JPS62148249A - Manufacture of laminated sheet - Google Patents

Abstract

PURPOSE:To make both films stickable strongly, by a method wherein a polyester film is heated by applying a plastisol composite containing a block material of a di-isocyanate polymeric product to the upper part of the polyester film, upon which the other polyester film or a vinyl chloride resin film is put and pressurized under heating. CONSTITUTION:After application of a plastisol composite containing a block material of a di-isocyanate polymeric product to the upper part of a polyester film, the foregoing plastisol composite is heated and melted under temperature terms of less than the dissocination temperature of the block material. Then a laminated sheet is manufactured by heating the foregoing plastisol composite at the temperature of more than the dissocination temperature of the block material and pressurizing the polyester film and the other polyester film or a vinyl chloride resin film under heating directly before or after putting the other polyester film or the vinyl chloride resin film upon the surface of the film to which the foregoing plastisol composite has been applied. The foregoing block material of the di-isocyanate polymeric product is suitably constituted so that mean molecular weight of the same falls within a range of 1,000-10,000.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a method for manufacturing a laminated sheet based on a polyester film that can be used as a substrate for an electric circuit, an insulator for electric wires, a decorative material, or the like.

``Prior Art'' Polyester film has poor adhesive properties, and when a synthetic resin layer is provided on its surface, the surface of the polyester film is treated with corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, or flame treatment to strengthen the bond between the two. After treatment and activation, a method of coating with a synthetic resin coating or the like has been adopted. Furthermore, in order to bond polyester films to each other or to bond polyester films to vinyl chloride resin films, methods such as applying an emulsion type or solution type adhesive and then bonding the films together have been adopted.

However, the degree of activation of the surface activated using the former method decreases over time, so a coating film must be formed immediately after the activation treatment, and the adhesion obtained by the activation treatment Power was not always something to be satisfied with. Bonding films using the latter method has the inconvenience of limited machinery and the need for a special adhesive.
It had to be removed, which was environmentally inconvenient.

Furthermore, as another method for increasing the adhesion of polyester films, a so-called etching method has been proposed in which the surface of the polyester film is swollen or partially dissolved with various agents. It is based on the principle that the film is immersed in a chemical such as an aqueous solution, trichloroacetic acid, or 7-enol to relax the crystal orientation near the surface of the film, and at the same time reduce the cohesiveness and improve the receptivity and adhesion of the binder.
Although strong adhesion can be obtained, some of these chemicals are harmful and have the disadvantage of being dangerous in handling, and causing environmental pollution due to the release of chemical gas into the atmosphere. There were disadvantageous problems such as the need to pay attention to

[Problems to be Solved by the Invention] The present inventors were actively studying methods for manufacturing various laminated sheets of polyester film that do not have the above-mentioned drawbacks, and had previously filed an application (VF Application No. 1811-1981).
96) Polyester films can be easily bonded together by applying a plastisol composition containing a diisocyanate polymer block used as an adhesive to a polyester film with a smooth surface, which is used in the method of laminating fiber knitted fabrics or nonwoven fabrics and other laminated materials. They discovered that the scales strongly adhere to the scales, and completed the present invention.

