JPH01299036A - Anti-sliding property sheet - Google Patents

Abstract

PURPOSE:To improve the anti-sliding property by making the polymer binder having a bridge structure and a specific physical property and the polymer particles having a specific physical property into a continuous film or discontinuous pattern, on at least the part of a sheet surface. CONSTITUTION:A coating layer is provided, which contains a polymer binder having a bridge structure and properties of glass transition temperature of 30 deg.C or less, breaking strength of 7-200kg/cm<2> and the elongation rate of 200% or more, and the particle with an average particle diameter of 1-1,000mu which has a bridge structure and property of glass transition temperature of 30 deg.C or less. As a polymer binder, synthetic rubber such as acryl resin, styrene, butadiene rubber, nitrile butadiene rubber and the like, as well as polyurethane resin are given. As a method of introducing the bridge structure, the method of using a bridge structure such as multifunctional compound, metallic compound, peroxide, or the method of irradiating with an active energy and the like, such conventional methods can be used appropriately. It is necessary for the polymer particle to have a bridge structure. The particle diameter of the polymer particle is preferably 50-400mu.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a sheet-like article having excellent 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 a certain degree of anti-slip properties, they have the drawbacks of stickiness, blocking, and easy detachment of the anti-slip layer, so they are practical anti-slip sheets depending on the application. It was hard to say.

On the other hand, by providing a foamable covering material containing microspheres that expand with heat on the base material, cushioning properties, sound insulation,
Efforts have been made to provide functions such as heat insulation and anti-slip properties (for example, JP-A-49-32966, JP-A-62-6).
0638, etc.), but these microspheres are bead-like objects containing easily volatile compounds such as butane and isopenkune, and are complicated to manufacture. It required processing and was disadvantageous in terms of processing cost.

In addition, adhesives, hook-and-loop fasteners,
In the method of fixing with a string or the like, it is difficult and complicated to determine the correct position during use, and it is also disadvantageous in terms of manufacturing cost.

[Means to solve the problem]

Under the above circumstances, the present inventors have conducted extensive studies on sheet-like articles with excellent anti-slip properties. It was discovered that by applying a binder and polymer particles having specific physical properties in a continuous film or discontinuous pattern, the anti-slip properties can be dramatically improved and a sheet suitable for practical use can be obtained.The present invention reached.

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.
~200kg/cm", a polymer binder with an elongation rate of 200% or more, a crosslinked structure, and a glass transition temperature of 3.
Average particle size of 1 to 1000μ made of polymer below 0°C
The present invention provides an anti-slip sheet characterized by having a coating layer containing particles of.

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

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 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.

For the purpose of controlling the glass transition temperature of the polymer binder used in the present invention to 30° C. or less, a plasticizer or the like may be added to the above resin as necessary.

The polymer particles used in the present invention have a crosslinked structure, a glass transition temperature of 30°C or less, and a particle size of 1 to 1000μ, and are of the type exemplified above as the polymer binder. Each resin can be used.

The above resins can be used alone or in combination.

It is necessary that the polymer particles used in the present invention have a crosslinked structure. Particles without a crosslinked structure are not preferable for the purpose of the present invention because the particles tend to adhere to each other and it is difficult to maintain the shape of the particles.

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

As a method for obtaining these resins as particles, any known method may be used as appropriate. For example, examples include a method in which suspension polymerization is carried out after particle formation at the stage of seven polymers, a method in which particle formation is also carried out at the stage of polymerizing monomers, and a method in which the polymer is formed into particles.The production method is not particularly limited. It is not used in the form of a dispersion in water or an organic solvent.

For the purpose of controlling the glass transition temperature of the polymer particles used in the present invention to 30° C. or less, a plasticizer or the like may be added to the resin as necessary.

The form of the polymer particles thus obtained varies depending on the manufacturing method, and various forms such as hollow, solid, porous, etc. can be used.

The particle size of the polymer particles used in the present invention is 1 to 1
000μ, preferably 5 to 500μ, more preferably 50 to 400μ. The above particle size can be measured, for example, by actually measuring on a photograph taken with an optical microscope or an electron microscope.

Fine particles with a particle size of less than 1 μm make little contribution to improving the anti-slip properties, and large particles with a particle size of more than 1000 μm are undesirable because they tend to fall off due to friction.

In the present invention, the polymer binder and polymer particles 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 to the sheet surface, a drying process is performed to form a coating layer on the sheet surface.

One of the features of the present invention is that the polymer binder has a glass transition temperature of 30°C or less and a breaking strength of 7 to 200 kg/cm.
m", elongation rate of 200% or more. More preferable ranges include a glass transition temperature of 0°C or less, a shear strength of 10=150 kg/cm2, and an elongation rate of 300% or more.

