JP2009066782A - Non-slip sheet and composition for anti-slip layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a non-slip sheet having a good anti-slip property and durability, while controlling volatilization of an organic solvent during production. <P>SOLUTION: The non-slip sheet includes a sheet shaped cellulose-based base material 4 and an anti-slip layer 8 which constitutes a surface layer on at least one surface of the cellulose-based base material 4. The anti-slip layer 8 is obtained by heating aqueous dispersion comprising (a) a copolymer having an acrylic carbonyl group, (b) an organic hydrazine derivative having two or more hydrazine residues of ≥0.02 mol and ≤1 mol per 1 mol of the carbonyl group, and (c) thermal expandable microcapsule particles 5 of more than 0.15 mass parts and less than 15 mass parts to total amount of the above (a) and the above (b) of 100 mass parts. The organic hydrazine derivative can be crosslinked at ordinary temperatures in the carbonyl group with the copolymer having the carbonyl group. The thermal expandable microcapsule particles 5 have a mean particle diameter of ≤20 μm, and an expansion initiation temperature of 80°C to 120°C. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an anti-slip sheet and an anti-slip layer composition for producing the same.

An anti-slip sheet in which an anti-slip layer is formed on the surface of a sheet-like substrate such as paper or film is known.
As the anti-slip layer, a resin composition containing thermally expandable microcapsules is applied to the surface of the substrate, and then the resin is cured by heating it, and the thermally expandable capsules are thermally expanded. Some are formed in an uneven shape on the surface.
For example, a resin layer containing a resin that flows by heating and a microcapsule that softens by heating is prepared, and if necessary, an anti-slip layer containing microcapsules that are expanded with a resin crosslinked by heating with a crosslinking agent as a matrix. It is known to form (Patent Documents 1, 2, and 3).
Moreover, what uses an aqueous emulsion as a resin matrix is also known (patent document 4).

The anti-slip layer is required to maintain a uniform uneven shape by the expanded microcapsules with high durability. For this purpose, the thermally expanded microcapsules need to be firmly fixed to the resin matrix on the substrate surface, and the resin matrix itself needs to be firmly fixed to the substrate.
In consideration of the working environment and the global environment, it is preferable not to use an organic solvent during production.

However, in the techniques of Patent Documents 1 to 3, although microcapsule particles are fixed with a crosslinked resin matrix, a crosslinked resin matrix is formed using a resin composition containing an organic solvent.
In the technique of Patent Document 4, an aqueous emulsion is used and the organic solvent does not volatilize. However, in order to ensure the durability of the resin matrix, a crosslinking step using an electron beam or the like has to be performed. For this purpose, a large-scale device is required.
Japanese Patent No. 2743898 Japanese Patent No. 3076524 JP-A-11-105176 JP-A-5-237974

  The present invention provides an anti-slip sheet that can suppress the volatilization of an organic solvent during production, does not require a large-scale apparatus, and has good slip resistance and durability. One task. Another object of the present invention is to provide a composition suitable for producing the anti-slip sheet.

  The inventors of the present invention have made various studies on the crosslinking system in an aqueous medium suitable for forming the anti-slip layer. The present invention has been completed. That is, the contents of the present invention are as follows.

The anti-slip sheet of the present invention has a sheet-like cellulose base material and an anti-slip layer constituting a surface layer of at least one surface of the cellulose base material,
The anti-slip layer comprises the following components (a) to (c):
(A) an acrylic carbonyl group-containing copolymer,
(B) An organic hydrazine derivative which is capable of crosslinking at room temperature with the carbonyl group-containing copolymer in the carbonyl group and having 0.02 mol or more and 1 mol or less and 2 or more hydrazine residues per 1 mol of the carbonyl group. ,as well as,
(C) Thermally expandable capsule particles having an average particle diameter of 20 μm or less and an expansion start temperature of 80 ° C. or more and 120 ° C. or less, and 0 for the total amount of 100 parts by mass of (a) and (b). Heating an aqueous dispersion containing thermally expandable capsule particles of more than 15 parts by weight and less than 15 parts by weight to thermally expand the thermally expandable capsule particles, and the carbonyl group-containing copolymer and the organic hydrazine derivative Is a non-slip sheet obtained by crosslinking

  According to this invention, since the aqueous dispersion is used, volatilization of the organic solvent is suppressed or avoided during film formation.

