JPH08143610A - Resin for non-slip agent and non-slip agent composition therefrom - Google Patents

Abstract

PURPOSE: To obtain a resin capable of retaining high non-slip performance without developing any blocking phenomenon even under repeated use, by emulsion polymerization of a radically polymerizable monofunctional vinyl monomer with a multifunctional vinyl monomer in the presence of polyvinyl alcohol. CONSTITUTION: This invention comprises conducting emulsion polymerization between a radically polymerizable monofunctional vlnyl monomer and a multifunctional vinyl monomer (e.g. ethylene glycol di(meth)acrylate, etc.) in the presence of polyvinyl alcohol and water. In addition, an emulsifier can be incorporated. The multifunctional vinyl monomer is charged at 0.1-20 pts.wt. based on 100 pts.wt. of the monofunctional vinyl monomer. The monofunctional vinyl monomer may contain an alkyl (meth)acrylate (pref. methyl (meth)acrylate) and/or a styrene-based compound (pref. styrene). The objective non-slip agent composition is obtained by incorporation of the resin with inorganic or organic particles.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antislip agent resin and an antislip agent composition using the antislip agent resin. More specifically, the present invention relates to a slip-preventing resin which is effective for preventing load collapse of corrugated cardboard, a corrugated cardboard box, a paperboard, a paper container, a paper bag, etc., and a slip-preventing agent composition using the slip-preventing resin.

[0002]

2. Description of the Related Art At present, a wide variety of food products, fertilizers and various industrial products are packaged in paper containers such as corrugated cardboard and cartons or various paper bags, and are transported or stored in multiple stacks. This package causes a load collapse or a load shift during transportation or storage, which causes problems such as damage to the contents and manpower required to restore the load again. Furthermore, with the recent diversification and specialization of paper and paperboard, improvements in various paper additives and improvements in papermaking technology have significantly improved paper quality such as smoothness and gloss of the paper surface. The friction coefficient on the surface has decreased, and slippage is more likely to occur than before, and problems such as load collapse are becoming more serious. In recent years, mechanization has progressed due to high labor costs and reduction of personnel, packaging lines have become more automated, transportation lines have become more efficient, and unmanned automated warehouses have developed and become faster. Even it is becoming a subject of trouble. Under such circumstances, the development of a load collapse prevention method is eagerly desired.

Conventionally, as a method of preventing the collapse or displacement of the corrugated cardboard cases and paper bags stacked on the pallet, a mechanical method such as fixing with a wooden frame, binding with a banding tape, or covering with a shrink film or sheet is used. Method,
There is a method of temporarily adhering the upper and lower containers with an adhesive, or a method of applying an anti-slip load collapse preventing agent (hereinafter referred to as an anti-slip agent) on the surface of the container.

However, in the mechanical method and the bonding method, the work must be carried out at the same time as the loading work, high-speed work is difficult, and a work space and manpower are required. In addition, unpacking is complicated, and if the cargo is to be reloaded during transportation, some kind of cargo collapse prevention processing must be performed again. Furthermore, in the case of mechanical methods, the disposal of wooden crates, bands, films and sheets, which become unnecessary after unpacking, is also a big problem, increasing the overall logistics cost. In addition, even with a band, the effect is not so high because the load may be misaligned during transportation and the band may be loosened during storage.

Further, the adhesive method cannot be applied to a container that requires an aesthetic appearance, because the surface of the paper container is damaged when unpacking or the adhesive remains on the surface.

From the above points, a method of applying an anti-slip agent on the surface of a container has been attracting attention as a method for preventing the collapse of cargo. In other words, the use of anti-slip agents does not require human labor, costs less than methods such as binding with banding tape or covering with shrink film or sheets, and wooden crates and bands that become unnecessary after unpacking. There are many advantages such as no waste such as films and sheets.

As such an anti-slip agent, a non-adhesive type (one which exerts an anti-slip effect by forming fine irregularities on the surface of a paper after being coated and dried to physically improve the friction coefficient) and Adhesive type (which retains its adhesiveness even after being coated on the surface of paper and then dried) and which exhibits an anti-slip effect due to this adhesiveness is general.

