JPH0518949B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention is applicable to vinyl leather, waterproof canvas, tents,
The present invention relates to a method for producing a laminate sheet comprising a plastisol composition and a fibrous knitted woven fabric or nonwoven fabric suitable for producing adhesive laminates of conveyor belts, industrial gloves, leather, and fibers. ``Prior Art'' Conventionally, laminates in which soft vinyl chloride resin or plastisol is bonded to knitted, woven or non-woven fabrics of synthetic fibers such as nylon or polyester have been produced by various methods. For example, when adhering plasticized vinyl chloride resin materials to each other or to other materials, a method in which polyester having active hydrogen is mixed into the plasticized vinyl chloride resin material and an organic polyisocyanate compound is applied as a curing agent to the adhesive surface. (Japanese Unexamined Patent Publication No. 51-97679) and a method in which a soft vinyl chloride resin material is pretreated with an acrylic resin composition and then bonded with a polyisocyanate adhesive (Japanese Unexamined Patent Application No. 59-169844) have been proposed. . However, since the former method involves mixing relatively high molecular weight polyester into the soft vinyl chloride resin material, it is not satisfactory in terms of plasticization efficiency, flexibility, cold resistance, hydrolysis resistance, etc. In addition, the manufacturing process and quality of soft vinyl chloride resin materials have been severely restricted, such as increased costs. In addition, since the organic polyisocyanate has a free isocyanate group (NCO) at the end, it has extremely high reactivity, and as described below,
There was a problem in that the adhesive strength varied greatly depending on the environment during the bonding process, that is, the atmosphere during the process such as temperature and humidity. In addition, as a means for improving the adhesion of plastisol, it is known to add and mix an organic polyisocyanate compound into plastisol. For example, British Patent No. 1455710 describes an isocyanate polymer obtained by trimerizing tolylene diisocyanate (TDI), and JP-A-57-105441 discloses a binary combination of TDI and diphenylmethane diisocyanate (MDI). An invention is disclosed in which isocyanate polymers of partially trimerized isocyanate-isocyanurate mixtures are added to plastisols. These isocyanate polymers have a free isocyanate group (NCO) at the end, so they have extremely high reactivity, and they have problems such as storage stability of the sol, uneven penetration when coating the base fabric, generation of air bubbles, etc., and quality stability. was significantly inferior in this respect. In other words, when plastisol is prepared by mixing an isocyanate polymer with terminal NCOs in an inert solvent, such as a plasticizer, the adhesive strength may be extremely low due to the influence of trace amounts of water and the metal catalyst remaining in the plasticizer. There were problems such as a decrease in viscosity, thickening or solidification over time, and the formation of bubbles. For this reason, it is necessary to suppress the amount of metal components to the minimum necessary.If the amount is extremely reduced, the problem arises that the formed sheet will be significantly colored, and it can only be applied in a very limited combination system, and the processing method There were also drawbacks such as restrictions on the work process. Also, Special Publication No. 59-52901, Japanese Patent Publication No. 59-120651
In the issue, the block urethane polymer was
No. 59-131669 describes a method of adding a block body dissociation accelerator such as mono- or polyamide containing active amino groups to a lactam block polyisocyanate, but these accelerators do not inhibit the desorption of polyvinyl chloride. It has the effect of accelerating hydrochloric acid, and is not satisfactory in terms of thermochromic properties (thermal coloring properties) and light resistance. In short, conventional techniques for processing using polyisocyanate adhesives alone or plastisol compositions containing them have the following problems. (1) Under the influence of molding conditions during processing, especially atmospheric humidity, woven or nonwoven fabrics and adhesive components absorb moisture, resulting in a decrease in adhesive strength and variations in adhesive strength. (2) When polyisocyanate with terminal NCO is used, the pot life of the sol is extremely short, so the processing method is limited to a lamination process immediately after coating, and it is not suitable for manufacturing laminated sheets in small quantities and in a wide variety of products. It is. (3) The range of processing conditions is narrow and the quality varies widely. (4) It is difficult to detect defective products during the process, and if a defective product occurs, it will affect the final product, so there is a risk of huge losses. "Problems to be solved by the invention" The present inventors aim to improve the conventional drawbacks even slightly,
