JPH0680953A - Antislip composition - Google Patents

Abstract

PURPOSE:To improve the antislip properties of the surface of a paper article or box by coating the surface with an antislip compsn. comprising a vinyl polymer emulsion and at least one terpene (co)polymer. CONSTITUTION:An antislip compsn. comprises 100 pts.wt. (solid base) vinyl polymer emulsion and 5-60 pts.wt. terpene (co)polymer and has antiblocking and antislip properties corresponding to a slip angle of 40 deg. or higher. The vinyl polymer has a glass transition point of 50 deg.C or lower, and the emulsion is obtd. by the emulsion (co)polymn. of a vinyl monomer, such as vinyl acetate, methyl (meth)acrylate, or styrene, in water. A functional monomer such as acrylic acid may be copolymerized to improve the characteristics of the vinyl polymer. The terpene polymer is obtd. by polymerizing an essential oil obtd. from natural rosin. The terpene copolymer is a terpene-phenol resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-slip composition for imparting anti-slip properties to paper containers such as corrugated cardboard cases and various paper bags for the purpose of preventing load collapse.

[0002]

2. Description of the Related Art Today, many products such as various industrial products, agricultural products, and marine products are packaged and transported in paper containers such as corrugated cardboard cases or various paper bags. Cardboard cases, paper bags, etc. stacked on pallets during the transportation of these packages are
It often causes the load to collapse, which is a big problem.

Conventionally, banding processing and shrinking processing have been carried out as a method of preventing the collapse of the load of corrugated cardboard cases and paper bags loaded on pallets, but they are time-consuming, costly and push up the overall distribution cost. There is a drawback that.

On the other hand, it is also attempted to prevent the load from slipping by applying an anti-slip agent to a cardboard case, a paper bag, etc., and various anti-slip agents have been proposed.

The mainstream of conventionally proposed anti-slip agents is a means of using particulate materials, and there are inorganic particles or a type in which they are used in combination with a binder resin, and types in which organic hollow or microcapsules are used in combination with a binder resin. there were.

However, in addition to the means of using the particulate matter, a type of anti-slip agent which does not use the particulate matter at all has been developed. The following are known as anti-slip agents of this type.

One of them is disclosed in Japanese Patent Application Laid-Open No. 48-60090, which contains atactic polypropylene or ethylene-vinyl acetate copolymer (EVA) as a main component and, if necessary, a terpene resin, Rosin derivative,
It is a mixture of styrene resin and the like as an accessory component.

The anti-slip agent is applied in a molten state by applying heat at the time of use, or is applied by being dissolved in an organic solvent such as toluene. When used by heating and melting, it solidifies when left to stand, so there is the inconvenience of having to heat each time before use. In addition, since the one dissolved in an organic solvent has a high viscosity, it is not possible to increase the solid content concentration, and the permeation of the solvent impairs the cosmetic appearance of the cardboard box surface or dissolves the printing ink. There is a concern about pollution. Further, the anti-slip effect is reduced due to the permeability of the organic solvent.

Particularly in this anti-slip agent, the main component is only atactic polypropylene or EVA, not an emulsion. The terpene-based resin or the like as a subcomponent can be used only in the range of 50% by weight or less in the slip preventive agent, usually 10 to 20% by weight, and if it is used in an amount of 50% by weight or more, the slip resistance is not exhibited. That is, atactic polypropylene or EVA must be used only as a main component, and if a large amount of terpene-based resin or the like is used, the slip resistance of atactic polypropylene or EVA decreases. Therefore, there is no disclosure about whether the slip resistance of atactic polypropylene or EVA is significantly improved by simply using a terpene resin or the like.

The other one is disclosed in JP-A-48-60091, which mainly contains an aqueous solution of an alkali metal salt of a resin acid. However, it has a low solubility in water and the aqueous solution concentration cannot be increased so much. Therefore, there is a limit to the anti-slip effect,
In addition to being blackish brown, it dissolves the printing ink,
There are problems such as contamination and color transfer on the surface of the cardboard box,
It also has the drawback of slow drying.

