JPH0351834B2 - - Google Patents

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention relates to a laminated flooring material, and more specifically, a laminated flooring material that is easy to construct using ordinary adhesives, durable for practical use, and that can be easily peeled off when replacing the flooring material. It is related to. (Prior art) Conventionally, this type of laminated flooring has been beautiful and clean, easy to maintain, inexpensive, and has good abrasion resistance and chemical resistance, so it has been widely used in stores and households. It is used quite a lot on the floor. This flooring material has a structure in which a soft synthetic resin layer is provided as an intermediate layer, a soft synthetic resin top layer is laminated on the surface thereof, and an asbestos sheet is laminated as a base material on the back surface. When this flooring material is installed with ordinary adhesive and put into practical use, when the flooring material is replaced, a large amount of asbestos on the back side remains on the underlying surface, causing unevenness on the underlying surface. A major drawback was that it would be difficult to install the flooring in its current state, and if the flooring was to be reinstalled, a large amount of asbestos remaining on the underlying surface would have to be removed with great effort. . Conventionally, in this type of flooring material, an intermediate layer of soft plastic foam is bonded to the surface side of a core layer made of long-fiber nonwoven fabric, and a surface layer made of soft plastic film is bonded thereon. Japanese Patent Publication No. 47-41848 relates to a laminated flooring material made by bonding dense soft plastic layers with a large amount of filler mixed into the surface, and a paper or non-woven fabric base material with a surface layer made of synthetic resin etc. JP-A-51-99821, Japanese Utility Model Application No. 105221-1987, and Japanese Utility Model Application Publication No. 1987-105221 based on the idea of forming a layer of release agent on the back side of the base of the formed floor, wall material, etc.
-No. 107902, No. 137930, No. 137930, No. 137930, No. 137930, No. 137930, No. 107902, No. 137930, No. 137930, No. 107902, No. 137930, No. 137930, No. 137930, No. 137930, No.
Publications such as No. 137931 are known. However, in the laminated flooring material disclosed in Japanese Patent Publication No. 47-41848, a core material layer made of long-fiber nonwoven fabric is used as a base material, and the surface thereof has an intermediate layer of soft plastic foam and a surface layer of soft plastic film thereon. It is characterized by bonding a dense soft plastic layer containing a large amount of filler to the back surface of the body (the back surface of the core material layer). In this case, first of all, the core material layer of the laminate is bonded. In order to bond a soft plastic layer with a dense structure mixed with a large amount of filler to the back side of the material, the soft plastic layer with a dense structure is bonded only at the surface part of the long fiber nonwoven fabric that constitutes the core material layer, and the two are completely bonded. Because they are not integrated, if a person walks on the flooring, drags a heavy object on the flooring, or repeatedly applies a local load with a chair with casters, etc., the joint surface may In order to prevent delamination, and secondly, to prevent the occurrence of wrinkles when bonding a soft plastic layer with a dense structure containing a large amount of filler to the back surface of the core material, the dense structure is It is necessary to apply tension to the soft plastic layer, and this tension causes the dense soft plastic layer to be bonded to the core layer with internal strain,
This internal strain causes the flooring to shrink economically, resulting in problems such as a significant deterioration in the dimensional stability of the flooring. Also, Japanese Patent Application Publication No. 51-99821, Utility Model Application No. 51-105221,
In the publications of Utility Model Application No. 51-107902, Utility Model Application No. 51-137930, and Utility Model Application No. 51-137931, a surface layer is formed using a synthetic resin or the like on the surface of a base mainly made of paper or nonwoven fabric. A release agent layer is formed on the back side of the base of the floor, wall material, etc., and in this case, the release agent layer on the back side of the base and the adhesive used to install the flooring material are used. Basically, they do not adhere to each other, so it is very easy to remove the flooring material. When the patient's hands are repeatedly loaded with a chair with casters or the like, peeling occurs at the interface between the release agent layer and the adhesive layer, which poses a serious practical problem. (Means for solving the problems) The present invention eliminates these conventional drawbacks, is sufficiently durable for practical use without problems such as peeling during practical use, and peels off at the adhesive interface on the base side when replacing the flooring material. The aim is to provide flooring materials that are possible. That is, the flooring material of the present invention has a heat-resistant synthetic resin layer formed by coating and impregnating a liquid synthetic resin composition on one side of a fibrous base material and solidifying it, and a soft synthetic resin intermediate layer on the other side. There is a laminated flooring material in which soft synthetic resin top layers are sequentially laminated, and the thermoplastic synthetic resin layer maintains an adhesive strength with the base adhesive in the range of 0.3 to 5 kg/2 cm width, In addition, when the laminated flooring material is peeled off from the base, the layer is characterized by being peeled off at the interface with the base adhesive. In the laminated flooring material of the present invention, a liquid synthetic resin composition is coated and impregnated on a fibrous base material 1, and a heat-resistant synthetic resin layer 2 is formed by one or more of the solidifying means of heating, ultraviolet irradiation, or electron beam irradiation. Then, a soft synthetic resin intermediate layer 3 is laminated on the surface of the fibrous base material opposite to the surface to which the liquid synthetic resin composition is applied by a calendering method, an extrusion method, a paste coating method, etc. , a printing layer 5 is formed by printing by a gravure printing method, a flexo printing method, a rotary screen printing method, a transfer printing method, etc., and a soft synthetic resin top layer 4 is further applied on this surface by a calendar method, an extrusion method, a paste method, etc. It is obtained by laminating layers using a coating method or the like. Heating, which is one of the above-mentioned solidification means, may be performed using any known heating method, such as electric heaters, infrared heaters, hot air blowing, Erofin, steam injection, high frequency induction heating, high frequency dielectric heating, etc. be able to.
Among the above-mentioned resin lamination methods, the paste coating method is common, and here, a method for manufacturing a flooring material using the paste coating method will be described. A liquid synthetic resin composition is coated and impregnated onto the fibrous base material 1, heated at 50°C to 250°C for 30 seconds to 15 minutes to solidify the liquid synthetic resin composition, and then exposed to ultraviolet light or A heat-resistant synthetic resin layer 2 is formed by irradiating with an electron beam, and a vinyl chloride resin plastisol is applied to the surface opposite to the surface to which the liquid synthetic resin composition is applied, and then heated at 120° C. to 250° C. for 30 seconds to 5 seconds. After heating for 30 seconds to 5 minutes at 150°C to 250°C to melt the vinyl chloride resin plastisol, Embossing is performed as necessary, and then ultraviolet rays or electron beam irradiation is performed as necessary. From the viewpoint of the design of the flooring material, it is preferable to form a printed layer 5 in which an arbitrary pattern is printed on the soft synthetic resin intermediate layer 3. Methods for printing arbitrary patterns include gravure printing, flexographic printing, rotary screen printing, etc. Printing ink may be printed directly on the surface of the soft synthetic resin intermediate layer, or printing ink may be printed on transfer paper. The material may be transferred onto the surface of the soft synthetic resin intermediate layer 3. Furthermore, rather than just printing, it is also possible to perform both printing and embossing, and in this case, it is also possible to perform printing and embossing at the same time, such as valley-dye embossing and head stain printing. Also, soft synthetic resin intermediate layer 3
When foaming with a chemical foaming agent, chemical embossing is also possible by printing a part of the pattern of the printing layer 5 with an ink containing a foaming inhibitor and/or foaming accelerator. Further, by printing a part of the pattern on the printing layer 5 with foaming ink and/or non-foaming ink, printing and unevenness can be synchronized. As a means for coating and impregnating the liquid synthetic resin composition on the fibrous base material 1, any commonly used method may be used, such as a knife coater, roll coater, gravure printer, rotary screen, curtain flow coater, date coating, etc. is preferred. When applying a liquid synthetic resin composition thinly and uniformly to a fibrous base material 1 such as glass paper with a low density of glass fibers (coarse mesh), it is important to prevent the liquid synthetic resin composition from seeping onto the back side of the glass paper. Gravure printers, roll coaters, rotary screens, etc. are suitable. In addition, the viscosity of the liquid synthetic resin composition is 1
It is necessary to adjust the viscosity appropriately depending on the fiber density and application method. For example, in the case of a fibrous base material 1 with a high fiber density, such as an asbestos sheet, the liquid synthetic resin composition can be applied with a viscosity ranging from low to high, and the appropriateness depends on each application method. The viscosity can be adjusted within the viscosity range, but for fibrous base material 1 that does not have a high fiber density, such as glass fiber paper with a glass fiber density of about 0.12 g/cc, apply the liquid synthetic resin composition using a knife coater. When applying the liquid synthetic resin composition, it is preferable to adjust the viscosity of the liquid synthetic resin composition to about 10,000 cps to 500,000 cps. In addition, when using a fibrous base material 1 with a low fiber density (coarse mesh), and even if the liquid synthetic resin composition is applied, the impregnation with the liquid synthetic resin composition is insufficient. When the soft synthetic resin intermediate layer 3 is laminated on the surface opposite to the surface on which the liquid synthetic resin composition is applied, air bubbles will enter the laminated interface, and if this is foamed, abnormal foaming may occur due to the influence of the air bubbles.