Plastisol that can be used under various conditions, for example, with various compounding agents, does not deteriorate its performance even in mixed atmospheres of high temperature and humidity, does not generate bubbles or color, can be stably processed, and has high adhesive strength. After developing a composition and conducting extensive studies to develop its uses, we discovered that the above objectives could be achieved by using a diisocyanate polymer block added to plastisol as an adhesion promoter. He has completed his invention. That is, an object of the present invention is to provide a method for producing a laminated sheet in which a woven or nonwoven fabric and a plastisol composition are closely adhered, which can produce a good laminated sheet even when processed under various conditions such as high temperature and humidity. "Means for Solving the Problems" Therefore, the gist of the present invention is to provide a method for laminating a fibrous woven fabric or non-woven fabric and a sheet or film-like laminate material. (b) heating and melting the plastisol composition at a temperature below the block body dissociation temperature; (c) applying the plastisol composition containing the diisocyanate polymer block to the plastisol composition. heating the plastisol composition to a temperature equal to or higher than the dissociation temperature of the block body immediately before or after stacking the sheet or film-like laminate on the coated surface; (d) combining the fibrous woven fabric or non-woven fabric with the sheet or film; The present invention relates to a method for manufacturing a laminated sheet, characterized by passing through a step of pressurizing a laminated material under heat. 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, contains vinyl chloride or a mixture of vinyl chloride and a comonomer copolymerizable therewith with an emulsifier and a water-soluble polymer. Paste resin with a particle size of 5 μ or less, preferably about 0.05 to 3 μ, produced by emulsion polymerization in the presence of a polymerization initiator, or vinyl chloride or vinyl chloride and co-produced in the presence of a dispersant and an oil-soluble polymerization initiator. A paste resin or a resin for mixing paste resins produced by a fine suspension polymerization method in which all or a portion of a mixture with a polymerizable comonomer is mechanically finely dispersed and then polymerized. Furthermore, a vinyl chloride resin with a large particle size 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 paste sol. Examples of comonomers that can be copolymerized with vinyl chloride include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laryunate, acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate, and methyl methacrylate and ethyl methacrylate. Methacrylic acid esters, maleic esters such as dibutyl maleate and diethyl maleate, fumaric acid esters such as dibutyl fumarate and diethyl maleate, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, Vinyl cyanides such as acrylonitrile and methacrylonitrile, ethylene,
α-olefins such as propylene and styrene; vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide;
It is preferably used in a range of 20% by weight or less. When vinyl chloride polymers are polymerized, an emulsifier containing an alkali metal salt is often used, but due to the adhesive properties of the composition of the present invention, the alkali metal content in the vinyl chloride polymer is 900 ppm. It is desirable to select and use emulsifiers as follows. Examples of emulsifiers that produce vinyl chloride polymers with a low alkali metal content include ammonium salts or alkali metal salts of fatty acids whose alkyl groups have 8 to 18 carbon atoms. Of course, the emulsifier is not limited to those mentioned above. Plasticizers, which are one component of plastisol compositions, are
There are no particular limitations as long as it can be used as a vinyl chloride polymer, but examples include di-n-butyl phthalate (DBP), di-n-octyl phthalate, di-2-ethylhexyl phthalate (DOP),
Phthalic acid plasticizers such as diisooctyl phthalate, octyldecyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, di-2-ethylhexyl isophthalate, di-2-ethylhexyl adipate (DOA), di-n-decyl adipate, adipine Fatty acid ester plasticizers such as diisodecyl acid, di-2-ethylhexyl azelaate, dibutyl sebacate, di-2-ethylhexyl sebacate, tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyldiphenyl phosphate, phosphoric acid Examples include phosphate ester plasticizers such as tricresyl, epoxy plasticizers such as epoxidized soybean oil, and epoxidized tall oil fatty acid-2-ethylhexyl, and these may be used alone or in combination of two or more. The amount of plasticizer to be used is appropriately selected depending on the desired solid content concentration, fluidity and foaming properties of the paste sol, the use of the foam, etc., and is 30 to 30 parts by weight per 100 parts by weight of the vinyl chloride polymer. 400 parts by weight, preferably in the range of 50 to 200 parts by weight. In addition, part of the plasticizer can be replaced with a diluent such as texanol isobutyrate or dodecylbenzene, or an organic solvent that swells the vinyl chloride polymer such as toluene or xylene. good. The amount of the diluent and organic solvent to be added is appropriately determined depending on the application. The plastisol composition contains as one component a diisocyanate polymer block, preferably a long chain alkyl phenol block of a diisocyanate polymer, in order to impart adhesive properties to the plastisol composition or to be used as an adhesive. are doing. It is preferable to use a diisocyanate polymer block, such as a long chain alkyl phenol block of diisocyanate polymer, having an average molecular weight in the range of 1,000 to 10,000. If the average degree of polymerization of the block body is less than 1000, the anchor effect as an adhesive cannot be sufficiently exerted, and the adhesive strength is insufficient;
If it is larger than 10,000, the viscosity of the sol composition will significantly increase, which is not preferable. Therefore, the diisocyanate (monomer) constituting the diisocyanate polymer is, for example, fatty acid diisocyanate such as hexamethylene diisocyanate or lysine diisocyanate, or alicyclic diisocyanate such as hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, or hydrogenated tolylene diisocyanate. , tolylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, xylene diisocyanate, and other aromatic diisocyanates.