If the glass transition temperature exceeds 30°C, the drying temperature must be considerably high, which may cause cracks in the polymer binder or melting of the polymer particles, making it impossible to obtain the desired anti-slip properties. .

In addition, if the breaking strength is less than 7 kg/cm", the polymer binder coating is easily destroyed by frictional force (and it becomes difficult to immobilize the polymer particles. On the other hand, if the breaking strength exceeds 200 kg/cm" or when the elongation rate is less than 200%, the polymer binder film has high strength or rigidity, making it difficult for the frictional force to be alleviated appropriately, and the polymer particles may be detached or may become slippery (
Both are undesirable.

Another feature of the present invention is the use of polymer particles having a glass transition temperature of 30'C or lower.

When using polymer particles with a glass transition temperature higher than 30'C or other particles such as silica powder, the particles are rigid and do not deform under stress, so the contact area does not increase and friction is reduced. I don't see any improvement in power.

In addition, because it is rigid, the frictional force is difficult to be alleviated appropriately,
On the contrary, it may become slippery, which is not desirable.

That is, the present invention aims to impart excellent anti-slip properties to sheet-like articles by combining a polymer binder with suitable flexibility and elasticity and polymer particles with suitable flexibility.

In the present invention, the sheet on which the polymer binder and polymer particles are applied may include nylon, acrylic,
Polyester, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, cotton, wool, rayon,
Examples include woven fabrics, non-woven fabrics, paper, laminated non-woven fabrics and films made of valves, vinylon, acetate, etc., and sheet-like substrates having irregularities formed by embossing etc. can also be used.

Further, the weight ratio (in terms of solid content) of the polymer binder and the polymer particles used in the present invention is preferably from 90:10 to 10:90, particularly from 85:15 to 20:8.
The ratio is preferably 0, and more preferably 70:30 to 30:70.

If the amount of polymer bigo is greater than the above range, the coating will have less unevenness due to the polymer particles, resulting in poor anti-slip performance. Furthermore, if the amount of the polymer binder is less than the above range, it becomes difficult to fix the polymer particles and form a film, which is not preferable. It is also possible to melt a portion of the polymer particles by heat so that they also function as a polymer binder.

In the present invention, the weight of the coating layer made of the polymer binder and polymer particles applied on the sheet surface is preferably 0.5 to 100 g/mz, more preferably 1 to 80 g/m2, and more preferably 1 to 80 g/m2 in terms of solid weight. Preferably 3-50
g/m".

Any method can be used to apply the polymer binder and polymer particles onto the sheet surface, such as printing, coating, and impregnation. However, known printing methods such as screen printing, gravure printing, and flexographic printing, and spray coating Known coating methods such as coating, roll coating, and coater coating can be preferably used.

In the present invention, the polymer binder and polymer particles are applied to at least a portion of the sheet surface in the form of a continuous film or in 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, it is desirable that the polymer binder and polymer particles be applied to an area of about 10% or more of the sheet surface.

After applying the polymer binder and polymer particles on the sheet surface, drying is performed. Hot air, infrared rays, microwaves, etc. are used as appropriate for the drying treatment.

The treatment temperature is determined as appropriate depending on the polymer binder and polymer particles used, but is usually 50 to 200°C.

Through these drying treatments, the polymer binder and polymer particles applied on the sheet surface volatilize water, organic solvent, etc., and form a coating layer in which the polymer particles are fixed on the sheet surface by the polymer binder. Ru.

[For production]

The sheet obtained in this way has a flexible and elastic coating made of a polymer binder with a crosslinked structure and specific physical properties, and an uneven structure made of flexible polymer particles, and has extremely low frictional force with contact objects. It was large and had excellent anti-slip properties. Furthermore, the coating layer had little stickiness and blocking properties, and was difficult to separate from the base sheet.

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 adhesives, hook-and-loop fasteners, strings, etc. in combination, if necessary.
Further, it is also possible to further form an overprint layer of a binder or the like on a part or the whole of the coating layer formed for the purpose of protecting the polymer particles.

〔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, but also has good blocking resistance and abrasion resistance.

Furthermore, compared to techniques using thermally foamable coating materials, this method has the advantage that operations are simple and processing costs are low in the production of the polymer material used and the coating process.

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 table cloths, cloths such as tray napkins, disposable body warmers, 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.

Production Example 1 1i! equipped with a stirring device, cooling tube, thermometer, and nitrogen introduction tube!
Pour 460g of water into a flask and add Gohsenol GH.
4.6 g of 2-ethylhexyl acrylate, 1 g of divinylbenzene, and 4 g of lauroyl MAM were added and dissolved. After stirring and atomization at 750 rpm for 30 minutes, the mixture was polymerized and aged at 80°C for 8 hours. Solid polymer particles having an average particle diameter of 75 μm and a glass transition temperature of −63° C. were obtained as an aqueous dispersion (a) with a solid content of 30%.