In such a case, the surface opposite to the surface to which the liquid synthetic resin composition is applied is sealed with, for example, vinyl chloride resin paste, or the liquid synthetic resin composition is applied to the fibrous base material 1. It is preferable to laminate the soft synthetic resin intermediate layer 3 after drying, heating and compressing between rolls to smooth the laminated surface. In addition, a heat-resistant synthetic material is used to bond the flooring material to the base to such an extent that it will not peel off during practical use, and to peel off at the interface with the heat-resistant synthetic resin layer 2 on the back side of the flooring material when the flooring material is peeled off. It is essential that the adhesive strength between the resin layer 2 and the adhesive layer is 0.3 to 5 kg/2 cm width.
If this adhesive strength is less than 0.3Kg/2cm width,
The adhesive strength with the substrate is too weak, resulting in peeling during practical use, and if the adhesive strength exceeds 5 kg/2 cm width, it becomes difficult to separate the flooring material from the substrate. ●Fibrous base material The fibrous base material 1 used in the present invention may be a single layer or two or more layers as long as it has excellent dimensional stability such as a felt sheet, woven fabric, knitted fabric, or nonwoven fabric. Although multi-layered ones can be used, in particular, from the viewpoint of dimensional stability, asbestos sheets, sheets mixed with at least two or more types of inorganic and/or organic fibers such as asbestos, glass fiber, paper, and polyester fibers, glass fiber paper, Paper or the like is preferred. Heat-resistant synthetic resin layer <liquid synthetic resin composition> The liquid synthetic resin composition for forming the heat-resistant synthetic resin layer 2 used in the present invention includes a soft synthetic resin intermediate layer 3 and a soft synthetic resin top layer. In lamination processing such as No. 4, it has a heat resistance that does not stick to the heated support in the heating furnace, and it also uses an adhesive for ordinary flooring construction. It adheres to a degree that does not cause peeling during practical use even after processing the flooring material, and provides strength to the extent that it can be peeled off at the interface between the heat-resistant synthetic resin layer 2 and the adhesive layer when the flooring material is peeled off. You can use anything you want. The liquid synthetic resin composition for forming the heat-resistant synthetic resin layer 2 used in the present invention is preferably the following, but the present invention is not limited thereto. A composition in which a vinyl chloride paste is blended with a large amount of an inorganic and/or organic filler with excellent heat resistance A composition in which a vinyl chloride paste is blended with a compound that crosslinks by means such as ultraviolet irradiation or electron beam irradiation Non-reactive type A composition in which a large amount of an inorganic and/or organic filler with excellent heat resistance is blended into a non-reactive liquid composition such as a synthetic resin emulsion or non-reactive synthetic rubber latex. A composition in which a large amount of an inorganic and/or organic filler with excellent heat resistance is blended into a non-reactive liquid composition such as a mold and synthetic rubber latex.A non-reactive synthetic resin emulsion or a non-reactive synthetic rubber latex. A composition in which a non-reactive liquid composition is blended with a compound that crosslinks by means such as ultraviolet irradiation or electron beam irradiation A reactive liquid composition such as a reactive synthetic resin emulsion or a reactive synthetic rubber latex A reactive liquid composition that crosslinks by heating Liquid composition consisting of a compound Liquid composition consisting of a compound crosslinked by ultraviolet irradiation or electron beam irradiation When the liquid synthetic resin composition for forming the heat-resistant synthetic resin layer 2 is the composition of, this vinyl chloride resin paste The composition contains 30 to 130 parts by weight of a plasticizer and 50 to 130 parts by weight of a stabilizer for 100 parts by weight of vinyl chloride resin.
400 parts by weight and, if necessary, a viscosity modifier,
It consists of an appropriate amount of coloring agent, etc. If the amount of plasticizer is less than 30 parts by weight based on 100 parts by weight of the vinyl chloride resin, the heat-resistant synthetic resin layer 2 will become too hard and its low-temperature properties will deteriorate, making it difficult to apply in winter, which is not preferable. Furthermore, if the amount of plasticizer exceeds 130 parts by weight per 100 parts by weight of vinyl chloride resin, not only will the heat-resistant synthetic resin layer 2 become extremely sticky, but especially when applied with a synthetic rubber latex adhesive, plasticizer Since a large amount of the agent migrates to the synthetic rubber adhesive layer and the adhesive strength is significantly reduced, problems such as warping and peeling of the flooring material occur during practical use, which is not preferable. The amount of inorganic and/or organic filler with excellent heat resistance is 50 parts by weight per 100 parts by weight of vinyl chloride resin.
If the amount is less than parts by weight, the heat-resistant synthetic resin layer 2
The material sticks to the support while it is heated in the heating furnace, making it impossible to achieve the intended purpose. or,
When the amount of the inorganic and/or organic filler with excellent heat resistance exceeds 400 parts by weight per 100 parts by weight of the vinyl chloride resin, the amount of the filler becomes too large and the heat-resistant synthetic resin layer 2 becomes brittle. The flooring material should not be prone to bending when it is installed. An inorganic and/or organic filler with excellent heat resistance and a larger particle size is more effective in preventing adhesion to a heated support in a heating furnace even when added in a relatively small amount. This is because the larger the particle size, the rougher the surface of the heat-resistant synthetic resin layer 2 and the smaller the contact area with the heated support. This is thought to be due to the arrangement of the inorganic and/or organic fillers with large particle sizes and excellent heat resistance, which prevents adhesion to the heated support. When the liquid synthetic resin composition for forming the heat-resistant synthetic resin layer 2 is the composition, the vinyl chloride resin paste composition contains 10 to 100 parts by weight of a plasticizer per 100 parts by weight of the vinyl chloride resin, 0.5 to 100 parts by weight of a compound crosslinked by ultraviolet irradiation or electron beam irradiation, an appropriate amount of stabilizer, and, if necessary, a polymerization initiator, photosensitizer, viscosity modifier, coloring agent, foam stabilizer, foaming agent, etc. It consists of an appropriate amount of an inorganic and/or organic filler with excellent heat resistance. If the amount of plasticizer is less than 10 parts by weight based on 100 parts by weight of the vinyl chloride resin, the heat-resistant synthetic resin layer 2 will become too hard and its low-temperature properties will deteriorate, making installation in winter difficult and undesirable. . Furthermore, if the amount of plasticizer exceeds 100 parts by weight per 100 parts by weight of vinyl chloride resin, not only will the heat-resistant synthetic resin layer 2 become extremely sticky, but also, especially when applied with a synthetic rubber latex adhesive, Since the plasticizer migrates to the synthetic rubber adhesive layer and the adhesive strength is significantly reduced, problems such as warping and peeling of the flooring material occur during practical use, which is not desirable. If the amount of the compound crosslinked by means of ultraviolet irradiation or electron beam irradiation is less than 0.5 parts by weight per 100 parts by weight of vinyl chloride resin, the degree of crosslinking is low and the support is heated in a heating furnace. It is impossible to achieve the intended purpose because it sticks to the target. In addition, the amount of compounds crosslinked by ultraviolet irradiation or electron beam irradiation is 100% of vinyl chloride resin.