As the non-adhesive type anti-slip agent, an inorganic or organic powdery material such as colloidal silica or alumina sol, or a foaming agent which is applied to the surface of paper to foam by heating is generally used. However, these non-stick type anti-slip agents cannot sustain the initial anti-slip effect,
The anti-slip effect decreases when the transshipment work is repeated. In particular, when an inorganic or organic powder is used, the particles fall off and the anti-slip effect is extremely reduced.
In order to maintain the anti-slip effect, a large amount of inorganic or organic powder or granules should be used, but this increases the cost and increases the amount of peeling off, or the coating surface may have inorganic or organic powder or granules. It is not very practical because it causes precipitation and causes problems such as deterioration of aesthetics. Further, when a foaming agent is used, a heat foaming step is required, and there are problems such as a decrease in work speed and an increase in cost.

As an adhesive type anti-slip agent, a resin for an anti-slip agent is generally used. Acrylic copolymer emulsions are often used as the anti-slip agent resin, and are used by an appropriate coating means. The solid resin of ethylene / vinyl acetate copolymer is used after being melted by heating. In addition, an acrylic / vinyl acetate copolymer, a petroleum resin, a tackifying resin such as rosin (or a rosin derivative thereof), and the like are also used. However,
Since these adhesive type anti-slip agents have adhesiveness on the coated surface after drying, they have drawbacks such as blocking, lowering of workability, surface damage, and dust and dirt adhering during transportation. On the other hand, if the amount of the anti-slip agent used is reduced to suppress the blocking phenomenon, the anti-slip effect will be reduced.

Further, a nitrogen-containing (meth) acrylic copolymer was synthesized in an organic solvent as a resin for an anti-slip agent having improved anti-blocking property and long-lasting anti-slip effect, and the organic solvent was mixed with water. After removal by boiling and quaternization, a crosslinked acrylic polymer emulsion obtained by copolymerizing a (meth) acrylic acid ester and a polyfunctional (meth) acrylic acid ester, or divinylbenzene and a (meth) acrylic acid ester Was synthesized with a glass transition point (hereinafter referred to as Tg) of 20 to 90 ° C. as a core composition, and an acrylic emulsion copolymer of Tg of −20 to −10 ° C. as a shell composition. A double-structured acrylic emulsion has been reported. The above-mentioned resin has improved the performance of the anti-slip agent by partially utilizing a polyfunctional monomer as its constituent element. However, the resin is manufactured in multiple steps, a step using an organic solvent is required, and the synthesis time is long.
There are also industrial disadvantages.

Polyvinyl alcohol is a non-adhesive type and an adhesive type that have been used and studied for a long time. Polyvinyl alcohol is a protective colloid,
It plays a role as a strength improver, paper strength enhancer, etc. of the anti-slip coating and has various effects. For example, in the non-adhesive type, it is used as a binder for an inorganic substance such as colloidal silica or a fine powder thereof. However, when colloidal silica or the like is a colloidal particle, the particle size is too small and the anti-slip effect is inferior to that of fine powder. On the other hand, in the case of the fine powder, there is a problem that the fine powder is removed due to friction, and the aesthetic appearance of the coated surface is easily impaired. In the case of the adhesive type, it is used as a protective colloid at the same time as polyvinyl acetate and other acrylic emulsions, but there is a problem in blocking resistance and Tg
The current situation is to mix high-resin resin emulsions and the like for balance.

[0012]

DISCLOSURE OF THE INVENTION The present invention does not cause a blocking phenomenon, can maintain a high anti-slip performance even after repeated use, and has a suitable adhesive property that does not cause paper breakage. An object is to provide a resin for lubricants and an anti-slip agent composition using the resin for anti-slip agents.

[0013]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, as a resin for a lubricant, a monofunctional vinyl monomer and a polyfunctional vinyl monomer in the presence of polyvinyl alcohol were used. A water-based resin obtained by polymerizing monomers is used as an anti-slip agent resin
Further, it has been found that an anti-slip agent composition containing an organic powder or granule meets the above-mentioned object. The present invention has been completed based on this new finding.

That is, the present invention provides (1) an anti-slip agent containing an aqueous resin obtained by emulsion-polymerizing a radically polymerizable monofunctional vinyl monomer and a polyfunctional vinyl monomer in the presence of polyvinyl alcohol and water. Resin,
(2) Anti-slip agent resin containing an aqueous resin obtained by emulsion-polymerizing a radically polymerizable monofunctional vinyl monomer and a polyfunctional vinyl monomer in the presence of polyvinyl alcohol, an emulsifier and water, and (3) The present invention relates to an anti-slip agent composition containing the above-mentioned anti-slip agent resin and an inorganic and / or organic powdery material as a main component.

