JPH11116723A - Antislip material composition and production of antislip material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition excellent in antislip properties and antiblocking property before and after foaming by blending fine particles containing a foaming agent with an aqueous resin emulsion obtained by emulsion polymerization of an unsaturated monomer mixture in the presence of a protective colloid comprising a water-dispersible copolymer having a specified glass transition temperature. SOLUTION: This composition consists of an aqueous resin emulsion which is obtained by subjecting a mixture (A) of unsaturated monomers containing polymerizable double bonds to emulsion polymerization in an aqueous dispersion medium comprising water having a water-dispersible copolymer (B) dispersed therein and which has a mean particle diameter of 0.03-0.08 μm, and fine particles which contain a foaming agent and which foam by heating. The component B has a Tg of at least 30 deg.C, consists of 3-40 wt.% ethylenically unsaturated carboxylic acid units and the balance of unsaturated monomer units copolymerizable therewith, and has a mean particle diameter of 0.005-0.03 μm in the aforementioned aqueous dispersion medium. The component A is a mixture of those monomers which, when copolymerized, give a copolymer having a Tg of -30 to 10 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a composition for an anti-slip material having excellent anti-slip properties and anti-blocking properties, and a method for producing an anti-slip material using the same.

[0002]

2. Description of the Related Art Conventionally known methods for imparting anti-slip properties to substrates such as paper, film and non-woven fabric include rubbers having high rebound resilience such as silicone rubber and urethane rubber, and inorganic particles such as silica. Alternatively, a method of applying a composition such as a foaming agent-containing particle that swells due to heat and a soft binder may be used.

[0003] Among them, those containing foaming agent-containing particles and a soft binder as basic components have excellent anti-slip properties and are used in a wide range of applications.

[0004]

However, when a soft binder is used, it is very difficult to achieve both anti-slip properties and blocking resistance before and after foaming. In other words, the anti-slip property and the anti-blocking property are contradictory properties. If the glass transition temperature of the binder is lowered too much in order to exhibit a certain degree of anti-slip property, blocking occurs during winding or lamination of the anti-slip coated base material before foaming. Problem, and sufficient blocking resistance cannot be obtained even after foaming. For this reason,
There is a possibility that the slip resistance may be reduced due to the adhesion of dust and the like.

SUMMARY OF THE INVENTION In view of the above problems, the present invention provides a composition for an anti-slip material capable of obtaining an anti-slip material having excellent anti-slip properties and anti-blocking properties before and after foaming, and production of an anti-slip material produced using the same. It provides a method.

[0006]

According to the first aspect of the present invention, there is provided an aqueous dispersion medium comprising a water-dispersible copolymer (A) dispersed in water.
The average particle diameter obtained by emulsion polymerization of the unsaturated monomer mixture (B) containing a polymerizable double bond is 0.03.
A composition for an anti-slip material comprising an aqueous resin emulsion (I) having a thickness of 3 to 0.08 μm and foaming agent-containing fine particles (II) which foams by heating, wherein the water-dispersible copolymer (A)
Is an unsaturated monomer having a glass transition temperature (Tg) of 30 ° C. or higher, 3 to 40% by weight of an ethylenically unsaturated carboxylic acid unit (A1) and copolymerizable with the above ethylenically unsaturated carboxylic acid. The unit (A2) is the balance, and the average particle diameter in the aqueous dispersion medium is 0.005 to 0.05.
3 μm, and the unsaturated monomer mixture (B) has a glass transition temperature (Tg) of -30 to 10 ° C. in a copolymer obtained by copolymerizing the unsaturated monomer mixture (B). The composition for anti-slip material to be used.

The operation and effect of the present invention will be described below. The composition for an anti-slip material according to the present invention comprises an aqueous resin emulsion (I) having the above-mentioned properties and a foaming agent-containing fine particle (II).

Therefore, when the composition for an anti-skid material according to the present invention is applied to a substrate and dried, the glass transition temperature (Tg)
The water-dispersible copolymer (A) having a high Tg forms a film on the surface layer, and further has the blowing agent-containing fine particles (II) having a high Tg, whereby the blocking can be suppressed. Thereafter, the film undergoes a phase transition by heating, for example, at a temperature equal to or higher than the Tg of the water-dispersible copolymer (A) and at a temperature equal to or higher than the foaming temperature of the foaming agent-containing fine particles (II). The coalesced (A) appears in the inner layer, the low Tg component derived from the copolymer of the unsaturated monomer mixture (B) appears in the surface layer, and the foaming agent-containing fine particles (II) further have surface irregularities due to foaming. Thereby, an anti-slip material having both good anti-slip property and anti-blocking property can be obtained.

