The esterification reaction was carried out for a period of time, and further under reduced pressure (10~
A polyester copolymer having an average molecular weight of 18,000 and a softening point of 140°C was obtained by carrying out a polycondensation reaction at 0.2 mmHg) for 2 hours. 300 parts of this polyester copolymer and 140 parts of n-butyl cellosolve were mixed in a container at 150 parts
Stir at ~170℃ for about 3 hours to obtain a homogeneous and viscous melt. 560 parts of water is gradually added to this melt, and after about 1 hour, a uniform pale white solid content is obtained.
Obtain a 30% aqueous dispersion and add thyroid to this.
150 to 500ppm to polyester copolymer,
3% polyethylene glycol with a molecular weight of 20,000,
Dilute by adding 1% sodium dodecylbenzenesulfonate, 5% sodium hypophosphite, 4500 parts of water, and 4500 parts of ethyl alcohol to obtain a solid content concentration of 3%.
A coating liquid was obtained. (3) Production of coated film The polyethylene terephthalate produced in (1) is
Melt extrusion at 280-300℃ and cooling with a cooling roll at 15℃ to obtain an unstretched film with a thickness of 1000 microns.This unstretched film is rolled 3.5 times in the longitudinal direction between a pair of rolls at different circumferential speeds at 85℃. Stretch, apply the above coating solution using an air knife method, dry with hot air at 70°C, and then apply it laterally at 98°C with a tenter.
The film was stretched 3.5 times and further heat-set at 200 to 210°C to obtain a biaxially stretched coated polyester film with a thickness of 100 microns. Further, the compound numbers of polyethylene glycol and its derivatives in the examples are as follows. Polyethylene glycol (MW20000) The compound number of the anionic antistatic agent is as follows. Sodium dodecylbenzenesulfonate The salt numbers are as follows. [] Sodium hypophosphite [] Potassium pyrophosphate [] Sodium tripolyphosphate In the table, TPA is equivalent to terephthalic acid, IPA is equivalent to isophthalic acid, SSI is 5-sodium sulfoisophthalate, EG is ethylene glycol, DEG
is diethylene glycol and NPG is neopentyl glycol.

[Table] Examples 2 to 3 Biaxially stretched films were obtained in the same manner as in Example 1 except that sodium hypophosphite was replaced with potassium pyrophosphate and sodium tripolyphosphate, respectively. Example 4 In place of the amount of SSI and PEG in Example 1
A biaxially stretched film was obtained in the same manner as in Example 1 except that NPG was used. Example 5 A biaxially stretched film was obtained in the same manner as in Example 1 except that part of the EG in Example 1 was replaced with PEG. Examples 6 to 7 Biaxially stretched films were obtained in the same manner as in Example 1 except that the amount of Thyroid 150 added was changed. Example 8 A biaxially stretched film was obtained in the same manner as in Example 1 except that the amount of sodium hypophosphite added in Example 5 was changed. Comparative Examples 1 and 2 Biaxially stretched films were obtained in the same manner as in Example 1 except that sodium hypophosphite and Thyroid 150 were not added. Comparative Examples 3 to 4 Biaxially stretched films were obtained in the same manner as in Example 1 except that the amount of PEG was changed to a value other than the claimed range. Comparative Examples 5 to 6 Biaxially stretched films were obtained in the same manner as in Example 1 except that the amount of antistatic agent was changed to a value other than the claimed range. Comparative Examples 7-8 A biaxially stretched film was obtained in the same manner as in Example 1 except that the amount of sodium hypophosphite was changed to a value other than the claimed range. Comparative Example 9 A biaxially stretched film was obtained in the same manner as in Example 1 except that Thyroid 150 in Example 1 was replaced with Thyroid 600 having a large particle size. Comparative Examples 10-11 Example 1 except that in Example 1, the amount of SSI and Thyroid 150 were added in amounts exceeding the claimed range.
A biaxially stretched film was obtained in the same manner as above.

