JPH01294031A - Slip-proof sheet - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a sheet-like article with extremely improved durability and significantly improved anti-slip properties.

[Problems to be solved by conventional techniques and inventions] Conventionally,
Methods of imparting anti-slip properties to sheet-like articles such as covers, sheets, mats, etc. and preventing the sheets from shifting or disarranging include printing or applying an anti-slip agent such as latex to the sheets, or using a soft binder and silica powder. A method of applying and drying a dispersion of colloidal silica
107597), when applying a soft binder,
Alternatively, a method of forming irregularities or protrusions by physical manipulation after coating is known. Although the products obtained by these methods have some degree of anti-slip properties, they have the drawbacks of being sticky, blocking, and the anti-slip layer easily coming off, so they are not practical anti-slip sheets depending on the application. It was hard to say.

On the other hand, by providing a foam coating material containing microspheres that expand with heat on the base material, cushioning properties, sound insulation,
Proposals have been made to add functions such as heat insulation and anti-slip properties (
For example, JP-A-49-32966, JP-A-62-
No. 60638, etc.), a coating material with particularly excellent anti-slip properties that can be used practically has not yet been found, and also has the disadvantage that the microspheres expanded by heat are easily destroyed or detached, making it impractical. It was difficult to say that the sheet was a good anti-slip sheet.

In addition, in the method of fixing with adhesive, hook-and-loop fastener, string, etc. in order to provide anti-slip properties, it is difficult and complicated to determine the correct position during use, and there are also problems in terms of manufacturing cost. It was a disadvantage.

[Means for Solving the Problems] Under the above circumstances, the present inventors have conducted intensive studies on sheet-like articles with excellent slip resistance and improved durability. A polymer binder with a crosslinked structure and specific physical properties and heat-foamable polymer beads are applied to a part of the part in the form of a continuous film or a discontinuous pattern, and then the polymer beads are heated and foamed. By forming one coating layer and then recoating a polymer with specific physical properties on the first coating layer to form a second coating layer, the anti-slip property is dramatically improved, and it is suitable for continued practical use. The inventors have also discovered that a suitable sheet can be obtained in which the microspheres expanded by heat do not break or come off, the anti-slip properties are maintained, and the durability is extremely improved, and the present invention has been achieved.

That is, the present invention has a crosslinked structure on at least a portion of the sheet surface, a glass transition temperature of 30°C or less, and a breaking strength of 7.
~200 kg/cta2, has a first coating layer consisting of a polymer binder with an elongation rate of 200% or more and a foam of thermally foamable polymer beads, and further has a first coating layer made of a polymer having a glass transition temperature of 30°C or less on the first coating layer. The present invention provides an anti-slip sheet characterized by having a second coating layer.

Furthermore, the present invention has a crosslinked structure on at least a portion of the sheet surface, a glass transition temperature of 30°C or less, and a breaking strength of 7 to 7.
200 kg/c+w", a polymer binder with an elongation rate of 200% or more and heat-foamable polymer beads are applied, and the polymer beads are heated to a temperature higher than the foaming temperature of the polymer beads to foam them to form a first coating layer, and The present invention also provides a method for producing an anti-slip sheet, characterized in that a second coating layer made of a polymer having a glass transition temperature of 30° C. or less is provided on the first coating layer.

Various polymers can be used as the polymer binder used in the first coating layer and the polymer used in the second coating layer of the present invention, as long as they have the above-mentioned physical properties.
For example, acrylic resins that are polymers or copolymers of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, etc. , styrene-butadiene rubber (SBR), carboxy-modified SBR,
Examples include synthetic rubbers such as nitrile-butadiene rubber (NBR) and butadiene rubber (BR), as well as polyurethane resins, polyvinyl chloride resins, and polyvinylidene chloride resins.

As a method for introducing a crosslinked structure, any known method can be used as appropriate, such as a method using a crosslinking agent such as a polyfunctional compound, a metal compound, or a peroxide, or a method of irradiating active energy rays.

The polymer binder used in the first coating layer must have a crosslinked structure, but the polymer used in the second coating layer may or may not have a crosslinked structure. Furthermore, if a resin with adhesive properties is used as the polymer, the resulting sheet will have both anti-slip properties and adhesive properties.