First, the constituent components of the water-based resin which is the resin (1) for anti-slip agent will be described.

The polyvinyl alcohol used in the present invention is not particularly limited as long as it is water-soluble, but usually has a polymerization degree of about 200 to 2500 and a saponification degree of 75% to.
100% partially saponified or fully saponified is preferred. In addition, silicon-containing polyvinyl alcohol, modified polyvinyl alcohol having a functional group such as a carboxyl group, an acetoacetyl group, and an acetal group can be similarly used.
Moreover, since polyvinyl alcohol affects the slight tackiness of the obtained anti-slip agent, the amount used is appropriately determined in consideration of these properties. That is, the amount of polyvinyl alcohol used is usually about 5 to 900 parts by weight, preferably 25 parts by weight, based on 100 parts by weight of the total amount of the monofunctional vinyl monomer.
It is preferable to set it to 250 parts by weight. If the amount is less than 5 parts by weight, the adhesiveness and / or adhesiveness of the resulting anti-slip agent becomes weak,
Further, when it exceeds 900 parts by weight, the viscosity of the obtained aqueous resin solution becomes high, which is not preferable in terms of workability. In addition, the resulting anti-slip agent has an excessively strong adhesive force and / or adhesive force, which causes paper breakage and the like, which is not preferable.

As the radically polymerizable monofunctional vinyl monomer, it is preferable to use (meth) acrylic acid alkyl ester and / or styrene compound.
As the (meth) acrylic acid alkyl ester, an alkyl group having 1 to 18 carbon atoms is preferable. For example,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, Examples include 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, and the like. Examples of styrene compounds include styrene, α-methylstyrene, vinyltoluene and the like.

As the radically polymerizable monofunctional vinyl monomer, in addition to the (meth) acrylic acid alkyl ester and the styrene compound, various anionic monofunctional vinyl monomers and cationic monofunctional vinyl monomers are used. Vinyl monomers and nonionic monofunctional vinyl monomers other than the above can be used. Among these radical-polymerizable monofunctional vinyl monomers other than these (meth) acrylic acid alkyl esters and styrene compounds, anionic monofunctional vinyl monomers are preferable. The amount of the monofunctional vinyl monomer other than the (meth) acrylic acid alkyl ester and / or the styrenic compound used is usually about 40% by weight or less, preferably 30% by weight or less of the monofunctional vinyl monomer.

Examples of the anionic monofunctional vinyl monomer include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid and muconic acid, and vinyl sulfone. Acid, styrene sulfonic acid, 2-acrylamide-
Organic sulfonic acids such as 2-methylpropanesulfonic acid, 2
Examples thereof include phosphoric acid vinyl monomers such as-(meth) acryloyloxyethyl acid phosphate, and sodium salts and potassium salts of these various organic acids. Examples of cationic monofunctional vinyl monomers include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl (meth).
Vinyl monomers having a tertiary amino group such as acrylamide, or salts thereof of inorganic acids or organic acids such as hydrochloric acid, sulfuric acid, acetic acid, or the tertiary amino group-containing vinyl monomers and methyl chloride, benzyl chloride, dimethyl sulfate, Examples thereof include vinyl monomers containing a quaternary ammonium salt obtained by reaction with a quaternizing agent such as epichlorohydrin. Nonionic monofunctional vinyl monomers include (meth) acrylamide, (meth) acrylonitrile, vinyl acetate, methyl vinyl ether, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) Phosphoric acid such as hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxybutyl acrylate, glycidyl (meth) acrylate, N-methylol (meth) acrylamide, urethane acrylates, diphenyl-2 (meth) acryloyloxyphosphate Examples thereof include ester vinyl monomers.

Further, in the present invention, it is essential to use a polyfunctional vinyl monomer in addition to the monofunctional vinyl monomer exemplified above. The anti-slip agent resin of the present invention is a resin in which the resin is wholly cross-linked by using a polyfunctional vinyl monomer. As a polyfunctional vinyl monomer,
For example, di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, hexamethylenebis Bifunctional such as bis (meth) acrylamides such as (meth) acrylamide, divinyl esters such as divinyl adipate, divinyl sebacate, allyl methacrylate, diallyl amine, diallyl dimethyl ammonium, diallyl phthalate, diallyl chlorendate, divinyl benzene, etc. Vinyl monomer; 1,3
5-triacryloylhexahydro-S-triazine,
Functional vinyl monomers such as triallyl isocyanurate, triallyl amine, triallyl trimellitate, N, N-diallyl acrylamide; tetramethylol methane tetraacrylate, tetraallyl pyromellitate,
Examples thereof include tetrafunctional vinyl monomers such as N, N, N ′, N′-tetraallyl-1,4-diaminobutane, tetraallylamine salt, and tetraallyloxyethane.