That is, the object of the present invention is to provide a laminating method for strongly adhering polyester films to each other or to a polyester film and a vinyl chloride resin film. This is a method for laminating a polyester film and another polyester film or a vinyl chloride resin film, which includes the steps of (a) applying a plastisol composition containing a diisocyanate polymer block onto the polyester film; 1]) Block dissociation γR of the plastisol composition
(c) Blocking the plastisol composition immediately before or after overlapping another polyester film or vinyl chloride resin film on the coated surface of the plastisol composition. (d) heating and pressurizing a polyester film and another polyester film or a vinyl chloride resin film under heat. Exists. To explain the present invention in detail, the vinyl chloride polymer which is the main component of the plastisol composition used in the present invention is prepared by combining vinyl chloride or a mixture of vinyl chloride and copolymerizable Como 77- with an emulsifier and Negative diameter 5 produced by emulsion polymerization in the presence of a water-soluble polymerization initiator
μ or less, preferably about 0.05^-3 μm pasterenone, in the presence of a dispersant and an oil-soluble polymerization initiator,
A paste resin produced by a fine suspension polymerization method in which all or a part of vinyl chloride or a mixture of vinyl chloride and a copolymerizable copolymerizable material is mechanically dispersed and then polymerized. Lennon for mixing. Furthermore, a vinyl chloride resin having a large diameter produced by ordinary suspension polymerization may be used in combination as long as it does not adversely affect the viscosity, fluidity, processability, etc. of the base sol. Examples of the copolymerizable copolymer with vinyl chloride include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl phosphate; acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate; methyl methacrylate, and ethyl acrylate; Methacrylic acid esters such as acrylate, maleic acid esters such as dibutyl maleate, noethyl maleate, dibutyl 7
77-luic acid esters such as malate and diethyl 7-malate, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, vinyl cyanides such as 7-crylonitrile and methacrylonitrile,
Examples include α-olefins such as ethylene, propylene, and styrene, and vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, and vinyl halides. Used within the range of 20% or less.

When polymerizing vinyl chloride polymers, an emulsifier containing an alkali group 4r salt is often used, but due to the adhesive properties of the plastisol composition, the alkali metal content in the vinyl chloride polymer must be 600 pp+n or less. It is desirable to select and use emulsifiers so that An example of an emulsifier for producing a vinyl chloride polymer having a low alkali metal content is an ammonium salt or alkali metal salt of a fatty acid having an alkyl group having 8 to 18 carbon atoms. Of course, the emulsifier is not limited to those mentioned above.

The plasticizer that is one component of the plastisol composition is not particularly limited as long as it is used for vinyl chloride polymers, but for example, non-n-butyl heptalate <DBP).
, di-n-octyl 7-talate, no-2-ethylhexyl 7-talate (D OP >, di-isooctyl 7-talate, 7
Octyldecyl heptalate, noisodecyl heptalate, butylbenzyl heptalate, di-2-ethylhexyl isophthalate, etc., 7-talic acid-based plasticizers, no-2-ethylhexyl heptalate (DOA), di-n-decyl adipate ,7
Fatty acid ester plasticizers such as diisodecyl dibate, so-2-ethylhexyl azelaate, dibutyl sebacate, di-2-ethylhexyl sebacate, tributyl phosphate, tri-2-ethylhexyl phosphate, and 2-ethyl phosphate.
Examples include phosphate ester plasticizers such as ethylhexyldiphenyl and tricresyl phosphate, epoxy plasticizers such as epoxidized soybean oil, and epoxidized tall oil fatty acid-2-ethylhexyl, and one or more of these. Mix and use. The amount of plasticizer used should be selected appropriately depending on the desired solid content concentration and fluidity of the paste sol, the performance of the laminated sheet to be obtained, the use of the laminated sheet, etc. , 100g of vinyl chloride polymer! The amount ranges from 30 to 400 parts by weight, preferably from 50 to 200 parts by weight. In particular, when considering the adhesion and flowability of plastisol, a range of 40 to 100 parts is appropriate.

In addition, a part of the plasticizer can be replaced with a diluent such as mineral spirit, tex/-isobutyrate, dodecylbenzene, or an organic solvent that swells the vinyl chloride polymer such as toluene or xylene.
It would be better to make it into a sol.

The amount of diluent and organic solvent to be added is appropriately determined depending on the intended use, but by using the diluent and organic solvent, the amount of plasticizer to be used can be reduced.

The plastisol composition can be used to impart adhesive properties to the plastisol composition or as an adhesive.
Neuson anate polymer professional.

