JPH0232171A - Anti-slip agent composition and corrugated board case using said composition - Google Patents

Abstract

PURPOSE:To obtain the subject anti-slip agent, containing a copolymer emulsion consisting essentially of ethyl acrylate with a specific glass transition temperature and having high slip resistance. CONSTITUTION:The objective anti-slip agent obtained by blending (A) 100 pts.wt. copolymer emulsion of a hard monomer containing ethyl acrylate having -22 to +10 deg.C glass transition temperature (Tg) in an amount of 70-92 pts.wt. based on 100 pts.wt. total amount of monomers and a functional group-containing monomer, such as acrylic acid, having a functional group with (B) one or two or more emulsions selected from the group of acrylic copolymer emulsions, acrylate-vinyl acetate-based copolymer emulsions or methyl methacrylate- butadiene copolymer latices or urethane emulsions in an amount of 50-200 pts.wt. expressed in terms of solids. Furthermore, the above-mentioned anti-slip agent is thinly applied to the surface of a corrugated board and dried to afford a corrugated box without causing disorder of cargo.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to an anti-slip agent applied to the surface of corrugated cardboard, an anti-slip agent composition thereof, and an anti-slip agent used to prevent corrugated pole cases from shifting during transportation. This relates to a cardboard case coated with.

More specifically, it relates to emulsion-type anti-slip agents and anti-slip agent compositions that are applied to the surface of corrugated cardboard printed by flexographic printing or the like at a stage before box manufacturing, and corrugated cardboard cases made by applying these. Beverages, alcohol,
An anti-slip agent with high slip resistance, an anti-slip agent composition, and a cardboard case coated with the same, used for the purpose of preventing cardboard cases packed with beer, confectionery, etc. from collapsing due to vibrations that occur during stacked transportation. It is related to.

[Conventional technology]

The typical conventional method for preventing cargo from collapsing has been to seal the cardboard case and then apply hot-melt adhesive in several lines on the surface of the case.

The problem with this method is that when a certain number of items are glued together with hot melt adhesive and transported as is, it is an extremely effective method to prevent the cargo from collapsing. When carrying out work such as reloading or reloading small parcels, the initial effect of preventing the load from collapsing obtained with hot melt is completely lost, and not only is it necessary to apply hot melt adhesive again, but the small portions are As a means of solving these problems, there was a problem that the adhesive application part caused the paper to break and the product image was significantly deteriorated. Research has been carried out on using an emulsion-type coating agent that combines a tackifier resin with a combined emulsion and a filler such as colloidal silica, but it lacks slip resistance, that is, the sliding angle, and the cardboard cases do not stick to each other. It is extremely difficult to balance co-authorship (blocking properties), frictional strength, etc., and practical research is required.

[Means to solve the problem]

As a result of intensive research to solve the above problem, the present researchers first determined that the glass transition temperature (hereinafter abbreviated as Tg) of ethyl acrylate as a main component was
It has been found that a copolymer emulsion of -22 to +10"C has extremely high slip resistance, that is, an extremely high slip prevention effect as the slip angle increases.

Next, as a means to improve the co-authorship (hereinafter referred to as blocking property) by laminating the corrugated pole case, different types of emulsions with glass transition temperatures (Tg) of -22 to +40°C, namely acrylic polymer emulsion, Acrylic IJ-acetic acid emulsion, etc. Blending a vinyl copolymer emulsion, methyl methacrylate-butadiene copolymer latex, or urethane emulsion maintains a high slip angle and is extremely effective in improving blocking properties, friction strength, and chipping properties. They discovered this and completed the present invention.

That is, the present invention provides: (1) a glass transition temperature (Tg) of -22 to +10°C;
(7) An anti-slip agent containing a copolymer emulsion containing ethyl acrylate as a main component; (2) A copolymer emulsion containing ethyl acrylate as a main component having a glass transition temperature (Tg) of -22 to +10°C; Tg is 120 parts by weight for 100 parts by weight of solid content of a)
- +40°C acrylic copolymer emulsion, acrylic-vinyl acetate copolymer emulsion, methyl methacrylate-butadiene copolymer latex, or one or two selected from the group of urethane emulsions.
The emulsion (b) consisting of seeds or more has a solid content of 5
An anti-slip agent composition containing 0 to 200 parts by weight,
and (3) a cardboard case coated with the above-mentioned anti-slip agent or anti-slip agent composition.