Further, in the present invention, when the aqueous dispersion is heated, the thermally expandable microcapsules are thermally expanded, and the aqueous medium of the aqueous dispersion is evaporated to flow the carbonyl group-containing copolymer particles. The fusion proceeds, and at the same time, the crosslinking reaction between the carbonyl group-containing copolymer and the organic hydrazine derivative on the surface of the copolymer particles is promoted.
The matrix in which the flow, fusion, and crosslinking reaction of the copolymer particles are promoted by heating and evaporation of the aqueous medium follows and hardens the microcapsule particles that are thermally expanded by heating. For this reason, the expanded microcapsule particles are firmly fixed to the anti-slip layer in a state where the micro-capsule particles are covered with a film of the anti-slip layer using a crosslinked copolymer of the cured copolymer as a matrix resin.
Thus, according to the present invention, an anti-slip sheet having an anti-slip layer having good anti-slip properties and durability can be obtained.

  Further, according to the present invention, since the aqueous dispersion has good permeability to the cellulosic base material, the carbonyl-containing copolymer is crosslinked in a state where the aqueous dispersion has permeated the base material. An anti-slip sheet firmly fixed to the substrate can be obtained.

  In this invention, it is preferable that the film forming temperature of the said carbonyl group containing copolymer is 0 degreeC or more and 60 degrees C or less. By having such a film forming temperature range, when the aqueous dispersion is supplied to the surface of the cellulosic substrate, the microcapsule particles can be uniformly dispersed and held on the substrate surface. At the same time, the adhesiveness after film formation and the curing of the film can be suppressed.

In the present invention, the carbonyl group-containing copolymer is preferably obtained by polymerizing a monomer composition containing an acrylamide group-containing monomer, and more preferably the acrylamide group monomer is diacetone acrylamide. Is included.
Further, the carbonyl group-containing copolymer is preferably obtained by polymerizing a monomer composition containing two or more monomers selected from acrylic acid, methacrylic acid, acrylic acid ester and methacrylic acid alkyl ester, Preferably, the carbonyl group-containing copolymer is obtained by polymerizing a monomer composition containing a styrene monomer.

The composition for forming an anti-slip layer of the present invention includes the following components (a) to (c):
(A) an acrylic carbonyl group-containing copolymer,
(B) An organic hydrazine derivative that is capable of crosslinking at room temperature with the carbonyl group-containing copolymer with the carbonyl group, and having 0.02 mol or more and 1 mol or less and 2 or more hydrazine residues per 1 mol of the carbonyl group. And (c) thermally expandable capsule particles having an average particle size of 20 μm or less and an expansion start temperature of 80 ° C. or more and 120 ° C. or less, with respect to 100 parts by mass of the total amount of (a) and (b). The composition for forming an anti-slip layer contains 0.15 parts by mass or more and less than 15 parts by mass of thermally expandable capsule particles.

  According to the resin composition for forming an anti-slip layer of the present invention, an anti-slip sheet having the above-described effects can be obtained.

Next, the anti-slip sheet and anti-slip layer forming composition of one embodiment of the present invention will be described in detail based on the drawings as appropriate.
For convenience, the resin composition for forming an anti-slip layer will be described first, and then the anti-slip sheet will be described.

[Resin composition for forming anti-slip layer]
A resin composition for forming an anti-slip layer (hereinafter also simply referred to as the present composition) contains an acrylic carbonyl group-containing copolymer, an organic hydrazine derivative, and thermally expandable microcapsule particles.
The present composition can take the form of an aqueous dispersion in which water or a water-based mixed liquid of an organic solvent compatible with water and water is used as an aqueous medium. The aqueous medium of the aqueous dispersion preferably consists only of water. Moreover, the aqueous medium can contain an alkali and an acid suitably according to the kind of functional group which a copolymer has.
In the present composition, the solid content of the following copolymer, organic hydrazine derivative, thermally expandable microcapsule particle and the like is preferably 15% by mass or more and 65% by mass or less.