As described above, according to the present invention, it is possible to provide a composition for an anti-slip material capable of obtaining an anti-slip material having excellent anti-slip properties and blocking resistance before and after foaming.

Next, the aqueous resin emulsion (I) according to the present invention will be described. The aqueous resin emulsion (I) is obtained by emulsion-polymerizing the unsaturated monomer mixture (B) using the water-dispersible copolymer (A) as a protective colloid. The average particle size of the aqueous resin emulsion (I) is 0.03 to 0.08 μm.

As a result, the uniform dispersibility of the foaming agent-containing fine particles (II) in the anti-slip material composition and the uniform foamability can be enhanced. This average particle size is 0.03
If it is less than μm, the dispersion stability of the foaming agent-containing fine particles (II) may be reduced, and the storage stability may be reduced. On the other hand, if it exceeds 0.08 μm, uniform foaming may not be obtained during heating.

Next, as described above, the aqueous resin emulsion (I) according to the present invention is obtained by emulsion-polymerizing the unsaturated monomer mixture (B) using the water-dispersible copolymer (A) as a protective colloid. Can be

In the above emulsion polymerization, other emulsifiers and other dispersants can be used in combination to such an extent that the excellent properties of the water-dispersible copolymer (A) according to the present invention are not impaired. . Other emulsifiers used in this manner include, for example, anionic surfactants such as sodium dialkyl sulfosuccinate, alkali metal salts of alkyl sulfonic acids, alkyl metal salts of oxyalkylated alcohols or alkyl phenols, and alkali metal salts of fatty acids. And nonionic surfactants.

In the above-mentioned emulsion polymerization, the water-dispersible copolymer (A) has a reduced dispersibility in the acidic region, so that special consideration is required in the acidic region. That is, when the above emulsion polymerization is performed using an unsaturated carboxylic acid such as acrylic acid or methacrylic acid, or when a persulfate is used as an initiator, the reaction system of the emulsion polymerization is in an acidic region. It is easy to tilt and may become unstable. Therefore, in such a case, it is desirable to add an alkali to the emulsion polymerization reaction system to stabilize the reaction system.

The water-dispersible copolymer (A) according to the present invention may be a mixture of two or more kinds having different compositions. Emulsion polymerization using them may be carried out in accordance with a conventional method, in which case a polymerization initiator is used.

As the polymerization initiator, it is preferable to use, for example, inorganic peroxides such as potassium persulfate, sodium persulfate, ammonium persulfate and hydrogen peroxide. Other polymerization initiators include azo initiators such as azobisisobutyronitrile and azobisvaleronitrile, and organic peroxide initiators such as benzoyl peroxide, lauroyl peroxide and t-butyl peroxide. You can also. In addition, Rongalit,
A redox initiator can be used in combination with a reducing agent such as L-ascobic acid, an organic amine, or a metal salt.

Next, the blowing agent-containing fine particles (II) according to the present invention will be described. The fine particles containing the blowing agent (I
Examples of I) include, for example, n- as a blowing agent in fine particles composed of a thermoplastic resin containing vinylidene chloride, acrylonitrile, methyl methacrylate, and styrene as main components.
Materials containing a low-boiling hydrocarbon such as butane, i-butane, pentane, and neopentane can be used.

Next, the water-dispersible copolymer (A) used in the present invention will be described in detail. As described above, the water-dispersible copolymer (A) contains 3 to 40% by weight of the ethylenically unsaturated carboxylic acid unit (A1) and an unsaturated monomer unit copolymerizable with the ethylenically unsaturated carboxylic acid ( A2) is a copolymer comprising the remainder. Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, and itaconic acid.

When the amount of the ethylenically unsaturated carboxylic acid is less than 3% by weight, even if an alkali is added, it is not sufficiently dispersed in water, and it may be difficult to realize stable emulsion polymerization. On the other hand, when it exceeds 40% by weight, the particle size of the particles of the aqueous resin emulsion (I) obtained after the emulsion polymerization increases,
When the composition for anti-skid material blended with the foaming agent-containing fine particles (II) is applied and foamed, the uniformity of foaming may be reduced. In addition, the phase transition hardly occurs, and the slip resistance may be insufficient. The lower limit of the content of the ethylenically unsaturated carboxylic acid is more preferably 5% by weight. The upper limit is more preferably set to 20% by weight.

The unsaturated monomer copolymerizable with the ethylenically unsaturated carboxylic acid constituting the water-dispersible copolymer (A) used in the present invention is not particularly limited. A substance can be exemplified.

