JPH02173071A - Anti-slip coating composition - Google Patents

Abstract

PURPOSE:To improve the anti-slip and anti-block properties by dispersing specified fine particles of an org. polymer into an org. polymer latex. CONSTITUTION:5-60wt.% (solid base) fine org. polymer particles having a mean particle diameter of 0.1-10mum and the lowest film-forming temp., when dispersed in an aq. medium, of at least 60 deg.C (e.g. polystyrene) is dispersed into 95-40wt.% (solid base) org. polymer latex having the lowest film-forming temp. of 60 deg.C or lower (e.g. butadiene copolymer latex).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an anti-slip agent, and in particular to a coating that can be applied to containers such as cardboard boxes to provide excellent anti-slip properties and boot-kicking resistance. Regarding the composition.

[Conventional technology and seven problems]

Many products such as cans of beer, carbonated drinks, coffee fruits, sports drinks, etc., foodstuffs such as vegetables and grains, and clothing are sold in containers such as cardboard boxes. When transporting or storing items in a pile, there is a problem that the items may collapse due to photographing or tilting. A common way to prevent cargo from collapsing is to tie it with string or rope, but it is time-consuming to tie, untie, and tie. Nari 几.

One way to treat containers to prevent them from slipping is to apply an anti-slip agent to the bottom or top of the container.

Conventionally, as such anti-slip agents, atactic polypropylene 19 contains ethylene-vinyl acetate copolymer 50-1
00 weight 1) 4-containing melt (% 1976-60090
No. 2), water bath solutions of anionic surfactants such as alkali metal salts of resin acids, alkali metal salts of natural or modified rosin (
t￥f Publication No. 48-60091), hot melt compositions containing resins such as atactic polyglobylene and petroleum resins, terpene resins, alkylphenol resins, rosins and modified rosins, and polybutene (% 1977-44990)
JP-A No. 53-3482), a composition comprising an organosilicon polymer obtained by reacting a siloxysilanol and an or-nosilylating agent in a polar organic solvent and a silicone oil (JP-A-53-3482)
8), a hot melt composition consisting of a wax, a tackifying resin, and an ethylene-vinyl acetate copolymer resin <JP-A-56-30854), an inorganic sol such as colloidal silica or an inorganic powder and a synthetic resin. Add a small amount of emulsion and apply 9 coats'j+ and water:
A composition containing particles such as 0 to 200 mesh (approximately 75 to 600 μ) large particle diameter D-rus beads, silica balloons, or synthetic resin, and a binder resin such as ethylene-vinyl acetate copolymer emulsion or styrene-butadiene resin latex. (Japanese Unexamined Patent Publication No. 59-108079) is known.

By the way, the important characteristics that an anti-slip agent should have are excellent applicability to the container base material, excellent appearance of the coated surface of the container (good transparency, gloss, etc. of the coating film), and excellent coating properties on the container base material. It has excellent adhesion (adhesiveness) to the material, it increases the frictional resistance of the coated surface to exhibit an anti-slip effect, and it also has excellent anti-blocking properties of the coated surface. Especially recently, when applying anti-slip treatment to corrugated boxes, anti-slip agents are often applied directly to the liner.
Anti-slip agents are required to have excellent anti-sinking properties as well as better blocking resistance than ever before.

However, hot-melt coating type anti-slip agents obtained by combining polypropylene, ethylene-vinyl acetate copolymer, tackifying resins such as petroleum resins and modified rosin, polybutene, and wax are highly temperature-dependent. However, it has the disadvantage that excellent blocking resistance cannot be obtained in summer, and cracks are likely to occur at low temperatures. Since a composition consisting of an organosilicon polymer and silicone oil is applied after being dissolved in an organic solvent such as toluene, it has problems in terms of environmental hygiene and also lacks blocking resistance. Inorganic anti-slip agents such as colloidal silica have excellent anti-blocking properties, but have the drawbacks of insufficient anti-slip properties and lack of strength of the anti-slip layer, making it easy to peel off. 19. Water-based anti-slip agents consisting of granules and binder resin have large particle diameters, and the transparency of the anti-slip layer tends to be lost, making it impossible to apply to the surface of printed containers, etc. The amount is large, which is economically disadvantageous, and has the disadvantage that a sufficient anti-slip effect cannot be obtained.