<Acrylic carbonyl group-containing copolymer>
The acrylic carbonyl group-containing copolymer (hereinafter also referred to as the present copolymer) is a copolymer obtained by copolymerizing a monomer composition containing at least one acrylic monomer.

Examples of the acrylic monomer used to polymerize the copolymer include acrylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, and β-carboxyethyl acrylate.
These can be used alone or in combination of two or more.
Acrylic acid and methacrylic acid are preferred.

Another acrylic monomer is represented by the general formula: CH ₂ = C (R ¹ ) COOR ² (where R ¹ is hydrogen or a methyl group, and R ² is an alkyl group having 1 to 18 carbon atoms). (Meth) acrylic acid alkyl ester monomers.
That is, methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, heptyl group, cyclohexyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, lauryl group, tridecyl group, tetradecyl group And acrylic acid alkyl esters comprising esters of acrylic acid or methacrylic acid having a linear or branched alkyl group having 1 to 18 carbon atoms such as stearyl group and octadecyl group.
These can be used alone or in combination of two or more.

Furthermore, this copolymer contains the hydrazine derivative mentioned later and the carbonyl group which can be bridge | crosslinked at normal temperature. Such a carbonyl group can be easily introduced into the copolymer by using a monomer containing a room temperature crosslinkable carbonyl group as a copolymerization component.
Such a carbonyl group-containing monomer is not particularly limited, and examples thereof include acrylamide monomers such as acrylamide having a carbonyl group.
Considering room temperature cross-linking properties with organic hydrazine derivatives described later, for example, monomers such as diacetone acrylamide, acrolein, formyl styrene, β-hydroxypropyl acrylate acetyl acetate can be used alone or in combination of two or more. .
Preferred are diacetone acrylamide, acrolein and vinyl methyl ketone, and more preferred is diacetone acrylamide. This is because diacetone acrylamide has a copolymerizability similar to that of an acrylic acid alkyl ester, and can easily obtain a copolymer in an emulsion and rapidly undergo a crosslinking reaction with an organic hydrazine derivative.

  The acrylic monomer already described also contains a carbonyl group, but does not substantially contribute to room-temperature crosslinking with an organic dihydrazite derivative, and therefore is not treated as a carbonyl group-containing monomer in this specification. .

Moreover, this copolymer can also use monomers other than a (meth) acrylic-acid type monomer, a (meth) acrylic acid ester-type monomer, and a carbonyl group containing monomer as a copolymerization component.
That is, styrene monomers such as styrene, vinyl monomers such as acrylonitrile, vinyl chloride, vinylidene chloride and vinyl ethyl ether, various olefin monomers such as ethylene, butadiene, isoprene and chloroprene can be provided. Preferably, a styrene monomer such as styrene can be used as a copolymerization component in order to improve the water resistance of the film.
Such various monomers can be appropriately used within a range advantageous for improving the film characteristics and the like.

The film forming temperature of the copolymer is preferably 0 ° C. or higher and 60 ° C. or lower.
This is because if it is lower than 0 ° C., adhesiveness is generated after film formation, and it is not preferable because of stickiness.
Further, when the temperature exceeds 60 ° C., film formation is not sufficient at the time of coating and film formation, and the ability to hold the heat-expandable microcapsules is insufficient, so that the heat-expandable microcapsule particles cannot be included in a uniformly dispersed state Because. Further, the film quality after film formation is hard and slippery.
More preferably, the film forming temperature is 5 ° C. or higher and 40 ° C. or lower.
The film forming temperature is measured with the apparatus described in 5.11 Minimum film forming temperature in accordance with the test method for JIS K6828 synthetic resin emulsion. As the minimum film-forming temperature measuring device, for example, a MET film-forming tester manufactured by Toyo Seiki Seisakusho Co., Ltd. can be used.

  In this copolymer, in addition to (meth) acrylic acid, ethyl (meth) acrylate, butyl (meth) acrylate, from the viewpoints of adhesion to the substrate, ease of film formation, and coefficient of friction after film formation Two or more selected from (meth) acrylic acid alkyl esters such as isopropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate can be preferably used as the copolymerization component.

