JP4988286B2 - Sheet material and sheet material manufacturing method - Google Patents

Description

  The present invention relates to a sheet material used for covering an article by being attached to the surface of the article, and a method for manufacturing the sheet material.

The surface of a car chair or the like is widely covered with a seat. And as such a sheet material, a fabric in which a design property is imparted to a woven fabric or a knitted fabric is widely used.
Those based on such fabric have sufficient performance in terms of strength, durability, and moisture permeability, but with outdoor styles generalized, water, seawater, snow, mud, sand, etc. are added. The number of people riding in cars with their clothes increased. In such a case, it has been pointed out that a fabric is easily soiled and it is very difficult to remove the soil.

Therefore, the resin sheet material is used for the above-mentioned purposes. Such a sheet material is described in Patent Document 1, for example.
In addition, imparting flame retardancy to seat materials used for car chairs is now one of the required physical properties, beyond the scope of common sense, when considering user safety.
JP 2006-7543 A

Polyvinyl chloride sheet materials described in Patent Document 1 and the like are excellent in terms of high strength, high durability, and low cost, and thus have been used for furniture and vehicles. However, in the case of a polyvinyl chloride material, maintenance of dirt and the like is easy, but it is difficult to impart moisture permeability. Therefore, stuffiness due to sweat occurs during use, which easily causes user discomfort. In addition, when producing a sheet made of polyvinyl chloride, it can be foamed into a foamed sheet, but the holes themselves become closed cells, and the moisture permeability is no different from that of a non-foamed sheet. Discomfort could not be avoided.
In addition, the polyvinyl chloride sheet may generate harmful gas when used, discarded, or incinerated, and thus has a problem both during use and after use.

  In addition, a sheet material made by extruding a polyurethane polymer instead of a polyvinyl chloride material has been proposed and put to practical use. However, because it is the same manufacturing method as a polyvinyl chloride sheet material, moisture permeability should be imparted. However, it was difficult to improve the moisture permeability to avoid the stuffiness caused by sweat.

Furthermore, a sheet material by a wet coagulation method relating to a polyurethane polymer has also been proposed. In the case of the sheet material by such a wet coagulation method, the moisture permeability is excellent, but on the other hand, the wear resistance is inferior compared with the above-described sheet material. Therefore, when such a sheet material is used, it is necessary to attach an abrasion-resistant film to the surface with an adhesive or the like. As a result, moisture permeability is lowered, and the process becomes complicated and expensive. turn into.
In addition, when a polyurethane-based polymer is used, it is difficult to impart flame retardancy compared to the case where polyvinyl chloride is used, and thus a large amount of flame retardant must be used. As a result, not only the soft texture peculiar to the polyurethane polymer is impaired, but also the strength, wear resistance and durability are lowered.

  Therefore, the present invention provides a sheet material having both moisture permeability, wear resistance and flame retardancy, and a method for producing the sheet material.

In order to achieve the above object, the present invention includes a step of coating a base material with a solution for a flame retardant layer in which a polyurethane polymer P1 and a flame retardant are dispersed or dissolved in an organic solvent A1, and a polyurethane polymer P1. Is dissolved in the organic solvent B1, and the organic solvent B1 compatible with the organic solvent A1 is immersed in the organic solvent B1 and then dried, A step of forming a high quality flame retardant layer, a step of applying a solution for a main layer in which a polyurethane polymer P2 is dissolved in an organic solvent A2 to the flame retardant layer, and a material that does not substantially dissolve the polyurethane polymer P2 A step of forming a porous main layer by using an organic solvent B2 that is compatible with the organic solvent A2 and immersing the substrate coated with the solution for the main layer in the organic solvent B2 and then drying the substrate. And polyurethane The organic solvent C to dissolve Rimmer P3, a coating solution prepared by dissolving the polymer P3 used, the porous primary layer coating solution to the surface partially coated and then dried to of the surface of the porous main layer possess a surface forming step, the organic solvent C, there is compatibility between the polyurethane polymer P2 of the main layer, the portion the surface layer on the surface of the porous main layer has been formed and the surface layer is not formed It is a manufacturing method of the sheet | seat material characterized by forming a part .