If the amount exceeds 100 parts by weight, the degree of crosslinking will become too high and the heat-resistant synthetic resin layer 2 will become hard and brittle, making it impractical. When the liquid synthetic resin composition for forming the heat-resistant synthetic resin layer 2 is a composition of It consists of 150 to 950 parts by weight of an inorganic and/or organic filler with excellent heat resistance per 100 parts by weight, and, if necessary, appropriate amounts of a viscosity modifier, a coloring agent, etc. The amount of inorganic and/or organic fillers with excellent heat resistance depends on the amount of synthetic resin or synthetic rubber contained in the emulsion or latex.
If the amount is less than 150 parts by weight relative to 100 parts by weight, the heat-resistant synthetic resin layer 2 will stick to the heated support in the heating furnace, making it impossible to achieve the intended purpose. . In addition, the amount of inorganic and/or organic fillers with excellent heat resistance depends on the amount of synthetic resin or synthetic rubber contained in the emulsion or latex.
If the amount exceeds 950 parts by weight per 100 parts by weight, the heat-resistant synthetic resin layer 2 becomes brittle and the flooring material becomes easy to fold during construction, which is not preferable. When the liquid synthetic resin composition for forming the heat-resistant synthetic resin layer 2 is a composition of
10 to 100 parts by weight of a compound crosslinked by heating, ultraviolet irradiation, electron beam irradiation, etc., per 100 parts by weight;
It also contains appropriate amounts of polymerization initiators, photosensitizers, catalysts, viscosity modifiers, colorants, foam stabilizers, and inorganic and/or organic fillers with excellent heat resistance, as required. If the amount of the compound crosslinked by heating, ultraviolet irradiation, electron beam irradiation, etc. is less than 10 parts by weight per 100 parts by weight of the synthetic resin or synthetic rubber contained in the non-reactive liquid composition, etc. The degree of crosslinking of the heat-resistant synthetic resin layer is low and it sticks to the support while it is heated in the heating furnace, making it impossible to achieve the intended purpose. In addition, if the amount of the compound crosslinked by means such as heating, ultraviolet irradiation, or electron beam irradiation exceeds 100 parts by weight per 100 parts by weight of the synthetic resin or synthetic rubber contained in the emulsion or latex, the degree of crosslinking will decrease. If it becomes too high, the heat-resistant synthetic resin layer 2 will become hard and brittle, making it impractical. Additionally, the addition of inorganic and/or organic fillers with excellent heat resistance may improve adhesion to adhesives for floor construction. When the liquid synthetic resin composition for forming the heat-resistant synthetic resin layer 2 is a composition of It consists of appropriate amounts of a regulator, a foam stabilizer, a colorant, an inorganic and/or organic filler with excellent heat resistance, etc. The above reactive synthetic resin emulsion,
If the synthetic rubber latex or the like is self-crosslinking, it will crosslink alone to form the heat-resistant synthetic resin layer 2, but if the heat resistance is to be further improved, the addition of a crosslinking agent is effective. Additionally, the addition of inorganic and/or organic fillers with excellent heat resistance may improve adhesion to adhesives for floor construction. When the liquid synthetic resin composition for forming the heat-resistant synthetic resin layer is a composition of , a polymerization initiator, a photosensitizer, a catalyst, a colorant, an inorganic and/or organic filler with excellent heat resistance, etc., in appropriate amounts. The addition of an inorganic and/or organic filler with excellent heat resistance to the liquid compound that is crosslinked by means such as heating, ultraviolet irradiation, or electron beam irradiation may improve the adhesive properties of floor construction adhesives. . <Conditions for solidifying the liquid synthetic resin composition> The following methods are suitable for solidifying the liquid synthetic resin composition for forming the heat-resistant synthetic resin layer 2, but the present invention is not limited thereto. It's not something you can do. In the case of a composition of 120% of the liquid synthetic resin composition
Preheat at 180°C to 180°C for 30 seconds to 6 minutes to make it semi-solid, then heat at 180°C to 250°C for 30 seconds to 5 minutes to melt the vinyl chloride resin, or preheat as described above. It is preferable to heat the liquid synthetic resin composition at 180 DEG C. to 250 DEG C. for 30 seconds to 5 minutes to melt the vinyl chloride resin. In the case of the above composition as well, it is preferable that the vinyl chloride resin be melted by heating under the same conditions as the above composition, and then crosslinked by irradiation with ultraviolet rays or electron beams. In the case of a composition, the liquid synthetic resin composition is heated to 50℃.
It is preferable to heat dry at ~180°C for 30 seconds to 15 minutes. In the case of a composition, the liquid synthetic resin composition is heated to 50℃.
~100℃ after heating and drying at ~150℃ for 30 seconds ~ 15 minutes
The liquid synthetic resin composition is heated at 200°C for 30 seconds to 10 minutes to crosslink, or the liquid synthetic resin composition is heated at 100°C to 200°C for 30 minutes.
It is preferable to heat for 15 seconds to 15 minutes to effect crosslinking.
In the case of emulsions and latexes, if they are heated at high temperatures from the beginning, they tend to foam abnormally due to the influence of moisture, but if there are no such problems, the two-stage heating described above is preferable; The one-step heating method is efficient. In the case of a composition of 50%, the liquid synthetic resin composition is
It is preferred that the compound be crosslinked by heating and drying at 180°C for 30 seconds to 15 minutes and then irradiating it with ultraviolet rays or electron beams. In the case of the composition, it is preferable to carry out crosslinking under the same conditions as in the case of the above-mentioned composition. In the case of the composition, crosslinking is preferably carried out by heating at 50°C to 200°C for 30 seconds to 15 minutes. In the case of the composition, the liquid compound can be crosslinked and cured in a shorter time by irradiating the liquid compound with ultraviolet rays or electron beams. If this compound contains a dispersion medium such as water or a solvent, it is preferable to heat the compound in advance to remove the dispersion medium before irradiating it with ultraviolet rays or electron beams. Ultraviolet irradiation can be performed using a low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, or ultra-high pressure mercury lamp, and the ultraviolet irradiation time can be varied depending on the strength of the mercury lamp used. That is, when the intensity of the mercury lamp is strong, the irradiation time can be shortened, whereas when the intensity of the mercury lamp is weak, the irradiation time needs to be lengthened. Furthermore, when irradiating with ultraviolet rays, it is preferable that the liquid synthetic resin composition be transparent or semi-transparent, and it is difficult to irradiate ultraviolet rays with opaque compositions. When the liquid synthetic resin composition is opaque, it is preferable to perform electron beam irradiation. Furthermore, electron beam irradiation has a faster production rate than ultraviolet irradiation, and can crosslink even opaque synthetic resin compositions containing large amounts of fillers. It is more advantageous. <Thickness of the heat-resistant synthetic resin layer> Thickness of the heat-resistant synthetic resin layer 2 obtained by coating and impregnating the fibrous base material 1 with a liquid synthetic resin composition (the thickness of the heat-resistant synthetic resin layer 2 obtained by coating the fibrous base material 1 with a liquid synthetic resin composition) Thickness (thickness subtracting thickness of fibrous base material 1 from thickness of impregnated material) is
It is preferable to set it to 3.0m/m or less. When the liquid synthetic resin composition is filled and impregnated into the fibrous base material 1, the thickness of the heat-resistant synthetic resin layer 2 is as thick as described above and there is no particular problem, but the liquid synthetic resin composition is difficult to impregnate. , in the case of a brittle fibrous base material, such as an asbate sheet, the thickness of the heat-resistant synthetic resin layer 2 is 0.02
m/m or less, part of the asbestos sheet may remain on the base when the flooring material is removed, so in such cases, the heat-resistant liquid synthetic resin layer 2
The thickness is preferably 0.02 to 0.3 m/m.