The amount of the polyfunctional vinyl monomer used is about 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 1 based on 100 parts by weight of the total of the monofunctional vinyl monomers. ~ 5 parts by weight. If the amount of the polyfunctional vinyl monomer is less than 0.1 part by weight, a crosslinked structure sufficient to enhance the anti-slip effect cannot be obtained, and if it exceeds 20 parts by weight, agglomeration or high concentration is caused. In any case, it is not preferable because it becomes difficult to obtain an aqueous resin solution.

Next, the components of the water-based resin which is the anti-slip agent resin (2) will be described.

The composition of the water-based resin of the anti-slip agent resin (2) is as follows:
In addition to the structure of the water-based resin of the anti-slip agent resin (1), only an emulsifier is used. Therefore, the same materials as the polyvinyl alcohol, the radical-polymerizable monofunctional vinyl monomer, and the polyfunctional vinyl monomer described in the anti-slip agent resin (1) can be used in the anti-slip agent resin (2).

The emulsifier is not particularly limited and various emulsifiers can be used. Examples of emulsifiers include known anionic emulsifiers and nonionic emulsifiers. Examples of the anionic emulsifier include long-chain sodium α-olefin sulfonate, alkyldiphenyloxyethylene alkylaryl ether sulfate ester salt and the like, and examples of the nonionic emulsifier include polyoxyethylene alkyl ether,
Examples thereof include polyoxyethylene polyoxypropylene block polymer and polyoxyethylene alkylphenyl ether. These anionic emulsifiers and nonionic emulsifiers may be used alone or in combination of two or more. The amount of the emulsifier to be used is not particularly limited, but if the resin composition content is extremely reduced, the anti-slip effect is adversely affected. Usually, it is about 15 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the monofunctional vinyl monomer.

Next, the method for producing the aqueous resin of the present invention will be described. The method for producing the aqueous resin of the present invention may be carried out by a known emulsion polymerization method. For example, in the case of (1), polyvinyl alcohol and water are charged into a predetermined reaction vessel and dissolved while heating, then a monofunctional vinyl monomer and a polyfunctional vinyl monomer are charged, and after emulsification, a radical polymerization initiator is added. A method of heating with stirring may be used. In the case of (2), polyvinyl alcohol and water are charged into a predetermined reaction vessel and dissolved while heating, and then an emulsifier, a monofunctional vinyl monomer and a polyfunctional vinyl monomer are charged and emulsified, and then a radical polymerization initiator. Is added and the mixture is heated with stirring. In addition, the dropping method of the monofunctional vinyl monomer and the polyfunctional vinyl monomer may be either batch dropping or divided dropping.

The solid content of the reaction system is usually about 10 to 50% by weight, preferably 15 to 30% by weight.
The reaction temperature may be in a temperature range that activates the radical polymerization initiator, and is usually about 40 to 90 ° C, preferably 50 to 80 ° C. Moreover, the reaction time is not particularly limited, but is usually about 30 minutes to 2 hours.

Examples of the radical polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide, water-soluble radical polymerization initiators such as an aqueous azo initiator, and the above-mentioned persulfates. Examples thereof include redox-based polymerization initiators in the form of a combination with a reducing agent such as sodium hydrogen sulfite and sodium thiosulfate. Usually, the amount of the initiator used is about 0.05 to 5% by weight, preferably 0.1 to 3% by weight, based on the total amount of the vinyl monomers (monofunctional vinyl monomer and polyfunctional vinyl monomer).
It is good to do.

Thus, the average particle diameter is usually 10 to 10.
An aqueous resin solution containing fine particles of about 300 nm is obtained. Further, when the aqueous resin solution is used as a resin for an anti-slip agent, the nonvolatile content is usually adjusted to about 10 to 30% by weight and the viscosity is adjusted to about 100 cps or less (25 ° C.) from the viewpoint of workability. preferable.