That is, an alkyl ester of acrylic acid or methacrylic acid having 1 to 18 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, t-butyl, 2-butyl, acrylic acid or methacrylic acid) Esters such as ethylhexyl, lauryl and stearyl), vinyl aromatic compounds (eg, styrene),
Vinyl halides (eg, vinyl chloride, vinylidene chloride), unsaturated monomers containing epoxy groups (eg, glycidyl methacrylate), unsaturated monomers containing hydroxyl groups (eg, 2-hydroxyethyl methacrylate, 3-
Hydroxypropyl acrylate), unsaturated carboxamides (eg, acrylamide, methacrylamide), N-alkyl and / or N-alkylol derivatives of unsaturated carboxamides (eg, N-methylacrylamide, N-isobutyl) Acrylamide, N-methylol acrylamide, N-methylol methacrylamide), saturated vinyl carboxylate (eg, vinyl acetate, vinyl propionate), acrylonitrile, methacrylonitrile, and the like.

Next, the average particle diameter of the water-dispersible copolymer (A) according to the present invention in the aqueous dispersion is 0.005 to 0.005.
0.03 μm. If the average particle size is less than 0.005 μm, the particle size of the particles of the aqueous resin emulsion (I) obtained after emulsion polymerization may increase.
Therefore, when the composition for anti-skid material obtained by blending the aqueous resin emulsion (I) with the foaming agent-containing fine particles (II) is applied and foamed, there is a possibility that the uniformity of foaming may be reduced. On the other hand, when it exceeds 0.03 μm, there is a possibility that the stability of emulsion polymerization may be reduced.

Incidentally, an unsaturated monomer copolymerizable with the ethylenically unsaturated carboxylic acid is selected in accordance with the amount of the ethylenically unsaturated carboxylic acid constituting a part of the water-dispersible copolymer (A). Therefore, it is preferable to balance hydrophilic / hydrophobic. This makes it possible to control the average particle size of the water-dispersible copolymer (A) in the aqueous dispersion.

For example, in a composition in which the amount of ethylenically unsaturated carboxylic acid is small, the amount of acrylic acid or methacrylic acid ester having an alkyl group having a small number of carbon atoms such as methyl methacrylate having relatively high hydrophilicity is increased. Is preferred.

On the other hand, in a composition in which the amount of ethylenically unsaturated carboxylic acid is large, the amount of acrylic acid, methacrylic ester or styrene having an alkyl group having a large number of carbon atoms such as butyl methacrylate having relatively high hydrophobicity is reduced. It is preferable to increase. The “average particle diameter” in the present specification indicates a weight average particle diameter measured by a dynamic light scattering method.

Next, the glass transition temperature (hereinafter abbreviated as Tg) of the water-dispersible copolymer (A) according to the present invention is 30.
° C or higher. By the way, generally, the Tg of a copolymer is [1
/ Tg = ΣWi / Tgi ”can be calculated by the Fox equation. In the above formula, Wi is the weight fraction of each component present in the copolymer, and Tgi is Tg (K) of the homopolymer of each component. The Tg of the homopolymer is
J. Brandup and H.C. Immergut Pol
ymer Handbook, 2nd edition, John Wil
ey & Sons, New York, 139-19
It is available in numerous publications, including page 2 (1975).

If the Tg is less than 30 ° C., the anti-slipping layer before foaming may have insufficient blocking resistance. The preferable upper limit of the Tg is 70 ° C.

The weight average molecular weight of the water-dispersible copolymer (A) is not particularly limited, but is preferably from 1,000 to 30,000 from the viewpoint of polymerization stability and phase transition. The more preferred upper limit is 20,000, and the more preferred lower limit is 5,000.

Next, a method for producing the water-dispersible copolymer (A) according to the present invention will be described. Examples of the production method include a method according to a conventional method such as solution polymerization performed in an organic solvent, bulk polymerization using no solvent, suspension polymerization in water, and emulsion polymerization. Among these methods, water-dispersible copolymer (A) having a uniform particle size distribution
It is preferable to use solution polymerization because it facilitates the production of.

The organic solvent used in the solution polymerization is
Although not particularly limited, isopropyl alcohol, n-
Examples thereof include alcohols such as butyl alcohol and s-butyl alcohol, and cellosolves such as butyl cellosolve.

Examples of the polymerization initiator used in the above solution polymerization include organic peroxides such as benzoyl peroxide and t-butyl hydroperoxide, and azo initiators such as azobisisobutyronitrile. It is also possible to use a chain transfer agent such as an organic halide or an alkyl mercaptan as a molecular weight regulator.