[Friendly means of solving problems]

The present inventors believed that a polymeric latex could be used to obtain a Sui-9 inhibitor with excellent anti-slip effects and anti-blocking properties, and after extensive research, a film made solely of polymeric latex showed the desired performance. could not be found. Therefore, we investigated the blending trap between polymer latexes and found that a coating composition obtained by adding organic polymer fine particles of a specific particle size to a film-forming polymer latex has a high slip angle that we aim for. (The angle at which a non-slip treated container begins to slide on a slope treated with W9 prevention) and excellent anti-blocking properties at the same time.
We have arrived at the present invention.

That is, the present invention provides organic polymer fine particles (A) having an average particle size of 0.1 μ to 10 μ, dispersed in an aqueous medium, and having a minimum film formation temperature of 60° C. or higher at 9 o'clock. Membrane temperature is 60℃
This is an anti-slip coating composition characterized by comprising an organic polymer latex (B) K mixed and dispersed.

The organic polymer fine particles, which are an essential component of the aqueous anti-slip coating composition of the present invention, can be used in the form of latex or powder, and are 0.1μ to 10μ, preferably 0.1μ to 10μ.
It is necessary to have an average particle diameter f in the range of 2μ to 7μ and a minimum film forming temperature of 60°C or higher. The minimum film forming temperature is 7 for latex, and for powder, add water or a dispersant such as a surfactant to water and add a submersion bath liquid to about 20 yen! Disperse at one time and apply the next one to a thickness of about 0.1 to 0.51 mm on a glass plate, and dry it to form a continuous film rather than a powder, with the lowest drying temperature of the following group. means.

When the average particle diameter is less than 0.1 μm or more than 10 μm, and when the minimum film forming temperature is less than 60° C., it is not possible to have a high 9 angle and excellent blocking resistance at the same time.

Examples of organic polymer fine particles include homopolymers or copolymers with high glass transition temperatures such as styrene, methyl methacrylate, and acrylonitrile, latexes such as phenol resins, phenol terpene resins, melamine resins, and urea resins, and their powders. You can sing O. These organic polymer fine particles can be prepared using the known emulsion polymerization method, suspension polymerization method, dispersion polymerization method (for example, U.S. Pat.
No. 82, etc.).

The coating composition of the present invention forms a dry coated surface with a moderate unevenness, containing hard organic polymer fine particles with a specific particle size and a good minimum film formation temperature, and has a high sliding angle. It is thought that this material exhibits excellent blocking resistance.

The organic polymer latex (B) used as an essential component in the anti-slip composition of the present invention needs to have a minimum film forming temperature of less than 60°C. If the minimum film formation temperature is 60°C or higher, the anti-slip coating layer becomes brittle and easily destroyed by impact. The deflection angle also becomes small, which is not preferable. Among polymer latexes with a minimum film formation temperature of less than 60°C, those with a glass transition temperature in the range of about -20°C to about 40°C are suitable for achieving a balance between sliding angle and blocking resistance. preferable. Films obtained from latex with a low minimum film formation temperature are
The flexibility and blocking resistance tend to decrease, but this can be improved by using a highly rubberized latex or by using a crosslinking agent in combination.

However, the film formed from latex at the film-forming temperature becomes hard and tends to reduce the sliding angle, but the reduction in the sliding angle can be suppressed by using a substance that softens the polymer, such as a solvent or plasticizer. is possible.

The organic polymer latex that can be used in the present invention is
The synthetic organic polymer latex and the natural one are Muratex.