In the present polymer, the copolymerization ratio of (meth) acrylic acid-based monomer such as (meth) acrylic acid and (meth) acrylic acid alkyl ester and an acrylamide-based carbonyl group-containing monomer can be appropriately adjusted according to the purpose. is there.
For example, from the viewpoint of the toughness of the film formed, the (meth) acrylic acid monomer in the copolymer is preferably 80% by mass or more and 99.9% by mass or less, more preferably 85% by mass. % To 98% by mass.
Moreover, it is preferable that an acrylamide type carbonyl group containing monomer is 0.1 to 20 mass% from a crosslinkable viewpoint, More preferably, it is 2 to 15 mass%.

This copolymer can be obtained by copolymerizing the above monomers in an organic solvent according to a polymerization method known per se.
Examples of the organic solvent that can be used for copolymerization include ester solvents such as ethyl acetate and butyl acetate; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; petroleum solvents such as mineral spirits and aromatic petroleum naphtha; Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol and isobutanol; ether solvents such as dioxane and tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, ethylene glycol monoisobutyl ether, ethyl Ethylene glycol ether solvents such as glycol mono tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono n-propyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono tert-butyl ether Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol monoisopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Roh n- propyl ether, propylene glycol ethers such as dipropylene glycol monoisopropyl ether solvent; and the like.
These can be used alone or in combination of two or more.

In addition, the polymerization initiator may be either oil-soluble or water-soluble.
Examples of the oil-soluble polymerization initiator include organic peroxides such as benzoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide; azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile) ) And the like.
Examples of water-soluble polymerization initiators include cumene hydroperoxide, tert-butyl peroxide, tert-butyl peroxylaurate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxyacetate, diisopropylbenzene hydroperoxide Organic peroxides such as: azobis (2-methylpropiononitrile), azobis (2-methylbutyronitrile), 4,4′-azobis (4-cyanobutanoic acid), dimethylazobis (2-methylpropionate) Azo compounds such as azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], azobis {2-methyl-N- [2- (1-hydroxybutyl)]-propionamide}; potassium persulfate , Ammonium persulfate, sodium persulfate Persulfates such as Um like.
These can be used alone or in combination of two or more.

In the copolymerization, a chain transfer agent can be used as necessary.
Such chain transfer agents include compounds having a mercapto group. For example, lauryl mercaptan, t-dodecyl mercaptan, octyl mercaptan, 2-ethylhexyl thioglycolate, 2-methyl-5-tert-butylthiophenol, mercaptoethanol, thioglycerol, mercaptoacetic acid (thioglycolic acid ), Mercaptopropionate, n-octyl-3-mercaptopropionate, and the like.
These can be used alone or in combination of two or more.

The above copolymerization reaction can usually be performed at a temperature of about 50 to about 200 ° C., preferably about 60 to about 120 ° C., and is completed under such conditions for 2 to 20 hours, preferably about 5 to 10 hours. be able to.
The copolymer thus produced preferably has a weight average molecular weight (Mw) of about 200,000 to 1,000,000 from the viewpoint of the strength of the film after film formation.

  In addition, in this specification, a weight average molecular weight is the value which converted the weight average molecular weight measured with the gel permeation chromatograph on the basis of the weight average molecular weight of polystyrene.

<Organic hydrazine derivative>
The present composition contains an organic hydrazine derivative that crosslinks with a carbonyl group contained in the copolymer.
The organic hydrazine derivative is not particularly limited, and an organic hydrazine derivative having two or more hydrazine residues is used.
Specifically, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecandiodiohydradiide, Acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 1,4-naphthoic acid dihydrazide, 4,4'-bisbenzene Dihydrazide, dimer acid dihydrazide, 2,6-pyridinedihydrazide, iminodiacetic acid dihydrazide, citric acid trihydrazide, cyclohexanetricarbo Acid trihydrazide, and the like.
These can be used alone or in combination of two or more.
As such an organic hydrazine derivative, preferably, adipic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide and ethylenediaminetetraacetic acid tetrahydrazide can be used, more preferably adipic acid dihydrazide. Is used. Adipic acid dihydrazide can react quickly with the carbonyl group of diacetone acrylamide at room temperature to form a film with excellent water resistance.