From the resin solution obtained by the above solution polymerization,
After distilling off the solvent under reduced pressure, water and alkali are added, and if necessary, the organic solvent is distilled off under reduced pressure, whereby an aqueous dispersion of the water-dispersible copolymer (A) according to the present invention can be obtained. At this time, the amount of the organic solvent remaining in the aqueous dispersion is
From the viewpoint of miniaturization of particles, the content is preferably 1% by weight or less of the copolymer. Further, it is more preferable that the content be 0.5% by weight or less.

Further, as the above-mentioned alkali, an organic amine such as ammonia, triethylamine, ethanolamine, 2-amino-2-methylpropanol or sodium hydroxide can be used. In the case of bulk polymerization, suspension polymerization or emulsion polymerization, it is essential to use a chain transfer agent for controlling the molecular weight.

Next, the unsaturated monomer mixture (B) according to the present invention will be described. In the unsaturated monomer mixture (B), the copolymer obtained by copolymerizing the unsaturated monomer mixture (B) has a Tg of -30 to -1.
0 ° C. If the Tg is lower than -30 ° C, the blocking property of the anti-slip layer after foaming may be insufficient. On the other hand, when the temperature exceeds 10 ° C., the slip resistance after foaming may be insufficient.

The anti-slip material composition according to the present invention may contain, if necessary, pigments such as silica, aluminum hydroxide, calcium carbonate, kaolin, titanium oxide, plastic pigment, release agents such as polyethylene wax, etc. Auxiliary agents such as surfactants, dispersants, antistatic agents, fire fighting agents, coloring agents, fluorescent dyes, antioxidants, and thickeners can be added and used.

Next, as in the second aspect of the present invention, the water-dispersible copolymer (A) is mixed with the unsaturated monomer mixture (B).
It is preferable to use 25 to 100 parts by weight with respect to 100 parts by weight. This makes it possible to ensure polymerization stability during the emulsion polymerization of the unsaturated monomer mixture (B), and to achieve both good blocking resistance before foaming and good slip resistance after foaming. If the amount is less than 25 parts by weight, the polymerization stability may decrease, the particle size of the resulting aqueous resin emulsion (I) may increase, and the blocking resistance before foaming may be insufficient. There is. On the other hand, if it exceeds 100 parts by weight, the uniformity of foaming may be reduced, and the slip resistance may be insufficient.

Next, as in the third aspect of the present invention, the unsaturated monomer mixture (B) comprises (a) an alkyl ester of acrylic acid or methacrylic acid having less than 8 carbon atoms of 20 to 9;
5% by weight, (b) 0 to 40% by weight of an alkyl ester of acrylic acid or methacrylic acid having 8 to 18 carbon atoms,
(C) 5 to 40% by weight of a vinyl aromatic compound and (d) 2 or more types selected from 0 to 30% by weight of other monomers (provided that (a) + (b) + (c) + ( d) = 100% by weight).

As a result, it is possible to obtain the effects of ensuring the stability of the emulsion polymerization and of making the obtained aqueous resin emulsion (I) into fine particles.

When the amount of the component (a) is less than 20% by weight, the particle diameter of the aqueous resin emulsion (I) may increase due to instability of polymerization. On the other hand, when the content of the component (a) exceeds 95% by weight, the amount of the ethylenically unsaturated carboxylic acid unit (A1) is reduced as a result, and the polymerization may be destabilized and aggregates may increase. .

When the number of carbon atoms is 8 or more, the hydrophobicity is improved, and the polymerization stability may be reduced. Note that the lower limit of the number of carbon atoms is preferably set to 1 in order to secure polymerization stability.

In the above component (b), when the number of carbon atoms exceeds 18, the copolymerizability is low, and the amount of the monomer after the polymerization may increase. When the component (b) exceeds 40% by weight, the particle size increases,
The polymerization stability may be significantly reduced.

When the amount of the component (c) exceeds 40% by weight, the particle size increases, and the polymerization stability may be significantly reduced. On the other hand, if it is less than 5% by weight, the particle size may increase. When the component of the above (d) is 30
If the amount is more than 10% by weight, the polymerization stability may be significantly reduced.

As the component (a), for example,
Methyl or ethyl acrylate or methacrylate, n-propyl, n-butyl, isobutyl,
Esters such as t-butyl can be mentioned. Also,
Examples of the component (b) include esters of acrylic acid or methacrylic acid such as 2-ethylhexyl, lauryl, and stearyl. Examples of the component (c) include styrene, 4-methylstyrene, and α-methylstyrene.