There is no particular restriction on the upper limit of the thickness of the heat-resistant liquid synthetic resin layer 2, but if the thickness of the heat-resistant synthetic resin layer 2 exceeds 3.0 m/m, the resulting flooring material will be extremely thick. , which is inconvenient for construction and is not very desirable. In addition, from the viewpoint of reducing the weight of the flooring material itself, the heat-resistant synthetic resin layer 2 can be foamed, but if the foaming ratio is increased, the foamed layer will break when the flooring material is peeled off. To avoid destruction, it is preferable that the density of the foam layer is 0.2 g/cc or more. As a method for forming the foam layer, a method using a chemical foaming agent, a method using mechanical foaming, etc. can be used. - Soft synthetic resin intermediate layer <composition> The soft synthetic resin composition for forming the soft synthetic resin intermediate layer 3 used in the present invention may be any material as long as it can withstand use as a flooring material, but vinyl chloride It is common to use resin paste,
The vinyl chloride resin paste composition will be described below. The vinyl chloride resin paste composition for forming the soft synthetic resin intermediate layer is made of vinyl chloride resin 100%
It consists of 20 to 120 parts by weight of a plasticizer, an appropriate amount of a stabilizer, and, if necessary, an appropriate amount of a viscosity modifier, a foaming agent, a foam stabilizer, a coloring agent, a filler, a metal powder, etc. If the amount of plasticizer is less than 20 parts by weight based on 100 parts by weight of the vinyl chloride resin, the soft synthetic resin intermediate layer 3 will become too hard, resulting in poor low-temperature properties (especially flexibility at low temperatures) and poor performance in winter. This is not desirable as it makes construction difficult. On the other hand, if the amount of plasticizer exceeds 120 parts by weight per 100 parts by weight of vinyl chloride resin, the migration of the plasticizer from the soft synthetic resin intermediate layer 3 to the soft synthetic resin top layer 4 will increase, resulting in poor quality of the flooring material. This is not preferable since it has the drawback that the surface becomes extremely sticky and as a result, the floor material surface becomes more contaminated. Furthermore, it is advantageous in terms of construction and cost to foam the soft synthetic resin intermediate layer 3 unless there is a special reason. Foaming methods include adding a chemical foaming agent to the vinyl chloride resin paste and decomposing the chemical foaming agent by heating to form foam, and adding a foam stabilizer to the vinyl chloride resin paste to create a foam mechanically. , and a method of adding the vinyl chloride resin paste and a hollow balloon-like substance, and any of these methods can be used in the present invention. The amounts of the chemical foaming agent, foam stabilizer, and hollow balloon-like substance are adjusted as necessary. In addition, in order to improve the cigarette ignition resistance of the flooring material, it is necessary to increase the thermal conductivity of the soft synthetic resin intermediate layer 3, and in this case, the soft synthetic resin intermediate layer 3 should have a non-foamed structure. There is a need.
In this case, by adding an inorganic filler and/or a metal powder, etc., the thermal conductivity of the soft synthetic resin intermediate layer 3 is increased, and the cigarette flame resistance of the flooring material is considerably improved. The amount of the inorganic filler added is preferably 400 parts by weight or less per 100 parts by weight of the vinyl chloride resin.
Further, the amount of metal powder added is preferably 600 parts by weight or less per 100 parts by weight of the vinyl chloride resin. of course,
It is also possible to use metal powder as an inorganic filler. The amount of inorganic filler is vinyl chloride resin
If the amount exceeds 400 parts by weight compared to 100 parts by weight, the mechanical strength of the soft synthetic resin intermediate layer 3 will be weakened, making it weak against bending, and the weight of the flooring material itself will increase, resulting in poor workability. Undesirable. Also, the amount of metal powder is based on 100 parts by weight of vinyl chloride resin.
If it exceeds 600 parts by weight, the mechanical strength of the soft synthetic resin intermediate layer 3 will be weakened, making it weak against bending, increasing the weight of the flooring material, and impairing workability, which is not preferable. <Thickness of the soft synthetic resin intermediate layer> The thickness of the soft synthetic resin intermediate layer 3 is generally 0.05 m/
m to 4.00 m/m, but is not particularly limited to this range. However, if the thickness of the soft synthetic resin intermediate layer 3 exceeds 4.00 m/m, the resulting flooring material will be very thick, which is inconvenient for construction and is not very preferable. Further, the soft synthetic resin intermediate layer 3 may be a foamed layer or a non-foamed layer. However, if the soft synthetic resin intermediate layer 3 is made of a non-foamed layer, the weight of the flooring material will be heavy and transportation and construction of the flooring material will be inconvenient, so it is better to use a foamed layer unless there is a special reason. In addition, methods for forming a foam layer include a method using a chemical foaming agent and a method using mechanical foaming, but when performing chemical embossing, a method using a chemical foaming agent is required.
In other cases, mechanical foaming can also be used. ●Soft synthetic resin top layer <composition> The soft synthetic resin composition for forming the soft synthetic resin top layer 4 used in the present invention has excellent mechanical strength and is suitable for use as a top layer of flooring materials. Any material may be used as long as it is durable, but vinyl chloride paste is generally used, and the vinyl chloride resin paste composition will be described below. The vinyl chloride resin paste composition for forming the soft synthetic resin top layer 4 contains 10 to 100 parts by weight of a plasticizer, an appropriate amount of a stabilizer, and, if necessary, a viscosity of 100 parts by weight of a vinyl chloride resin. It comprises appropriate amounts of a modifier, a colorant, a filler, a compound crosslinkable by means such as ultraviolet irradiation or electron irradiation, and a photosensitizer. If the amount of plasticizer is less than 10 parts by weight based on 100 parts by weight of vinyl chloride resin, the soft synthetic resin top layer 4 will become too hard, the surface will be slippery as a flooring material, and the low-temperature properties (especially The flexibility at low temperatures deteriorates, making construction difficult in winter, which is not preferable. On the contrary, the amount of plasticizer is vinyl chloride resin
If the amount exceeds 100 parts by weight, the surface of the flooring material becomes extremely sticky, and as a result, the surface of the flooring material becomes seriously contaminated, which is not preferable. When printing is performed on the surface of the soft synthetic resin intermediate layer 4, the soft synthetic resin top layer 4 needs to be transparent or translucent; however, in other cases, the soft synthetic resin top layer 4 4 may be opaque, and in this case, it is more advantageous in terms of cost to use a filler. In addition, in order to improve the cigarette flame resistance of the flooring material, it is necessary to improve the heat resistance of the soft synthetic resin top layer 4, and in this case, it is necessary to improve the heat resistance of the soft synthetic resin top layer 4. It is necessary to add a crosslinking compound and, if necessary, a photosensitizer and the like to the vinyl chloride resin paste composition for forming the soft synthetic resin top layer 4. When the means for crosslinking the compound contained in the soft synthetic resin top layer 4 that is crosslinked by ultraviolet irradiation, electron beam irradiation, etc. is ultraviolet irradiation, it is better to use a photosensitizer in combination. When the means for crosslinking the compound is electron beam irradiation, there is no need to use a photosensitizer together. The amount of the compound crosslinked by means such as ultraviolet irradiation or electron beam irradiation is preferably 10 to 100 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount of the compound crosslinked by means such as ultraviolet irradiation or electron beam irradiation is less than 10 parts by weight per 100 parts by weight of vinyl chloride resin, the degree of crosslinking will be low and the cigarette flame resistance will be poor and the intended purpose will not be met. It is unattainable.