The above resins can be used alone or in combination of a plurality of resins. These resins can be used in the form of an emulsion dispersed in water or a solution dissolved in an organic solvent. Emulsifiers and organic solvents used to obtain these forms may be those that are generally known, and they may be produced using known methods.

In order to lower the glass transition temperature of the Bolimano 1 inder used in the first coating layer of the present invention and the polymer used in the second coating layer to 30°C or less, a plasticizer or the like is added to the above resin as necessary. You can also do that.

The heat-expandable polymer beads used in the present invention are bead-like objects whose shell walls are made of thermoplastic resin and which contain low-boiling compounds such as butane and isopentane inside.The resin softens when heated, It also refers to a compound that foams because the low-boiling point compound is gasified and converted into pig intestines. Any form may be used, and for example, those commercially available in the form of an aqueous dispersion, such as the product name Matsumoto Microspheres (manufactured by Matsumoto Yushi Pharma Co., Ltd.), can be used. The particle size of these heat-expandable polymer beads can be freely controlled by the manufacturing method, but for the purpose of the present invention,
A thickness of 300μ is preferred, and a diameter of 5 to 200μ is particularly preferably used.

In addition, the expansion ratio during heating and foaming can be controlled freely depending on the bead manufacturing method, but it is usually 2 to 7 times (
diameter ratio).

Small beads with a particle size of less than 3 μm make little contribution to improving the anti-slip properties even when heated and foamed, and beads with a particle size of more than 300 μm are undesirable because they tend to fall off due to friction after being heated and foamed.

In the present invention, the polymer binder and heat-expandable polymer beads used in the first coating layer are mixed together and then applied onto the sheet surface.

When mixing both, it is also possible to add a thickener, preservative, etc. to improve the stability, printability, coating suitability, etc. of the mixture.

After applying these on the sheet surface, a first coating layer is formed on the sheet surface by performing preliminary drying and heat foaming treatment as described later.

Subsequently, a polymer having a glass transition temperature of 30° C. or less is applied onto the sheet surface on which the first coating layer has been formed. It is also possible to add thickeners, preservatives, etc. to improve the stability, printability, coating suitability, etc. of this polymer. Thereafter, a drying process is performed to form a first covering layer, which is a foamed covering layer, and a second covering layer, which is a protective covering layer, on the sheet surface.

One of the features of the present invention is that the polymer binder used in the first coating layer has physical properties such as a glass transition temperature of 30°C or less, a breaking strength of 7 to 200 kg/co+", and an elongation of 200% or more. A more preferable range is that the glass transition temperature is 0°C or less and the breaking strength is 10 to 150 kg/
c+w”, the elongation rate is 300% or more.

When the glass transition temperature exceeds 30° C., it is necessary to increase the pre-drying temperature considerably, which may cause cracks in the polymer binder film or foaming of the heat-expandable polymer beads during the pre-drying. The desired anti-slip properties cannot be obtained.

Furthermore, if the breaking strength is less than 7 kg/cm2, the polymer binder coating is likely to be destroyed by frictional force, making it difficult to immobilize the polymer beads. On the other hand, if the breaking strength exceeds 200 kg/cm'' or the elongation rate is less than 200%, the polymer binder film is high strength or rigid, making it difficult to moderate the frictional force suitably and causing the polymer beads to break. Or, it may become slippery, both of which are undesirable.

Another feature of the present invention is that a polymer having a glass transition temperature of 30° C. or less, preferably 0° C. It is to have a second coating layer coated.

The glass transition temperature of the polymer used for the second coating layer is 3.
If the temperature exceeds 0°C, it is necessary to increase the drying temperature considerably, which may cause cracks in the polymer coating or damage to the already foamed thermal foam contained in the first coating layer previously applied during drying. This results in re-foaming of the plastic polymer beads, making it impossible to obtain the desired anti-slip properties.

In the present invention, the sheets on which the first coating layer and the second coating layer are applied include nylon, acrylic, polyester, polyethylene, polypropylene, polyvinyl chloride,
Woven fabrics, non-woven fabrics, paper, laminated non-woven fabrics or films made of polyvinylidene chloride, cotton, wool, rayon, pulp, vinylon, acetate, etc. can be mentioned, and these sheet-like base materials can also be textured by embossing or the like. can also be used.