Synthetic organic polymer latexes include dienes such as butadiene, imbrene, and chloroprene; aromatic vinyls such as styrene, vinyltoluene, and alpha-methylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, and acrylic. 120 such as butyl acid, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, octyl methacrylate, etc.! Alkyl esters of acrylic acid and methacrylic acid: vinyl esters such as vinyl acetate, vinyl propionate, etc.; Ethylenically unsaturated carboxylic acids such as monoesters of; Hydroxyacrylic esters such as 2-hydroxyethyl acrylate, methacrylic a, 2-hydroxyethyl; Glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate, glycidyl methacrylate, etc. ; Vinyl halides such as vinylidene chloride; N-alkoxyalkyl acrylamides such as N-methylol acrylamide, N-methylol methacrylamide, N-butoxymethyl acrylamide; acrylamide and methacrylamide; radically polymerizable monomers such as ethylene; All examples include latex (emulsion) obtained by combining one or more gold emulsions; tackifying resins such as wax, petroleum resin, and rosin derivatives; and emulsions obtained by emulsifying polyurethane and solid rubber. Among latexes and emulsions, diene-based latex, acrylic ester-based latex, ethylene-vinyl acetate-based latex, and vinylidene chloride-based latex can be suitably used, as well as composite latex such as heterolayer structure latex and blended latex. These latexes are manufactured by known emulsion polymerization methods.

The proportion of the organic polymer fine particles (A) of the present invention is preferably in the range of 5 to 60 weight, particularly 10 to 40 weight, and the proportion of the organic polymer latex (B) + 140-95 weight. A range of 60-90 yen* is particularly preferable. If the proportion of the organic polymer fine particles (A) exceeds 5% by weight and the proportion of the organic polymer latex (B) exceeds 95% by weight, the sliding angle will be small and the blocking resistance will be poor, which is not preferable. When the proportion of organic polymer fine particles (A) exceeds 60% by weight and the proportion of organic polymer latex (B) is less than 40%, excellent anti-blocking properties are exhibited, but the I'lv angle becomes small, I don't like it.

When the anti-slip coating composition of the present invention is applied to containers, for example, corrugated boxes, it can be applied directly to the liner base paper (using a flexographic printing machine, etc.) to form an anti-slip coating layer. Alternatively, the liner base paper and the core base paper may be thermally bonded together with a layering agent, and then coated on a corrugated paperboard or a corrugated box to form an anti-slip coating layer. The coating amount is not limited to %, but is approximately 1 to 201)7m”c solid content)
The range is preferable because the effect of the anti-slip coating composition of the present invention can be easily exhibited and it is also economically advantageous.

-! The coating composition of the present invention exhibits its performance under the usual drying conditions of 60°C to ISO'C and within 1°C.

The coating composition of the present invention is composed of organic polymer fine particles (A) and organic polymer latex (B), but other additives may be used in combination as long as the effects of the present invention are not impaired. Such additives include water-soluble urea-melamine resins, melamine resins and epoxy resins, inorganic fillers such as calcium carbonate, clay and talc, water-soluble thickeners such as sodium polyacrylate and cellulose derivatives, tackifying resins, Examples include nonionic and anionic emulsifiers, metal oxides, crosslinking agents such as jepoxy compounds, fungicides, antifungal agents, starch, casein, and colloidal silica.

[Effects of the present invention]

The anti-slip coating composition of the present invention has an unprecedentedly high sliding angle and excellent blocking resistance, and is an extremely valuable anti-slip agent industrially.

〔Example〕

Below, l! #The present invention will be explained by giving an example, but the present invention is not limited thereto.