  According to the present invention, a solution for a flame retardant layer in which a polyurethane-based polymer P1 and a flame retardant are dispersed or dissolved in an organic solvent A1 is applied to a base material to form a porous flame retardant layer. After forming the porous main layer, the surface layer can be formed while dissolving the surface of the porous main layer using the coating solution in which the polymer is dissolved, so the porous flame retardant layer and the porous The main layer and the surface layer formed on the surface thereof can form a surface layer that improves abrasion resistance while ensuring moisture permeability. Moreover, the flame retardant layer can be made porous, and both moisture permeability and wear resistance can be improved while imparting flame retardancy without impairing the soft texture unique to polyurethane-based polymers.

  The concentration of the polymer in the coating solution can be 3 to 15% by mass (claim 2).

Further, the portion where the surface layer is not formed may be formed in an island shape .

  And the sheet | seat material can be manufactured using the manufacturing method of the sheet | seat material in any one of Claims 1-3 (Claim 4).

  ADVANTAGE OF THE INVENTION According to this invention, the sheet | seat material which has a flame retardance, moisture permeability, and abrasion resistance can be provided, without impairing the soft feel peculiar to a polyurethane-type polymer.

  The sheet material 1 of the present invention has a layer structure as shown in FIG. 1, and includes a base material 10, a flame retardant layer 20, a main layer 11, and a surface layer 12, and from the front side, the surface layer 12 and the main layer. 11, the flame retardant layer 20 and the substrate 10 are arranged in the order of layers.

The base material 10 is made of a woven fabric, a knitted fabric, a non-woven fabric, or a brushed product thereof formed using fibers. And while the base material 10 has air permeability, it can apply the flame retardant layer solution used as the flame retardant layer 2 and the main layer solution used as the main layer 11 as described later. It can be applied.
As the specific material of the base material 10, those conventionally used can be used, for example, natural fibers such as cotton, hemp, and silk, regenerated fibers such as rayon, cupra, and tencel, polyester, polyamide There are synthetic fibers such as fibers, and those formed using these blended and interwoven fibers can be used.

  And the flame retardant layer solution is applied to the base material 10 to form the flame retardant layer 20. Moreover, after forming the flame retardant layer 20, the main layer solution is applied to form the main layer 11. Further, the surface layer 12 is formed after the main layer 11 is formed.

  As shown in FIG. 1, the flame retardant layer 20 and the main layer 11 of the sheet material 1 of the present embodiment are porous because they are formed by a wet coagulation method. Moreover, although the flame retardant layer 20 includes the flame retardant 15, in the present embodiment, the flame retardant layer 20 uses the solid flame retardant 15 and is dispersed throughout the flame retardant layer 20. Yes.

The flame retardant layer solution used to form the flame retardant layer 20 is obtained by dissolving the polyurethane polymer P1 in the organic solvent A1 and dispersing or dissolving the flame retardant 15. The main layer solution used to form the main layer 11 is obtained by dissolving the polyurethane polymer P2 in the organic solvent A2.
And specifically, although the flame retardant layer solution and the main layer solution can be prepared using the following, the polyurethane polymer P1 and the organic solvent A1 used for the flame retardant layer solution and The polyurethane polymer P2 and the organic solvent A2 used in the main layer solution may be the same or different from each other.

The polyurethane polymers P1 and P2 used in the flame retardant layer solution and the main layer solution are resins having a urethane bond. Specifically, polyester-type polyurethane, polyether-type polyurethane, polycarbonate-type polyurethane, polyether A conventionally well-known thing, such as a polycarbonate type polyurethane, can be used. Furthermore, when the sheet material is used for an application requiring high durability such as a vehicle, a polycarbonate type polyurethane and a polyether polycarbonate type polyurethane are suitable.
These polyurethanes may be modified with other polymers having different skeletons, and examples thereof include various types such as silicon modification, fluorine polymer modification, and polyacrylate polymer modification polyurethane.

The hardness of the polyurethane polymers P1 and P2 used in the flame retardant layer solution and the main layer solution can be arbitrarily selected. The hardness, durability of the sheet material 1, the strength, because it affects the texture or the like, In view of this, preferably in the range of stress M ₁₀₀ Tensile at 100% elongation is 2.94MPa~29.4MPa Particularly preferred are those having M ₁₀₀ of 3.92 MPa to 9.81 MPa.
In addition, these polyurethane polymers P1 and P2 may be used alone or in combination with a plurality of types, and can be made to correspond to the use and required characteristics of the sheet material.
The method of measuring the tensile stress M ₁₀₀ is intended to be measured by JIS K 6251.