Further, in the present invention, the weight ratio (in terms of solid content) of the polymer binder and the heat-expandable polymer beads used in the first coating layer is preferably 95:5 to 40:60, particularly 95:5 to 40:60.
0:10 to 50:50 is preferred. If the amount of polymer binder is greater than the above range, the coating will have less unevenness due to foaming of the polymer beads, resulting in poor anti-slip performance. On the other hand, if the amount of the polymer binder is less than the above range, it becomes difficult to fix the heat-foamable polymer beads and form a film, which is not preferable.

In the present invention, the weight of the first coating layer made of a polymer binder and a foamed body of thermally foamable polymer beads applied on the sheet surface is 0.1 g/m'' as a solid weight.
~30g/m'' is preferred, more preferably 0.5g
/mz~20g/m” T: AZ).

Further, in the present invention, the weight of the second coating layer made of a polymer having a glass transition temperature of 30° C. or less is 0.000.
It is preferably 1 g/++" to 20 g/m", more preferably 0.5 g/a+" to 15 g/m2.

Any method can be used to apply the mixture of the polymer binder and heat-expandable polymer beads and the polymer onto the sheet surface, such as printing, coating, and impregnation, but screen printing, gravure printing, flexographic printing, etc. Known printing methods and known coating methods such as spray coating, roll coating, and coater coating can be preferably used.

In the present invention, the polymer binder and heat-expandable polymer beads are applied to at least a portion of the sheet surface in the form of a continuous film or a discontinuous pattern. As the discontinuous pattern, periodic patterns such as dots, grids, dots, diagonal lines, and waves are suitable, but irregular patterns may also be used.

In order to obtain sufficient anti-slip performance, these polymer binders and heat-expandable polymer beads should be added to the surface of the sheet approximately 1
It is desirable that the coating be applied to an area of 0% or more.

After applying the polymer binder and heat-foamable polymer beads on the sheet surface, preliminary drying is performed at a temperature lower than the boiling point of water or an organic solvent, and a heat-foaming treatment is performed. As a means for heating and foaming treatment, hot air, infrared rays, microwaves, hot rolls, etc. are appropriately used. The treatment temperature is determined as appropriate depending on the polymer binder and heat-expandable polymer beads used, but is usually 50 to 200°C, preferably 80 to 160°C.
It is ℃.

Through these pre-drying and heat-foaming treatments, the polymer binder and heat-foamable polymer beads applied on the sheet surface volatilize water or organic solvents and form a resin film.
The heat-expandable polymer beads are then expanded to form a foamed coating. This state is maintained even after cooling, and a first coating layer is formed in which the foamed polymer beads are fixed on the resheeted surface by the polymer binder.

Next, after applying a polymer having a glass transition temperature of 30°C or less so that the first coating layer is sufficiently coated on the sheet surface on which the first coating layer has been formed, it is heated at a temperature lower than the boiling point of water or an organic solvent, etc. Perform drying. As the drying means, hot air, infrared rays, microwaves, etc. are appropriately used. The treatment temperature is determined as appropriate depending on the polymer beads used in the first coating layer and the polymer used in the second coating layer, but is usually 50 to 200°C, preferably 80 to 160°C.

By this drying process, a second coating layer is formed on the sheet surface on which the first coating layer is formed.

[For production]

The thus obtained sheet of the present invention has a much greater frictional force with the contact body than a sheet without the second coating layer, and is not only a sheet with extremely excellent slip resistance, but also has a second coating layer, that is, a protective coating. As a result of this formation, the sheet maintained its anti-slip properties even during continued practical use, and its durability was greatly improved. When a covering layer was formed and finally foamed, the effectiveness of forming the second covering layer according to the present invention was not observed.

The anti-slip sheet of the present invention can be suitably used by itself in applications requiring anti-slip properties, but it is also possible to use an adhesive, hook-and-loop fastener, string, etc. in combination, if necessary.

〔Effect of the invention〕

The anti-slip sheet of the present invention has dramatically improved anti-slip properties compared to conventional technology, and does not shift or become disorganized not only under static usage conditions but also under dynamic usage conditions. It is possible to set the position accurately, and it is also extremely easy to install.

Further, the anti-slip sheet of the present invention not only has excellent anti-slip properties and durability, but also has good anti-blocking properties.

Therefore, the anti-slip sheet of the present invention can be used for hygiene and medical supplies such as sanitary napkins, disposable diapers, and bandages, household goods such as tissues and rugs, and covers for seat headrests, armrests, and pillows. It can be suitably used as sheet-like articles that require anti-slip properties, such as tablecloths, cloths such as tray napkins, sheets, and mats.