The Tg of the obtained aqueous resin is usually −
It is 10 to 50 ° C or higher, preferably 0 to 40 ° C, more preferably 20 to 40 ° C. When Tg is less than -10 ° C, it is not preferable in terms of blocking resistance. If it exceeds 50 ° C, the anti-slip effect tends to decrease, which is not preferable.

The anti-slip agent resin (1) or (2) using such an aqueous resin solution is used as an anti-slip agent composition in which inorganic and / or organic powdery particles are mixed. The inorganic powder is not particularly limited, and examples thereof include silicon dioxide, aluminum oxide, calcium carbonate, calcium sulfate, calcium titanate, potassium titanate, zinc oxide, magnesium oxide, kaolin, clay, and silica sand. Among these inorganic powders, it is preferable to use silicon dioxide and aluminum oxide because they are excellent in stability after mixing with the anti-slip agent resin, proper adhesive strength and anti-slip effect after drying. In addition, as the organic powder,
Wood powder is included. These powders can be used in the form of colloid or fine powder.

The mixing ratio of the inorganic and / or organic powdery particles to the above-mentioned aqueous resin, which is a resin for anti-slip agents, is usually
The amount of the aqueous resin (solid content) is about 0.1 to 30% by weight, preferably 1 to 20% by weight, more preferably 1 to 10% by weight. If it exceeds 30% by weight, the tackiness and adhesion performance of the water-based resin will be deteriorated, and the stability as a lubricant will be poor and the viscosity will be high. If the amount is less than 0.1% by weight, the adhesive performance of the water-based resin is too strong, and a problem such as paper peeling tends to occur during peeling. Further, the anti-slip effect of the inorganic or organic powder is also reduced. The order of mixing the inorganic and / or organic powder and the aqueous resin solution and the mixing method are not particularly limited as long as they are sufficiently uniform. Usually, it may be carried out by a method such as batch charging at room temperature, divided charging, dropping charging and the like, followed by sufficient stirring.

The composition obtained by mixing the above water-based resin, which is a resin for anti-slip agents, with inorganic and / or organic powder is p
It is preferable to adjust to H4-10, preferably 6-9. When the pH is out of the above range, it is not preferable in terms of product stability and handling safety, but the pH may be out of the above range in consideration of the method of use.
When adjusting the pH, an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, calcium hydroxide or ammonia may be used.

The anti-slip agent composition of the present invention thus obtained has a non-volatile content of 10 to 10 in consideration of easiness of handling.
It is preferable to adjust the viscosity to about 50 wt% and the viscosity to about 200 cps or less.

Further, the anti-slip agent composition of the present invention includes methyl solosolve acetate, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol,
Derivatives of polyhydric alcohols such as butyl carbitol and carbitol acetate may be added as a film forming aid.

As a method of applying the anti-slip agent composition of the present invention, a spray, a wire bar, a blade coater, an air knife coater, a roll coater or the like can be adopted, and when introducing a drying step, an oven, a drum dryer or the like can be used. A known drying device can be adopted. Examples of the article to be coated with the anti-slip agent composition include cardboard, carton, cardboard box, paperboard, paper container, paper bag, polyethylene bag and the like.

[0036]

According to the present invention, the initial adhesiveness is high,
It is possible to provide a slip-preventing composition that maintains high anti-slip performance even after repeated use, suppresses the blocking phenomenon, and has an appropriate adhesive property without causing paper breakage. The anti-slip agent composition of the present invention has such an excellent effect that a cross-linking type resin containing polyvinyl alcohol, which is used as a resin for an anti-slip agent and has relatively high adhesiveness, is an inorganic and / or organic powder particle. It is considered that by mixing an appropriate amount of the body, the anti-slip agent composition was made to have a slight tackiness, and the blocking phenomenon could be suppressed by the effect of the inorganic and / or organic powdery material. Such an anti-slip agent composition is particularly useful as an adhesive type. Further, since no waste such as a wooden frame, band, film or sheet which becomes unnecessary after unpacking is discharged, it can contribute to resource saving and environmental problems.

[0037]

EXAMPLES The present invention will be described more specifically below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition,% in each example is based on weight.