  Since the flame retardant layer solution and the main layer solution are made by dissolving the polyurethane polymers P1 and P2 in the organic solvent A1 and the organic solvent A2, the organic solvent A1 and the organic solvent A2 dissolve the polyurethane polymers P1 and P2. What can be used is used. The organic solvents A1 and A2 can be organic solvents used in a conventionally known wet coagulation method. For example, aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone, dichloromethane, Examples thereof include halogen solvents such as chloroform, ketone solvents such as dimethyl ketone and methyl ethyl ketone, cyclic ether solvents such as tetrahydrofuran and dioxane, and aromatic organic solvents such as toluene and xylene.

  In particular, among the solvents used for the organic solvents A1 and A2, an aprotic polar solvent is preferable in consideration of the influence on the environment, workability in the wet coagulation method, simplicity, and the like. Moreover, you may mix and use 2 or more types of these solvents as needed.

  The solution for the flame retardant layer is obtained by dissolving the polyurethane polymer P1 in the organic solvent A1 and dispersing or dissolving the flame retardant 15. The flame retardant 15 is obtained after the polyurethane polymer P1 is dissolved in the organic solvent A1. Can be adjusted by dispersing or dissolving. The dispersion or dissolution of the flame retardant 15 may be performed when the polyurethane polymer P1 is dissolved in the organic solvent A1, or may be performed before the polyurethane polymer P1 is dissolved in the organic solvent A1.

Further, the concentration of the polyurethane-based polymer P1 dissolved in the organic solvent A1 can be selected arbitrarily depending on the solvent, but is preferably 10 to 30% by mass, particularly preferably 15 to 25% by mass. is there. When the concentration is lower than these ranges, the ratio of the pores to the volume in the flame retardant layer 20, that is, a wet film having a high porosity can be obtained and high moisture permeability can be imparted, but the viscosity of the flame retardant layer solution When the flame retardant 15 is dispersed, the flame retardant 15 is liable to settle, and not only can stable processing be prevented, but it is also difficult to impart flame retardancy. Further, the strength of the formed flame retardant layer 20 itself also decreases, making it unsuitable for uses that require high strength such as for vehicles.
On the other hand, when the concentration is higher than these ranges, the strength of the flame retardant layer 20 itself is increased, but the porosity is decreased and the moisture permeability is decreased. Further, the viscosity of the flame retardant layer solution itself is remarkably increased, which makes it difficult to apply the coating, or to remove the solvent so that a porous film cannot be obtained.

  Next, the flame retardant 15 used for the solution for the flame retardant layer may be either liquid or solid. Specifically, conventionally known flame retardants 15 such as halogen, halogen-antimony, phosphate ester, phosphorus nitrogen, magnesium hydroxide, aluminum hydroxide, and silicon can be used. If a flame retardant 15 that dissolves in the organic solvent B1 is used, it is difficult to form a porous layer because the flame retardant layer solution is applied to the substrate 10 and then immersed in the organic solvent B1. In addition, since it is impossible to impart essential flame retardancy, it is desirable to avoid such things. In view of recent environmental problems, it is preferable to use a flame retardant 15 other than halogen-based or halogen-antimony-based.

  The amount of the flame retardant 15 used in the flame retardant layer solution can be selected depending on the type of the base material 10 to be used, the type of polyurethane polymer, the thickness and weight of the main material layer, and the type of the flame retardant 15. Preferably it is 0.5 to 3.5 times with respect to the polyurethane polymer P1. Particularly preferably, it is 1 to 2.5 times. If it is lower than these ranges, it will be difficult to impart flame retardancy, and if it is higher than these ranges, flame retardancy can be imparted, but the soft texture unique to polyurethane polymers will be impaired, making it even more difficult. The strength of the fuel layer 20 itself is reduced, and the fuel layer 20 cannot be used for applications that require high strength such as for vehicles.