As the component (d), for example,
Unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid), unsaturated carboxylic amides (eg, acrylamide, methacrylamide), saturated vinyl carboxylic esters (eg, vinyl acetate, vinyl propionate),
Acrylonitrile, methacrylonitrile, vinyl halide (eg, vinyl chloride, vinylidene chloride), unsaturated monomer containing epoxy group (eg, glycidyl methacrylate), unsaturated monomer containing hydroxyl group (eg, 2
-Hydroxyethyl methacrylate, 3-hydroxypropyl acrylate), carbonyl-containing monomers having at least one aldehyde group or keto group and a polymerizable double bond (eg, acrolein, diacetone acrylamide, formylstyrene, vinyl alkyl ketone) ) And the like.

Next, it is preferable that the blowing agent-containing fine particles (II) be used in an amount of 0.1 to 30% by weight based on 100 parts by weight of the aqueous resin emulsion (I). Thereby, both good anti-slip property and anti-blocking property can be achieved by uniform foaming at the time of heating.

If the amount is less than 0.1% by weight, the anti-slip property and anti-blocking property after foaming may be insufficient.
On the other hand, if it exceeds 30% by weight, it may be difficult to achieve uniform foaming.

Next, a fifth aspect of the present invention provides a composition for an anti-skid material according to any one of the first to fourth aspects, which is coated on a substrate and dried, and then the water-dispersible copolymer (A )) And a foaming layer on a substrate by heating to a foaming temperature above the glass transition temperature (Tg) and above the foaming temperature of the foaming agent in the foaming agent-containing fine particles (II). In the method of manufacturing the anti-slip material.

Thus, as described above, good anti-blocking properties before foaming and good anti-slip properties after foaming can be expected.

As described above, according to the present invention, an anti-slip material having excellent anti-slip properties and anti-blocking properties before and after foaming can be obtained.

Incidentally, examples of the substrate include paper, synthetic paper, film, nonwoven fabric and the like. In addition, as a method of coating the base material, a known coating machine such as a bar coater, an air knife coater, a gravure coater, and a roll coater can be used. From the viewpoint of anti-slip effect and cost, the amount of coating is 1 to 40 g / dry weight.
m ² is preferable.

Next, in the method for producing an anti-slip material according to the present invention, a composition for an anti-slip material is applied to a substrate and dried. The drying temperature in this case is determined by the T of the water-dispersible copolymer (A).
Although it depends on g, it cannot be said unconditionally, but it is desirable to carry out at 50 to 100 ° C. As a result, a film having the water-dispersible copolymer (A) having a relatively high Tg in the surface layer is formed, and blocking can be suppressed. Therefore, the base material before foaming can be wound.

Thereafter, the T of the water-dispersible copolymer (A)
The base material on which the composition for anti-skid material has been applied and dried is heated to a temperature of at least g and the foaming temperature of the foaming agent in the foaming agent-containing fine particles (II) to obtain a foamed layer. Due to this heating, the coating undergoes a phase transition, and a component having a low Tg derived from the copolymer of the unsaturated monomer mixture (B) appears in the surface layer, and the foaming of the blowing agent-containing fine particles (II) is reduced. A good anti-slip effect can be obtained by the synergistic effect.

Of course, at the time of application of the anti-slip material composition, the water-dispersible copolymer (A) has a Tg or more and the blowing agent-containing fine particles (I
By heating above the foaming temperature of the foaming agent in I),
Drying and foaming can be performed simultaneously.

[0054]

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiment Example 1 In this example, production examples 1 to 5 of a water-dispersible copolymer (A), a production method of an aqueous resin emulsion (I), and a composition for an anti-slip material were produced by using these substances. The anti-slip material produced by applying the composition for anti-slip material to a substrate will be described in detail with reference to Examples and Comparative Examples relating to the evaluation of anti-slip properties.

The composition for an anti-slip material according to this example will be briefly described. Average particle size obtained by emulsion-polymerizing an unsaturated monomer mixture (B) containing a polymerizable double bond in an aqueous dispersion medium obtained by dispersing a water-dispersible copolymer (A) in water. Is an aqueous resin emulsion (I) having a particle size of 0.03 to 0.08 μm and a foaming agent-containing fine particle (II) which foams by heating.