The organic hydrazine derivative is preferably contained in an amount of 0.02 mol or more and 1 mol or less per mol of the room temperature crosslinkable carbonyl group.
This is because within this range, the film strength after film formation increases. Moreover, it is because the film intensity | strength after film-forming will become low too much that it is less than 0.02 mol, and when it exceeds 1 mol, it may exhibit toxicity later because of an excess hydrazine.
More preferably, it is 0.05 mol or more and 0.5 mol or less.

<Heat-expandable microcapsule particles>
The composition contains thermally expandable microcapsule particles.
As the thermally expandable microcapsule particles, for example, any particles prepared by an appropriate method such as a coacervation method or an interfacial polymerization method can be used.
The heat-expandable microcapsule particles contain low-boiling hydrocarbons such as n-butane, i-butane, pentane, and neopentane as substances encapsulated in the shell, and vinylidene chloride, acrylonitrile, (meth) acrylic acid as the shell. Some use a thermoplastic resin whose main component is a (meth) acrylic acid ester such as methyl and an aromatic vinyl compound such as styrene.
Examples of such thermally expandable microcapsule particles include Matsumoto Microsphere (registered trademark) F from Matsumoto Yushi Seiyaku Co., Ltd. and EXPANCEL (trademark) from Nippon Philite Co., Ltd.

The average particle size of the microcapsules (before expansion) is preferably 20 μm or less. It is because a coating film will become thick when it exceeds 20 micrometers.
The expansion start temperature is preferably 80 ° C. or higher and 120 ° C. or lower. This is because if the temperature falls below 80 ° C., the shell does not expand, and if the temperature exceeds 120 ° C., the shell is destroyed. More preferably, it is 80 degreeC or more and 100 degrees C or less.

Moreover, it is preferable that content of a thermally expansible microcapsule particle is more than 0.5 mass part and less than 10 mass parts with respect to 100 mass parts of this copolymer (total mass of a monomer).
This is because the slip resistance is insufficient when the amount is 0.5 parts by mass or less, and the cost is increased when the amount is 15 parts by mass or more. More preferably, they are 1 mass part or more and 5 mass parts or less.

  In addition, the present composition contains an inorganic filler such as calcium carbonate, titanium oxide, magnesium hydroxide, clay, sodium silicate, magnesium carbonate, or the like to prevent blocking, change the texture, and reduce costs. Other additives such as a dispersant for ensuring dispersibility, a surfactant, a preservative, and the like can be included as necessary.

[Non-slip sheet]
Next, an anti-slip sheet provided with an anti-slip layer obtained by using the present composition as an aqueous dispersion of the copolymer will be described.
An example of the non-slip sheet is shown in FIG.
The anti-slip sheet (hereinafter simply referred to as “this sheet”) 2 includes a sheet-like cellulosic substrate 4 and an anti-slip layer 8 formed on at least one surface thereof. The anti-slip layer 8 has a convex portion 7 made of microcapsule particles 6 obtained by forming a film by supplying the present composition as an aqueous dispersion.
The anti-slip layer 8 may be formed on both surfaces of the cellulosic substrate 4.
In addition, when the anti-slip layer 8 is formed only on one surface of the cellulosic substrate 4, a layer suitable for fixing the sheet 2 itself such as an adhesive layer on the surface where the anti-slip layer 8 is not formed. May be formed.

The cellulosic substrate 4 in the present sheet is formed into a sheet shape using a cellulosic material. A typical example is paper. In addition, a nonwoven fabric, a woven fabric, a knitted fabric, etc. may be sufficient. Examples of the paper include various types of paper such as high-quality paper, bleached kraft paper, kraft paper, thin paper, pure white roll paper, imitation paper, paperboard, cardboard, and corrugated paper.
Although the thickness of the sheet-like cellulose base material 4 is not specifically limited, It is suitably determined according to the application location, intensity | strength, etc. of a non-slip sheet.