It contains as one component a long-chain alkylphenol block or an oxybenzoic acid ester block of a noisocyanate polymer. The average molecular weight of the block body of the noisocyanate polymer is preferably in the range of 1, OOO-, 10, (100).The average degree of polymerization of the block body is 1, rl t) than O If it is too small, the 7-anker effect as a contact λ1 cutter cannot be fully exhibited and the adhesive strength is insufficient.On the other hand, if it is greater than 10,000, it will significantly increase the viscosity of the sol composition, which is not preferable. . Therefore, the diisocyanate (monomer) constituting the diisocyanate polymer is, for example, a fatty acid diisocyanate such as hexamethylene diisocyanate or linone diisocyanate, or an alicyclic diisocyanate such as hydrogenated diphenylmethane diisocyanate, inphorone diisocyanate, or hydrogenated tolylene diisocyanate. Examples include aromatic diisocyanates such as diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, and quizylene diisocyanate. Among these, aromatic diisocyanates, particularly trilenenoisocyanate-11 diphenylmethane diisocyanate, are preferred.

The diisocyanate polymer is, for example, ethyl acetate,
Known catalysts, such as tertiary amines, in an inactivated solution such as methyl acetate, butyl acetate, methyl ethyl ketone, nooxane, chlorobenzene, or in a plasticizer such as a heptatarate, phosphate, adipate or trimelate ester. , is obtained by polymerizing Mannich base fatty acids using an alkali metal, alcolade, etc. by a known method, and then a blocking reaction is performed with a blocking agent such as a long-chain alkylphenol or an oxybenzoic acid ester to form a diisocyanate polymer. A long chain alkylphenol block or oxybenzoin acid ester block is produced. When a polymerization reaction or a blocking reaction is carried out in a highly volatile solvent, it is desirable to finally perform a solvent replacement treatment with an appropriate high-boiling point solvent, such as a plasticizer.

As the diisocyanate polymer used in the present invention, it is particularly preferable to use one containing an isocyanurate ring obtained by polymerizing diisocyanate monomers. Those containing isocyanurate rings are produced according to the method described above. Of course, the diisocyanate polymer may also be a so-called incyanate group-terminated polyurethane, polyurea, etc., which are obtained by the reaction of a diisocyanate and an active hydrogen compound.

The alkyl esters used as blocking agents are phenols having an alkyl group having 4 or more carbon atoms as a substituent, such as butylphenol, hexylphenol, octyl esters, nonyl esters. Examples of oxybenzoic and esters include 0-oxybenzoin acid ester, m
-oxybenzoic acid ester, p-oxybenzoic andester, among which p-oxybenzoic acid ester, p-oxybenzoic acid ester,
- It is preferable that it is a substituted product. One of the groups constituting the oxybenzoinkandester is, for example, +n- and p-
In the case of substituents, n-hebutyl group, n-octyl group, 2
-Long-chain alkyl groups such as ethylhexyl, nonyl, and dodecyl groups; alkoxyalkyl groups bonded to long-chain polyoxyethylene groups or polyoxypropylene groups; or oxyethylene groups and oxypropylene groups to long-chain alkyl groups; A bonded alkoxyalkyl group is preferred.

In the case of a 0-substituted group, methyl group, ethyl group, isopropyl group, isoamyl group, n-butyl group, isobutyl group, 5ec-butyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, nonyl , an alkyl group such as a dodecyl group, an alkoxyalkyl group bonded to a (poly)oxyethylene or (poly)oxypropylene group, a heptalyl group such as a phenyl group, a benzyl group, etc.

Furthermore, the blocking agent is not limited to those mentioned above, and other blocking agents such as lactams may be used.

The appropriate amount of the blocking agent to be used is approximately equivalent to the free incyanate groups of the diisocyanate polymer.

The amount of the blocked diisocyanate polymer added is preferably in the range of 1 to 725 parts by weight per 100 parts by weight of the vinyl chloride polymer, and the effective N in the plastisol composition is
C○ is 0.03 to 1% by weight, preferably 0.03 to 0.
Preferably it is present in an amount of 6% by weight, particularly in the range 0.05-0.5% by weight.

For example, when using a 33% by weight diluted butyl 7 tallate solution of oxybenzoic acid ester blocked noisocyanate polymer after polymerization and pronolation in butyl 7 tallate, per 100 parts by weight of vinyl chloride polymer. , 2 to 50 parts by weight, and if the amount of plasticizer is insufficient, the deficiency is supplemented to prepare a plastisol composition.