The water-dispersible copolymer (A) is
A glass transition temperature (Tg) of 30 ° C. or more, and 3 to 40% by weight of an ethylenically unsaturated carboxylic acid unit (A1)
And an unsaturated monomer unit (A2) copolymerizable with the above-mentioned ethylenically unsaturated carboxylic acid, and the average particle diameter in the aqueous dispersion medium is 0.005 to 0.03 µm.
m. The unsaturated monomer mixture (B) has a glass transition temperature (Tg) of a copolymer obtained by copolymerizing the unsaturated monomer mixture (B) in the range of −30 to 10 ° C.

The anti-slip material according to the present embodiment will be briefly described. After the composition for anti-slip material is applied and dried on a substrate, the water-dispersible copolymer (A) in the composition for anti-slip material has a glass transition temperature (Tg) or higher, and the particles in the fine particles (II) containing a foaming agent. It is a non-slip material obtained by providing a foam layer on a base material by heating the foaming agent to a foaming temperature or higher to exhibit a non-slip effect.

Next, Production Examples 1 to 5 of the respective water-dispersible copolymers (A) will be described below. Parts and% in each of the production examples are parts by weight and% by weight unless otherwise specified.

Production Example 1 First, isopropyl alcohol 2 was placed in a reactor equipped with a temperature adjuster, a stirrer, a reflux condenser, a supply container, and a nitrogen inlet tube.
00 parts were charged and replaced with nitrogen. On the other hand, as a raw material for obtaining the water-dispersible copolymer (A) according to Production Example 1, Table 1
Was prepared.

In Table 1, acrylic acid and methacrylic acid are shown as the ethylenically unsaturated carboxylic acid units (A1). In Table 1, the unsaturated monomer units (A) copolymerizable with the ethylenically unsaturated carboxylic acid
As 2), methyl methacrylate, ethyl acrylate, butyl acrylate, and styrene are shown. In Table 1, the polymerization initiator ABN indicates azobisisobutyronitrile, and BPO indicates benzoyl peroxide. The chain transfer agent t-DM indicates t-dodecyl mercaptan.

After heating the reactor to 80 ° C., 100 parts of the monomer mixed solution shown in Table 1 was supplied from a supply container, and 3 parts of ABN dissolved in 100 parts of isopropyl alcohol were supplied from another supply container. It was added uniformly over 2 hours. After completion of the addition, the reactor was kept at 80 ° C. and aged for 1 hour to obtain a uniform polymer solution in which the water-dispersible copolymer (A) was formed.

Next, after excess isopropyl alcohol was distilled off under reduced pressure using a rotary evaporator, deionized water was added, and ammonia was further added for neutralization. Thereafter, the remaining isopropyl alcohol is distilled off under reduced pressure by azeotropic distillation, and the neutralization with ammonia and the addition of deionized water are repeated to obtain a resin solid content of pH 8.3 and water-dispersible copolymer (A) of 27%. Was obtained.

The obtained water-dispersible copolymer (A) was subjected to GPC
(Gel permeation chromatography), the weight average molecular weight of this polymer was about 15,000.
The particle size was found to be 0.023 μm.

Production Examples 2 to 4 Using the same apparatus as in Production Example 1, the monomer composition, solvent, polymerization initiator and the like were changed as shown in Table 1 to obtain uniform polymer solutions. Thereafter, the solvent was distilled off, replaced with water and neutralized to obtain a resin dispersion containing a water-dispersible copolymer (A) as shown in Table 1.

Production Example 5 Using the same apparatus as in Production Example 1, completely saponified polyvinyl alcohol (degree of polymerization 1700, acetic acid group 1 mol%) was placed in the reactor.
1.5 parts and 0.04 part of partially saponified polyvinyl alcohol (degree of polymerization 1700, acetic acid group 10 mol%) were dissolved and added to 210 parts of water. Further, benzoyl peroxide 0.1.
9 parts and 5 parts of t-dodecyl mercaptan are converted to styrene 60
Of butyl acrylate and 10 parts of methacrylic acid, and the mixture was vigorously stirred and reacted at 80 ° C. for 3 hours. Thereafter, the mixture was filtered through 150 mesh to obtain a pearl-like polymer.

When the obtained polymer was measured by GPC, it was found that the weight average molecular weight of this polymer was about 25,000. Deionized water,
Dissolved by adding ammonia, and finally,
A resin dispersion containing a water-dispersible copolymer (A) having a pH of 8.1 and a resin solid content of 25.5% was obtained. The average particle size of the water-dispersible copolymer (A) was 0.010 μm.

Example 1 Using the same apparatus as in Production Example 1, 50 parts of water and an aqueous dispersion of the water-dispersible copolymer (A) according to Production Example 1 (water-dispersible copolymer) were placed in a reactor in the apparatus. 160 parts of the polymer (adjusted to a polymer concentration of 25%) were inserted. Table 2
As shown in the above, the amount of the water-dispersible copolymer (A) in the polymerization reaction system was 40 parts.