(4) The present invention relates to a method for manufacturing a cardboard case in which the above-mentioned anti-slip agent or anti-slip agent composition is applied before making the case to prevent the package from collapsing.

Glass transition temperature (hereinafter abbreviated as Tg) of the present invention -2
A copolymer emulsion containing ethyl acrylate as a main component at a temperature of 2 to +10°C refers to the following:
A monomer containing 70 to 95 parts by weight of ethyl acrylate and the remainder being methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, styrene, and acrylonitrile, which yields a polymer with a high glass transition temperature. One or more hard monomers selected from the group of hard monomers (hereinafter abbreviated as hard monomers), acrylic acid, methacrylic acid, n
- Monomers having a functional group such as methylol acrylamide, acrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl methacrylate, etc. (hereinafter abbreviated as functional monomer) One or more functional monomers selected from the group W4 can be used.

If the amount of ethyl acrylate in the copolymer emulsion containing ethyl acrylate as a main component is 70 parts by weight or less, slight tackiness cannot be obtained and the effect as an anti-slip agent is not expressed, and if it is 95 parts by weight or more. Not only does it not provide stability during emulsion polymerization, but it also suffers from problems such as blocking properties, deterioration of aesthetic appearance due to adhesion of lumps, etc., and deterioration of frictional strength, resulting in lack of practicality.

Although the type and composition ratio of the hard monomer and the functional monomer are not particularly specified, the use of the functional monomer is essential.

That is, from the viewpoint of stability during emulsion polymerization, stability during storage, and further stability when blending different emulsions, it is appropriate to use the functional group monomer in the range of 2 to 10 parts by weight in Mo/7-ml. It is.

The copolymer emulsions or copolymer latexes with a Tg of -22 to +40''C used in the present invention include styrene-butyl acrylate, methyl methacrylate-butyl acrylate, and styrene-2-ethylhexyl as acrylic copolymer emulsions. Acrylate, methyl methacrylate-2-ethylhexyl acrylate,
Examples include copolymer emulsions such as styrene-methyl methacrylate-butyl acrylate and acrylonitrile-butyl acrylate, and a more preferable Tg range is -5 to ±30°C.

As an acrylic-vinyl acetate copolymer emulsion,
Examples include copolymer emulsions of vinyl acetate and 2-ethylhexyl acrylate, butyl acrylate, ethyl acrylate, etc., and more preferable Tg ranges include:
It is in the range of -5 to +30°C.

A more preferable Tg range for the methyl methacrylate-butadiene copolymer latex is -15 to -
It is in the range of 5°C.

Any of the copolymer emulsions mentioned above can be used as long as they are produced by conventionally known methods, and these various copolymer emulsions are easily available as commercial products.

Furthermore, as the urethane emulsion mentioned above, urethane emulsions that are usually used as adhesives, coating agents, etc. can be used, and the Tg is generally in the range of 0 to -30°C, and these are easily available as commercial products. available at.

These urethane emulsions can be prepared using conventional methods such as polypropylene glycol,
Glycols such as polyoxyethylene glycol and polyoxypropylene glycol, tolylene diisocyanate (TDI), diphenylmethane diisocyanate) (
Isocyanates such as MDI) and dimethylolpropionic acid are reacted under a nitrogen blanket at a temperature of 60 to 80°C for about 4 hours, and the resulting polyurethane prepolymer having isocyanate groups at the terminals is reacted with ethanolamine,
A urethane emulsion can be obtained by administering it to a mixture of aliphatic amines such as jetanolamine and triethanolamine and water while stirring vigorously.

By blending one or more emulsions selected from the above group of copolymer emulsions, copolymer latexes, and urethane emulsions into a copolymer emulsion containing ethyl acrylate as a main component, blocking properties, Frictional strength etc. are imparted.

The anti-slip agent composition used in the present invention includes the above-mentioned T.
The copolymer emulsion, copolymer latex, or urethane emulsion with a Tg of -120 to +40°C is added to 100 parts by weight of a solid copolymer emulsion mainly composed of ethyl acrylate with a Tg of -20 to +10°C. The appropriate blending ratio is in the range of 50 to 200 parts by weight as solid content.

When the amount is less than 50 parts by weight, blocking properties, frictional strength, adhesion of lumps, etc. are lacking, and when it is more than 200 parts by weight, the desired anti-slip effect is reduced, which is a practical problem.