On the other hand, if the amount of the compound crosslinked by means such as ultraviolet irradiation or electron beam irradiation exceeds 100 parts by weight per 100 parts by weight of vinyl chloride resin, the degree of crosslinking will be too high and the surface of the flooring material will become too hard and slippery. Not only that, but the flooring also warps during use, making it impractical. <Thickness of the soft synthetic resin top layer> The thickness of the soft synthetic resin top layer 4 is 0.05~m/m~
2.00m/m is preferred. If the thickness of the soft synthetic resin top layer 4 is less than 0.05 m/m, the soft synthetic resin top layer 4 will quickly wear out due to people walking, etc., and the life of the flooring material will be shortened, so it is preferable. do not have.
Furthermore, if the thickness of the soft synthetic resin top layer 4 exceeds 2.00 m/m, the floor material itself becomes hard, which is inconvenient to install, and it is also prone to shrinkage or shrinkage, which is not very preferable. <Aspects of the soft synthetic resin top layer> The soft synthetic resin top layer 4 may be colorless and transparent, or transparent or opaque colored in any color. The layer 4 may contain monochromatic or multicolored synthetic resin powder, chips, lumps, etc. colored in any desired color. If the monochromatic or multi-colored synthetic resin powder, chips, or lumps colored in any color are transparent or translucent, they can be combined with the printed pattern on the surface of the soft synthetic resin intermediate layer 3 to form a mosaic. If the synthetic resin powder, chips, lumps, etc. are opaque and have a monochromatic or multi-colored color, the synthetic resin powder, chips, lumps, etc.
A unique design is expressed using lumps, etc. Furthermore, by imparting heat resistance to the soft synthetic resin top layer 4, even if a lit cigarette is left on the surface of the flooring material or a lit cigarette is smudged on the surface of the flooring material, the surface of the flooring material will remain intact. To provide a cigarette flame-resistant flooring material that does not discolor or cause scorch marks. A method for imparting heat resistance to the soft synthetic resin top layer 4 is to mix a soft synthetic resin composition with a compound that can be crosslinked by heating, ultraviolet irradiation, electron beam irradiation, etc., and then heat, ultraviolet irradiation, or electron beam irradiation. Although there are methods of crosslinking using UV irradiation or electron beam irradiation, methods of crosslinking using ultraviolet irradiation or electron beam irradiation are preferred from the viewpoint of crosslinkability. Further, when embossing is performed on the soft synthetic resin top layer 4, it is preferable to perform the embossing before irradiation with ultraviolet rays or electron beams. In order to improve the cigarette ignition resistance of the flooring material, as mentioned above, the soft synthetic resin top layer 4 is given heat resistance, and the soft synthetic resin intermediate layer 3 and the heat-resistant synthetic resin layer 2 are made of a non-foamed structure. It is preferable to mix a large amount of filler and/or metal powder to improve heat conduction with the floor material itself. ●Compounds and additives used in the present invention <vinyl chloride resin> Heat-resistant synthetic resin layer 2, soft synthetic resin intermediate layer 3,
The vinyl chloride resin used in the vinyl chloride resin paste composition for forming the soft synthetic resin top layer 4 includes commonly used emulsion polymerized vinyl chloride resins, suspension polymerized vinyl chloride resins, bulk polymerized vinyl chloride resins, etc. Vinyl chloride resin can be used. Also,
In addition to vinyl chloride homopolymer, vinyl acetate,
Copolymers of vinyl chloride and one or more of ethylene, alkyl ethers, acrylic esters, methacrylic esters, etc. can also be used, and these homopolymers and copolymers can be used alone or in combination. Also, other polymers can be blended with the vinyl chloride resins as described above. Examples of resins that can be blended include, but are not limited to, acrylonitrile-butadiene copolymer, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, and acrylic resin. <Plasticizer> As the plasticizer, commonly used plasticizers can be used, examples of which are listed below. Examples of phthalate ester plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, didodecyl phthalate, butyl benzyl phthalate, dimethyl glycol phthalate, and ethyl phthalyl ethyl. Glycolate, methyl phthalyl ethyl glycolate, butylphthalyl butyl glycolate, diisodecyl phthalate, etc. are used. Examples of phosphorous ester plasticizers include tributyl phosphate, tricresyl phosphate, triphenyl phosphate, trichloroethyl phosphate, trioctyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, arylalkyl phosphate, Diphenyl monoorthoxenyl phosphate and the like are used. Examples of fatty acid ester plasticizers include methyl acetyl ricinolate, dioctyl adipate, dioctyl azelate, dibutyl sebacate, dioctyl sebacate, triacetyl blycerin, glycerol butyrate, diisodecyl succinate, diisodecyl adipate, succinic acid mixed alkyl ester, etc. is used. In addition, trimellitic acid ester plasticizers such as trioctyl trimellitic acid, epoxy plasticizers such as epoxidized soybean oil and various epoxy resins, polyester polymer plasticizers, etc. can also be used. Furthermore, for the purpose of reducing the viscosity of the vinyl chloride resin paste, small amounts of viscosity modifiers such as gasoline, octane, benzene, toluene, naphtha,
A volatile diluent such as a dodecylbenzene derivative or a viscosity reducing agent such as various surfactants may be used in combination with the plasticizer. <Stabilizer> Any stabilizer that is normally used for vinyl chloride resin can be used. Specifically, in addition to metal stabilizers such as cadmium, zinc, barium, calcium, strontium, aluminum, magnesium, cerium, sodium, lead, and tin,
Organic phosphorus compounds, polyhydric alcohols, epoxy compounds, etc. can be used alone or in combination of two or more. The amount of the stabilizer added is preferably 0.1 to 10 parts by weight per 100 parts by weight of the vinyl chloride resin. <Synthetic resin emulsion, synthetic rubber latex> Any commonly used synthetic resin emulsion or synthetic rubber latex can be used as the non-reactive synthetic resin emulsion or synthetic rubber latex. Specifically, vinyl chloride resin emulsion, vinyl chloride-ethylene copolymer emulsion, vinyl chloride-vinylidene chloride copolymer emulsion, vinyl chloride-vinyl acetate copolymer emulsion, vinylidene chloride resin emulsion, vinyl acetate resin emulsion, and acetic acid. Synthetic resin emulsion such as vinyl-acrylic copolymer emulsion, ethylene-vinyl acetate copolymer emulsion, acrylic resin emulsion, acrylic-styrene copolymer emulsion, urethane resin emulsion, or SBR latex, NBR latex, CR latex, IIR Synthetic rubber latex such as latex can be used. These may be used alone or in combination of two or more. In addition to the above emulsions and latexes, solutions of synthetic resins and synthetic rubbers dissolved in organic solvents or water can also be used in the same way as the above emulsions and latexes. Any commonly used synthetic resin emulsion or synthetic rubber latex can be used, but specifically, reactive groups such as carboxyl groups, hydroxyl groups, and amide groups are introduced into the emulsion or latex polymer. Products that are heat-crosslinked by adding an initial condensate of melamine or urea as a crosslinking agent, or products that have reactive groups such as glycidyl groups or methylol groups introduced into emulsions or latex polymers, such as acrylic esters or methacrylic esters. An emulsion obtained by copolymerizing the main component with glycidyl acrylate or glycidyl methacrylate and tert-butyl or amyl acrylate, or an emulsion obtained by copolymerizing styrene acrylate and acrylamide and then adding methylol Self-crosslinking emulsions and latexes such as emulsions obtained by oxidation can be used. Reactive synthetic resin emulsions and synthetic rubber latexes include acrylic resin emulsions, vinyl acetate resin emulsions, vinyl acetate-acrylic copolymer emulsions, vinyl chloride-vinyl acetate copolymer emulsions, SBR latexes, NBR latexes, CR latexes, etc. It is raised. These may be used alone or in combination of two or more. It is also possible to use these reactive synthetic resin emulsions and synthetic rubber latexes in combination with the non-reactive synthetic resin emulsions and synthetic rubber latexes.