Further, the following was prepared as a feed X which was an unsaturated monomer (B) containing a polymerizable double bond. At this time, the amount of the unsaturated monomer mixture (B) is 100
Department. Further, a feed Y acting as a polymerization initiator and a pH adjuster was prepared. Feed X (based on 100 parts of monomer composition in Table 2) Ethyl acrylate 20 parts Butyl acrylate 50 parts Styrene 30 parts Feed Y water 40 parts Sodium persulfate 0.5 part Sodium hydroxide 0.12 parts

Next, after replacing the inside of the reactor charged with the water-dispersible copolymer (A) and the initiator solution with nitrogen gas, 10% of the above-mentioned feed X was added into the reactor. The mixture was heated to 85C. Next, 10% of the feed Y is charged into the reactor, and then the feed X and the remainder of the feed Y are 3 to
The mixture was uniformly supplied to the reactor over 3.5 hours. After the completion of the supply, emulsion polymerization was carried out at a temperature of 85 ° C. for 1.5 hours to obtain an aqueous resin emulsion (I).

The aqueous resin emulsion (I) had a resin concentration of about 40%. Furthermore, when this aqueous resin emulsion (I) was measured by a dynamic light scattering method,
The particle size was found to be 0.04 μm. To the aqueous resin emulsion (I) thus produced, 5 parts of fine particles (II) containing a foaming agent were added and stirred to obtain a composition for an anti-slip material. In this example, as the blowing agent-containing fine particles (II), fine particles made of a vinylidene chloride-acrylonitrile copolymer containing i-butane as a blowing agent were used.

Examples 2 to 5 and Comparative Examples 1 to 5 Using the same apparatus as in Production Example 1, the water-dispersible copolymer (A), the unsaturated monomer mixture (B) and the polymerization initiator were as shown in Table 2.
The water-based resin emulsion (I) was synthesized in the same manner as in Example 1 except for the following changes. The same foaming agent-containing fine particles (II) as above were added to the aqueous resin emulsion (I) to obtain a composition for an anti-slip material. The results are summarized in Table 2.

Next, slip-proof materials to be used as test specimens were prepared from the slip-resistant material compositions according to the examples and comparative examples obtained by the above-described procedure. This test piece was prepared by applying the above composition for anti-skid material to the surface of a high-quality paper as a base material using an applicator so that the dry coating film becomes 20 g / m ² and drying at 90 ° C. for 3 minutes. . This is a test piece A. Further, the composition for an anti-skid material was applied to the substrate under the same application conditions, dried at 90 ° C. for 3 minutes, and further heated at 150 ° C. for 30 seconds to prepare a test piece. This is a test piece B.

Next, the performance evaluation of the aqueous resin emulsion (I) in this example and the test pieces A and B as anti-slip materials was performed according to the following procedure. <Evaluation of Polymerization Stability> The aqueous resin emulsion (I) obtained in each of the above Examples and Comparative Examples was filtered through a 150-mesh wire net, and the amount of aggregates in the aqueous resin emulsion (I) was measured. Thereby, the polymerization stability at the time of production was evaluated according to the following criteria. The results of this test are described in the row of “Polymerization stability” in Table 2. ◎ less than 0.1% of aggregates ○ 0.1 to 1% of aggregates △ 1 to 5% of aggregates × more than 5% of aggregates

<Blocking test before foaming> The coated surfaces of the test piece A coated with the anti-slip material composition were overlapped with each other, and a load of 0.1 kg / cm ² was applied to the test piece A at 40 ° C., 1 ° C.
Left for days. Thereafter, the state where both were peeled was evaluated according to the following criteria. The results of this test are shown in the row “after heating at 90 ° C.” in Table 2. ◎ Peeling off without any resistance ○ Peeling off with a strength of less than 20 g / 25 mm △ Peeling off with a strength of less than 10 to 20 g / 25 mm × A strength of 20 g / 25 mm or more is required

<Blocking Test after Foaming> The coated surfaces of the test piece B coated with the anti-slip material composition were overlapped with each other, and a load of 0.1 kg / cm ² was applied thereto at 40 ° C. and 1 ° C.
Left for days. Thereafter, the state where both were peeled was evaluated according to the following criteria. The results of this test are described in Table 2 in the column “after heating at 150 ° C.”. ◎ Peeling off without any resistance ○ Peeling off with a strength of less than 20 g / 25 mm △ Peeling off with a strength of less than 10 to 20 g / 25 mm × A strength of 20 g / 25 mm or more is required

