JPH0410858B2 - - 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 a high degree of crystallinity, excellent transparent gloss, mechanical properties, chemical resistance, and heat resistance. Because of these properties, it is rapidly being used in a wide range of applications year by year. However, since general polyester films have a high degree of electrical insulation, they have the disadvantage that they tend to generate and accumulate static electricity, causing various problems due to static electricity. for example,
In the film forming process, printing, adhesion, bag making, packaging, and other secondary processing processes, there may be a reduction in work efficiency such as wrapping around rolls, electric shock to the human body, difficulty in handling, the occurrence of printing whiskers, and film This can cause dirt on the surface and reduce the product value. 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 film, 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 forming the film, 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 polyester itself, the addition of antistatic agents may cause deterioration of the polymer during film-forming, and may cause discoloration and deterioration of physical properties. It was difficult because there were problems such as bringing 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. Further, the conventional method of applying an antistatic agent to the film surface requires an extra processing step, which is 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 sealing agent. Currently, in order to improve the properties of the film, appropriate surface treatments are usually applied to the film depending on the application. 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, that is, the difficulty in simultaneously imparting transparency, antistatic properties, and easy adhesion properties. As a result, we have completed the present invention. (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 resin (B) Inert particles (C) Polyethylene glycol or its derivatives or/and (D) Anionic antistatic agent (E) Thiocyanate or/and Periodic Table ~
At least one metal halide selected from alkali metals and alkaline earth metals.
A thermoplastic film laminate and a melt-extruded unstretched thermoplastic characterized by laminating on at least one side a polyester resin composition blended at a weight ratio of (A)/(B)=100000/0.5 to 3000 On at least one side of the resin film or uniaxially stretched thermoplastic resin film, (A) a mixed dicarboxylic acid component containing a dicarboxylic acid containing sulfonic acid metal base in an amount of 0.5 to 15 mol % based on the total dicarboxylic acid component and a glycol component. Water-insoluble polyester copolymer (B) Inert particles and (C) Polyethylene glycol or its derivative or/and (D) Anionic antistatic agent (E) Thiocyanate or/and Periodic table ~
(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
This is a method for producing a thermoplastic resin film, 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 even if the polyester copolymer is stirred in hot water at 80°C, the polyester copolymer will not dissipate in the 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 dicarboxylic acids containing metal sulfonic acid 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. Examples of polyethers include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. 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 distillation, transesterification, and then polycondensation. 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 laminating the polyester copolymer onto a film, the polyester copolymer and the raw material resin for the film may be simultaneously coextruded from separate extrusion ports of an extruder, or a molten sheet of the polyester copolymer may be laminated onto 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 adopted. can be formed on the film, which is more preferable in terms of ease of slipping and transparency. In order to obtain the aqueous dispersion of the polyester copolymer described above, 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 ~120℃. 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 ~ 5000 (F) ~ (G) = 100 / It is important to satisfy the range of 50 to 10,000. Compared to polyester copolymers, (A) to (F) contain less 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. Conversely, if (A)/(F) is less than 100/5000, or (F)/(G) exceeds 100/50, the amount of water-soluble organic compounds in the aqueous dispersion will increase, making it difficult to use during in-line coating. There is a risk of explosion due to the solvent, and therefore it is necessary to take explosion-proof measures, which further causes environmental pollution and increases costs, so it is necessary to consider recovery of the compound. 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, the inorganic particles (B) to be added to this dispersion include chalk, chiyolk, heavy carbon, light carbon, ultrafine carbon, basic magnesium carbonate, dolomite, special calcium carbonate, kaolin, and calcined clay. , birofluorite, bentonite, serisarite, zeolite, nepheline, sinite,
Talc, attabuldyanite, synthetic aluminum silicate,
Inorganic materials such as synthetic calcium silicate, diatomaceous earth, silica powder, finely divided silicic acid, finely divided silicic anhydride, aluminum hydroxide, barite, precipitated barium sulfate, natural gypsum, gypsum, calcium sulfite, and organic materials such as cross-linked benzoguanamine resin. Any of them may be used in terms of transparency and slipperiness, but natural and synthetic silicic acid products 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)=