For example, since the content of effective NGO in the diluted solution of 33-layered Nobutyl 7 Talate is different, the diluted solution is added in 14 portions as appropriate so as to obtain the desired NGO content of the plastisol composition. If the effective NC○ is less than 0.03% by weight, the adhesive effect will be small, and if it is more than 1% by weight, undesirable phenomena such as increased sol viscosity and coloring will likely occur, and moisture absorption and rapid adhesive reactions will occur. This is accompanied by the phenomenon of bubble generation at the adhesive interface, which tends to cause a decrease in adhesive strength.

The plastisol composition used in the present invention preferably contains an adhesion promoter, such as an accelerator for dissociating the pro-link form of the oxybenzoic and ester blocked noisocyanate polymer. The dissociation promoter is, for example, a free or organic compound of an alkali metal, lead,
Examples include metal-free +N or organic compounds such as tin, cadmium, and zinc, and it is desirable to use at least one of these species.

Examples of the alkali metal compound include fatty acids, especially fatty acids whose alkyl group has 8 to 18 carbon atoms, alkyl sulfuric acids, alkyl sulfonic acids, potassium salts and sodium salts of polyoxyethylene adducts thereof, and potassium salts. Examples include zinc-based and sodium-zinc-based composite stabilizers.

Metal compounds other than alkali metals include white lead, basic lead silicate, tribasic lead sulfate, tribasic lead phosphite,
Silica gel co-precipitated lead silicate, inorganic metal compounds such as zinc white,
Organic compounds such as metal salts such as cadmium, barium, calcium, zinc, lead, tin or magnesium, such as lauric acid, stearic acid, ricylic acid, naphthenic acid, salicylic acid, 2-ethylhexoic acid fatty acids or resin acids. Further examples include zinc octylate, butyltin laurate, dioctyltin malate, dibutyltin mercaptide, and the like. Organic acid liquid composite stabilizers such as calcium-zinc, barium-zinc, magnesium-zinc, and cadmium-barium-zinc stabilizers, which are usually commercially available as stabilizers for vinyl chloride resins, can also be used.

In the case of an alkali metal compound, the amount of dissociation promoter to be used is 600% of the alkali metal relative to the vinyl chloride polymer.
Preferably, it is contained in the plastisol composition in an amount of ppm or less. If the emulsifier used in the production of the vinyl chloride polymer already contains alkali metal, the content of alkali metal is determined by adding up the amount as the amount of alkali metal, and calculating the amount of M of the alkali metal compound in an appropriate amount. Preferably, a #II accelerator is added. If the alkali metal content exceeds 600 ppm, the viscosity stability during sol preparation or the obtained sol, as well as the adhesion reaction, will be inhibited, and processability will be significantly deteriorated, and adhesive strength will tend to decrease.

When using metal compounds other than alkali metals as a dissociation agent, they may act as stabilizers.
The amount added is not particularly limited, but the objective can usually be achieved with 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of the vinyl chloride polymer.

Furthermore, when an alkali metal compound and a metal compound such as lead, tin, cadmium, or zinc are used together, the adhesive strength is synergistically improved.

To produce a plastisol composition, a vinyl chloride polymer, a plasticizer, an adhesion promoter, and, if necessary, a dissociation promoter and other additives are uniformly mixed.

In the present invention, (1) uses a vinyl chloride polymer that is completely sealed and stored immediately after production; (2) performs a vacuum defoaming process during plastisol production before adding an adhesion agent; (3) improves adhesion. After adding the imparting agent, it is preferable to carry out stirring and mixing by purging the gas phase with a vacuum +11U bubble or by replacing the gas phase with an inert gas such as nitrogen.

1ffl of plastisol composition is usually 100-250°C.
It is preferable to gel it with, for example, 7 of TDI tribody
The dissociation temperature of the block form of the mixture of 7-lupronochloride is in the range of 165 to 175 °C (although the dissociation temperature of the oxybenzoic acid ester block is preferably 150 °C or higher). , the dissociation temperature is lower than that of the former, and the range of use is wider.