In the main layer solution, the concentration of the polyurethane polymer P2 dissolved in the organic solvent A2 can be selected according to the solvent, but is preferably 5 to 30% by mass, particularly preferably 10 to 10. 25% by mass.
When the concentration is lower than these ranges, a ratio of the pores to the volume in the main layer 11, that is, a wet film having a high porosity can be obtained and high moisture permeability can be imparted, but the viscosity of the solution for the main layer is remarkably high. It becomes low, and it becomes easy to generate a back-through or the like during coating on the substrate. Further, the strength of the formed main layer 11 itself also decreases, making it unsuitable for applications requiring high strength such as furniture and vehicles.
On the other hand, when the concentration is higher than these ranges, the strength of the main layer 11 itself increases, but the porosity decreases and the moisture permeability decreases. In addition, the viscosity of the main layer solution itself is remarkably increased, which makes it difficult to apply the coating, or to remove the solvent remarkably, so that a porous film cannot be obtained.

In addition, in order to improve physical properties such as durability and moisture permeability of the sheet material 1, other components such as additives, pore conditioners, and fillers may be added to the flame retardant layer solution and the main layer solution as necessary. Can be added.
As other components, for example, for the purpose of improving the physical properties of the sheet material 1, acrylic beads, ceramic beads, those in which these are dispersed in polyurethane, isocyanate-based crosslinking agents for imparting heat resistance, etc. Yes, these other components can be added to the flame retardant layer solution or the main layer solution.

In addition, as another component, there is a pore adjusting agent that adjusts the shape of the pores of the main layer 11 and the flame retardant layer 20, such as nonion, cation, anionic surfactant, alcohol solvent, polyethylene oxide, etc. Hydrophobic substances such as hydrophilic polymer additives, paraffinic oils and aromatic solvents can be added to the main layer solution. The addition amount of these pore modifiers may be a commonly used amount, preferably about 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyurethane polymers P1 and P2, and two or more kinds of the above regulators. You may use together.
Examples of other components include a colorant added for designability. As the colorant, it is preferable to select a colorant suitable for a conventionally known wet coagulation method, and a particularly preferable one is a vehicle having high durability.

When the sheet material 1 is manufactured, first, the flame retardant layer solution is applied to the base material 10.
In the step of applying the flame retardant layer solution, a commonly used method can be employed, and examples thereof include various methods such as a comma coating method, a doctor knife coating method, a reverse roll coating method, and a bar coating method. In particular, doctor knife coating capable of relatively thin coating is preferred.

The coating amount can be arbitrarily changed depending on the weight and thickness of the base material 10 and the main layer 11 and the type of the flame retardant 15 used in the solution for the flame retardant layer, but is preferably 50 to 200 g / m ² . If it is less than this range, it is difficult to simply impart flame retardancy, and if it is greater than this range, flame retardancy can be imparted, but the texture becomes extremely hard.

And the thing which applied the solution for flame retardant layers to the base material 10 is immersed in the organic solvent B1 compatible with the organic solvent A1, and it is made to dry after that, and the flame retardant layer 20 is formed.
When immersed in the organic solvent B1, the organic solvent A1 in the flame retardant layer solution elutes into the organic solvent B1, so that the flame retardant layer 20 is formed by the polyurethane polymer P1 and the flame retardant 15 contained in the flame retardant layer solution. It is formed. As shown in FIG. 1, the flame retardant layer 20 becomes porous and is formed on the substrate 10.
In addition, although drying after being immersed in the organic solvent B1 may be performed completely, drying to some extent may be sufficient. In such a case, drying performed after application of the solution for the main layer or drying performed after application of the coating solution For example, the remaining organic solvent B1 can be evaporated and dried.

  Further, the main layer 11 is formed by applying the solution for the main layer to the substrate 10 on which the flame retardant layer 20 is formed.

  In the step of applying the main layer solution, a commonly used method can be employed, such as a comma coating method, a doctor knife coating method, a reverse roll coating method, a gravure coating method, a bar coating method, and the like. Can be mentioned.

And after apply | coating the solution for main layers, it is made to immerse in the organic solvent B2, and it is made to dry after that, and the main layer 11 is formed.
The organic solvent B2 used after coating the main layer solution is compatible with the organic solvent A2, but can be the same as the organic solvent B1.

When immersed in the organic solvent B2, the organic solvent A2 in the main layer solution is eluted in the organic solvent B2, and the main layer 11 is formed by the polyurethane polymer P2 contained in the main layer solution. The main layer 11 is porous and formed on the flame retardant layer 20 as shown in FIG.
Moreover, the drying after being immersed in the organic solvent B2 is sufficiently performed.