  The anti-slip layer 8 is obtained by supplying the composition to the surface of the cellulosic substrate 4 and heating it to form a film. Hereinafter, based on FIG. 2, the formation process (the manufacturing method of this sheet | seat 2) of the antiskid layer 8 is demonstrated.

As shown in FIG. 2A, an aqueous dispersion of the present copolymer prepared using a suitable aqueous medium on the surface of the cellulose-based substrate 4 (including thermally expandable microcapsule particles and an organic hydrazine derivative). The present composition 10 is supplied.
When the present composition 10 is supplied to the surface of the cellulose-based substrate 4, the present composition 10 forms a film having a certain thickness on the surface of the cellulose-based substrate 4.
When the film forming temperature of the copolymer is 5 ° C. or more and 60 ° C. or less, when the composition 10 is supplied to the surface of the cellulosic substrate 4 at room temperature, the composition 10 On the surface, the heat-expandable microcapsule particles (before expansion) 5 can be held in a film shape while being held in a uniformly dispersed state.

  At this time, in this composition 10, the carbonyl group in the copolymer and the organic hydrazine derivative are undergoing a crosslinking reaction. However, in the present composition 10, the present copolymer and the organic hydrazine derivative are in progress. The cross-linking reaction is not immediately completed due to the concentration relationship.

  It does not specifically limit about the supply method to the cellulose base material 4 of this composition 10, A well-known various method is employable. For example, a bar coater, an air knife coater, a gravure coater, a roll coater or the like can be used.

Next, the composition 10 is heated as shown in FIG.
The expansion start temperature of the thermally expandable microcapsule particles 5 in the composition 10 is 80 ° C. or higher and 120 ° C. or lower, preferably 80 ° C. or higher and 100 ° C. or lower. The boiling point of the aqueous medium in the composition 10 is about 100. ° C. For this reason, the microcapsule particles 5 in the present composition 10 are heated so that they can be thermally expanded, that is, at least 80 ° C.

The method for heating the present composition 10 on the cellulosic substrate 4 is not particularly limited, and an appropriate heat source or furnace form may be appropriately selected from a known heating furnace and employed.
Usually, a heating and film-forming process can be implemented by introduce | transducing what supplied this composition 10 on the cellulose base material 4 to the heating furnace which has a suitable heat source.
For example, in heating with a hot air dryer, conditions such as a set temperature of 105 ° C. or more and 140 ° C. or less and a heating time of 30 seconds or more and 5 minutes or less can be set.

The heating facilitates the flow of the dispersed copolymer particles, and the aqueous medium in the composition 10 evaporates. As a result, the dispersed copolymer particles are brought close to each other, Fusion is promoted. At the same time, the cross-linking reaction between the carbonyl group in the cross-linkable copolymer and the organic hydrazine derivative is promoted by increasing the concentration by heating and evaporation of the aqueous medium.
On the other hand, the thermally expandable microcapsule particles 5 are thermally expanded by heating.
Thus, by heating the present composition 10, in the present composition 10, the evaporation of the aqueous medium, the flow and fusion of the present copolymer particles, the crosslinking reaction of the present copolymer, The expansion of the capsule particles 5 proceeds simultaneously.

Since the aqueous medium evaporates by heating, flow and fusion of the copolymer particles and a crosslinking reaction between the copolymer and the organic hydrazine derivative, which is an external crosslinking agent, occur. The resin matrix-forming components of the layer 8 (the present copolymer and the organic hydrazine derivative) allow and follow the expansion of the encapsulated microcapsule particles 5 with heating.
Then, a cross-linked membrane formed by encapsulating the expanded microcapsule particles 6 reliably, that is, as shown in FIG. 2 (c), a convex portion 7 in which the expanded microcapsule particles 6 are covered with a resin matrix. The anti-slip layer 8 as a resin film can be obtained.
Thus, the present sheet 2 (FIG. 1) is manufactured.

  The thickness of the anti-slip layer 8 of the anti-slip sheet 2 obtained in this manner can be determined as appropriate according to the purpose of use of the anti-slip sheet, but in general, it is reduced in thickness, cushioning properties, soft touch, etc. From the point, it can be 3 μm or more and 1 mm or less, more preferably 10 μm or more and 1 mm or less.