Production Example 2 In Production Example 1, 2-ethylhexyl acrylate 20
The same operation was performed except that 0g was changed to 200g of ethyl acrylate, and the stirring rotation speed was changed from 750 rpm to 350 rpm.
0%, average particle size 145μ, glass transition temperature -23°C
) was obtained.

Production Example 3 The same operation as in Production Example 1 was carried out except that 1 g of divinylbenzene was changed to 1.5 g, and the stirring rotation speed was changed from 750 rotations/min to 200 rotations/min. ) (solid content 30%, average particle size 375μ, glass transition temperature -61°C) was obtained.

Production Example 4 In Production Example 1, 2-ethylhexyl acrylate 200
The same operation was performed except that g was changed to 200 g of styrene to obtain a dispersion (d) of polymer particles (solid content: 30%, average particle diameter: 80 μm, glass transition temperature: 100° C.).

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.
was charged, and the temperature was raised to 60°C while purging with nitrogen. With the start of polymerization, 2-ethylhexyl acrylate 1
72g and N-methylolacrylamide 6 as a crosslinking agent.
g and 2 g of itaconic acid were added over 1 hour.

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

210 g of this emulsion, 490 g of the polymer particle dispersion (a) obtained in Production Example 1, 80 g of water, and 4.2 g of carboxymethyl cellulose (hereinafter abbreviated as CMC) as a thickener.
g was mixed in a homomixer for 30 minutes to obtain a mixture (A).

Using a gravure printing machine (manufactured by Hirano Metal, gravure roll: solid plate, grid 30 mesh), line speed 4 m /
A nonwoven fabric made of polyethylene and rayon (basis weight 20 g/m
After coating, it was dried at a temperature of 80°C (hot air circulation drying oven, residence time 1 minute) to obtain an anti-slip sheet.

Example 2 467 g of water and 8 g of Emulgen 920 (manufactured by Kao ■, polyoxyethylene nonylphenyl ether) were added to 12 flasks.
g, butyl acrylate 20g and V- as a polymerization initiator.
500.1 g was charged, and the temperature was raised to 60° C. while purging with nitrogen. With the start of polymerization, butyl acrylate 17
After dropping 0 g and acrylic acid Log over 1 hour,
Aged for 6 hours at 60'C. After cooling, add 2.7 g of magnesium hydroxide as a crosslinking agent and mix to reduce the solid content to 30%.
A metal crosslinked acrylic emulsion was obtained. The glass transition temperature of this material was -45°C.

490 g of this emulsion, 210 g of polymer particle dispersion (a) obtained in Production Example 1, 80 g of water, CMC4
, 2g in a homomixer for 30 minutes to obtain mixture (B).
I got it.

The solid content of mixture (B) was 5.5 g/m with a bar coater.
After coating it on a non-woven fabric (basis weight 25g/+*) made of polyethylene and polypropylene so that it becomes ``, drying it,
An anti-slip sheet was obtained.

Example 3 High carboxy modified acrylic emulsion AH812 (manufactured by Japan Synthetic Rubber ■, solid content 47%, glass transition temperature -24
0.5 g of calcium hydroxide as a crosslinking agent was added to 223.4 g of the polymer particle dispersion obtained in Production Example 1 (
a) 350 g, 207 g of water, and 4.2 g of CMC were mixed for 30 minutes in a homomixer to obtain a mixture (C).

By the same operation as in Example 1, the solid content of mixture (C) was reduced to 5.
A nonwoven fabric made of polyethylene, polypropylene, and polyester (basis weight 25 g/m"
) (gravure roll: grid 30 mesh, diagonal pattern as shown in Figure 1, 1 indicates coated area 1, 2 indicates non-coated area), then dried at 80°C to make it anti-slip. I got a sex sheet.

Example 4 467 g of water, 8 g of Cortamino 86p conc. 9.5 methyl acid, and V-500, 1 as a polymerization initiator were placed in a flask of IF.
g was charged, and the temperature was raised to 60°C without replacing with nitrogen. Upon initiation of polymerization, 103 g of ethyl acrylate, 69 g of methyl methacrylate, and 6 g of N-methylolacrylamide and 2 g of itaconic acid as crosslinking agents were added over 1 hour. Thereafter, it 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 16°C.

350 g of this emulsion, 350 g of polymer particle dispersion (a) obtained in Production Example 1, 80 g of water, C
4.2 g of MC was mixed in a homomixer for 30 minutes to obtain a mixture (D). The mixture (
D) was coated on a nonwoven fabric (1120 g/m") made of polyethylene and rayon so that the solid content was 6 g/m" and dried to obtain an anti-slip sheet.