In addition to the above-mentioned emulsions and latexes, solutions of synthetic resins and synthetic rubbers having the above-mentioned reactive groups dissolved in organic solvents or water can also be used in the same manner as the above-mentioned emulsions and latexes. <Compounds that crosslink by heating, ultraviolet rays, or electron beam irradiation> The following compounds can be used as compounds that crosslink by heating, ultraviolet irradiation, or electron beam irradiation, but the present invention is not limited to these in any way. isn't it. ethylene glycol, propylene glycol,
Aliphatic polyhydric alcohols such as butylene glycol, 1,6-hexanediol, neohentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, trimethylolmethane, glycerin, pentaerythritol, dipentaerythritol, and acrylic acid or methacrylic acid. Acrylic polyfunctional compound obtained from; triallylisocyanurate, tris-
Isocyanurate derivatives such as (2-methacryloyl, oxyethyl)-isocyanurate; bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, etc. containing at least two or more epoxy groups in one molecule. An acrylic modified epoxy resin obtained from an epoxy compound and an unsaturated monobasic acid; a reactive product of a polyvalent cycloacetal compound and a glycol unsaturated monocarboxylic acid monoester or a polyhydric alcohol unsaturated monocarboxylic acid ester monool; There are certain unsaturated cycloacetal resins; acrylic-modified polyester resins such as oligoester acrylate; acrylic-modified polyurethane resins; unsaturated polyester resins; diallyl phthalate, etc., and these may be used alone or in combination of several kinds. Furthermore, monofunctional monomers such as styrene monomers, methacrylic acid ester monomers, and acrylic ester monomers may be used in combination with the above-mentioned polyfunctional compounds as reactive thinning agents. The amount of the polyfunctional compound added is preferably 10 to 100 parts by weight per 100 parts by weight of the resin. <Heavy Initiator, Catalyst> As the polymerization initiator, commonly used ones can be used. For example, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide,
t-Butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl 2,5-di(t-
butylperoxy)hexane, 2,5 dimethyl 2,5-(t-butylperoxy)hexane,
1,3-bis(t-butylperoxyisopropyl)benzene, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane,
n-butyl 4,4-bis(t-butylperoxy)valate, benzoyl peroxide, p-
Organic peroxides such as chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butyl peroxybenzoate, and t-butyl peroxyisopropyl carbonate are common, and these can be used alone or in combination of two or more. and use it. Further, as the catalyst, amines such as dimethylaniline and dimethyl para-toluidine, and metal compounds such as cobalt naphthenate and zinc naphthenate are generally used. The amount of polymerization initiator added is 0.5 to 10% of the polyfunctional compound.
Weight % is appropriate. <Photosensitizer> As the photosensitizer, commonly used ones can be used. For example, benzoin, α-methylbenzoin, α-allylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, benzophenone, p-bromobenzophenone, 4,4′ -tetramethyldiaminobenzophenone, diphenyl disulfide, benzyl, etc., and these can be used alone or in combination of two or more. The amount of photosensitizer added depends on the amount of the polyfunctional compound.
0.5% to 10% by weight is suitable. Furthermore, when the polyfunctional compound is crosslinked by electron beam irradiation, it is not necessary to use a photosensitive agent or the like. <Crosslinking agent> Polyhalogenated synthetic resin compositions of the above-mentioned polyfunctional compounds, such as vinyl chloride resin, copolymers of vinyl chloride and vinyl acetate, ethylene, alkyl ethers, acrylic esters, methacrylic esters, etc., vinylidene chloride When using a synthetic resin composition such as resin or chloroprene rubber, 2-dibutylamino-4,6-dithiocyanuric acid, 2-dicyclohexylamino-4,6-
dithiocyanuric acid, 2-dibenzylamino-4,
6-dithiocyanuric acid, 2-diphenylamino-
4,6-dithiocyanuric acid, 2-anilino-4,
A crosslinking agent such as 6-dithiocyanuric acid or a metal salt of such a dithiocyanuric acid derivative, and, if necessary, an acid acceptor such as magnesium oxide, calcium oxide, zinc oxide, barium oxide, lead oxide, calcium carbonate, and the like. , a crosslinking accelerator, etc. can also be added. The amount of the crosslinking agent added is preferably 0.5 to 20 parts by weight based on 100 parts by weight of the halogenated synthetic resin. As a crosslinking agent that is added to synthetic resin emulsion or synthetic rubber latex as necessary, an initial condensate of melamine or urea is used, but the present invention is not limited to these in any way. . <Fillers with excellent heat resistance> Inorganic and/or organic fillers with excellent heat resistance basically do not undergo physical or chemical changes such as melting or decomposition at processing temperatures. You can use anything you want, but here's an example. Calcium carbonate, magnesium carbonate, clay, talc, silica, diatomaceous earth, silica sand, pumice powder, slate powder, mica powder, asbestos, aluminum hydroxide, aluminum oxide, aluminum sulfate, barium sulfate, potassium sulfate, glass bulbs, foaming Inorganic fillers such as glass bulbs, fly ash bulbs, volcanic glass hollow bodies (shirasu balloons), powdered cellulose (cellulose powder), polyvinyl alcohol fibers,
Organic fillers such as cork powder, wood flour, thermosetting resin powder, thermosetting resin hollow spheres, etc. can be used. <Chemical foaming agent> As the chemical foaming agent used in the present invention, commonly used chemical foaming agents can be used, and examples thereof are listed below. N,N'-dinitrosopentamethylenetetramine, N,N'-dimethyl-N,N'-dinitrosoterephthalamide, azodicarbonamide, azobisisobutyronitrile, benzelsulfonylhydrazide, P,P'-oxybis( benzenesulfonylhydrazide), benzene-1,3-disulfonylhydrazide, toluenesulfonylhydrazide, and the like. <Foam stabilizer> When forming a foam layer by mechanical foaming, it is preferable to use a foam stabilizer, but any commonly used formulation agent can be used, such as methylsiloxane emulsion, Silicone foam stabilizers such as methylsiloxane and xylene solutions, fluorine foam stabilizers, fatty acid condensates, alkylaryl sulfonates, metal soaps of oleic acid and ricinoleic acid, guanidine salts, quaternary ammonium compounds, aldehyde-amines condensation products etc. are used. <Viscosity modifier> Viscosity modifiers are broadly classified into thinners and thickeners.