  The coating amount of the main layer solution is larger than the coating amount of the flame retardant layer solution, and the main layer 11 is thicker than the flame retardant layer 20.

  Further, the surface layer 12 is formed on the surface of the main layer 11, that is, on the side opposite to the substrate 10. The surface layer 12 is formed using a coating solution in which a predetermined polymer P3 is dissolved in an organic solvent C.

  The organic solvent C used in the coating solution is compatible with the polyurethane polymer P2 of the main layer 11 and can dissolve the surface of the main layer 11 by applying the coating solution. is there. Therefore, the surface layer 12 formed on the surface of the main layer 11 has good adhesion to the main layer, and the surface layer 12 is unlikely to peel off during use, thereby improving the wear resistance.

  Examples of the organic solvent C include aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone, halogen solvents such as dichloromethane and chloroform, ketone solvents such as dimethyl ketone and methyl ethyl ketone, and cyclic ethers such as tetrahydrofuran and dioxane. An organic solvent such as an aromatic solvent such as a solvent, toluene, and xylene can be used, and the same organic solvent A1 or organic solvent A2 may be used.

  In addition, the coating solution is a solution in which a predetermined polymer P3 is dissolved, can give an appropriate viscosity, and can be obtained with a suitable viscosity at the time of coating, and by drying after coating, A surface layer 12 that is a layer of the polymer can be formed.

As the polymer P3 used in the coating solution, any resin may be used as long as the adhesion to the main layer 11 can be secured, but polyurethane, polyamide, polyacrylate, and the like can be employed. Polyurethane polymers are preferred, and polycarbonate polyurethanes and polyether polycarbonate polyurethanes are particularly preferred because they are uses that require high durability.
And the same thing as the polymer P2 used for the main layer 11 can be used as the polymer P3 of a coating solution.
Further, as the polymer P3 used in the coating solution, resins other than polyurethane, polyamide, and polyacrylate can be used, and fluorine-based and olefin-based resins can also be used.

The concentration of the polymer P3 added to the coating solution is preferably about 3 to 15% by mass although it depends on the type of the polymer P3 used. If the concentration is less than 3%, the viscosity of the coating solution becomes too low, and the workability of the coating work tends to be lowered. If the concentration exceeds 15%, it is difficult to apply thinly because the viscosity of the coating solution is high, and since the polymer 12 is contained in a large amount even in the same amount of coating solution, the surface layer 12 is formed thick, so that moisture permeability The decrease in the size tends to increase.
Note that the viscosity of the coating solution depends largely on the concentration of the polymer P3 in the coating solution. Therefore, when the polymer P3 has a low concentration, the viscosity of the coating solution tends to be low. In such a case, the coating solution can be thickened using a lipophilic clay mineral thickener or the like.

  In the step of applying the coating solution to the surface of the main layer 11, a commonly used method can be employed, such as a comma coating method, a doctor knife coating method, a reverse roll coating method, a gravure coating method, a bar coating method, or the like. There are methods, and in particular, a gravure coating method and a screen coating method, which are methods suitable for coating a coating solution, are preferred.

In this way, the coating solution is applied to the surface of the main layer 11 and dried again to form the surface layer 12, whereby the sheet material 1 is manufactured. And this surface layer 12 is a thin layer, and hardly reduces moisture permeability.
Furthermore, it can also be laminated on the surface of the surface layer 12 for imparting design properties and further improving the strength. As a specific example, there is a case where a material for newly imparting a function such as water repellent finish is applied to the surface. In addition, when laminating | stacking another material on the surface of the surface layer 12, it is performed, maintaining moisture permeability.

  Moreover, it is also possible to give an embossing process for the provision of the further design property. In the sheet material 1 of the present invention, since the main layer 11 is porous, the embossed mold is good, and any emboss pattern can be handled.

The coating solution can be applied to the whole, but it can be partially applied as in the sheet material 2 shown in FIG. 2 to partially form the surface layer 12. And in the sheet material 2, physical properties, such as abrasion resistance, improve about the part in which the surface layer 12 was formed, moisture permeability can be ensured about the part in which the surface layer 12 is not formed, and the whole performance of the sheet material 2 is improved. Can be made.
Furthermore, by applying a portion where the coating solution is applied in a lattice shape, the whole of the coated portions can be connected, and a portion where the coating solution is not applied can be formed in an island shape. Then, when the surface layer 12 is formed by partially coating in this way, the exposed portion of the main layer 11 becomes an island-island shape with respect to the portion where the surface layer 12 is formed, and wear resistance, etc. The physical properties can be further improved.
In addition, when manufacturing the sheet | seat material 2, about processes other than the application | coating solution application process, it is the same as that of the case of the sheet | seat material 1, and also in the application | coating solution application | coating process except the point which changes the range to apply | coat. It is.