$ Examples 1 to 5 and Comparative Examples 1 to 3 Carboxy-modified polystyrene latex L8801 [Asahi Kasei Corporation, average particle size 0.5μ, minimum film formation temperature 90
℃ or above] and carboxy-modified 8B latex (prototype A) obtained by polymerizing 56 parts of styrene, 41 parts of butadiene, and 3 parts of acrylic acid by a conventional emulsion polymerization method and having a minimum bottom film temperature of about 10 degrees Celsius (prototype A). Blend in the proportions (by weight) shown in
Apply to corrugated board liner base paper with a wire bar to approximately 5 g/rIL2 (dry solid content), 1) 0°C, 3
Leave the coated liner base paper to dry for a minute. The sliding angle and blocking resistance of the obtained coated base paper were measured using the following method. Table 1 shows the measurement results of 7.

Measurement of 9 angles The liner coated with the above blended latex was pasted on a glass plate with the coated side facing up, then the same coated liner was stacked so that the coated sides were in contact with each other, and then placed on top of that. A load of 97 cm'' was applied (attached), the glass plate was gradually tilted, and the angle at which the applied liner on the top surface started to slide was measured.

Conditions during measurement: 23°C, 6096RH.

- Layer two anti-blocking coated 9 liners with the coated surfaces on top of each other, apply a load of 300cm" in lie, 40"C.

After being left for 18 hours under 90 RH, it was peeled off and the degree of adhesion was graded into four grades and evaluated.

◎ No adhesion at all O Slight adhesion Δ Slight adhesion Ifi'! is coated on the liner under the same coating and drying conditions as in Examples 1 to 5 to prevent debris from forming. r-shape [Sase, bending angle y
and blocking resistance were measured. The results are shown in Table 2. The types of organic polymer fine particles and organic polymer latex newly used in this example are as follows.

Organic polymer fine particles (A) 0.2μ polystyrene: styrene? Normal emulsification・1.
0μ polystyrene - 7.0μ styrene/methyl methacrylate copolymer 9 products obtained by polymerization: 9 products obtained by polymerization of styrene gold: Near-ON sealed styrene and 3ONm% methyl memethacrylate Phenol terpene WB obtained by total suspension polymerization: Yasushi Oil Industries Co., Ltd.
Metalon 2130 ■ Machine polymer latex (B) ・Carboxy-modified SB = Asahi Kasei Kogyo Co., Ltd. (fired acrylic latex board: Asahi Kasei Kogyo Co., Ltd.) Tron A
-55 - Acrylic latex: Comparative example 4 manufactured by Asahi Kasei Industries, Ltd.
~8 ff1e shown in Table 2, organic polymer fine particles (A) having the minimum film forming temperature and particle size, and organic polymer latex (B) ft having the minimum film forming temperature, blended in the proportions shown in Table 2,
The coating was applied to a liner under the same coating and drying conditions as in Examples 1 to 5, and the sliding angle and blocking resistance were all measured. This result is shown in 1K.

The types of organic polymer noble particles (A) and organic polymer latex (B) used in this comparative example are shown below.

Organic polymer fine particles (A) ・0.04 μ carboxy modified: styrene, methacrylic polystyrene ・15 μ polystyrene carboxy modified S8 1 Colloidal silica carboxy edible SB L-2 Nine products obtained by emulsion polymerization of methyl acid and acrylic acid : Obtained by suspension polymerization method: Asahi Kasei Koki Co., Ltd. Grade: Snowtex C manufactured by 8 San Kagaku Co., Ltd. Prototype manufactured by Asahi Kasei Co., Ltd. Styrene/acrylonitrile/butadiene/methacrylic U7-based borimer

Claims (2)

[Claims] (1) Organic polymer fine particles (A) with an average particle diameter of 0.1 μ to 10 μ and a minimum film formation temperature of 60°C or higher when dispersed in an aqueous medium are used. An anti-slip coating composition characterized by being mixed and dispersed in an organic polymer latex (B) of (2) In a mixture of 100% by weight (solid content) of organic polymer fine particles (A) and organic polymer latex (B), the proportion of organic polymer fine particles (A) is 5 to 60% by weight in terms of solid content. The anti-slip coating composition according to claim 1, characterized in that the anti-slip coating composition falls within the range