Example 1 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube, a monomer dropping funnel and a thermometer, 64 g of polyvinyl alcohol (trade name: Airbol 103, manufactured by Air Products and Chemicals) and 448 g of water. Was charged, and the mixture was stirred with heating to dissolve it into an aqueous solution. After cooling this aqueous solution to 40 ° C., 96 g of a mixed monomer consisting of butyl acrylate, styrene, and acrylonitrile (the weight mixing ratio is 57: 37: 6 in order), 4.8 g of ethylene glycol diacrylate and 212 g of water were added at a constant rate. It was emulsified at (250 ± 10 rpm). The temperature was raised under a nitrogen stream, and potassium persulfate and sodium thiosulfate were added at 60 ° C. so that the concentration in the system was 6.0 × 10 ⁻³ mol / liter to start polymerization. The reaction was carried out for 60 minutes so that the polymerization temperature did not exceed 80 ° C to obtain an aqueous resin solution. The aqueous resin solution contained fine particles having an average particle diameter of about 10 to 100 nm, had a nonvolatile content of 21% and a viscosity of 20 cps. The Tg of the aqueous resin was 25 ° C.

While stirring 485 g of the obtained aqueous resin solution at room temperature, 10 g of colloidal silica (trade name: Snowtex O, manufactured by Nissan Chemical Co., Ltd.) and 5 g of alumina sol (trade name: Alumina sol 100, manufactured by Nissan Chemical Co., Ltd.) Was gradually added. After adding, continue stirring for 30 minutes,
Furthermore, the pH was adjusted to 8.5 with a 0.5% aqueous sodium hydroxide solution to obtain the anti-slip agent composition of the present invention. Nonvolatile content is 20
%, The viscosity at 25 ° C. was 30 cps.

Example 2 In Example 1, as the polyfunctional vinyl monomer,
An aqueous resin solution was obtained in the same manner as in Example 1 except that 5.0 g of diethylene glycol diacrylate was used. The aqueous resin solution contained fine particles having an average particle diameter of about 10 to 100 nm, had a nonvolatile content of 21% and a viscosity of 21 cps.
The Tg of the aqueous resin was 26 ° C.

Further, the same procedure as in Example 1 was conducted to obtain pH 8.5.
An anti-slip agent composition was obtained. The nonvolatile content was 20% and the viscosity at 25 ° C was 28 cps.

Example 3 The same procedure as in Example 1 was carried out except that 2.5 g of dialkylsulfosuccinic acid ester soda salt (trade name Neocor P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as the emulsifier. A resin solution was obtained. The aqueous resin solution contains fine particles having an average particle diameter of about 10 to 50 nm and has a nonvolatile content of 21
%, The viscosity was 23 cps. The Tg of the aqueous resin was 23 ° C.

Further, the same procedure as in Example 1 was conducted to obtain pH 8.5.
An anti-slip agent composition was obtained. The nonvolatile content was 20% and the viscosity at 25 ° C was 30 cps.

Example 4 An aqueous resin solution was obtained in the same manner as in Example 1 except that 96 g of butyl acrylate and styrene (weight mixing ratio was 61:39 in order) were used. The aqueous resin solution contained fine particles having an average particle diameter of about 10 to 100 nm, had a nonvolatile content of 21% and a viscosity of 19 cps.

Further, the same procedure as in Example 1 was conducted to obtain pH 8.5.
An anti-slip agent composition was obtained. The nonvolatile content was 20% and the viscosity at 25 ° C was 28 cps.

Comparative Example 1 An aqueous resin solution was obtained in the same manner as in Example 1 except that ethylene glycol diacrylate was not used. The aqueous resin solution has an average particle size of 10 to 15
Contains fine particles of about 0 nm, non-volatile content 21%, viscosity 20
It was cps. The Tg of the aqueous resin was 24 ° C.

Further, the same procedure as in Example 1 was conducted to obtain pH 8.5.
An anti-slip agent composition was obtained. The nonvolatile content was 20% and the viscosity at 25 ° C was 32 cps.

Comparative Example 2 The same procedure as in Example 1 was repeated except that 2.5 g of sodium dialkylsulfosuccinate ester (trade name Neocor P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as an emulsifier in Comparative Example 1. A resin solution was obtained. The aqueous resin solution contains fine particles having an average particle diameter of about 10 to 100 nm and has a nonvolatile content of 2
The viscosity was 1% and the viscosity was 24 cps. Also, the Tg of the aqueous resin
Was 22 ° C.

Further, the same procedure as in Example 1 was carried out to obtain pH 8.5.
An anti-slip agent composition was obtained. The nonvolatile content was 20% and the viscosity at 25 ° C was 30 cps.