  As described above, in the present sheet 2, since the microcapsule particles 6 are reliably covered with the resin matrix in the antislip layer 8 and the microcapsule particles 6 are suppressed from being exposed, the antislip property is durable. It is demonstrated continuously with good quality.

In the present sheet 2, since the present composition 10 is an aqueous dispersion, volatilization of harmful organic solvents can be remarkably or completely avoided during heating.
Furthermore, since this composition 10 is an aqueous dispersion, it has permeability to the surface layer of the cellulose-based substrate 4. As a result, the present copolymer and the organic hydrazine derivative in the present composition 10 are cross-linked even inside the surface layer of the cellulosic substrate 4 and exhibit an anchor effect. For this reason, the anti-slip layer 8 is firmly fixed to the surface of the cellulosic substrate 4, and the durability of the anti-slip property is ensured.

The anti-slip sheet of the present invention is used to prevent slipping of products by inserting them between products when stacking products, tableware on an unstable table such as a table in a transport body including various vehicles, etc. It can be used for anti-slip applications that suppress the fall and movement of
In addition, the anti-slip sheet of the present invention includes floors, stairs, handrails and shelves, bookshelves and cupboards, desks and tables, surface treatments, mats, carpets, linings such as tatami mats, table cloths, shoes, cardboard and gloves. It can also be used for anti-slip applications such as forming.

Based on the composition shown in Table 1, each coating liquid was prepared about Examples 1-5 and Comparative Examples 1-5, and the anti-slip sheet was produced.
That is, after preparing a monomer mixture (acrylic carbonyl group-containing copolymer monomer) with the composition shown in Table 1, an emulsion polymerization solution was prepared using an initiator, an emulsifier and water, and a hydrazide mixture was added thereto. Thus, an emulsion polymerization adjusting solution was obtained. A thermally expandable microcapsule was added to the emulsion polymerization adjusting solution to prepare a coating solution.
Hereinafter, taking Example 1 as an example, the preparation process of the coating liquid from the preparation of the emulsion polymerization liquid and the preparation process of the non-slip sheet will be described. For Examples 2 to 5 and Comparative Examples 1 to 5, anti-slip sheets were prepared in accordance with Example 1.

In a 1 L flask equipped with a stirrer having a temperature control function, a reflux condenser, and a raw material inlet, 100 parts by mass of ion-exchanged water, 2 parts by mass of sodium dodecylbenzenesulfonate as an emulsifier, 0. 6 parts were added and the temperature was raised to 70 ° C. with stirring.
There, a mixed solution of 46 parts by mass of styrene, 1.6 parts by mass of acrylic acid, 10 parts by mass of ethyl acrylate, 39.7 parts by mass of 2-ethylhexyl acrylate, and 2.7 parts by mass of diacetone acrylamide was spent for 4 hours. And dripped.
After completion of dropping, the mixture was held at 70 ° C. for 1 hour, then heated to 80 ° C. and further held for 1 hour. After cooling, the pH was adjusted to 8-9 with aqueous ammonia to obtain an aqueous copolymer dispersion (emulsion polymerization solution).

Next, 1.8 parts by mass of 20% adipic acid dihydrazide previously diluted with 9 parts by mass of hot water at 60 ° C. as a compound having a hydrazide group is added to the emulsion polymerization liquid, and dispersed uniformly with a stirrer. Thus, an emulsion polymerization adjusting liquid was obtained.
To this emulsion polymerization adjusting solution, 3 parts by weight of Matsumotomi spheres (thermal expansion microcapsules) having a particle size of 5 μm was added with respect to 100 parts by weight of the monomer mixture, and forced stirring was performed with a disper for 20 minutes.
Although not shown in Table 1, 0.03 parts by mass of SN deformer 363 manufactured by San Nopco Co., Ltd. was added as an antifoaming agent. Further, although not shown in Table 1, 0.35 parts by mass of an alkali thickening type thickener was added to adjust the viscosity of the coating liquid, and the viscosity of the liquid was adjusted to 1750 mPa · s.