In this anti-slip agent, an alkali metal salt of a natural rosin or a modified rosin is used as an alkali metal salt of a resin, and the surface activity of the anti-slip agent enables the anti-slip property to be improved, thereby improving the strength of the anti-slip coating. Therefore, there is a description that an emulsion such as polyvinyl acetate can be blended. However, there is no suggestion as to whether or not an emulsion such as polyvinyl acetate can always be used in a stable state in combination with an alkali metal resinate, and whether or not an emulsion can exhibit anti-slip properties simply in combination with an emulsion. Absent.

[0012]

An object of the present invention is to coat the surface of a paper container such as a corrugated cardboard case or a paper bag so that it has a slip angle of 40 ° or more and has non-slip properties, and does not cause blocking. Another object of the present invention is to provide an anti-slip composition having excellent anti-slip properties, which does not impair the cosmetic properties.

[0013]

DISCLOSURE OF THE INVENTION As a result of research on the basic physical properties of the anti-slip composition of the present invention, the inventors have found that if the so-called tackiness is increased, the slip resistance (friction resistance) is increased. Focusing on the phenomenon, we have conducted intensive studies on the relationship between tackiness and shear resistance. As a result, depending on the base resin and the tackifier, there may be a gap between the maximum value of the tack force and the maximum value of the adhesive force, that is, when the content of the tackifier increases, the tack force and It was found that the adhesive strength increases, but the appearance of the maximum value may deviate. Further, based on this new finding, the inventors have found a composition capable of significantly improving the anti-slip property by tack and at the same time suppressing the blocking of the resin, and completed the present invention.

That is, by incorporating one or a mixture of two or more of a terpene polymer and a terpene copolymer into the vinyl polymer emulsion, it has excellent anti-slip properties and excellent blocking resistance. It was found that an anti-slip agent can be obtained.

[0015]

Composition and Action of the Invention The anti-slip composition of the present invention is an aqueous anti-slip coating composition prepared by mixing one or more terpene polymers and terpene copolymers with a vinyl polymer emulsion.

The vinyl polymer emulsion used in the present invention includes vinyl acetate and methyl acrylate,
Acrylic esters such as ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, butadiene, acrylonitrile, ethylene, etc. The homopolymerization or copolymerization of the vinyl monomer can be exemplified. Usually, vinyl acetate emulsion, ethylene-vinyl acetate copolymer emulsion, acrylic copolymer emulsion, styrene-butadiene copolymer emulsion and the like are common.

In order to improve the properties of these vinyl polymer emulsions, acrylic acid, methacrylic acid, crotonic acid, maleic acid, acrylamide and its derivatives, 2-hydroxyethyl acrylate and methacrylic acid 2
It is also possible to copolymerize functional monomers such as hydroxyethyl, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether. In order to synthesize a polymer emulsion from these vinyl-based monomers, it is most common to synthesize by an emulsion polymerization method in water, but the polymer powder is emulsified and dispersed in water, or the polymer solution is dispersed in water. An emulsion can also be obtained by emulsifying and dispersing.

The vinyl polymer emulsion used in the present invention preferably has a glass transition temperature of 50 ° C. or lower, and particularly preferably -20 ° C. to +20.
It is in the range of ° C. If the glass transition temperature is higher than 50 ° C, it tends to be difficult to form a film at room temperature, and tackiness may not be easily exhibited. On the other hand, when the temperature is lower than -20 ° C, the adhesive strength becomes too strong, and blocking tends to occur easily. The concentration of the emulsion itself is usually about 30 to 65%.

The terpene polymer used in the present invention is known as a so-called terpene resin. Naturally produced pine resin is divided into a rosin portion and an essential oil portion by steam distillation, solvent extraction, distillation, etc. It is a polymerization reaction of some components. This essential oil portion is called turpentine oil, and its main components are mainly α-pinene, β-pinene, and dipentene.