〔Example〕

EXAMPLES The present invention will be explained in more detail by showing Examples and Comparative Examples below, but the present invention is not limited only to these Examples.

Note that % and parts in the examples are based on weight unless otherwise specified.

Example 1 467 g of water in 12 flasks, 86 p of Cortamine (manufactured by Kao ■, cationic surfactant, solid content 63%)
9.5 g, 20 g of 2-ethylhexyl acrylate, and 0.1 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator.
2-ethylhexyl acrylate 17
2 g and 6 g of N-methylol acrylamide as a crosslinking agent.
and 2 g of itaconic acid were added over 1 hour.

Thereafter, the mixture was aged at 60° C. for 6 hours to obtain a self-crosslinking acrylic emulsion with a solid content of 30%. The glass transition temperature of this material was -65°C.

23.3 g of this emulsion, thermally foamable polymer beads (trade name: Matsumoto Microsphere-F-50, solid content 71%, average particle size 17μ, manufactured by Matsumoto Yushi Seiyaku ■)
4.2g and 39.1g of water at 200N! The mixture was placed in a beaker and mixed for 10 minutes using a homomixer to obtain a mixture (A).

A 400 mesh screen made of stainless steel
Himilan (ionomer resin manufactured by Mitsui Polychemicals ■) is laminated on a nonwoven fabric made of polyethylene and rayon (basis weight 20 g/m") so that the solid content of A) is 3 g/m" (basis weight 20 g/m"). ) The sheet was coated on the nonwoven fabric surface of the sheet. After coating, it was dried with hot air at a temperature of 80°C for 2 minutes, and then heated and foamed at a temperature of 110°C for 2 minutes to form the first coating layer (a). I got it.

In another 1ffi flask, 467 g of water, 92 Emulgen
0 (manufactured by Kao ■, polyoxyethylene nonylphenyl ether), 20 g of butyl acrylate, and 1 g of V-500 as a polymerization initiator, and then replaced with nitrogen.
The temperature was raised to 0°C. Upon initiation of polymerization, 170 g of butyl acrylate and 10 g of acrylic acid were added dropwise over 1 hour, and then aged at 60°C for 6 hours. After cooling, 2.7 g of magnesium hydroxide as a crosslinking agent was added and mixed to obtain a metal crosslinked acrylic emulsion with a solid content of 30%. The glass transition temperature of this product was -45°C.

This emulsion was diluted 3 times with ion-exchanged water and coated on the sheet (a) using stainless steel M300 Mency Tareen so that the solid content of the polymer was 1.3 g/m''.After coating, It was dried with hot air at a temperature of 80° C. for 2 minutes to obtain an anti-slip sheet provided with a second coating layer.

Example 2 23.3 g of the metal crosslinked acrylic emulsion before dilution of the polymer for the second coating layer used in Example 1, thermally foamable polymer pieces (trade name: Matsumoto Microspheres)
F-30, solid content 71%, average particle size 14.5 μm, manufactured by Matsumoto Yushi Seiyaku ■) and 39.1 g of water were placed in a 200-cm beaker and mixed for 10 minutes in a homomixer, resulting in mixture (B). I got it.

Mixture (B) with stainless steel 300 mesh screen
) A nonwoven fabric made of polyethylene and polypropylene (basis weight 25 g/a+") so that the solid content is 8 g/m"
It was applied to the nonwoven surface of a sheet laminated with Himilan. After coating and drying with hot air for 5 minutes at a temperature of 60°C,
The material was heated and foamed at a temperature of 20"C for 2 minutes to obtain a sheet H)) coated with the first coating layer.

Next, an anti-slip sheet was obtained by applying a second coating layer to Sea 1-(b) in the same manner as in Example 1.

Example 3 High carboxy modified acrylic emulsion AH812 (manufactured by Japan Synthetic Rubber ■, solid content 47%, glass transition temperature -24
℃) 1277g, calcium hydroxide 2 as a crosslinking agent
, 6g, thermally foamable polymer beads (Matsumoto Microspheres-F-30) 563g, carboxymethylcellulose (CMC) as a thickener 33g, and water 15g.
Mix 70g in a homomixer for 1 hour to obtain mixture (C)
I got it.