Example 5 Metal crosslinked acrylic emulsion 10 used in Example 2
g, 10 g of polymer particle dispersion (b) obtained in Production Example 2
, 69g of water, 0.9g of CMC at Starsea 5
After mixing for a period of time, a mixture (ε) was obtained.

The solid content of mixture (E) was 20g/11 using a bar coater.
2 on a cotton cloth (basis weight 100 g/mff1) and dried at 90°C for 10 minutes to obtain an anti-slip sheet.

Example 6 5 g of metal crosslinked acrylic emulsion used in Example 2
, 5 g of polymer particle dispersion (c) obtained in Production Example 3, 8 g of water
9 g of CMC and 1.2 g of CMC were mixed for 5 hours in a Starsea to obtain a mixture (F).

The solid content of mixture (F) was 17g/at using a bar coater.
It was coated on paper (smooth paper treated with a wax-based sizing agent, basis weight 25 g/m'') to give the following properties, and then dried at 90° C. for 10 minutes to obtain an anti-slip sheet.

Comparative Example 1 A nonwoven fabric sheet coated with a polymer was obtained in the same manner as in Example 1 except that the polymer particle dispersion (a) was not used.

Comparative Example 2 Self-crosslinking acrylic emulsion 70 used in Example 1
0g, 140g of silica powder with an average particle size of 5μ, 150g of colloidal silica with an average particle size of 15μ, 80g of water, C
4.2 g of MC was mixed to obtain a mixture (G).

This mixture (G) was applied in the same manner as in Example 1 to obtain a nonwoven fabric sheet.

Comparative Example 3 In Example 2, a nonwoven fabric sheet was obtained by performing the same operation except for changing the polymer particle dispersion (a) obtained in Production Example 1 to the polymer particle dispersion (d) obtained in Production Example 4. .

Test Example 1 The glass transition temperature (Tg), breaking strength, and elongation rate of each polymer binder used in Examples 1 to 6 and Comparative Examples 1 to 3 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 so that the film thickness after drying was approximately 1 mm.
Pour in the desired amount, leave it horizontally at room temperature for 3 days to dry, then dry it in a hot air circulation drying oven at 105°C for another 2 hours! A film of the polymer binder was obtained.

To measure the glass transition temperature, cut out approximately 20 mg of the above film as a sample, and test it with DSC-IB (PERK TN
- manufactured by ELMER) 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 with a width of 1 cm and a length of 15 cm and using Tensilon IITM-III (manufactured by Toyo Seiki ■) at a tensile speed of 300 mm for 7 minutes. Ta.

The glass transition temperatures of the polymer particles obtained in Production Examples 1 to 4 were measured using the above-mentioned apparatus using powder obtained by drying each dispersion as a sample.

On the other hand, the anti-slip sheets obtained on each side were evaluated for anti-slip properties, anti-blocking properties -1, and anti-blocking properties -2 by the following methods.

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 2. Note that FIG. 2(a) is a side view of the anti-slip property measuring device, and FIG. 2(a) is a plan view.

The coated side of test piece 3 (50 x 180 mm+) is facing down, and a load 4 (225 g, 50 x 150 mm) is placed on top of it.
) and tensile load (230g, including saucer 10g)
Put it on a string and pull it. If it does not shift within 1 minute, increase the tensile load by 20g to 250g and pull. When it did not shift within 1 minute, the tension was continued to be increased by 20 g, and the tensile load (F) when it shifted within 1 minute was measured. Measurement is 3
The results were calculated and the average value was taken as the anti-slip value.

The larger this value is, the greater the anti-slip property is.

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

I Pro King -1 Two test pieces (50X 180++ua) were overlapped with the coating layers, temporarily sandwiched between two pieces of glass, and the load was 3750.
g and leave it at 40°C, 190% R11 for 24 hours.

Thereafter, the presence or absence of blocking was observed, and this was expressed in three stages.

O: No blocking occurs at all.

Δ: Slight blocking 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.

PRO KING-2 Two test pieces (50 x 18 pieces 111) were overlapped with the coated side and the opposite side, and the other operations were performed in accordance with blocking resistance-1 for evaluation.

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

Furthermore, even during continued use, the polymer particles did not fall off or break, and the anti-slip properties were maintained.

[Brief explanation of the drawing]

FIG. 1 is a developed view of a gravure roll with a diagonal pattern used in Example 3. Figure 2 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 area 2: Non-coated area 3: Test piece 4: Load 5: Target surface 6: Stand 7: Pulley applicant Kaoru Furuya Figure 1

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, a coating layer containing a polymer binder with an elongation rate of 200% or more, and particles with an average particle size of 1 to 1000μ made of a polymer having a crosslinked structure and a glass transition temperature of 30°C or less. Anti-slip sheet.