As the viscosity reducing agent, commonly used ones can be used, examples of which are listed below. If the liquid synthetic resin composition is an oil dispersion system such as vinyl chloride resin plastisol or a solution of synthetic resin or synthetic rubber dissolved in an organic solvent, gasoline, octane, benzene, toluene, xylene, naphtha, dodecylbenzene derivatives, methyl ethyl ketone, Volatile diluents such as methyl isobutyl ketone, various surfactants, etc. are used, and when the liquid synthetic resin composition is an aqueous dispersion system such as a synthetic resin emulsion, synthetic rubber latex, or an aqueous solution of synthetic resin or synthetic rubber, Alcohols such as water, methanol, ethanol, and isopropyl alcohol are used. In addition, commonly used thickeners can be used, examples of which are listed below. When the liquid synthetic resin composition is an oil dispersion system as described above, metal soaps such as aluminum stearate, aluminum oleate, zinc stearate, silica, bentonite, polymerized oil, etc. are used. In the case of water dispersion systems such as silica, bentonite, chemically modified precipitated calcium carbonate, ammonium salts of polymeric organic acids, water-soluble acrylic polymers, acrylic emulsion copolymers, crosslinked acrylic emulsion copolymers,
Ammonium, polymethacrylate, ammonium polyacrylate, sodium polyacrylate, modified sodium polyacrylate, partially oxidized polyacrylic ester, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose sodium glycolate, polyvinyl alcohol, aqueous ammonia, etc. are used. can. When adjusting the viscosity of the liquid synthetic resin composition to a viscosity suitable for processing, these viscosity modifiers are added in appropriate amounts as necessary. (Examples) Examples are given below to explain the present invention in more detail, but the present invention is not limited to these Examples. Formulation Examples Typical formulation examples and comparative formulation examples of liquid synthetic resin compositions for forming the heat-resistant synthetic resin layer 2 are shown in the table below.
1 and Table 2. Table 3 shows typical blending examples of the vinyl chloride resin composition for forming the soft synthetic resin intermediate layer 3, and further shows typical formulation examples of the vinyl chloride resin composition for forming the soft synthetic resin top layer 4. Examples of formulations are listed in Table 4. In addition, an example of production to obtain the acrylic modified polyester resin used in Tables 1 and 4 below is shown. That is, 304 g of tetrahydrophthalic anhydride, 318 g of diethylene glycol, 144 g of acrylic acid,
2000 c.c. of toluene, 98% sulfuric acid in an amount equivalent to 2.5% by weight relative to the total amount excluding toluene, and phenothiazine in an amount equivalent to 0.08% by weight relative to acrylic acid were added, and the mixture was stirred at approximately 110°C. Tsutsu,
Water produced by the esterification reaction was flowed out of the system as an azeotrope with toluene. After about 8 hours, almost the theoretical amount of water flowed out, so the reaction was stopped and the reactor was cooled. The obtained reaction solution was mixed with 3% by weight ammonia.
After washing with 1200 c.c. of an aqueous solution containing 20% by weight of ammonium sulfate, and subsequently washing with an aqueous solution containing 20% by weight of ammonium sulfate, 0.1g of hydroquinone was added to the toluene layer and the toluene was removed at 50°C under a reduced pressure of 6 mmHg. Then, acrylic modified polyester resin C was obtained. The obtained acrylic modified polyester resin C is a pale yellow liquid with a viscosity of 4250 centipoise (25°C) and an acid value of 0.18.
The acryloyl group equivalent was 347.

【table】

【table】

【table】

【table】

[Table] Example 1 On glass fiber paper with a dense fiber structure of 0.25 m/m, the vinyl chloride resin paste of Formulation Example 1 was applied to a thickness of 0.20 m/m using a doctor knife coater, and the paste was coated in a heating furnace. Heat and solidify at 200°C for 2 minutes to form a heat-resistant synthetic resin layer, cool and then roll up. and,
Apply the vinyl chloride resin paste of Formulation Example 7 to a thickness of 0.05 m/m using a doctor knife coater on the side opposite to the applied side of the above vinyl chloride resin paste, and harden by heating at 180°C for 1 minute in a heating oven. After that,
After printing a predetermined pattern on this surface using a gravure printing machine, the vinyl chloride resin paste of Formulation Example 9 was applied to a thickness of 0.03 m/m using a doctor knife coater, and the mixture was heated in a heating furnace at 200°C for 3 minutes. Heat and foam,
After cooling, it was rolled up to obtain a flooring material with a total thickness of 2.0 m/m. At this time, the heat-resistant synthetic resin layer formed from the vinyl chloride resin paste of Formulation Example 1 was
Even when it came into contact with the support heated to 200° C. in the heating furnace, it did not stick to it and easily passed through the heating furnace to obtain the above-mentioned flooring material. This flooring material was pasted on plywood using a synthetic rubber latex adhesive, dried for about a week, and then peeled off. As a result, it was confirmed that it could be peeled off cleanly from the interface between the heat-resistant synthetic resin layer and the adhesive layer. done. Also, cut this flooring material into a size of 200m/m x 200m/m, and
It was pasted on a 300m/m x 300m/m plywood board using a synthetic rubber latex adhesive, dried at room temperature for 7 days, and then left at a temperature of 70°C for 200 hours.
As a result of checking whether the flooring material is warped or not,
No warping was observed, and it was confirmed that this flooring material had the basic characteristics required as a removable flooring material. The test results are shown in Table-5. Example 2 The vinyl chloride resin paste of Formulation Example 2 was applied to a thickness of 0.20 m/m using a doctor knife coater on glass fiber paper with a dense fiber structure of 0.25 m/m.
After heating and solidifying in a heating furnace at 200℃ for 2 minutes,
Using three 80W/cm high-pressure mercury lamps, irradiation distance 15
Ultraviolet rays are irradiated at a speed of 6 m/min to form a heat-resistant synthetic resin layer and the film is wound up. Then, the vinyl chloride resin paste of Formulation Example 7 was applied to the surface opposite to the surface to which the above-mentioned vinyl chloride resin paste was applied, using a doctor knife coater to a thickness of 0.5 m/m, and heated in a heating path at 180°C for 1 minute. After solidification, a predetermined pattern was printed on the surface using a gravure printing machine, and then the vinyl chloride resin paste of formulation row 9 was applied to a thickness of 0.30 m/m using a doctor knife coater, and then heated to a thickness of 200 m/m in a heating furnace. The mixture was heated and foamed at ℃ for 3 minutes, cooled, and then rolled up to obtain a flooring material with a total thickness of 2.0 m/m. At this time, the heat-resistant synthetic resin layer formed from the vinyl chloride resin paste of Formulation Example 2 easily passes through the heating furnace without sticking to the support heated to 200°C in the heating furnace. We were able to obtain the above flooring material. This flooring material was tested for releasability and warping in the same manner as in Example 1, and it was confirmed that this flooring material had the basic performance necessary as a removable flooring material. The test results are in Table-5
Shown below. Examples 3 to 6 The self-crosslinking synthetic resin emulsions or self-crosslinking synthetic rubber latexes of Blend Examples 3 to 6 were placed on coarse glass fiber paper with a fiber structure of 0.22 m/m, and the total thickness after drying was 0.4 m/m. Coat with a doctor knife coater until the film is coated, heat dry at 140°C for 5 minutes to form a heat-resistant synthetic resin layer, and roll up. Then, the vinyl chloride resin paste of Formulation Example 7 was applied to a thickness of 0.5 m/m on the side opposite to the applied side of the synthetic resin emulsion or synthetic rubber latex, and the paste was placed in a heating oven.
After heating and solidifying at 180°C for 1 minute, printing was performed in the same manner as in Example 1, and then the vinyl chloride resin paste of Formulation Example 9 was applied to the surface at a thickness of 0.3 m/m,
A flooring material was created under the same conditions as in Example 1. The heat-resistant synthetic resin layer formed from the above synthetic resin emulsion or synthetic rubber latex is
Even when it came into contact with a support heated to 200°C, it did not stick to the support and easily passed through the heating furnace, yielding the above-mentioned flooring material. Example 1 about this flooring material
As a result of testing for removability and the presence of warpage using the same method as above, it was confirmed that this flooring material had the basic performance required as a removable flooring material. The test results are shown in Table-5. Example 7 The self-crosslinking acrylic resin emulsion of Formulation Example 4 was coated on glass fiber paper with a coarse fiber structure of 0.3 m/m using a doctor knife coater so that the total thickness after drying was 0.4 m/m. A heat-resistant synthetic resin layer was formed and wound up under the same conditions as in Examples 3 to 6.