Using a gravure printing machine (manufactured by Hirano Metal ■, gravure roll; solid plate, grid 40 mesh), line speed 1m/
Printing was carried out on the non-woven fabric surface of Shinit, which was made by laminating Himilan on a non-woven fabric made of polyethylene, polypropylene and polyester (25 g/m2) so that the solid content of mixture (C) was 1.5 g/m2.

After printing, the first coating layer was pre-dried in a hot air circulation drying oven at 60°C (residence time: 2 minutes), and then heated and foamed in a hot air circulation drying oven at 110°C (residence time: 2 minutes). A long sheet (C) was obtained.

Next, an anti-slip sheet was obtained by applying a second coating layer to the sheet (c) in the same manner as in Example 1.

Example 4 467 g of water, 9.5 g of Cortamine 86p conc., 12 g of ethyl acrylate, 8 g of methyl methacrylate, and 1 g of V-500 as a polymerization initiator were placed in a 1F flask, and the temperature was raised to 60°C without purging with nitrogen. Shina. Upon initiation of polymerization, 103 g of ethyl acrylate, 69 g of methyl methacrylate, and 6 g of N-methylol acrylamide and 2 g of itaconic acid as crosslinking agents were added over 1 hour. Thereafter, the mixture was aged at 60° C. for 6 hours to obtain a self-crosslinking acrylic emulsion with a solid content of 30%. The glass transition temperature of this product was 16°C.

233 g of this emulsion, heat-expandable polymer beads (
Matsumoto Microsphere-F-5o) 42g, water 3
91g was mixed for 10 minutes in a homomixer, and the mixture (0
) was obtained.

The mixture (
(b) A non-woven fabric made of polyethylene and polypropylene (25g per tsubo
/m'') was printed on the nonwoven fabric side of a sheet laminated with Himilan.

After printing, the first coating layer was pre-dried in a hot air circulation drying oven at 80°C (residence time: 2 minutes), and then heated and foamed in a hot air circulation drying oven at 110°C (residence time: 2 minutes). A long sheet (d) was obtained.

Next, an anti-slip sheet was obtained by applying a second coating layer to the sheet (d) in the same manner as in Example 1.

Example 5 Metal-crosslinked acrylic emulsion (glass transition temperature -4) before dilution of the polymer for the second coating layer used in Example 1
5℃1 solid content 30% > 1165g, thermally foamable polymer beads (Matsumoto Microspheres-F-30) 21
0 g, carboxymethylcellulose (CM
C) 11.3g and 315g of water in a homomixer
Mixing was carried out for 0 minutes to obtain a mixture (E).

Gravure printing machine (gravure roll: lattice 65 menshi,
Using a diagonal line pattern as shown in Fig. 2 (in which 1 indicates the coated area and 2 indicates the non-coated area), the solid content of the mixture (E) was 3 g/m 2 at a line speed of 4 m/min. A nonwoven fabric made of polyethylene and polypropylene (tsubo'f2
Printing was carried out on the nonwoven fabric surface of a sheet laminated with Himilan (5 g/m").

After printing, the first coating layer was pre-dried in a hot air circulation drying oven at 80°C (residence time: 30 seconds), and then heated and foamed in a hot air circulation drying oven at 130°C (residence time: 30 seconds). A long sheet 1-(e) was obtained.

Next, to acrylic adhesive emulsion N.

Plaster K (manufactured by Shin Nakamura Chemical Industry ■, solid content 46
%, glass transition temperature -65℃1 non-crosslinked type) 100
0g was diluted with 533g of water to obtain a polymer emulsion with a solid content of 30%. The solid content of this polymer is 11g/l
112 on the above sheet (e) using a gravure printing machine (solid plate, lattice 30 mesh) at a line speed of 4 m/min. After printing, it was dried in a hot air circulation drying oven at 80° C. (residence time: 30 seconds) to obtain an anti-slip sheet coated with a second coating layer.

Example 6 SBR (glass transition temperature -20°C) ssg was dissolved in 900 g of toluene, this was used as a polymer solution for the second coating layer, and stainless steel 300 was added to the long sheet 1-(e) obtained in Example 5. Coating was performed using a mesh screen so that the solid content of the polymer was 2 g/n+''. After coating, the temperature was 60°C.
The sheet was dried with hot air at a temperature of 1 hour to obtain an anti-slip sheet coated with a second coating layer.