Among these, aromatic diisocyanates, particularly tolylene diisocyanate and diphenylmethane diisocyanate are preferred. The diisocyanate polymer is then treated with a well-known catalyst in an inactivating solution such as ethyl acetate, methyl acetate, butyl acetate, chlorobenzene or in a plasticizer such as a phthalate, phosphate, adipate or trimellitate. , for example, by polymerization using a known method using a tin-based or amine-based catalyst, and then a blocking reaction is performed with a blocking agent, such as an alkyl phenol, to produce a long-chain alkyl phenol block of the diisocyanate polymer. . When a polymerization reaction or a blocking reaction is carried out in a highly volatile solvent, it is desirable to finally perform a solvent substitution treatment with a suitable high-boiling point solvent, such as a plasticizer. The alkylphenol used as a blocking agent is a phenol having an alkyl group having 4 or more carbon atoms as a substituent, and includes, for example, butylphenol, hexylphenol, octylphenol, nonylphenol, etc. It is not limited. Furthermore, the blocking agent is not limited to alkylphenols, and other agents such as lactams may also be used.
The appropriate amount of the blocking agent to be used is approximately equivalent to the free isocyanate groups of the diisocyanate polymer. The amount of the blocked diisocyanate polymer added is 2 to 25 parts by weight per 100 parts by weight of the vinyl chloride polymer.
It is preferred that the effective NCO in the plastisol composition be present in the range of 0.1 to 1% by weight, preferably 0.2 to 0.6% by weight. For example, when using a dibutyl phthalate diluted solution of 50% by weight of a blocked diisocyanate polymer after polymerization and blocking in dibutyl phthalate, per 100 parts by weight of vinyl chloride polymer,
A plastisol composition is prepared by using 4 to 50 parts by weight of the plasticizer and, if the amount of plasticizer is insufficient, making up for the deficiency. Furthermore, since the content of effective NCO in the 50% by weight dibutyl phthalate diluent also varies, the diluent is adjusted and added as appropriate so as to achieve the desired NCO content of the plastisol composition. Effective NCO
If it is less than 0.1% 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 are likely to occur, and bubbles may form at the adhesive interface due to moisture absorption and rapid adhesive reaction. This phenomenon is observed, which tends to cause a decrease in adhesive strength. Preferably, the plastisol composition contains an adhesion promoter, such as an accelerator for disassociating the blocks of the long chain alkyl phenol blocked diisocyanate polymer. Examples of the dissociation promoter include inorganic or organic compounds of alkali metals, and inorganic or organic compounds of metals such as lead, tin, cadmium, and zinc.
It is preferable to use seeds. 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, or potassium salts of polyoxyethylene adducts thereof;
Examples include sodium salts, potassium-zinc type and sodium-zinc type composite stabilizers. Metal compounds other than alkali metals include lead, white, basic lead silicate, tribasic lead sulfate,
Tribasic lead phosphite, silica gel co-precipitated lead silicate,
Inorganic metal compounds such as zinc white, metal salts such as cadmium, barium, calcium, zinc, lead, tin or magnesium, such as lauric acid, stearic acid, ricinoleic acid, naphthenic acid, salicylic acid, 2-ethyl hexoic acid fatty acid or resin acid. Organic compounds such as zinc octylate,
Examples include dibutyltin laurate, dioctyltin malate, dibutyltin mercaptide, and the like.
Furthermore, 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 the dissociation promoter used is in the range of 40 to 900 ppm, preferably 200 to 800 ppm of the vinyl chloride polymer.