<Slip Resistance> The friction angle of the anti-slip layer of the test piece B was evaluated based on the friction angle with respect to high quality paper in accordance with the friction coefficient test method for paper and paperboard according to "JIS P 8147". The results of this test are shown in Table 2 in the column "Slip resistance after heating at 150 ° C". ◎ 60 degrees or more ○ 50-60 degrees △ 40-50 degrees × 40 degrees or less

The above test results will be described with reference to Table 2. As can be seen from Table 2, Examples 1 to 5 of the present invention
According to the figure, it can be seen that a composition for an anti-skid material excellent in both blocking resistance and anti-slip properties can be obtained.

Comparative Example 1 has low blocking resistance after heating at 150 ° C. because the surface irregularity due to foaming of the foaming agent-containing fine particles (II) does not occur, and Comparative Example 2 has water-dispersible copolymer (A). Because of too many unsaturated carboxylic acid units, the phase transition hardly occurred and the anti-slip property was insufficient.

In Comparative Example 3, the water-dispersible copolymer (A)
Comparative Example 4 had low blocking resistance due to low Tg of
Was low in slip resistance due to the high Tg of the copolymer of the unsaturated monomer mixture (B). In addition, it was found that Comparative Example 5 had a very low blocking resistance because the copolymer of the unsaturated monomer mixture (B) had a low Tg and thus the coating after the phase transition exhibited tackiness.

[0080]

[Table 1]

[0081]

[Table 2]

[0082]

According to the present invention, there are provided a composition for a slip resistant material capable of obtaining a slip resistant material excellent in slip resistance and blocking resistance before and after foaming, and a method for producing a slip resistant material prepared using the same. be able to.

────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code FI C09D 151/00 C09D 151/00 C09K 3/14 540 C09K 3/14 540K (72) Inventor Tatsuhiko Yoshimatsu 1 Nihonbashi Muromachi, Chuo-ku, Tokyo Chome 13-4 Heisei Techno Co., Ltd. (72) Inventor Satoshi Umezu 146-1, Kamidejima, Iwai City, Ibaraki Pref.

Claims (5)

[Claims] 1. An unsaturated monomer mixture (B) containing a polymerizable double bond is emulsion-polymerized in an aqueous dispersion medium obtained by dispersing a water-dispersible copolymer (A) in water. An anti-slip material composition comprising an aqueous resin emulsion (I) having an average particle diameter of 0.03 to 0.08 μm and foaming agent-containing fine particles (II) which foams by heating. The polymer (A) has a glass transition temperature (Tg) of 30 ° C. or more, and has an ethylenically unsaturated carboxylic acid unit (A1) of 3 to 40% by weight, which is copolymerizable with the above ethylenically unsaturated carboxylic acid. The unsaturated monomer unit (A2) is the balance, the average particle size in the aqueous dispersion medium is 0.005 to 0.03 µm, and the unsaturated monomer mixture (B) is Of the copolymer obtained when copolymerized Slip material composition of glass transition temperature (Tg), characterized in that in the range of -30~10 ℃. 2. The method according to claim 1, wherein the water-dispersible copolymer (A) is used in an amount of 25 to 100 parts by weight based on 100 parts by weight of the unsaturated monomer mixture (B). Anti-slip material composition. 3. The unsaturated monomer mixture (B) according to claim 1 or 2, wherein (a) 20 to 95% by weight of an alkyl ester of acrylic acid or methacrylic acid having less than 8 carbon atoms; It is selected from 0 to 40% by weight of an alkyl ester of an acid or methacrylic acid having 8 to 18 carbon atoms, (c) 5 to 40% by weight of a vinyl aromatic compound, and (d) 0 to 30% by weight of other monomers. 2 or more (however,
(A) + (b) + (c) + (d) = 100% by weight. A) a composition for an anti-slip material. 4. The method according to claim 1, wherein:
A composition for an anti-slip material, wherein the blowing agent-containing fine particles (II) are used in an amount of 0.1 to 30% by weight based on 100 parts by weight of the aqueous resin emulsion (I). 5. The glass transition temperature (Tg) of the water-dispersible copolymer (A) after coating and drying the composition for anti-skid material according to claim 1 on a substrate. A method for producing an anti-slip material, characterized in that the anti-slip effect is exhibited by heating the foaming agent in the foaming agent-containing fine particles (II) above the foaming temperature of the foaming agent and providing the foamed layer on the base material.