The coating solution thus produced was applied to 50 g / m ² bleached kraft paper (30 cm × 21 cm) with a wet film thickness of 35 μm using an applicator having a width of 5 cm and a thickness of 0.05 mm. After the coating, it was immediately put into a hot air drier previously adjusted to a set temperature of 120 ° C., and heated and dried.

  About the obtained non-slip | slipping sheet | seat of Example 1, the coating-film state was observed visually and the static friction coefficient was measured. The static friction coefficient was measured by SLIP ANGLE TETER AN manufactured by Toyo Seiki Seisakusho Co., Ltd. Moreover, the measurement was performed based on the friction coefficient test method of JIS P8147 paper and paperboard. The results are also shown in Table 1.

As shown in Table 1, all of the anti-slip sheets of Examples 1 to 5 were in a good coating state, and the static friction coefficient was 52 ° to 55 °.
On the other hand, in the anti-slip sheets of Comparative Examples 1 to 5, whether the coating film strength is low and the coating film is broken, the surface is rough, or the friction coefficient is too low, and the anti-slip sheet It did not function as a sheet.

It is sectional drawing which shows the slip prevention sheet of one Embodiment of this invention. It is sectional drawing which shows the manufacturing process of the non-slip sheet of one Embodiment of this invention.

Explanation of symbols

2 Non-slip sheet 4 Cellulose base material 5 Thermally expandable microcapsule particles (before expansion)
6 Thermally expanded microcapsule particles 7 Convex part 8 Anti-slip layer 10 Composition for forming anti-slip layer

Claims (7)

A sheet-like cellulosic substrate;
An anti-slip layer constituting a surface layer of at least one surface of the cellulose-based substrate;
The anti-slip layer comprises the following components (a) to (c):
(A) an acrylic carbonyl group-containing copolymer,
(B) An organic hydrazine derivative which is capable of crosslinking at room temperature with the carbonyl group-containing copolymer in the carbonyl group and having 0.02 mol or more and 1 mol or less and 2 or more hydrazine residues per 1 mol of the carbonyl group. ,as well as,
(C) Thermally expandable capsule particles having an average particle diameter of 20 μm or less and an expansion start temperature of 80 ° C. or more and 120 ° C. or less, and 0 for the total amount of 100 parts by mass of (a) and (b). Heating an aqueous dispersion containing thermally expandable capsule particles of more than 15 parts by weight and less than 15 parts by weight to thermally expand the thermally expandable capsule particles, and the carbonyl group-containing copolymer and the organic hydrazine derivative An anti-slip sheet obtained by crosslinking The anti-slip sheet according to claim 1,
The anti-slip sheet | seat whose film forming temperature of the said carbonyl group containing copolymer is 0 degreeC or more and 60 degrees C or less. The anti-slip sheet according to claim 1 or 2,
The carbonyl group-containing copolymer is an anti-slip sheet obtained by polymerizing a monomer composition containing an acrylamide monomer containing a carbonyl group. The anti-slip sheet according to claim 3,
The non-slip sheet, wherein the acrylamide monomer includes diacetone acrylamide. The anti-slip sheet according to any one of claims 1 to 4,
The carbonyl group-containing copolymer is a non-slip sheet obtained by polymerizing a monomer composition containing two or more types of monomers selected from acrylic acid, methacrylic acid, acrylic acid ester and methacrylic acid alkyl ester.   The anti-slip sheet according to claim 5, wherein the carbonyl group-containing copolymer is obtained by polymerizing a monomer composition containing a styrene monomer. The following components (a) to (c):
(A) an acrylic carbonyl group-containing copolymer,
(B) An organic hydrazine derivative that is capable of crosslinking at room temperature with the carbonyl group-containing copolymer with the carbonyl group, and having 0.02 mol or more and 1 mol or less and 2 or more hydrazine residues per 1 mol of the carbonyl group. ,as well as,
(C) Thermally expandable capsule particles having an average particle diameter of 20 μm or less and an expansion start temperature of 80 ° C. or more and 120 ° C. or less, and 0 for the total amount of 100 parts by mass of (a) and (b). A composition for forming an anti-slip layer containing thermal expandable capsule particles of more than 15 parts by weight and less than 15 parts by weight.