It is preferable that the plastisol composition contains within this range. 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 by dissociating an appropriate amount of the alkali metal compound. It is necessary to add an accelerator. If the alkali metal content is less than 40 ppm, the adhesive strength will be extremely low, and if it exceeds 900 ppm, it will increase the hygroscopicity during sol preparation or the obtained sol, which will actually inhibit the adhesive reaction and cause bubble generation. This tends to lead to a decrease in adhesive strength. When a metal compound other than an alkali metal is used as a dissociation promoter, it may act as a stabilizer, and the amount added is not particularly limited, but it is usually added to 100 parts by weight of the vinyl chloride polymer.
0.5 to 10 parts by weight, preferably 2 to 5 parts by weight can achieve that purpose. 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 prepare a plastisol composition, a vinyl chloride polymer, a plasticizer, an adhesion promoter, and if necessary, a dissociation promoter, other additives, and the like are uniformly mixed. For example, by using a vinyl chloride polymer that has been completely sealed and stored immediately after production, a vacuum defoaming process is performed during plastisol production before adding an adhesion agent, and then an adhesion agent is added. After that, the gas phase is preferably degassed under vacuum or replaced with an inert gas such as nitrogen, and the mixture is stirred and mixed. Plastisol compositions are preferably gelatinized usually at 10 to 250°C; for example, in the case of a mixture of nonylphenol blocks of TDI trimer, the dissociation temperature of the blocks is in the range of 165 to 175°C. When producing a composition, the introduction of moisture into the composition should be avoided as much as possible, and specifically, relative humidity should be avoided.
It is desirable to prepare in an atmosphere of 80% or less. Generally, when mixed in an atmosphere with a relative humidity of 80% or more, the sol will absorb at least a trace amount of water of 0.2% by weight or more. The fibrous knitted fabric or nonwoven fabric used in the laminated sheet of the present invention includes knitted woven fabrics or nonwoven fabrics manufactured from natural fibers such as cotton, hemp, silk, and wool, or synthetic fibers such as nylon, polyester, vinylon, and polyacrylonitrile. In particular, woven or nonwoven fabrics made of synthetic fibers such as polyester and nylon are preferably used from the viewpoint of adhesion with the sol composition and processability. The laminated sheet of the present invention is a gelled sheet or film obtained by heating and melting and solidifying a plastisol composition containing blocks of a diisocyanate polymer at a temperature below the dissociation temperature of the blocks, and the above-mentioned textile fabric or non-woven fabric. The purpose is to bring them into close contact. In order to adhere the above-mentioned gelatinized sheet or film to the fiber knitted or woven fabric or non-woven fabric, the sheet-like base material such as the fiber knitted or woven fabric or non-woven fabric is coated with a reverse roll, a knife coater, a spray, a curtain flow, a dip coating, a rotary roll, etc. The plastisol composition is applied using various coating methods such as screen, flat screen, flexography, and gravure printing, then heated at a temperature below the dissociation temperature of the block body, melted and solidified by cooling, and then continuously coated. It is manufactured and rolled into a composite sheet with adhesive properties, which is then used or stored for small-lot, multi-product laminated sheets. The laminated sheet of the present invention, for example, one in which laminated materials such as soft vinyl chloride resin sheets or films are bonded together, is most suitable for applications such as vinyl leather, waterproof canvas, tents, and conveyor belts. This laminated sheet is made of a plastisol composition containing blocks of a diisocyanate polymer, which is heated to a temperature higher than the dissociation temperature of the blocks to melt them, and woven or non-woven fabrics are bonded thereto. Woven or non-woven fabrics and sheet or film laminated materials are heated above the dissociation temperature of the block.