Comparative Example 3 An aqueous resin solution was obtained in the same manner as in Example 4 except that ethylene glycol diacrylate was not used. The aqueous resin solution has an average particle size of 10 to 150.
Containing fine particles of about nm, nonvolatile content 21%, viscosity 19c
It was ps.

Further, the same procedure as in Example 1 was conducted to obtain pH 8.5.
An anti-slip agent composition was obtained. The nonvolatile content was 20% and the viscosity at 25 ° C was 29 cps.

The anti-slippery compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3, or the aqueous resin solutions obtained in Comparative Example 1 as Comparative Example 4 or Example 1 as Comparative Example 5 were obtained. The aqueous resin solutions were used as they were, and each was used as a stock solution or diluted with ion-exchanged water to a predetermined ratio, and the performance was evaluated by the following methods.

(Anti-slip performance) A stock solution, or a two- or three-fold diluted anti-slip agent composition or resin for an anti-slip agent was added to
Kraft paper of g / m ² was uniformly sprayed with a sprayer at a rate of 24 g (weight of diluted anti-slip agent composition or resin for anti-slip agent) / m ² . This was dried and the evaluation sample was created.
This evaluation sample was used as a slip tester (No. 162-SL).
H, manufactured by Yasuda Seiki Seisakusho Co., Ltd. was used, and the angle at which the test piece started to slide on the same contact surface was measured 5 times in succession. The measurement results of the undiluted solution are shown in Table 1, the measurement results of the two-fold diluted solution are shown in Table 2, and the measurement results of the three-fold diluted solution are shown in Table 3.

(Adhesiveness) A slip-resistant composition or a slip-resistant resin diluted two-fold, three-fold or five-fold was added to kraft paper (3).
It was uniformly sprayed with a sprayer at a ratio of 10 g (weight of the anti-slip agent composition after dilution or the resin for anti-slip agent) / m ² onto 0 mm × 60 mm), and was overlaid with the same quality unkrafted kraft paper. An evaluation sample was prepared by applying a load of 50 g / cm ^{2 to} these for 2 hours. This evaluation sample was used to evaluate the peel strength against tension on the left and right by Tensilon and the peeling of the paper during peeling according to the following criteria. The results are shown in Table 4.

(I) Adhesive strength against pulling to the left and right ⊚: 10 kg / 30 mm or more. ◯: 5 to 10 kg / 30 mm. Δ: 1 to 5 kg / 30 mm. X: Less than 1 kg / 30 mm.

(Ii) Stripping of paper during peeling ⊚: None. ○: Slightly present. Δ: There is some. X: There are quite a few.

(Blocking resistance) Undiluted solution and anti-slip agent diluted 2-fold or 3-fold were evenly sprayed onto 78 g / m ² kraft paper with a sprayer to give 24 g (weight of anti-slip agent composition or resin for anti-slip agent after dilution). Sprayed at a rate of / m ² . This was dried and a load of 50 g / cm ² was applied for 24 hours to prepare an evaluation sample. This evaluation sample was peeled 90 degrees, and the degree of blocking was visually determined. The results are shown in Table 4. ⊚: No blocking ∘: Slight blocking, but no paper peeling. Δ: There is some blocking (no peeling of paper). X: Blocking and peeling off the paper.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

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Claims (5)

[Claims] 1. An anti-slip agent resin containing an aqueous resin obtained by emulsion-polymerizing a radically polymerizable monofunctional vinyl monomer and a polyfunctional vinyl monomer in the presence of polyvinyl alcohol and water. 2. An anti-slip agent resin containing an aqueous resin obtained by emulsion-polymerizing a radically polymerizable monofunctional vinyl monomer and a polyfunctional vinyl monomer in the presence of polyvinyl alcohol, an emulsifier and water. 3. The amount of the polyfunctional vinyl monomer used is 0.1 to 2 with respect to 100 parts by weight of the monofunctional vinyl monomer.
The anti-slip agent resin according to claim 1 or 2, which is 0 part by weight. 4. The resin for an anti-slip agent according to claim 1, wherein the monofunctional vinyl monomer contains a (meth) acrylic acid alkyl ester and / or a styrene compound. 5. An anti-slip agent composition containing the resin for anti-slip agent according to any one of claims 1 to 4, and an inorganic and / or organic powdery material as a main component.