100000/5 to 3000. 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-O _{( C2H4O} ) _-nR ' 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 A number of ~100 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: It is possible. R・O(-C ₂ H ₄ O(- _n H (R: lauryl, n
octyl, stearyl, cetyl) (R: octylphenyl, nonylphenyl, dodecylphenyl) (R: lauryl, stearyl) (R: lauryl, stearyl) (R: lauryl, stearyl) (R: lauryl, stearyl) Polyethylene glycol or its derivatives are used in an amount of 1 to 20% based on the water-insoluble polyester copolymer. In addition, anionic antistatic agents include higher alcohols, phosphoric acid ester salts of alkylphenol oxide adducts, various other phosphoric acid derivatives such as phosphonic acids, phosphinic acids, and phosphite esters, Na salts of higher alcohol sulfuric esters,
Organic amine salts, sulfuric ester salts of alkylphenol ethylene oxide adducts, alkyl sulfonates, sulfuric acid derivatives such as alkylaryl sulfonic acids, sodium salts of stearate sarcosinate, 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. Further, it is preferable to use a thiocyanate and a halide of an alkali metal or an alkaline earth metal from the periodic table because the antistatic property is improved. Examples of thiocyanates include ammonium, sodium, potassium, lithium, calcium, iron, barium, and magnesium salts of thiocyanate, as well as halides of alkali metals and alkaline earth metals from the periodic table. Examples include sodium fluoride, potassium fluoride, sodium chloride, potassium chloride, calcium chloride, sodium bromide,
Examples include, but are not limited to, halogenated salts such as potassium bromide, calcium bromide, sodium iodide, and potassium iodide. But 1
If it is less than 15%, the antistatic property will be poor, and if it is more than 15%, the haze and blocking resistance will be poor. If the amount of polyethylene glycol and derivatives and anionic antistatic agent is too small, antistatic properties cannot be exhibited, and if too large, easy adhesion and transparency will be reduced. 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. The polyester film obtained by the method described above has excellent transparency, easy sliding properties, antistatic properties, and easy adhesion properties. 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
It is 300ppm or less. The coated polyester film produced by the above method can be used as a base film for magnetic tapes, as a base film for label stickers, as a base film for chemical mats, as a film for overhead film, as a film for food packaging, and for other uses. It can be used for. Examples of the present invention will be described below. In the examples, parts and % are based on weight. Example 1 (1) Production of polyethylene terephthalate Lead hydroxide pbO in 200ml of ethylene glycol
Dissolve 2.2g of pb(OH) ₂ (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 197° C., the boiling point of ethylene glycol, to obtain a transparent solution in about 30 minutes. Next, polyethylene terephthalate was produced using this solution as a polycondensation catalyst. dimethyl terephthalate
620 parts of ethylene glycol, 480 parts of ethylene glycol, and 0.036 parts of zinc acetate Zn (OAc) _{2.2H 2 O} as a transesterification catalyst were placed in a transesterification reactor, and the transesterification reaction was carried out.
The temperature was gradually increased from 150℃ to 230℃, and the temperature was increased to 120℃.
It took several minutes to complete the distillation of methanol. Next, the contents were transferred to a polycondensation apparatus, 2.7 parts of the above catalyst 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 over 1 hour to carry out the polycondensation reaction under a high vacuum of 0.5 mmHg. The polymer obtained after 25 minutes had an intrinsic viscosity of 0.63 and a melting point of 262°C. (2) Production of aqueous dispersion of polyester copolymer Dimethyl terephthalate 117 parts (49 mol%), dimethyl isophthalate 117 parts (49 mol%), ethylene glycol 103 parts (50 mol%), diethylene glycol 58 parts (50 mol%) %), 0.08 parts of zinc acetate, and 0.08 parts of antimony trioxide were heated to 40 to 220°C in a reaction vessel, transesterified for 3 hours, and then 9 parts of 5-sodium sulfoisophthalic acid (2 mol%) was added. The esterification reaction was carried out at 220 to 260°C for 1 hour, and the polycondensation reaction was further carried out for 2 hours under reduced pressure (10 to 0.2 mmHg) to obtain an average molecular weight of 18,000 and a softening point.
A polyester copolymer at 140°C was obtained. 300 parts of this polyester copolymer and n-butyl cellosolve
140 parts of water were stirred in a container at 150-170℃ for about 3 hours to obtain a homogeneous and viscous melt. 560 parts of water was gradually added to this melt, and after about 1 hour a uniform pale white color was obtained. An aqueous dispersion with a solid concentration of 30% was obtained, and Thyroid 150 was further added to the polyester copolymer.
500ppm, 5% polyethylene glycol with a molecular weight of 20000, 1% sodium dodecylbenzenesulfonate
%, 4500 parts of water and 4500 parts of ethyl alcohol were added to obtain a coating liquid with a solid content concentration of 3%. (3) Production of coated film The polyethylene terephthalate produced in (1) is
Melt extrusion at 280-300°C and cooling with a cooling roll at 15°C to obtain an unstretched film with a thickness of 1000 microns.