Cross-linked by NCO and firmly bonded. To produce a laminated sheet, for example, a composite sheet is first produced, then a sheet or film-like laminate material is laminated thereon, and then heated to a temperature higher than the dissociation temperature of the block body and pressure bonded; A plastisol composition is applied to the block, a sheet or film-like laminate material is superimposed on the plastisol composition, and the plastisol composition is melted and gelled by heating at a temperature higher than the dissociation temperature of the block body,
A method such as pressure bonding is adopted. The following methods are most commonly employed: (a) A step of applying a plastisol composition containing a diisocyanate polymer block onto a fibrous woven fabric or a nonwoven fabric. (b) A step of heating and melting the plastisol composition at a temperature below the dissociation temperature of the block to obtain the necessary (c) Immediately before stacking the sheet or film-like laminate material on the surface coated with the plastisol composition, the plastisol composition is heated to a temperature higher than the dissociation temperature of the block body to form a sheet or film. After stacking the film-like laminate materials or stacking the sheet or film-like laminate material on the surface coated with the plastisol composition, a step (d) of heating the plastisol composition to a temperature equal to or higher than the dissociation temperature of the block body. ) The fiber knitted fabric or nonwoven fabric and the laminated material are pressurized under heat, and are manufactured by passing through the steps of cooling. In addition to vinyl chloride resin sheets or films, the laminated material bonded to the composite sheet may be made of natural leather, sheets or films made of synthetic resins other than vinyl chloride resins, or synthetic fibers such as nylon fibers, polyester fibers, and acrylic fibers. Knitted fiber fabrics and non-woven fabrics are also used. Further, the vinyl chloride resin sheet or film may be obtained by any manufacturing method, such as an extrusion method, an inflation method, a calendering method, a casting method, and the like. "Effects of the Invention" The composite sheet used in the present invention has excellent adhesive properties even in a high temperature and humidity atmosphere because the plastisol composition used for its production contains a diisocyanate polymer block. It can be produced without damaging the composition, and by heating the diisocyanate polymer block contained in the composition to a temperature higher than its dissociation temperature, it firmly adheres to not only woven fabrics or non-woven fabrics but also other materials to be laminated. A laminated sheet with excellent quality stability can be obtained. Moreover, the complex used in the present invention is 130
Since the blocking agent does not dissociate under low-temperature heating below .degree. C., various or complicated lamination processing methods can be employed. Furthermore, the present invention solves the problems of the prior art described above, that is, it is possible to check the quality at the manufacturing process stage of the laminated sheet.
Damages caused by defects in final manufacturing can be minimized. "Examples" Next, the laminated sheet of the present invention will be explained in detail using Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. In addition, the viscosity of the plastisol composition and the peel strength of the laminated sheet in Examples were measured as follows. (1) Sol viscosity measurement Using Tokyo Keiki B8H type viscometer, sol temperature
Sol viscosity was measured at 5 r.pm at 23°C. The sol for daily sol viscosity measurement was stirred briefly using a stirring bar for 1 minute 2 hours before the measurement. (2) Peel strength Plastisol composition, 0.55 mm thickness, 335 g/m ²
After coating a filament woven polyethylene phthalate fabric with a knife coater to a thickness of 0.1 to 0.2 mm, it was placed on release paper and heated for 90 seconds at 145℃, 160℃, and 175℃ in a hot air circulation dryer. , and laminated with polyethylene terephthalate woven fabric to obtain a composite sheet. The composite sheet was left for 7 days, and a 0.25 mm thick soft vinyl chloride resin sheet and the filament-woven polyethylene terephthalate woven fabric were superimposed on the sol composition coated surface, respectively.
After preheating at 170℃ for 1 minute, press plate spacing is 0.8mm (using press frame 0.8mm thick), and the same temperature is 50Kg/cm ² load is 30
It was pressed for seconds, and after cooling, it was taken out to obtain a laminated sheet. It was cut into test pieces with a width of 2.54 cm and a length of 8 cm, one end of the test piece was peeled off, and a 180T type peel test was performed in the length direction at a tensile speed of 50 mm/min. The average peel strength of the five test pieces was (Unit: Kg/inch). Example 1, Comparative Example 1 Vinyl chloride paste resin (average degree of polymerization 1450) 100 parts by weight DOP 60 Epoxy stabilizer (trade name FEP-13, manufactured by Adeka Argus) 3 Ba-Zn stabilizer and dissociation promoter agent (product name AC-
303, manufactured by Adeka Argus) 3. Nonylphenol block form of TDI polymer (average molecular weight 1182, 50wt% DBP solution, effective NCO content 4wt%) 10. (Amount of solution) Plastisol composition with the above composition uniformly distributed A test piece was prepared using the method described in the above-mentioned peel strength measurement method, and the peel strength was measured and is shown in Table 1. For comparison, a non-block form of TDI polymer (average degree of polymerization 550, 25wt% DBP solution, NCO content 3.8wt%) was used as an adhesion promoter, but the same procedure as in Example 1 was used, did.