Example 7 The self-crosslinking acrylic emulsion (glass transition temperature: 16°C, solid content: 30%) used for the first coating layer in Example 4 was used as a polymer emulsion for the second coating layer, and a gravure printing machine (solid plate, The sheet (e) obtained in Example 5 was printed at a line speed of 4 m/min using a grid of 40 mesh (40 mesh) so that the solid content of the polymer was 2 g/cm2. After printing, dry in a hot air circulation drying oven at 80℃ (residence time 30
sec) to obtain an anti-slip sheet coated with a second coating layer.

Example 8 Self-crosslinking acrylic emulsion AE516 (manufactured by Japan Synthetic Rubber, solid content 45%, glass transition temperature -48°C)
1780g, thermally foamable polymer beads (Matsumoto Microspheres-F-30) 280g, carboxymethyl cellulose (CMC) as a thickener 16.5g and water 1
270g was mixed in a homomixer for 1 hour, and the mixture (F
) was obtained.

Gravure printing machine (gravure roll; grid 40 mesh:
Using a polka dot pattern as shown in Figure 1 (in which 1 indicates the coated area and 2 indicates the non-coated area), the solid content of the mixture (F) was 1 g/m2 at the line speed Log/min. So that
Mizuki (smooth paper treated with wax-based sizing agent, basis weight 25
g/m”).

After printing, the first coating layer is pre-dried in a hot air circulation drying oven at 80°C (residence time: 30 seconds), and then heated and foamed in a hot air circulation drying oven at 120°C (residence time: 1 minute). A long sheet ('') was obtained.

After that, use the same method as in Example 1 to see! - (f) second
An anti-slip sheet provided with a coating layer was obtained.

Example 9 In the same manner as in Example 8, a gravure roll with a 65-lattice mesh and a diagonal pattern as shown in Figure 2 was used, and the mixture (
Cotton cloth (basis weight 10
0g/l11").

After printing, drying and heat treatment were performed in the same manner as in Example 8 to obtain a long sheet (9) coated with the first coating layer.

Thereafter, a second coating layer was applied to the sheet (6) in the same manner as in Example 1 to obtain an anti-slip sheet.

Comparative Example 1 A sheet (5) coated with only the first coating layer was obtained in the same manner as in Example 1 except that the thermally foamable polymer beads were not used.

Comparative Example 2 To 70 g of the self-crosslinking acrylic emulsion used for the first coating layer of Example 1, 14 g of silica powder with an average particle size of 5 μ and an average particle size of 15 mJ! 15 g of colloidal silica were mixed to obtain a mixture (G). This mixture (G) was coated in the same manner as in Example 1 to obtain a sheet (i) with only the first coating layer applied.

Comparative Example 3 Instead of the metal crosslinked acrylic emulsion used in the first coating layer of Example 2, a polymer binder without a crosslinked structure was prepared. That is, 467 g of water, 9208 g of Emulgen, 20 g of butyl acrylate, and 1 g of V-500 as a polymerization initiator were placed in a flask No. 11, and the temperature was raised to 60°C while purging with nitrogen. At the same time as the polymerization started, 180 g of butyl acrylate was added. After dripping for 1 hour, 60℃
The mixture was aged for 6 hours to obtain a butyl acrylate emulsion with a solid content of 30%. The glass transition temperature of this material is -53℃
Met.

23.3 g of this emulsion, 4.2 g of thermally foamable IJ7-beads (Matsumoto Microspheres-F-30)
, 39.1 g of water was placed in a 200-meter beaker and mixed for 10 minutes in a homomixer to obtain a mixture (H).

This was coated, dried, and heated and foamed in the same manner as the mixture (B) of Example 2 to obtain a sheet (j) in which only the first coating layer was applied, the binder having no crosslinked structure.

Comparative example 4 17! 467g of water and 9208g of Emulgen in the flask.
, butyl methacrylate 20g and V- as a polymerization initiator.
500.1 g of butyl methacrylate was charged, and at the same time as the temperature was raised to 65°C while replacing with nitrogen, 0 polymerization was started.
A mixture of 20 g and 60 g of methyl methacrylate was added dropwise over 1 hour, and then aged at 65°C for 5 hours to reduce the solid content to 3.
A 0% emulsion was obtained.