In the sheet materials 1 and 2 of the present invention, since the flame retardant layer 20 is closer to the base material 10 than the main layer 11, the surface layer 12 and the main layer 11 have a great influence on characteristics such as wear performance. Therefore, even if the characteristics of the flame retardant layer 20 to which the flame retardant is added are deteriorated, the characteristics of the sheet materials 1 and 2 as a whole can be secured, and the flame retardant layer 20 can increase the flame resistance. it can.
Moreover, since both the main layer 11 and the flame retardant layer 20 are porous, moisture permeability can be ensured.

Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to the following description examples as long as the gist thereof is not exceeded.
And the sheet materials of Examples 1 to 4 and Comparative Examples 1 to 3 manufactured by the method shown below were used for (1) moisture permeability, (2) flame retardancy, (3) wear test 1, and (4) wear. Test 2, (5) It evaluated by five types of bending resistance.

(1) About moisture permeability, it measured based on JISL1099-1993A-1 method.
(2) About flame retardance, combustibility was confirmed based on JIS D 1201-1998, and the burning rate (mm / min.) Was measured.
(3) About abrasion test 1, the Taber abrasion test was performed 2000 times with a wear wheel with a load of 9.8 N and CS-10, and the appearance change was evaluated. And, when the appearance change is up to the gloss change of the skin layer, “○”, when the porous layer is destroyed “X”, when the porous layer is completely removed and the base material is exposed Was evaluated as “XX”.
(4) For wear test 2, using a Gakushin type wear tester, change the appearance every 1000 times with No. 10 canvas and load of 9.8N as the wear object, and test up to the upper limit of 20000 times went. Evaluation is the number of appearance changes and the appearance change is `` ○ '' when the skin layer is glossy, `` X '' when the porous layer is broken, `` X '', the porous layer is completely lost The case where the base material was exposed was performed as “XX”.
(5) The bending resistance was measured according to the JIS L 1096-1999 Gurley bending rebound test.

Example 1
A polycarbonate-based polyurethane was used as the polyurethane-based polymer, and a flame retardant layer solution was prepared with the following composition.
・ Rezamin CU9443 (urethane 30% manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ Peco frame STC (Clariant Japan) 75 parts ・ Dimethylformamide 60 parts Also, the urethane polymer is blended in a solvent. The urethane content of resamine CU9443 used in Example 1 is 30%. Peco flame STC is a phosphorus nitrogen flame retardant. And the ratio of the flame retardant in the state which the solvent evaporated is 2.5 times with respect to solid content of a polyurethane polymer.

The fiber base material used as the base material 10 used in Example 1 was a raised fabric of a plain woven fabric of warp 52 / inch and weft 40 / inch using a blended yarn of 65% polyester and 35% rayon. Was used.
The above flame retardant layer solution is applied to the raised surface of the substrate with a knife coater at a coating amount of 120 g / m ² , then immersed in water at a temperature of 25 ° C. for 4 minutes, and further immersed in warm water at 40 ° C. for 15 minutes. After dipping and squeezing with a mangle having a pressure of 0.4 MPa, it was dried in an oven at 140 ° C. to obtain a wet porous flame retardant structure.

Moreover, the solution for main layers was prepared with the following formulation.
・ Rezamin CU8614 (urethane 30%, manufactured by Dainichi Seika K.K.) 100 parts ・ 70 parts dimethylformamide 2 parts of Titanium oxide 55% from Chemical Industries Co., Ltd. ・ Rezamin CUT-30 (75% surfactant manufactured by Dainichi Seika Kogyo Co., Ltd.) 3 parts

The wet porous flame retardant composition is immersed in water and squeezed with a mangle having a pressure of 0.4 MPa, and the main layer solution is applied to the coated surface of the wet porous flame retardant composition with a bar coater. Apply 800g / m ^{2 of} work amount, then immerse in water at 25 ° C for 4 minutes, further immerse in warm water at 40 ° C for 15 minutes, squeeze with mangle with pressure of 0.4 MPa, and dry in oven at 140 ° C Thus, a wet porous structure was obtained.
Next, the coating solution was adjusted with the following formulation. In this coating solution, polyurethane is used as a polymer.
· Crisbon NY-328 (Dainippon Ink & Chemicals, Inc. urethane 25%) 100 parts · Dimethylformamide 100 parts · Methyl ethyl ketone 100 parts And the coating solution prepared as described above, width 0.25mm, depth 70μm The sheet material of Example 1 was obtained by coating using a grid type gravure coater and drying in an oven at 140 ° C.