[Table] From the results of Example 1, the heating temperature during composite sheet production was set to be below the dissociation temperature of the block, that is, 160°C.
The peel strength of those heated at the following temperatures is extremely high, and that of those heated and melted and solidified at 175℃, the composition surface peels after being left for a long period of time, probably due to the generation of free NCO, and the peel strength is relatively high. It exhibited only weak peel strength. Also, in the case of the comparative example, the strength was low due to peeling between the bonded material and the sol composition surface. In addition, regardless of the heating temperature during composite sheet production, the peel strength of sheets laminated with soft vinyl chloride resin sheets at a pressing temperature of 130°C is 2.
Kg/inch or less, and no substantial adhesive strength was generated. Example 2 In Example 1, in the plastisol composition
Nonylphenol block form of TDI polymer
A plastisol composition was prepared so that the 50 wt%-DBP solution was 15 parts by weight. After a predetermined number of days had elapsed, the composition was coated on a polyester woven fabric to a thickness of 0.1 to 0.2 mm, heated and melted at 145° C. for 90 seconds, and cooled and solidified to produce a composite sheet. A soft vinyl chloride resin sheet was laminated onto this composite sheet, and the peel strength of the laminated sheet after lamination was measured. In addition, the composite sheet obtained by applying the sol composition after 0 days of elapsed time was left in an atmosphere of 35° C. and 80% relative humidity for a period equivalent to the number of days of elapsed time of the sol composition.
The soft vinyl chloride resin sheets were laminated, and the peel strength was measured in the same manner as above, and the adhesive strength with the vinyl chloride resin sheet after being left in the sol or the composite sheet was compared, and the results are shown in Table 2.

[Table] The composite sheet used in the present invention shows no decrease in adhesive strength even after 30 days have passed after manufacturing the composite sheet, and there is a large difference between the composite sheet and the laminated sheet manufactured after leaving the sol composition as it is. On the contrary, it has the advantage that it can be operated when the sol composition has a low viscosity in terms of coating operation. Example 3 The sol composition and plastisol composition used in Example 1 were applied to a polyester woven fabric in the form of a grid by a depping treatment to adhere to a basis weight of 100 g/m ² , and gelled in a drying oven at 160°C for 90 seconds to form a composite sheet. was manufactured, rolled up and stored. After one week, the surface temperature of this composite sheet was 170℃.
Immediately after reheating until
A laminated sheet was produced by pressing with a pressure roll, and the peel strength was measured. The gel layer of the adhesive sol firmly fixes the polyester base fabric and welds it to the PVC resin sheet.
In addition, bridging was formed between the vinyl chloride resin sheets, and a laminated canvas with excellent peel strength of 7 kg/inch was obtained. The peel strength of the TDI polymer in which the nonylphenol block body was not blended by the method of Example 3 was
It showed a low value of 4.1Kg/inch. Comparative Example 2 Same as Example 1 except that TDI nonylphenol block form (average molecular weight 614, 50wt%-DBP solution, effective NCO content 6.8wt%) was used as the adhesion promoter.
A composite sheet and a laminated sheet were manufactured in the same manner as in the above. The heating temperature and pressing temperature during the production of the composite sheet and laminated sheet were 145°C and 170°C, respectively. The peel strength of the obtained laminated sheet was 2.9Kg/inch
showed an extremely low value.

Claims (1)

[Claims] 1. A method for laminating a fibrous knitted woven fabric or nonwoven fabric and a sheet or film-like laminate material, comprising: (a) applying a plastisol composition containing a diisocyanate polymer block onto the fibrous knitted woven fabric or nonwoven fabric; (b) heating and melting the plastisol composition at a temperature below the block body dissociation temperature; and (c) immediately before or after stacking a sheet or film-like laminate on the surface coated with the plastisol composition. After that, the plastisol composition is heated to a temperature equal to or higher than the dissociation temperature of the block body, and (d) the fibrous knitted fabric or nonwoven fabric and the sheet or film-like laminate are heated and pressed. A method for manufacturing a laminated sheet. 2. The method for producing a laminated sheet according to claim 1, wherein the diisocyanate polymer block is a long-chain alkylphenol block of an aromatic diisocyanate polymer. 3. The method for producing a laminated sheet according to claim 1 or 2, wherein the diisocyanate polymer block has an average molecular weight in the range of 1,000 to 10,000.