When producing a composition, the incorporation of moisture into the composition should be avoided as much as possible, and specifically, it is desirable to prepare the composition in an atmosphere with a relative humidity of 80% or less. Generally 80% relative humidity
When mixed in the atmosphere described below, at least 0.2% by weight or more of trace water will be absorbed into the sol.

The polyester film used for the laminated sheet of the method of the present invention has a wall thickness of 30 to 300 μm, preferably 50 to 15 μm.
It is desirable to use one in the 0μ range. on the other hand,
After applying the plastisol composition to this polyester film, another polyester film to be superimposed on the plastisol composition surface may be of the same type and thickness as the polyester film described above, and may be made of vinyl chloride resin. The film used is a semi-rigid or flexible film of vinyl chloride resin whose main component is vinyl chloride obtained from a homopolymer of vinyl chloride or a copolymer of vinyl chloride and a monomer capable of co-polymerization. The 9-vinyl chloride resin may be produced by any polymerization method such as a suspension polymerization method, an emulsion polymerization method, or a bulk polymerization method. Moreover, a polyester film or a vinyl chloride resin film is manufactured by extrusion molding, inflation molding, calendering, or casting.

In order to produce a laminate sheet using the method of the present invention, for example, it is manufactured through the following steps.

(,) The plastisol composition containing the polyester film-metal polymer bronch body is processed by, for example, a reverse roll, a knife coater, a spray,
Various application methods such as curtain 70-, dip coating, rotary screen, flat screen, 7 lexo, gravure printing, etc. (b) The applied plastisol composition is heated and melted at a temperature below the block body dissociation temperature, and if necessary, the whole is cooled and solidified. (c) Next, another polyester film or IIW for vinyl chloride is applied to the coated side of the plastisol composition.
Layer the film. At this time, the plastisol composition is
The films may be heated to a temperature equal to or lower than the dissociation temperature of the blocks before they are stacked together, or they may be heated to a temperature equal to or higher than the dissociation temperature of the blocks after the films are stacked. Further, the films may be superimposed by superimposing formed films on each other, or by extruding polyester resin or vinyl chloride resin into a film form using an extrusion tool or the like.

(d) The laminated polyester film and the polyester film are the vinyl chloride resin film.
- Manufactured through the steps of heating and pressurizing as described above, [Effects of the Invention I] According to the method of the present invention, the noisocyanate intermediate to be blended into a plastisol composition for coating on a polyester film. Because the NCOs are blocked, plastisol compositions can be prepared and applied to polyester films in relatively hot and humid atmospheres. After coating on a polyester film, a polyester film or a vinyl chloride + M 1M film is placed on top of the polyester film, and then heated and pressurized to a temperature below the temperature at which the block dissociates. , strongly bonded. In addition, even if the plastisol composition is applied to a polyester film, it is thickly melted (heated at a temperature below the dissociation temperature of the block), cooled, and solidified, and stored as a composite sheet, the adhesive properties of the composite sheet will be lost. Um, without a doubt, Mako1
: ((C) Under low Z1 heating of 1'C or less, dissociation of block cutting does not proceed, so various or complicated lamination methods can be adopted using this composite sheet. .C) Production of the J+/I sheet of the present invention a
The quality tick at the l-culm stage becomes 11'l'fl12, which can reduce the f-HA force by 1 (1 harm f-HA) due to defects in the final product.

It can also be used as a method for manufacturing flat cables, etc. by sandwiching bare electric wires or band-shaped conductors between the films in the process of manufacturing the laminated sheet, where other polyester films or vinyl chloride + 64 resin films are interposed. .

[Example 1] Next, the method of the present invention will be explained in detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is stated.

In addition, the viscosity of the plastisol composition and the peel strength of the composite sheet or laminated sheet in Examples were measured as follows.

(1) Measurement of sol viscosity using a Tokyo Keikiwa B 8 H type viscometer, with a sol temperature of 23
The 5r, p, +o sol viscosities at °C were measured.

The sol for oral sol viscosity measurement was stirred briefly using a stirring rod for 1 minute 2 hours before the measurement.