Then, the vinyl chloride resin paste of Formulation Example 8 was applied to the surface opposite to the applied surface of the self-crosslinking type acrylic resin emulsion at a thickness of 1.3 m/m, and was heated and solidified in a heating oven at 180° C. for 1 minute. After that, a predetermined pattern is printed on this surface using a gravure printing machine,
Apply the vinyl chloride resin paste of Formulation Example 10 to a thickness of 0.3 m/m using a doctor knife coater, heat and melt in a heating furnace at 200°C for 3 minutes, emboss with a specified aperture, and then apply 80W. / cm high-pressure mercury lamps, three lamps were used to irradiate ultraviolet rays at a speed of 3 m/min at an irradiation distance of 15 cm to form a heat-resistant vinyl chloride resin top layer and obtain a flooring material with a total thickness of 2.0 m/m. .
At this time, the heat-resistant synthetic resin layer formed from the self-crosslinking acrylic resin emulsion of Formulation Example 4 does not stick easily even when it comes into contact with the support heated to 200°C in the heating furnace. It passed through a heating furnace, and the above-mentioned flooring material could be obtained. This flooring material was tested for releasability and warping in the same manner as in Example 1, and as a result, it was confirmed that this flooring material had the basic performance necessary as a removable flooring material. In addition, as a result of conducting the following cigarette rubbing test and cigarette leaving test on this flooring material,
It was confirmed that it has excellent resistance to cigarette flames. <Tobacco fire resistance test method> Cigarette rubbing test Rub a lit cigarette on the surface of the flooring material, extinguish it,
Observe the flooring surface for discoloration and damage. Evaluation was performed according to the following criteria. Grade 5: No damage or discoloration to the flooring surface. Grade 4: No damage to the flooring surface, discoloration to light yellow. Grade 3: No damage to the flooring surface, partial black discoloration. Grade 2: Partial dents, overall black discoloration. Grade 1 Severe burn damage, overall black discoloration Cigarette storage test A lit cigarette was left on the surface of the flooring material, and the time until scorch marks appeared on the flooring material was measured. The longer the time, the better the cigarette flame resistance. Comparative Examples 1 to 2 The vinyl chloride resin paste of Comparative Formulation Examples 1 to 2 was applied to a thickness of 0.20 m/m using a doctor knife coater on glass fiber paper with a dense fiber structure of 0.25 m/m, and then heated in a heating furnace. Heat and solidify at 200°C for 2 minutes to form a synthetic resin layer, cool and then roll up. Then, the vinyl chloride resin paste of Formulation Example 7 was applied to the surface opposite to the surface to which the vinyl chloride resin paste was applied at a thickness of 0.5 m/m using a doctor knife coater, and heated at 180°C for 1 minute in a heating furnace. After heating and solidifying, a predetermined pattern was printed on the surface using a gravure printing machine, and then the vinyl chloride resin paste of Formulation Example 9 was applied to a thickness of 0.30 m/m using a doctor knife coater, and then heated in a heating furnace. When heated at 200℃ for 3 minutes,
When the synthetic resin layer formed from the vinyl chloride resin paste of Comparative Formulation Example 1 comes into contact with the support heated to 200°C in the heating furnace, it sticks to the support, and the foamed material is foamed in the heating furnace. It was not possible to obtain the desired flooring material by cutting. Comparative Example 3 The ethylene-vinyl acetate copolymer emulsion of Comparative Formulation Example 3 was coated on glass fiber paper with a coarse fiber structure of 0.22 m/m using a doctor knife coater so that the total thickness after drying was 0.3 m/m. The resin layer is applied by heating and drying in a heating oven at 80°C for 10 minutes to form a synthetic resin layer, and after cooling, it is rolled up. Then, the vinyl chloride resin paste of Formulation Example 7 was applied to the surface opposite to the applied surface of the ethylene-vinyl acetate copolymer emulsion to a thickness of 0.55 m/m using a doctor knife coater, and heated to a thickness of 180 m/m in a heating furnace. When attempting to solidify by heating at ℃, the synthetic resin layer formed from the ethylene-vinyl acetate copolymer of Comparative Formulation Example 3 was heated to 180℃ in the heating furnace.
When it comes into contact with a support heated to ℃, it sticks to it,
It was not possible to obtain the desired flooring material by cutting it in the heating furnace. Comparative Example 4 The vinyl chloride resin paste of Formulation Example 7 was coated on 0.8 m/m asbestos paper with a thickness of 0.3 m/m using a doctor knife coater, and after solidifying by heating at 180°C for 1 minute in a heating furnace, After printing a predetermined pattern on this surface using a gravure printing machine, the vinyl chloride resin paste of Formulation Example 9 was applied to a thickness of 0.30 m/m using a doctor knife coater, and heated to 200°C in a heating furnace.
The material was heated for 3 minutes to create a flooring material. As a result of testing the removability of this flooring material in the same manner as in Example 1, it was found that a thick asbestos layer remained partially on the base.
The base was so uneven that it was impossible to construct a flooring material on top of it, and it could not be said to be a removable flooring material. Further, in order to compare the cigarette flame resistance of this flooring material with the flooring material prepared in Example 7, a test was conducted in the same manner as in Example 7, and as a result, it was confirmed that the cigarette flame resistance was poor.

【table】

[Table] (Effects) In the present invention, by coating and impregnating the fibrous base material 1 with a liquid synthetic resin composition, the fibrous base material 1 is integrated with the liquid synthetic resin composition, and further, the fibrous base material 1 is integrated with the liquid synthetic resin composition. The method of solidifying the liquid synthetic resin composition is by heating, ultraviolet irradiation, or electron beam irradiation, and since there is almost no internal distortion during processing, it is difficult to use the flooring material as described in Japanese Patent Publication No. 47-41848 in practical use. There are no problems such as peeling between the eyebrows or deterioration of the dimensional stability of the flooring material due to internal distortion during bonding of the dense soft plastic layer containing a large amount of filler. Furthermore, as a liquid synthetic resin composition to be applied and impregnated onto the fibrous base material 1, it can be used as an adhesive for flooring construction to adhere to the base to such an extent that no peeling occurs during practical use, and when the flooring material is to be peeled off, Since a material that peels off at the interface between the adhesive and the heat-resistant synthetic resin layer 2 obtained by solidifying the liquid synthetic resin composition is used, there are no problems such as peeling during practical use of the flooring material. Additionally, the laminated flooring material of the present invention has the advantage that the base material does not remain on the floor surface compared to conventional flooring materials based on asbestos sheets, and re-installation is easy. It is.

[Brief explanation of drawings]

The figure is an enlarged sectional view showing an embodiment of the present invention. 1... Fibrous base material, 2... Heat resistant synthetic resin layer,
3... Soft synthetic resin intermediate layer, 4... Soft synthetic resin top layer, 5... Printing layer.

Claims (1)

[Scope of Claims] 1. A heat-resistant synthetic resin layer formed by coating and impregnating a liquid synthetic resin composition on one side of a fibrous base material and solidifying it, and a soft synthetic resin intermediate layer and a soft synthetic resin on the other side. The laminated flooring is made by sequentially laminating top layers, and the heat-resistant synthetic resin layer has adhesive strength with the base adhesive in the range of 0.3 to 5 kg/2cm width, and the laminated flooring has A laminated flooring material characterized by having a layer that peels off at the interface with the adhesive on the base side when it is peeled off from the base.