(Example 2)
The same flame retardant layer solution as that described in Example 1 was used.
The fiber base material used in Example 2 is a 75 denier / 72 filament polyester multifilament yarn on the front heel of a warp knitting machine (28 gauge), and a 50 denier / 24 filament polyester multifilament yarn on the back heel. Each was supplied and knitted into a half structure, and then a tricot with one side raised was used. Then, the flame retardant layer solution is applied to the substrate raised surface with a knife coater, the coating amount is 120 g / m ² , then immersed in water at a temperature of 25 ° C. for 1 minute, and squeezed with a mangle with a pressure of 0.4 MPa, A wet porous flame retardant composition was obtained.

And the polycarbonate-type polyurethane was used as a polyurethane-type polymer, and the solution for main layers was adjusted with the following mixing | blendings.
・ Rezamin CU9443 (urethane 30% manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ 70 parts of dimethylformamide 2 parts of titanium oxide 55% manufactured by Kagaku Kogyo Co., Ltd. And, the above main layer solution was applied to the coating surface of the wet porous flame retardant composition using a bar coater, followed by application of 800 g / m ^{2 of} coating temperature. It was immersed in water at 25 ° C. for 4 minutes, further immersed in warm water at 40 ° C. for 15 minutes, then squeezed with a mangle having a pressure of 0.4 MPa, and dried in an oven at 140 ° C. to obtain a wet porous structure.
Except for the above, the same formulation as in Example 1 was used.

(Example 3)
The sheet material of Example 2 was embossed under the following conditions to obtain the sheet material of Example 3.
The embossing is performed under conditions of 150 ° C., 5 MPa, and 1 minute, and is embossed with a skin tone.

Example 4
The sheet material of Example 2 was subjected to gravure coating with a surface treatment agent to impart design properties, and then embossed in the same manner as in Example 3 to obtain the sheet material of Example 4. The formulation of the surface treating agent used in Example 4 is as follows.
・ Lackskin U-1834M (Seiko Kasei Co., Ltd. urethane 14%) 100 parts ・ Lackskin U-1840G (Seiko Kasei Co., Ltd. urethane 14%) 10 parts ・ Methyl ethyl ketone 10 parts

(Comparative Example 1)
A polycarbonate-based polyurethane was used as the polyurethane-based polymer, and a flame retardant layer solution was prepared with the following composition. Moreover, although the urethane polymer and the flame retardant are blended in a state dispersed in a solvent, the amount of the flame retardant itself is 2.5 times the solid content of the polyurethane polymer.
・ Rezamin CU9443 (urethane 30% manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ PECO FRAME STC (phosphorus nitrogen-based flame retardant manufactured by Clariant Japan Co., Ltd.) 75 parts ・ 60 parts of dimethylformamide and fiber used in Comparative Example 1 The base material made by supplying 75-denier / 72-filament polyester multifilament yarn to the front heel of a warp knitting machine (28 gauge) and 50-denier / 24-filament polyester multifilament yarn to the back heel, respectively, into a half structure A tricot knitted and then brushed on one side was used. And the said flame retardant layer solution was coated on the substrate raised surface with a knife coater at a coating amount of 120 g / m ² and dried in an oven at 140 ° C. to obtain a nonporous flame-retardant structure.