As described above, the anti-slip agent and anti-slip agent composition of the present invention, when applied thinly to the surface of a corrugated cardboard case and dried at room temperature, exhibits an extremely excellent anti-slip effect and improves blocking properties, frictional strength, and chipping. Because it has excellent adhesion properties, its practical value is extremely high.

When using this anti-slip agent, antifoaming agents, thickeners, surfactants, and even powder polymers (
Fillers such as acrylic, styrene, polyester, etc.) or colloidal silica may be added.

[Examples] Hereinafter, in order to further specifically explain the present invention, production examples,
Although the present invention will be described with reference to Examples and Comparative Examples, the present invention is not limited to these Examples.

In addition, in the following, unless otherwise specified, parts or percentages represent weight.

Production Examples 1 to 6 In a flask equipped with a stirrer, 60 g of distilled water and 0.5 g of sodium dodecylhenzenesulfonate were charged, and the temperature was raised to 70°C while stirring under a nitrogen sole, and 0.5 g of potassium sulfate was added.
Administer g.

Next, pre-emulsified monomer 1 was added in the proportions shown in Table 1.
40 g was continuously administered at a constant speed over 3 hours, and the remaining monomer was further polymerized at the same temperature for 3 hours to complete emulsion polymerization.

After cooling to room temperature, adjust the pH to 7.0 with ammonia water,
The main component is ethyl acrylate, which is filtered through a 100-mesh wire mesh and has a Tg of -122 to +10°C for use in the present invention.
A copolymer emulsion with a solid content of 50% was obtained.

Examples 1 to 16 Solid content of copolymer emulsions obtained in Production Examples 1 to 6: 10
0 parts by weight, acrylic copolymer emulsion, acrylic-vinyl acetate copolymer emulsion, methyl methacrylate-phtadiene copolymer latex, and urethane emulsion were stirred and mixed in the proportions shown in Table 2. An inventive anti-slip agent composition was obtained.

■Acrylic emulcidin A (TgO”C) (manufactured by Mitsui Toatsu KK, trade name Almatex E103 solid content 45%,
pH8.0, viscosity 300cps, styrene, butyl acrylate, methacrylic acid, acrylamide copolymer) ■Acrylic emulsion-B (Tg + 15℃) (
Manufactured by Mitsui Toatsu KK, trade name Almatex E208) Solid content 45%, pH 8.0, viscosity 1000 cps, styrene, methyl methacrylate, butyl acrylate, methacrylic acid, acrylamide, hydroxyethyl methacrylate copolymer) ■Acrylic- Vinyl acetate copolymer Emulsin-A (T
gOoC) (manufactured by Showa Kobunshi Kogyo KK, trade name Polysol 747,
Solid content 50%, pH 3.5, viscosity 3000 cps) Acrylic-vinyl acetate copolymer emulsion B (Tg
(10℃) (manufactured by Showa Kobunshi Kogyo KK, trade name Polysol RR8E,
Solid content 41%, pH 4.5, viscosity 15000cps)■
Methyl methacrylate butadiene copolymer latex-A (Tg -13°C) (manufactured by Mitsui Toatsu KK, trade name Polylac 501, solid content 4
8%, pH 7.0, viscosity 100 cp3) ■ Methyl methacrylate butadiene copolymer latex-B (Tg
-8℃) (Mitsui Toatsu KK, product name Polylac 707, solid content 4
8%, pH 7.0, viscosity 100cps) ■Urethane emulsilane (manufactured by Sanyo Chemical Industries KK, trade name Sunblane IIX-1)
12OA, solid content 36%, pH 4.5, viscosity 22.0
OOcps) This anti-slip agent composition was tested by the method shown below, and the results are shown in Table 3.

Reference Example 1 DEG Wipe Preparation The anti-slip agent composition of the present invention was uniformly applied to the surface of a double-sided corrugated board at a solid content of 1.0 to 1.5 g/r4. At this time, since the coating amount was extremely low, it was diluted 3 times with water, the coating amount was calculated from the theoretical concentration, and the coating was applied using air spray.

Then, it was dried at room temperature for 30 minutes or more and subjected to the following test.

Reference example 2゜ (Test method) Il of paper and paperboard according to JIS P-8147 In accordance with the measurement method using the slope method of the friction coefficient test method, the angle at which a 1000 g weight starts to slide is indicated. (A large slip angle indicates a high slip prevention effect.

≦Place the surfaces coated with the outsourced anti-slip agent composition, and
00'X 2kg load per 100a+m, 4
The blocking state after being left in a constant temperature room at 0°C for 24 hours was observed and displayed as shown below.