The terpene polymer can be obtained by reacting this turpentine oil as a raw material in a solvent such as toluene in the presence of a Lewis acid catalyst. Depending on the polymerization conditions, a low molecular weight polymer that is liquid at room temperature to a solid resin high molecular weight polymer having a softening point of about 130 ° C. can be obtained. In addition, there are α-pinene polymers obtained by polymerizing only α-pinene, β-pinene polymers having different softening points, and terpene-based hydrogenated polymers having various softening points obtained by hydrogenation. In general, terpene polymers are light-colored, have excellent weather resistance, have good acid resistance and alkali resistance, and have excellent compatibility with various resins.

On the other hand, a terpene-phenol resin is generally used as the terpene-based copolymer, which is synthesized by a copolymerization reaction of α-pinene and phenol. The softening point ranges from liquid at room temperature to solid at a softening point of about 160 ° C. This terpene-phenol copolymer has a wide range of compatibility with other resins and is also excellent in solubility in various solvents. Not only natural terpenes but also those produced by a synthetic method in recent years are used, but it goes without saying that polymers and copolymers of these synthetic products can be used as well.

Regarding the proportion of at least one of the terpene polymer and the terpene copolymer added to the vinyl polymer emulsion, the composition of the vinyl polymer, the glass transition temperature and other characteristics, and the terpene polymer to be added. Since the softening point of the terpene copolymer and the like are related, it is necessary to find the optimum ratio by experiment in each case, but it is 5 to 60% by weight, preferably 20 to 50% by weight in terms of solid content. It is suitable to mix within the range.
If it is less than 5% by weight, the anti-slip effect is difficult to be exhibited, and if it exceeds 60% by weight, blocking resistance is deteriorated, which is not preferable.

1 of terpene polymers and terpene copolymers
As a method of mixing one or a mixture of two or more kinds with the vinyl polymer emulsion, it is possible to dissolve these resins in a solvent such as toluene or xylene, and directly add a diluted solution to mix them. There is also a method in which the emulsion is emulsified and dispersed in water to form a stable emulsion and then added. Alternatively, it may be added directly. In any case,
The characteristics of the terpene polymer and the terpene copolymer are that they are excellent in weather resistance and chemical resistance and have a wide compatibility with various synthetic resins, so that they can be easily mixed with a vinyl polymer emulsion.

The anti-slip composition of the present invention contains, in addition to the above-mentioned main components, an aqueous dispersion of polyethylene wax or natural waxes in a solid content of 0.1 to 10 wt. % Is preferably contained. When the content of waxes is less than 0.1% by weight, it is not effective for blocking resistance, and when it exceeds 10% by weight, transparency is deteriorated and slip resistance is also deteriorated, which is not preferable.

Inorganic or organic color pigments such as titanium dioxide and phthalocyanine blue, which are usually used for general coating agents and adhesives, or extender pigments such as calcium carbonate, talc and white carbon, are used for the anti-slip property of the present invention. It may be appropriately added to the composition for the purpose of coloring, reinforcing the base resin, adjusting the viscosity, and the like. Further, it is no problem to use ordinary dispersants, defoamers, thickeners, preservatives and the like according to their respective purposes.

The anti-slip composition of the present invention can be applied by a roll coating method, a curtain coating method, a spray coating method, a flexographic printing method, a gravure printing method, or the like. For example, it is needless to say that the composition of the present invention can be applied to the liner surface of the corrugated fiberboard base paper, or to the corrugated fiberboard sheet or cardboard case. Also for large craft bags,
It can be preprinted on the kraft base paper or applied after bag making.

[0027]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In addition, "part" in the following examples means a "weight part."