(2) Peel strength (a) T-type peel strength The obtained composite sheet or laminated sheet was heated at a temperature of 23°C.
After leaving it in a constant temperature and humidity room with 50% humidity for 1 phase,
Cut the test piece into one corner of 1 inch, peel off one end of the test piece, and pull it in the length direction at a tensile speed of 50111111/(18 at ain).
A 0°T-type peel test was conducted, and the average peel strength of five test pieces was expressed in units of 1 (g/1 nch).

(b) After cross-cutting the plastisol composition layer (vinyl chloride resin film layer) of Composite Sea F obtained in accordance with the base material test method JIS C2107, it was confirmed that no air bubbles would be formed under the seven-layer X-antave. Paste as per ASTM D2197
A 90° cellophane tape peeling test was conducted according to .

Peeling speed of cellophane tape is 500 +nm/ +oi
It was set as n. The number of peeled pieces out of 100 squares spaced at 1 mm intervals is shown.

Examples 1 and 2, Comparative Example 1 <Preparation method of plastisol composition> Vinyl chloride paste renone (average degree of polymerization 1450) 100 parts by weight DOP
60 #Epoxy stabilizer (product name FEP-13,7 Dekaa joined the company 91) 3
Part by weight Ba-Zn stabilizer and dissociation promoter (trade name AC303,
7Deforce 7-Gas Co., Ltd.) 3 Adhesive agent
Appropriate amounts of each of the above ingredients were added at 23°C and 50%H.
It was left in a room with constant temperature and humidity in an R atmosphere for several days, and then weighed.
Mixing was performed in a constant temperature room according to the following procedure.

An amount equivalent to 45 parts by weight of DOP, base trenone, an epoxy stabilizer, and a stabilizer/dissociation promoter were charged into a Hobart mixer, and after uniformly mixing and kneading, vacuum defoaming was performed once.

Next, as an adhesion imparting agent, a 1)-benzoic acid-2-ethylhexyl ester block of TDI trimer (33% by weight with an average molecular weight of 13 (10), D
32% by weight of BP soluble fi (Example 1) and TDI trimer/nylphenol 10 2-mer (average molecular weight 1182)
The DBP solution (Example 2) was added and mixed, the remaining DOP was added and mixed uniformly, and vacuum defoaming was performed again to prepare a plastisol composition.

<Manufacture of composite sheet> Approximately 100μ of the above plastisol composition was applied to a 90μ thick polyethylene terephthalate film (hereinafter referred to as PET).
It was coated with a thick coating, placed in a hot air circulation oven at 150°C for 5 minutes, and then cooled and solidified.

The peel strength of this composite sheet was measured and shown in Table 1.

A sol composition was prepared in the same manner as in Example 1 except that no adhesion imparting agent was added, and after producing a composite sheet, the peel strength was measured and is also listed in Table 1 as Comparative Example 1.

<Manufacture of laminated sheet> (1) fima J
160°C1170'C and 18
After preheating for 1 minute at each temperature of 0°C, the press plate interval is 0.
．． Using a 25 mm press machine, it was pressed for 1 minute at the same temperature as the preheating temperature and a load of 2501 KH/can2, and was taken out after cooling. The T-peel strength of the two polyester films on the front and back sides was measured, and the adhesion of the laminated sheet was visually evaluated, and the results are shown in Table 1.

(2) ml sheet B The vinyl chloride resin layer of the above composite sheet is 160.17
After preheating for 1 minute at each temperature of 0 and 180 °C,
Immediately overlay a 90μ thick polyethylene terephthalate film and heat at the same temperature as the preheating temperature and at 250 kg/
It was pressed for 1 minute under a load of 0 m2, and then taken out after cooling. Measure the T-peel strength of two polyester films on the front and back sides,
In addition, the 'M adhesion was determined visually and is listed in Table 1.

As is clear from Table 1, the plastisol composition used in the present invention has good adhesion to the polyester film, and furthermore, after laminating the polyester film or vinyl chloride resin film, the temperature rises to a temperature that allows the blocks to be sufficiently dissociated. It can be seen that even better adhesion is exhibited by doing so.