【table】

[Table] The haze in Table 2 was measured according to JIS K6714 using a haze meter manufactured by Nippon Seimitsu Kogaku. The friction coefficient is a value measured on both coated and uncoated surfaces using Tensilon manufactured by Toyo Seiki Co., Ltd. in accordance with ASTM-1894. Blocking property was tested by cutting the coated and uncoated surfaces into 8 x 12 cm pieces, sandwiching them between two silicone rubber sheets, sandwiching them between glass plates, and applying a 2 kg load from the top of the glass plates. Multiply this at 40℃ and 80
%RH for 24 hours, then remove the film and visually judge the blocking state between the films. 5% or less of the blocking area is ○, 5 to 20% is △, and 20% or more is ×. Indicated. Adhesive properties include polyvinyl alcohol, vinyl chloride vinyl acetate copolymer, and polymethyl methacrylate with a highly compatible red dye added to a thickness of 3 μm.
Then, I applied Nichiban sellotape and peeled it off so that the peeling angle was 180°. It was ranked as 10 if there was no peeling at all, 5 if half of it was peeled off, and 1 if all of it was peeled off. The surface resistance was measured using a specific resistance measuring device manufactured by Takeda Riken under conditions of an applied voltage of 500 V, 20° C., and 65% RH. In Table 2, the method of the present invention exhibits good characteristics in all of the haze friction coefficient, blocking properties, adhesion properties, and surface resistance (antistatic properties). However, when sodium hypophosphite is not added (Comparative Example 1), the antistatic property is poor, when Thyroid 150 is not added (Comparative Example 2), the slipperiness is poor, and when the amount of PEG is too small (Comparative Example 3), the antistatic property is poor. ) has poor antistatic properties, and when the amount of PEG is too large (Comparative Example 4), haze, blocking properties,
When the antistatic properties are poor and the amount of antistatic agent is too low (Comparative Example 5), the antistatic properties are poor, and when there is too much antistatic agent (Comparative Example 6), haze, blocking properties, and adhesion are poor, and hypophosphorous When the amount of sodium chloride is too low (Comparative Example 7) When the antistatic property is poor and the amount of sodium hypophosphite is too high (Comparative Example 8) When the haze and blocking properties are poor and the particle size of the thyroid is large (Comparative Example 9) It can be seen that the haze and slip properties are poor and the SSI amount is too large (Comparative Example 10), and the blocking property is poor and the Thyroid 150 amount is too large (Comparative Example 11) that the haze is poor. Example 9 A film was prepared in the same manner as in Example 1 except that the coating liquid was changed to the following composition.
Various characteristics were evaluated. The results obtained are shown in Table 3. Coating liquid Polyester copolymer aqueous dispersion (30%) 1000 parts Cyroid 150 (vs. polyester copolymer)
5000ppm Sodium dotecylbenzenesulfonate (for polyester copolymer) 10% Sodium hypophosphite (for polyester copolymer) 5% Water 4500 parts Ethyl alcohol 4500 parts Example 10 In Example 9, the antistatic agent was The same procedure as in Example 9 was carried out except that sodium tesilbenzenedisulfonate was used instead. The results obtained are shown in Table 3. Example 11 A film was prepared in the same manner as in Example 1 except that the coating liquid was changed to the following composition, and various properties were evaluated. Coating liquid Polyester copolymer aqueous dispersion (30%) 1000 parts Silicon dioxide particles (0.05μ) (vs. polyester copolymer) 8000ppm Polyethylene glycol #6000 (vs. polyester copolymer) 10% Sodium hypophosphite (vs. Polyester copolymer) 5% Water 4500 parts Ethyl alcohol 4500 parts The results obtained are shown in Table 3.

[Table] (Effects of the Invention) As described above, the thermoplastic resin film laminate obtained by the method of the present invention has the advantage of being transparent and having good antistatic properties and easy adhesion.

Claims (1)

[Scope of Claims] 1 (A) A water-insoluble polyester copolymer formed from a mixed dicarboxylic acid component containing a dicarboxylic acid containing a sulfonic acid metal group in an amount of 0.5 to 15 mol % based on the total dicarboxylic acid component and a glycol component. (B) inert particles (C) polyethylene glycol or its derivatives or/and (D) anionic antistatic agent and (E) phosphate (A)/(B)=100000/0.5-3000, (A)/ (C)=
100/1~20, (A)/(D)=100/0.1~10, (A)/(E)=
1. A thermoplastic resin film laminate, characterized in that a polyester resin composition blended at a weight ratio of 100/1 to 15 is laminated on at least one side. 2. The thermoplastic resin composition according to claim 1, wherein the inert particles have an average primary particle size of 0.01 to 10 μ. 3. The thermoplastic resin film laminate according to claims 1 to 2, wherein the thermoplastic resin film is a polyester film. 4. On at least one side of the melt-extruded unstretched thermoplastic resin film or uniaxially stretched thermoplastic resin film, (A) mixed dicarboxylic acid containing 0.5 to 15 mol % of sulfonic acid metal base-containing dicarboxylic acid based on the total dicarboxylic acid components. A water-insoluble polyester copolymer formed from a glycol component and a glycol component. (B) Inert particles and (C) polyethylene glycol or its derivative or/and (D) anionic antistatic agent and (E) phosphate (F) a water-insoluble organic compound with a boiling point of 60 to 200°C (G) water (A)/(B)=100000/0.5~3000, (A)/(C)=100/1
~20, (A)/(D)=100/0.1~10, (A)/(E)=100/1
~15, (A)/(F)=100/20~5000, (F)/(G)=100/50
1. A method for producing a thermoplastic resin film laminate, which comprises applying a polyester resin composition blended at a weight ratio of ~10,000 and then further biaxially or uniaxially stretching.