[0028]

Example 1 55 parts of an ethylene-vinyl acetate copolymer emulsion (solid content 55%, glass transition temperature Tg = -5 ° C.), 0.4 parts of a dispersant and 50% toluene of a terpene polymer having a softening point of 125 ° C. Gradually add 30 parts of the solution with stirring. The viscosity increases as it is added. Water 13.4
Parts, ammonia water 0.6 parts, defoamer 0.4 parts, preservatives 0.
Two parts were added, and the mixture was stirred until it became uniform to prepare the anti-slip agent of the present invention.

The anti-slip agent was evaluated by a sliding angle test, a blocking evaluation test and a drying property.

In the sliding angle test, the anti-slip agent prepared in the present example was coated on a K liner for corrugated board with a bar coater in a solid state and dried, and a test piece was prepared according to "Corrugated board industry standard JCS T 005- 1990 ". The results are shown in Table 1.

In the blocking evaluation test, the anti-slip agent prepared in Example 1 was solidly applied to a K liner for corrugated board, dried, and then two test pieces of 25 mm × 100 mm were pressure-bonded on the coated surface to give 350 g / cm ² . Load is applied, temperature 40 ℃, 80% R
After being left for 24 hours in a constant temperature and temperature chamber of H, a peeling test was performed using a tensile tester, and the blocking resistance was visually judged from the state of the peeled surface.

Further, as for the drying property, the anti-slip agent is solidly coated on the K liner for corrugated board, and the one which is dried within 3 minutes and loses the tackiness is marked with ⊚, and the one which disappears within 3 to 8 minutes is marked with ○.
The evaluation was carried out by using the mark, the mark within 15 minutes was marked with Δ, and the one that took more time to dry was marked with x. The results are summarized in Table 1.

[0033]

Example 2 An ethylene-vinyl acetate copolymer emulsion (solid content 55%, Tg = -5 ° C.) was added to 63 parts, and a dispersant was added.
4 parts and 23.1 parts of a 50% toluene solution of an α-pinene polymer having a softening point of 80 ° C. are gradually added with stirring to obtain a uniform state. To this, 12.5 parts of water, 0.4 of ammonia water
Parts, antifoaming agent 0.4 parts, and preservative 0.2 parts were added, and the mixture was stirred until it became uniform to obtain an anti-slip agent of the present invention. Similar to Example 1, this was subjected to a sliding angle test, a blocking resistance test, and a drying property test, and the results shown in Table 1 were obtained.

[0034]

Example 3 70 parts of an ethylene-vinyl acetate copolymer emulsion (solid content 55%, Tg = -5 ° C.) was added with a dispersant of 0.
4 parts and 15.4 parts of a 50% toluene solution of a terpene-phenol copolymer having a softening point of 100 ° C. are added with stirring to obtain a uniform state. 0.4 parts of ammonia water,
The antifoaming agent of the present invention was obtained by adding 0.4 parts of an antifoaming agent, 0.2 parts of a preservative and 13.2 parts of water to adjust the viscosity. The same test as in Example 1 was carried out and evaluated. The results are shown in Table 1.

[0035]

Example 4 55 parts of an ethylene-vinyl acetate copolymer encapsulation (solid content 55%, Tg = -5 ° C.) was added with a dispersant of 0.5 parts.
4 parts and 21.6 parts of a 70% toluene solution of a liquid terpene polymer having a softening point of 30 ° C. were gradually added with stirring, and the stirring was continued until uniform. 21.8 parts water,
0.6 parts of ammonia water, 0.4 parts of antifoaming agent and 0.2 parts of preservative were added to adjust the viscosity to obtain the anti-slip composition of the present invention. This was subjected to a sliding angle test, a blocking resistance test and a drying test in the same manner as in Example 1, and the results shown in Table 1 were obtained.