And the polycarbonate-type polyurethane was used as a polyurethane-type polymer, and the solution for main layers was adjusted with the following mixing | blendings.
・ Rezamin CU9443 (urethane 30% manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts ・ 70 parts dimethylformamide ・ Seika Seven BS780S (Carbon Black 25% manufactured by Dainichi Seika Kogyo Co., Ltd.) 15 parts ・ Seika Seven BS012 (Daiichi Seisen 2 parts of titanium oxide 55% manufactured by Kagaku Kogyo Co., Ltd. And, the above-mentioned solution for the main layer is applied to the coating surface of the non-porous flame retardant composition using a bar coater, followed by application of a coating amount of 800 g / m ^2. It was immersed in water at 25 ° C. for 4 minutes and further immersed in warm water at 40 ° C. for 15 minutes, then squeezed with a mangle having a pressure of 0.4 MPa and dried in an oven at 140 ° C. to obtain a wet porous structure.
Since it is manufactured as described above, in the sheet material of Comparative Example 1, the flame retardant layer is not porous, the coating solution is not applied, and the surface layer is not formed.

(Comparative Example 2)
The coating solution was prepared with the following formulation. In this coating solution, polyurethane is used as a polymer.
· Crisbon NY-328 (Dainippon Ink & Chemicals, Inc. urethane 25%) 100 parts · Dimethylformamide 100 parts · Methyl ethyl ketone 100 parts And the coating solution prepared as described above, width 0.25mm, depth 70μm The wet-type porous structure obtained in Comparative Example 1 was coated using a grid type gravure coater, and dried in an oven at 140 ° C. to provide a surface layer on the wet-type porous structure. And after coating the following surface treating agent and providing designability, the embossing of the skin tone was given on conditions of 150 degreeC, 5 Mpa, and 1 minute, and the sheet material of the comparative example 2 was obtained.
The composition of the surface treating agent used in Comparative Example 2 is the same as that in Example 4, and is as follows.
・ Lackskin U-1834M (Seiko Kasei Co., Ltd. urethane 14%) 100 parts ・ Lackskin U-1840G (Seiko Kasei Co., Ltd. urethane 14%) 10 parts ・ Methyl ethyl ketone 10 parts

(Comparative Example 3)
The sheet material of Comparative Example 2 was embossed under the following conditions to obtain a sheet material of Comparative Example 3.
Embossing is performed at 150 ° C., 5 MPa, for 1 minute, and embossed in a skin tone.
As described above, in the sheet materials of Comparative Examples 2 and 3, the surface layer is formed, but the flame retardant layer is not porous.

  Table 1 shows various evaluation results of the sheet materials of Examples 1 to 4 and Comparative Examples 1 to 3.

  As shown in Table 1, the sheet materials of Examples 1 to 4 are flame retardant, and are superior in moisture permeability, wear properties, and flexibility as compared to the sheet materials of Comparative Examples 1 to 3.

It is sectional drawing which showed the layer structure of the lamination sheet of this invention. It is sectional drawing which showed the layer structure of the lamination sheet of this invention.

1, 2 Sheet material 10 Base material 11 Main layer 12 Surface layer 20 Flame retardant layer

Claims (4)

Coating a base material with a solution for a flame retardant layer in which a polyurethane polymer P1 and a flame retardant are dispersed or dissolved in an organic solvent A1, and
The organic solvent B1 that does not substantially dissolve the polyurethane polymer P1 and is compatible with the organic solvent A1 is immersed in the organic solvent B1 after the base material coated with the flame retardant layer solution is immersed in the organic solvent B1. Drying to form a porous flame retardant layer;
Coating the flame retardant layer with a solution for the main layer obtained by dissolving the polyurethane-based polymer P2 in the organic solvent A2,
The organic solvent B2, which does not substantially dissolve the polyurethane polymer P2 and is compatible with the organic solvent A2, is immersed in the organic solvent B2 after the substrate coated with the main layer solution is immersed in the organic solvent B2. Drying to form a porous main layer;
Using the coating solution in which the polymer P3 is dissolved in the organic solvent C in which the polyurethane polymer P3 is dissolved, the coating solution is partially coated on the surface of the porous main layer and then dried, and the porous main layer the surface layer possess a forming process on the surface,
The organic solvent C is compatible with the polyurethane polymer P2 of the main layer,
A method for producing a sheet material, characterized in that a portion where a surface layer is formed and a portion where a surface layer is not formed are formed on the surface of a porous main layer .   The method for producing a sheet material according to claim 1, wherein the concentration of the polymer in the coating solution is 3 to 15% by mass. The method for producing a sheet material according to claim 1, wherein the portion where the surface layer is not formed is formed in an island shape.   A sheet material manufactured using the method for manufacturing a sheet material according to claim 1.

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