This unstretched film was stretched 3.5 times in the longitudinal direction between a pair of rolls at different circumferential speeds at 85°C, and the above coating solution was applied using an air knife method, dried with hot air at 70°C, and then heated at 98°C using a tenter. The film was stretched 3.5 times in the transverse direction 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 Further, the inorganic salt No. is as follows. [I] Sodium bromide [] Sodium iodide [] Potassium thiocyanate In Table 1, 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, NPG is neopentyl glycol and PEG is polyethylene glycol. Examples 2 to 3 Biaxially stretched films were obtained in the same manner as in Example 1, except that sodium bromide in Example 1 was replaced with sodium iodide and potassium thiocyanate, respectively. Example 4 Instead of SSI amount and DEG in Example 1
A biaxially stretched film was obtained in the same manner as in Example 1 except that NPG was used.

[Table] Example 5 A biaxially stretched film was obtained in the same manner as in Example 1 except that part of the EG 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 bromide added in Example 5 was changed. Comparative Examples 1-2 A biaxially stretched film was obtained in the same manner as in Example 1 except that sodium bromide and Thyroid 150 were not added. Comparative Examples 3 to 4 A biaxially stretched film was 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 in Example 1 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 bromide was changed to a value other than the claimed range. Comparative Example 9 Example 1 except that Thyroid 600 with a large particle size was used instead of Thyroid 150 in Example 1.
A biaxially stretched film was obtained in the same manner as above. Comparative Example 10 Example 1 except that in Example 1, the amount of SSI and Thyroid 150 were added in an amount exceeding the claimed range.
A biaxially stretched film was obtained in the same manner as above.

[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 plate. Multiply this at 40℃ and 80
%RH for 24 hours, then remove the film and visually judge the blocking condition 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.
The adhesive was applied so that it would look like this, and Nichiban sellotape was applied and peeled off at a peeling angle of 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 bromide is not added (Comparative Example 1), antistatic properties are poor, when Thyroid 150 is not added (Comparative Example 2), slipperiness is poor and when the amount of PEG is too small (Comparative Example 3).
has poor antistatic properties, and when the amount of PEG is too large (Comparative Example 4), haze, blocking properties, and slip properties are poor.
When there is too little antistatic agent (Comparative Example 5), antistatic properties are poor; when there is too much antistatic agent (Comparative Example 6), haze, blocking properties, and adhesion are poor, and when there is too little sodium bromide ( Comparative Example 7) When antistatic properties are poor and sodium bromide is too large (Comparative Example 8),
When the haze and blocking properties are poor and the thyroid particle size is large (Comparative Example 9) When the haze and slip properties are poor and the amount of SSI is too large (Comparative Example 10) When the blocking properties are poor and the amount of thyroid 150 is too large ( Comparative Example 11) It can be seen that the haze is poor. (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 resin formed from a mixed dicarboxylic acid component having 0.5 to 15 mol% of a dicarboxylic acid containing a sulfonic acid metal base in the total dicarboxylic acid component and a glycol component. Active particles (C) polyethylene glycol or its derivatives or/and (D) anionic antistatic agent (E) thiocyanate or/and periodic table ~
At least one metal halide selected from alkali metals and alkaline earth metals.
A thermoplastic film laminate, characterized in that a polyester resin composition blended in a weight ratio of (A)/(B)=100000/0.5 to 3000 is laminated on at least one side. 2. The thermoplastic resin film laminate according to claim 1, wherein the inert particles have an average primary particle size of 0.01 to 10 μm. 3 Polyethylene glycol or its derivatives
The thermoplastic resin according to claims 1 to 2, wherein (C) is blended in a weight ratio of (A)/(C) = 100/1 to 20 with respect to the water-insoluble polyester copolymer (A). Film laminate. 4 Claims 1 to 3 in which the anionic antistatic agent (D) is blended in a weight ratio of (A)/(D)=100/0.1 to 10 with respect to the water-insoluble polyester copolymer (A). Thermoplastic resin film laminate as described in . 5 Thiocyanate or/and alkali metal or alkaline earth metal halide (E) from the periodic table is a water-insoluble polyester copolymer (A)
The thermoplastic resin film laminate according to claims 1 to 4, wherein the thermoplastic resin film laminate is blended in a weight ratio of (A)/(E)=100/1 to 15. 6. The thermoplastic resin film laminate according to claims 1 to 5, wherein the thermoplastic resin film is a polyester film. 7. 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 a derivative thereof or/and (D) an anionic antistatic agent (E) thiocyanate or/and Periodic table~
(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.