[0036]

Example 5 Polyvinyl acetate emulsion (solid content 55
%, Tg = 10 ° C.), 50 parts of a 50% toluene solution of a dispersant 0.4 and a terpene-phenol copolymer,
12.1 parts of 50% toluene solution of α-pinene polymer was added to each to make a uniform state. Ammonia water (0.6 parts), defoaming agent (0.4 parts) and preservative (0.2 parts) were added to the product, and the viscosity was adjusted with 11.3 parts of water to obtain the anti-slip agent of the present invention. Table 1 shows the results of evaluation performed by performing the same tests as in Example 1.
Shown in.

[0037]

Example 6 Acrylic ester copolymer emulsion (solid content: 50%, Tg = 0 ° C.) (66 parts) was mixed with a dispersant (0.4).
Parts, 13.2 parts of a 50% toluene solution of a terpene-phenol copolymer, and 9.4 parts of a 70% toluene solution of a liquid terpene polymer, respectively, to make a uniform state. To this, 0.4 parts of ammonia water and 0.4 parts of a defoaming agent were added, and the viscosity was adjusted with 10.2 parts of water to obtain an anti-slip composition of the present invention. Example 1
The same test was performed. The results are shown in Table 1.

[0038]

EXAMPLE 7 66 parts of a styrene-butadiene copolymer emulsion (solid content 50%, Tg = -15 ° C.), 22.4 parts of a 50% toluene solution of an α-pinene polymer and a dispersant of 0.4.
Add parts to make it uniform. To this, 0.6 parts of ammonia water, 0.4 parts of an antifoaming agent and 10.2 parts of water were added and stirred to make a uniform state. Evaluation was made by the same test as in Example 1. The results are shown in Table 1.

[0039]

Comparative Example 1 80 parts of water was added to 20 parts of sodium gum rosin salt and dissolved while heating to prepare a black-brown aqueous solution of gum rosin sodium salt having a solid content of 20%.

This was used as Comparative Example 1 and evaluated in the same manner as in Example 1 by a sliding angle test, a blocking test and a drying property.

[0041]

[Comparative Example 2] 16 parts of gum rosin sodium salt was dissolved in 76 parts of water while heating to prepare a blackish brown gum rosin sodium salt aqueous solution. Allow to cool to room temperature and add polyvinyl acetate emulsion (solid content 50%, Tg
(= 30 ° C.) 8 parts were added and stirred to prepare Comparative Example 2. Since the rosin sodium salt aqueous solution and the polyvinyl acetate enzion were partially precipitated, the supernatant was used for evaluation.

[0042]

Comparative Example 3 27 parts of polymerized rosin sodium salt was dissolved in 67 parts of water while heating to prepare a polymerized rosin sodium salt aqueous solution. Allow to cool to room temperature, and add acrylic acid ester copolymer emulsion (solid content 50%,
6 parts (Tg = −5 ° C.) were added and stirred. Polymerized rosin sodium salt aqueous solution and acrylic acid ester copolymer emulsion were not completely compatible, and when left overnight, a small amount of acrylic acid ester copolymer emulsion settled at the bottom, so use the supernatant liquid As in Example 1, the evaluation was carried out by a sliding angle test, a blocking test and a drying property.

[0043]

The anti-slip composition of the present invention was developed by paying attention to the difference between tackiness and adhesiveness. As is clear from Table 1 above, the anti-slip properties of a slip angle of 40 ° or more are obtained. It can be said that it is a composition having excellent blocking resistance and having practically excellent anti-slip properties even in the actual distribution process. In addition, the composition of the present invention does not cause precipitation or separation even when left for a long time, and has excellent storage stability.

[0044]

[Table 1]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Higashiyama 4-1-1186 Daikai, Fukushima-ku, Osaka City, Osaka Prefecture Rengo Co., Ltd. Central Research Institute (72) Inahiro Sakai 976-4 Umegaoka-cho, Akishino, Nara

Claims (1)

[Claims] 1. An anti-slip composition comprising a vinyl polymer emulsion containing one or more terpene polymers and terpene copolymers.