The glass transition temperature of this product was 41°C.

23.3g of this emulsicon, thermally foamable polymer heath (product name: Matsumoto Microsphere-F-30)
4.2 g and 39.1 g of water were placed in a 200@l beaker and mixed for 10 minutes in a homomixer to obtain a mixture (1).

Using the same method as in Comparative Example 3, the solid content of mixture (I) was reduced to 6 g.
/m'' on the nonwoven fabric surface of a sheet in which Himilan was laminated to a nonwoven fabric (basis weight 25 g/m'') made of polyethylene and polypropylene. 60℃ after coating
The sheet was dried for 5 minutes at 120° C. and then foamed for 2 minutes at 120° C. to obtain a sheet (k) on which only the first coating layer was applied.

Comparative Example 5 467 g of water, 9.5 g of Cortamine 86p conc., 20 g of ethyl acrylate, and 1.0 g of V-50 as a polymerization initiator were placed in a flask of 172, and the flask was replaced with nitrogen.
At the same time as the temperature was raised to 5° C. and the polymerization started, 165 g of ethyl acrylate, glycidyl methacrylate Log as a crosslinking agent, and 5 g of acrylic acid were added dropwise over 1 hour.

Thereafter, it was aged at 65° C. for 5 hours to obtain a self-crosslinking acrylic emulsion with a solid content of 30%. The glass transition temperature of this product was -21°C.

233 g of this emulsion, heat-expandable polymer beads (
Product name: Matsumoto Microsphere-F=30) 42
g, 391 g of water was mixed in a homomixer for 10 minutes,
A mixture (J) was obtained.

Gravure printing machine (gravure roll: solid plate).

Hymilan was applied to a nonwoven fabric (125 g/m") made of polyethylene, polypropylene, and polyester at a line speed of 4 m/min using a lattice mesh (40 mesh) at a line speed of 4 m/min so that the solid content of the mixture (J) was 3.5 g/rtr2. Printing was performed on the nonwoven surface of the laminated sheet.

After printing, pre-drying in a hot air circulation drying oven at 80°C (residence time 30 seconds), heating and foaming treatment in a hot air circulation drying oven at 145°C (residence time 30 seconds), leaving only the first coating layer. Sea 1) was obtained.

Comparative Example 6 Sheet coated with only the first coating layer obtained in Example 2 (b
) was used as a comparative example.

Comparative Example 7 A long sheet (C) to which only the first coating layer obtained in Example 3 was applied was used as a comparative example.

Comparative Example 8 In Example 2, after coating the mixture (B), the temperature was 60°C.
The sheet (m) was dried with hot air for 5 minutes at a temperature of 5 minutes to obtain a sheet (m) that was not subjected to heat foaming treatment.

Next, a sheet was obtained by applying a second coating layer to (m) in the same manner as in Example 2, and then heated and foamed to obtain an anti-slip sheet.

Comparative Example 9 Regarding the sheet (j) provided with the first coating layer in which the polymer binder obtained in Comparative Example 3 does not have a crosslinked structure,
A sheet provided with a second coating layer was obtained in the same manner as in Example 1.

Test Example 1 The glass transition temperature (
Tg), breaking strength, and elongation were measured.

Samples for measurement were prepared as follows. That is, the emulsion or solution of each polymer binder was placed on a bat whose surface was treated with Teflon until the film thickness after drying was approximately 111 mm.
The mixture was poured in an amount equal to 1 in., left horizontally at room temperature for 3 days to dry, and then further dried for 2 hours in a hot air circulation drying oven at 105°C to obtain a film of the polymer binder.

To measure the glass transition temperature, cut out approximately 20 mg of the above film as a sample, and use DSC-IB (PERKIN-EL
(manufactured by MER) at a temperature increase rate of 4° C./min.

In addition, the breaking strength and elongation rate were measured by punching out the above film into a strip of width Lcm+ and length 15cm and using Tensilon UTM-III (manufactured by Toyo Seiki ■) at a tensile speed of 300+am/min. .

On the other hand, regarding the anti-slip sheets obtained on each side, the following methods were used to evaluate the anti-slip properties -1, anti-slip properties -2, and anti-blocking properties -
1. Blocking resistance-2 was evaluated.