O...No co-adhesion phenomenon Δ...Shipping during peeling (peeling phenomenon grows with noise) ×... Difficult to peel Cotton broadcloth #40 for child
A cloth was attached, and the anti-slip agent coated surface was subjected to HWI at a load of 500 g and a speed of 30 times/win, and the presence or absence of changes after 500 times of friction was indicated as shown below.

O...No abnormality Δ...The anti-slip agent partially peeled off as a rubbery substance.
After the cardboard coated with the anti-slip agent was left indoors for 3 days, it was observed whether dust could be gradually removed using a brush, and the results were displayed as shown below.

O: Easily removable Δ: Slight adhesion observed ×: Unremovable Comparative Example 1 The copolymer emulsion obtained in the Production Example was treated in the same manner as in the Example. It was subjected to a test and the results are shown in Table 3.

Comparative Example 2 Acrylic copolymer emulsilane (Tg
0°C) was subjected to a test in the same manner as in the example, and the results are shown in Table 3.

Comparative Example 3 The methyl methacrylate-butadiene copolymer latex (Tg -13°C) used in Example 5 alone was subjected to a test in the same manner as in Example, and the results are shown in Table 3.

Comparative Example 4 The urethane emulsion used in Example 7 was subjected to a test in the same manner as in Example, and the results are shown in Table 3.

Comparative Example 5 Ethylene-vinyl acetate copolymer emulsion (trade name, manufactured by Kuraray) LatzEVAI4000, TgO ℃ solid content 55%, pH 5.0, viscosity 2000 cps) and acrylic adhesive emulsion (manufactured by Mitsui Toatsu Chemical KK, manufactured by KK, ?1
T-Tack 5057, Tg-30℃ 1 solid content 48
%, pH 8.0, viscosity 3000 cps, rosin-based tackifying resin desversion blended product) at a ratio of 1:1 and subjected to a test in the same manner as in the example, and the results are shown in Table 3.

Table 3 [Effects of the Invention] As is clear from Table 3, the anti-slip agent composition of the present invention can be used to prevent the load from collapsing in a cardboard case.
When applied, it exhibits excellent slip resistance, as well as blocking properties, frictional strength, and flake adhesion properties, making it suitable for food, beverages, alcohol, beer, and confectionery that are transported in cardboard cases. It has high practical value as an anti-slip agent for packaging materials, and its significance is great.

Patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. An anti-slip agent containing a copolymer emulsion containing ethyl acrylate as a main component and having a glass transition temperature (Tg) of -22 to +10°C. 2. (a) Glass transition temperature (Tg) is -22 to +10°C based on 100 parts by weight of solid content of a copolymer emulsion mainly composed of ethyl acrylate, (b) Tg is -20
- +40°C acrylic copolymer emulsion, acrylic-vinyl acetate copolymer emulsion, methyl methacrylate-butadiene copolymer latex, or one or two selected from the group of urethane emulsions.
An emulsion consisting of seeds or more with a solid content of 50 to 2
An anti-slip agent composition containing 0.00 parts by weight. 3. A cardboard case coated with the anti-slip agent according to claim 1 or the anti-slip agent composition according to claim 2. 4. A method for manufacturing a cardboard case capable of preventing cargo from collapsing, characterized by applying the anti-slip agent according to claim 1 or the anti-slip agent composition according to claim 2 to the surface of the cardboard at a stage before box manufacturing. 5. The slip prevention according to claim 2 or 3, wherein the copolymer emulsion containing ethyl acrylate as a main component contains 70 to 95 parts by weight of ethyl acrylate in 100 parts by weight of the total amount of monomers, with the remainder being hard monomers and functional group monomers. agent or anti-slip agent composition. 6. The functional group monomer is 2 in 100 parts by weight of the total amount of monomers.
5. The anti-slip agent composition of claim 4, wherein the amount is in the range of 10 parts by weight. 7. Acrylic polymer emulsion and acrylic vinyl acetate copolymer emulsion have a Tg range of -5 to +
The anti-slip agent composition according to claim 2, wherein the temperature is 30°C. 8. The anti-slip agent composition according to claim 2, wherein the methyl methacrylate-butadiene copolymer latex has a Tg in the range of -15 to -5°C. 9. The anti-slip agent composition according to claim 2, wherein the urethane emulsion is used as an adhesive or a coating agent, and has a Tg of 0 to -30°C.