Example 3 and Example 4 The plastisol compositions prepared in Example 1 and Example 2 were the same as in Example 1 and Example 2, respectively, except that the stabilizer and dissociation promoter was replaced with jade basic lead sulfate. Composite sheets and laminated sheets were produced in the same manner, and their peel strength and adhesion were measured and are listed in Table 2.

1-1→) ++=OL,, J41, Table 2 From the above results, by using the lead-based stabilizer and dissolution S cutting, the dissociation temperature of the block body shifts to a lower temperature side,
It can be seen that the adhesion to the polyester film is also improved. From the results in Tables 1 and [/'2, plastisol A
150°C after coating on polyester film
If the temperature is below, most of the isocyanate polymer can remain in the blocked state in the vinyl chloride jHM film, and even if the composite sheet is stored for a long time, the lamination temperature will be lower when manufacturing the laminated sheet. By increasing the temperature, it can be easily and firmly bonded to other polyester films.

Example 5.6, Comparative Example 2 In Example 1, Example 2, and Comparative Example 1, i! ! The prepared plastisol composition was applied to a thickness of approximately 100 μm on a polyethylene terephthalate film, placed in a hot air circulation system at 130°C for 1 minute at a temperature at which the block would hardly dissociate, and then cooled and solidified to produce a composite sheet. did.

Using these sheets, a laminate sheet A and a laminate sheet B were obtained in the same manner as in Example 1, with the press temperature being 130°C, 150°C or 170°C.

Measure the T-type and base grain peel strength of these composite sheets and the T-type peel strength of laminated sheet A and laminated sheet) B,
It is shown in Table 3.

From the results in Table 3, it can be seen that when a plastisol composition applied to a polyester film is heated below the dissociation temperature of the incyanate block contained therein, although it adheres to the polyester film, the peel strength is extremely weak, and once it is attached to other films, etc. After stacking the blocks, the blocks are heated and pressurized at a temperature higher than the dissociation temperature to ensure strong adhesion, and can be used as an MM receipt.

In addition, the T-type peel strength for practical use is 0.2 k
It is necessary to have H/1 nch or more.

Patent applicant Mitsubishi Kasei Vinyl Co., Ltd. Agent Patent attorney Hase - (1 idiot) Procedural amendment (voluntary) 1 Indication of case 1985 Patent Application No. 290249
No. 2 Title of the invention Method for manufacturing a laminated sheet 3 Person making the amendment 4 Agent 5 Date of amendment order Voluntary amendment 6 Number of inventions increased by amendment 07 Pair of amendments and clarity! Column 8 of Detailed Description of the Invention j from a'I? IIi positive content or more

Claims (5)

[Claims] (1) A method for laminating a polyester film and another polyester film or a vinyl chloride resin film, including (a) applying a plastisol composition containing a diisocyanate polymer block onto the polyester film; (b) (c) heating and melting the plastisol composition at a temperature below the block body dissociation temperature; and (c) applying another polyester film or vinyl chloride resin film to the surface coated with the plastisol composition, immediately before or after stacking the plastisol composition. , a lamination characterized by passing through a step of heating the plastisol composition to a temperature equal to or higher than the dissociation temperature of the block body, and (d) a step of pressurizing the polyester film and another polyester film or vinyl chloride resin film while heating. Method of manufacturing sheets. (2) The method for producing a laminated sheet according to claim 1, wherein the diisocyanate polymer block is a long chain alkylphenol block or an oxybenzoic acid ester block of an aromatic diisocyanate polymer. (3) The method for producing a laminated sheet according to claim 1 or 2, wherein the diisocyanate polymer contains an isocyanurate ring. (4) The method for producing a laminated sheet according to claim 2, wherein the aromatic diisocyanate is tolylene diisocyanate or diphenylmethane diisocyanate. (5) The method for producing a laminated sheet according to claim 1, wherein the diisocyanate polymer block has an average molecular weight in the range of 1,000 to 10,000.