Furthermore, the state of the coating layer was observed using an electron microscope (100x magnification), and the detachment of the thermally foamable polymer beads and the state of destruction of the thermally foamable polymer beads were investigated.

The results are shown in Table-1.

The anti-slip properties were measured in a constant temperature room at 25° C. using a slip resistance measuring device as shown in Figure 3. In addition, FIG. 3(a) is a side view of the anti-slip property measuring device, and FIG. 3(b) is a plan view, 3 is a test piece, 4 is a load,
5 is an object plane, 6 is a platform, and 7 is a pulley.

That is, the coated surface of test piece 3 (50 x 180 mm+) faced down, and a load 4 (225 g, 50 x 150
nua), and then apply a tensile load of 230 g (including 10 g of saucer) to the string and pull it. If it does not shift within 1 minute, increase the tensile load by 20g to 250g and pull. If it does not shift within 1 minute, increase it by 20g and continue pulling, 1
The tensile load was measured when it was dropped within minutes.

The measurement was performed three times each, and the average value was determined to be the anti-slip value.

The larger this value is, the greater the slip resistance is.

As the target surface 5, cotton (Kanakin No. 3, for JIS color fastness test, compliant with JIS L 0803) was used.

Ribs! -1 The following measurement method was used for the purpose of evaluating the durability of the anti-slip sheet.

That is, using the cotton used in the measurement of anti-slip property -1 as the target surface, the coated surface of the test piece was facing down and a G load (225 g, 5
0 x 15f)nun) and quickly move it 150mm in one direction. After repeating this operation 10 times, this was used as a test piece 3 and measured according to the method for measuring anti-slip property-1.

1 Blowing-1 Two test pieces (50 x 180 mm) were overlapped with their coating layers, sandwiched between two glass plates, a load of 3750 g was placed on them, and the test pieces were left at 40°C, 190% R1+ for 24 hours. Thereafter, the presence or absence of blocking was observed, and this was expressed in three stages.

○: No bronking occurs at all.

Δ: Slight bronking occurs and when the test piece is peeled off,
I hear a small sound.

× Ni blocking occurs, and when the test piece is peeled off, the base material breaks.

Blocking -2 Two test pieces (50 x 180 mm) were stacked on each other with the coated surface and the opposite surface, and other operations were performed with blocking resistance = 1 for evaluation.

The test piece used in 11. Anti-slip properties of public plates - 2 was taken out and the state of the coating layer was observed under an electron microscope (100x magnification), and the presence or absence of detachment and destruction of the thermally foamable polymer beads was determined in 3 stages. evaluated.

○: Almost no detachment or destruction.

Δ: A considerable number of beads were detached or destroyed.

×: Most of the particles are detached or destroyed.

From Table 1, it is clear that the anti-slip sheet obtained by the present invention has significantly superior anti-slip properties and extremely improved durability compared to other comparative examples.

[Brief explanation of the drawing]

FIG. 1 is a developed view of a gravure roll with a polka dot pattern used in Example 8, and FIG. 2 is a developed view of a gravure roll with a diagonal pattern used in Examples 5 and 9. Figure 3 is a schematic diagram of the anti-slip property measuring device used in the test example.
(a) is a side view, and (b) is a plan view. 1: Coated part 2: Non-coated part 3: Test piece 4: Load 5: Target surface 6: Stand 7: Pulley Applicant's agent Kaoru Furuya Fig. 2 Fig. 1 Fig. fa 3

Claims (1)

[Claims] 1. At least a portion of the sheet surface has a crosslinked structure, has a glass transition temperature of 30°C or less, and has a breaking strength of 7 to 200 kg.
/cm^2, has a first coating layer consisting of a polymer binder with an elongation rate of 200% or more and a foam of thermally foamable polymer beads, and further has a glass transition temperature of 30°C on the first coating layer.
An anti-slip sheet characterized by having a second coating layer made of the following polymer. 2. A polymer binder having a crosslinked structure, a glass transition temperature of 30° C. or less, a breaking strength of 7 to 200 kg/cm^2, and an elongation rate of 200% or more and thermally foamable polymer beads are provided on at least a portion of the sheet surface. and heating the polymer beads to a temperature higher than the foaming temperature of the polymer beads to foam the polymer beads to form a first coating layer, and further on the first coating layer, a second coating layer made of a polymer having a glass transition temperature of 30° C. or less. A method for producing an anti-slip sheet, comprising: