KR100573964B1 - Anti-slip agent and preparation method thereof - Google Patents

Abstract

The present invention relates to an anti-slip agent and a method for preparing the anti-slip agent, comprising an anti-slip agent or the anti-slip agent containing 0.2 to 2% by weight based on the total solid content of a cellulose-based material or an acrylic thickener including a cellulose derivative. The anti-slip agent further comprising at least one selected from acrylic thickener, rubber latex, wax dispersant, or tackifier, between the paper packaging material during palletizing of the paper packaging material, so as to provide interlayer slip during transport and transportation after loading. It prevents slippage, and at the time of separation from loading, there is no breakage of the paper material or it becomes extremely weak, which facilitates the separation and is also used as an environmentally friendly alternative to the currently commercially available plastic wrapping. It is possible.

Antislip, Cellulose, Acrylic Thickener, Rubber Latex, Wax Dispersant, Tackifier

Description

Anti-slip agent and preparation method of the anti-slip agent

The present invention is an antislip agent comprising 0.2 to 2% by weight of a cellulose-based material or an acrylic thickener including a cellulose derivative based on total solids content or an acrylic thickener, rubber latex, wax dispersant or tackifier to the antislip agent. It relates to an antislip agent further comprising one or more.

Korean Laid-Open Patent No. 195-0043894 makes a flexible acrylic latex having a low solids content and low glass transition temperature, and separately making another acrylic latex having a relatively high glass transition temperature, and mixing the acrylic latexes and neutralizing them with ammonia water. A method for preparing an acrylic slipper is provided. However, the Republic of Korea Patent Publication No. 195-0043894 is a method of synthesizing two kinds of acrylic polymers, respectively, and mixing them, which is not only difficult to manufacture, but also causes a lot of problems that may occur due to variations in physical properties.

Therefore, there is a demand for the development of an economical anti-slip agent because the solid content is relatively low and the manufacturing process and physical property adjustment is very simple.

Accordingly, the present invention provides an economical anti-slip agent and anti-slip agent manufacturing method with a relatively low solids content, easy manufacturing process and physical property adjustment, advantageous in terms of recycling and recycling, and short manufacturing time. There is this.

In order to achieve the above object, the present invention is an anti-slip containing cellulose or cellulose derivatives introduced with a methyl group, hydroxyethyl group, hydroxypropyl group or hydroxypropylmethyl group in the cellulose, 0.2 to 2.0% by weight based on the total solid content Offer

In addition, the present invention provides an anti-slip agent containing 0.2 to 2.0% by weight of the acrylic thickener based on the total solid content.

When the cellulose and cellulose derivative or acrylic thickener is less than 0.2% by weight based on solids content, it is impossible to express viscosity, initial fixation force and state fixation force required as an antislip agent, and when it exceeds 2.0 wt%, viscosity and initial fixation force The physical properties of the back are possible, but in the dry release required as an anti-slip agent, the state holding force is too strong, causing a problem that the paper packaging material is torn.

In addition, the present invention is composed of a cellulose derivative or a cellulose derivative in which a methyl group, a hydroxyethyl group, a hydroxypropyl group or a hydroxypropylmethyl group is introduced into cellulose and an acrylic thickener, and the total solid content is 0.2 to 2.0% by weight. An anti-slip agent is provided.

The acrylic thickener can be used as an anti-slip agent alone, but in this case, if the state adhesive strength is matched, the viscosity required as the anti-slip agent may be too low, which may lead to a stiffness when applied. It is so strong that it cannot meet the required dry release properties, resulting in the viscosity, initial fixation, dry release properties and state adhesion required by antislip agents by use in combination with cellulose or cellulose derivatives.

If the total solid content is less than 0.2% by weight, it is impossible to express viscosity, initial fixation force and state fixation force required as an antislip agent, and if it exceeds 2.0% by weight, physical properties such as viscosity and initial fixation force are possible but antislip. In the dry release required as the agent, the state holding force is so strong that the paper packaging material is torn.

The present invention also provides a cellulose or cellulose derivative in which a methyl group, hydroxyethyl group, hydroxypropyl group or hydroxypropylmethyl group is introduced into cellulose; Acrylic thickeners; And it comprises one or more selected from rubber latex, wax dispersant or tackifier, and provides an anti-slip agent, characterized in that the total solid content of 0.2 to 20% by weight.

If it is out of the content range of the total solid component, it is impossible to meet the stability, viscosity, initial fixing force, dry release property and state fixing force, which are physical properties required by the anti-slip agent. In particular, as the solid component increases, it becomes impossible to adjust the stability, viscosity, dry release property and state adhesion to meet the required physical properties.

The cellulose or cellulose derivatives used in the present invention have a molecular weight that can exhibit a viscosity suitable for an antislip agent even with a very fine solid content, for example, a molecular weight having a number average molecular weight (Mn) of 80,000 or more, and the cellulose derivative Is most preferably hydroxypropylmethylcellulose.

The acrylic thickener used in the present invention is acidic as an emulsion polymer which is radically polymerized using an acid such as acrylic acid or methacrylic acid as a homopolymer or copolymer. Has a low viscosity spherical form of colloidal particles, but when the pH is increased by alkaline organic compounds such as ammonia water, caustic soda water, triethylamine, etc., the acrylic thickener is added to the water by ionization of the carboxyl group. It disperses and dissolves in so that the viscosity increases.

The cellulose or cellulose derivative and acryl-based thickeners are not necessarily used in combination, and antislips may be prepared by using each, but combined use is more effective as an antislip agent.

In addition, since the difference in adhesion strength due to the change in the material and the coating amount of the paper as the deposition material is relatively severe in the actual field, in the present invention, the rubber as a compounding aid that serves to cover or control more such variables and changes. A latex, wax dispersant or tackifier may be selected and added to the antislip agent consisting of cellulose or cellulose derivative and acrylic thickener.

The rubber latex serves to enhance affinity with the coating film and paper, initial fixation force, and state adhesion when dried, and include chloroprene rubber latex (CR latex; Chloroprene rubber latex; CR latex) and natural rubber latex (NR latex; Natural rubber latex). ), Nitro butadiene rubber latex (NBR latex; Nitro butadiene rubber latex) or styrene butadiene rubber latex (SBR latex; Styrene butadiene rubber latex) and the like can be used, but SBR latex is most preferred in terms of stability and suitability.

The wax dispersant serves to improve dry releasability, and polyethylene dispersant, ammonium stearate dispersant or potassium stearate dispersant may be used. However, since the wax dispersant plays an important role in re-peeling property, the most inexpensive and stable ammonium stearate dispersant is Most preferred.

The tackifier serves to improve initial adhesion, initial fixability, and state adhesiveness, and usable water based tackifier resins include a hydrogenated carbon resin dispersion and a rosin ester resin dispersant. (Rosin ester resin dispersion), Terpene phenol resin dispersion, rosin and modified rosin (potassium soap of a modified tall oil rosin), but in terms of efficiency and stability It is preferable to use.

In addition, the anti-slip agent of the present invention may be added to the bubble inhibitor as other additives.

Specific components and ratios of the anti-slip agent according to the present invention are shown in Table 1 below.

Raw material name Solid content Actual input weight% of raw material (raw material self input) Actual input solids% water 0% 2 to 99.7 0 Cellulose (derivative) 100% 0.2-4.0 0.2-4.0 Acrylic thickener 25% 0 to 10.0 0 to 2.5 Alkaline organic compounds 25% 0 to 1.0 0 to 0.25 Rubber latex 50% 0 to 4.0 0 to 2.0 Wax dispersant 30% 0 to 66 0 to 19.8 Tackifier 25% 0 to 20.0 0 to 5.0 Bubble inhibitor 100% 0.1 0.1 total - 100 0.2-20.0

In addition, the present invention comprises the steps of dispersing and dissolving a cellulose derivative in which methyl, hydroxyethyl, hydroxypropyl, or hydroxypropylmethyl groups are introduced into cellulose or cellulose in water (first step); Adding an acrylic thickener to the solution obtained in the first step and mixing (second step); And adding one or more selected from a rubber latex, a wax dispersant, or a tackifier to the solution obtained in the second step (third step), wherein the total solid content is 0.2 to 20% by weight. It provides a method for producing an anti-slip agent.

More specifically, if the base material is a cellulose-based water-soluble polymer or a cellulose-based derivative, and mixed with an acrylic thickener, which is an acrylic water-dispersion copolymer, as a base material in order to maximize the viscosity compared to the solid content, the antislip agent may be used in a very small amount of solids. The required physical properties and viscosity can be obtained. Although it can act as an anti-slip agent by itself, in order to become an anti-slip agent of excellent physical properties including all the variables such as the variety of materials, variation and coating amount of the adhered material, a formulation capable of adjusting the state adhesive force and initial fixing force is required. In order to adjust the physical properties accordingly, a rubber-based latex, wax dispersant or tackifier is used to prepare an excellent anti-slip agent that can adjust the final adhesive strength and physical properties to meet the required physical properties.

The cellulose or cellulose derivative of the first step is dispersed at a temperature of 80 ° C. or higher and dissolved while cooling, or dispersed at room temperature, and treated by dissolving an alkaline material selected from ammonia water, caustic soda water or triethylamine to prepare an antislip agent.

The method of mixing the acrylic thickener of the second step is different depending on the method of dissolving cellulose or cellulose derivative. When cellulose or cellulose derivative is dispersed at 80 ° C. or higher and dissolved while cooling, the mixture is mixed at 60 ° C. or lower and then at room temperature. In the case of dispersing cellulose or cellulose derivatives at room temperature, when the cellulose or cellulose derivatives are dispersed at room temperature, an acryl-based thickener is mixed together and then treated with an alkali to dissolve to prepare an antislip agent. .

In the third step, in order according to the input amount and the ratio of the individual property control agents set in advance, at least 10 minutes at each step is sufficiently mixed, the entire composition is mixed and then mixed for at least 1 hour to confirm the final properties , Correct. The mixing is performed at 20 rpm or more and 500 rpm or less, and the lower the mixing speed, the longer the mixing time is corrected.

Hereinafter, preferred examples and comparative examples are presented to help understand the present invention. However, the following examples are merely provided to more easily understand the present invention, but do not limit the present invention.

<Examples 1 to 5>

As shown in the composition and composition ratio (expressed in weight percent) shown in Table 2 below, hydroxypropylmethylcellulose (HPMC) was dispersed and dissolved in water, mixed with an acrylic thickener, and neutralized with caustic soda water to prepare an antislip agent. It prepared and performed the following experiment.

Specifically, the preparation method of the anti-slip agent injecting the total amount of 700g in 1L container based on Example 2 is as follows.

Agitator was installed in a 1 L flask to allow stirring and 687.4 g of water (0% solids) [98.2 wt%; 0% by weight based on the solid content of the final product] 3.5g [0.5% by weight of hydroxypropylmethylcellulose (100% of solid components) surface-treated at room temperature (around 25 ° C) while mixing at 100 rpm; 0.5 wt%] was added based on the solids content of the final product, and 7 g [1.0 wt%] of an acrylic thickener (25% solids); 0.25 wt%] in terms of the solids content of the final product was added and mixed uniformly for 5 minutes, followed by 1.4 g [0.2 wt%] of caustic soda water (25% solids); 0.05 wt%] is added based on the solid content of the final product, followed by stirring and dispersing for about 1 hour to neutralize and dissolve to complete a transparent melt having a final pH of 6 to 8, and bubbles independent of the present patented technology. An inhibitor was prepared by mixing an appropriate amount of Nopco NXZ of San Nopco Korea.

1) Nozzle coating characteristic

The nozzle coating characteristics of the antislip agent prepared in Example were tested using a nozzle having a nozzle diameter of 0.3 mm and a pressure gage of 3.5 kgf / cm 2 with a distance of about 10 cm between the nozzle and the coating surface.

In Table 2 below, the case where the phenomenon of splashing occurs during application using a nozzle having a 0.3 mm diameter is indicated by Splashing, and the state that the application phenomenon is easy and the state without splashing during application is indicated as Good.

2) Initial holding

After 1 minute of cross-coating with 20cm × 10cm of corrugated material, apply the same material that is not applied. After bonding, shear slipping at 1, 3, and 5 minutes respectively. ) To determine the presence or absence of holding / slipping, and compared the initial fixation state.

At this time, if it is fixed within 3 minutes, Excellent, and if it is fixed at 3-5 minutes, Good, if it is fixed more than 5 minutes, marked as good.

3) Peel strength

After 1 minute of cross-coating with 20cm × 10cm corrugated material, apply the same material that has not been applied, and leave it for 1 day at room temperature under a load of 3kg. Relative comparison. At the time of peeling using a tensioner, the deviation was severe and did not proceed every experiment.

As a measurement for relative comparison, the higher the peel strength, the better, but excellent physical properties as an anti-slip agent only when there is no tearing of the paper, Table 2 shows the relative comparison result for the purpose of a composite comparison with the dry release property.

The higher the force, the lower the force is, and the lower, good, high, and so high values are set for comparison.

4) Dry release

After applying, bonding and leaving in the same manner as the Peel strength, the degree of tearing or breaking of the paper and paper fibers on the surface of the corrugated cardboard in the forced peeling state was compared.

5) Surface Remaining

After coating, bonding, and leaving in the same manner as the Peel strength, it was visually checked whether the adhesive application site was different from the original corrugated paper and the ink (print or pattern) state on the forced peeling state.

From the experimental results of Examples 1 to 5 described in Table 2, the physical properties are different depending on the type and content of the raw materials, the physical properties of Example 2 is the most excellent, which controls the mixing ratio and the total solid content considering the properties of the raw materials It can be seen that there is a difference in the final physical properties.

Furtherance Solid content Example 1 Example 2 Example 3 Example 4 Example 5 water 0% 97.8 98.2 97.1 94.9 90.9 HPMC 100% 2 0.5 0.5 0.5 - Acrylic thickener 25% - 1.0 2.0 4.0 8.0 NaOH (25%) 25% 0.1 0.2 0.3 0.5 1.0 Bubble inhibitor - 0.1 0.1 0.1 0.1 0.1 Total 100 100 100 100 100 Solid content (%) 2 0.75 1.1 1.7 2.3 Nozzle Coating Characteristics Good Good Good Good Splashing Initial fixation Not good Good Good Good Good Peel strength High Lowest Lower Medium So high Dry release P F / T N F / T L F / T S F / T F F / T Surface Remains (Marks) No No No No No

* HPMC = Hydroxy Propyl Methyl Cellulose.

* F / T: Fiber tear, NF / T: No fiber tear, LF / T: Little F / T, SF / T: Small F / T, PF / T: Partial fiber tear, FF / T: Full F / T .

<Examples 6 to 10>

Except for adding SBR latex to the composition of Example 2 in the amount described in Table 3 was prepared in the same manner as in Example 2, and tested for physical properties (stirring for about 30 minutes under the same stirring conditions as Example 2). box).

Furtherance Solid content Example 6 Example 7 Example 8 Example 9 Example 10 water 0% 98.1 97.9 97.7 97.2 96.7 HPMC 100% 0.5 0.5 0.5 0.5 0.5 Acrylic thickener 25% 1.0 1.0 1.0 1.0 1.0 NaOH (25%) 25% 0.2 0.2 0.2 0.2 0.2 SBR latex 50% 0.1 0.3 0.5 1.0 1.5 Bubble inhibitor - 0.1 0.1 0.1 0.1 0.1 Total 100 100 100 100 100 Solid content (%) 0.8 0.9 1.0 1.25 1.5 Nozzle Coating Characteristics Good Good Good Good Good Initial fixation Good Good Good Excellent Excellent Peel strength Lower Good Good High So high Dry release A N F / T N F / T N F / T L F / T P F / T B S F / T P F / T F F / T F F / T F F / T Surface Remains (Marks) No No No No No

* In paper used to measure dry release property, A means the strongest paper force and B means the weakest paper force.

<Examples 11 to 15>

Except that the SBR latex or ammonium stearate dispersant was added to the composition of Example 2 in the amount described in Table 4, and was prepared in the same manner as in Example 2, the physical properties of the paper box with the lowest paper strength test It was stirred for about 30 minutes under the same stirring conditions as in Example 2.

Furtherance Solid Example 11 Example 12 Example 13 Example 14 Example 15 water 0% 98.1 97.9 97.7 97.6 97.4 HPMC 100% 0.5 0.5 0.5 0.5 0.5 Acrylic thickener 25% 1.0 1.0 1.0 1.0 1.0 NaOH (25%) 25% 0.2 0.2 0.2 0.2 0.2 SBR latex 50% - - - 0.3 0.3 Ammonium stearate dispersion 30% 0.1 0.3 0.5 0.3 0.5 Bubble inhibitor - 0.1 0.1 0.1 0.1 0.1 Total 100 100 100 100 100 Solid content (%) 0.75 0.76 0.77 0.91 0.92 Nozzle Coating Characteristics Good Good Good Good Good Initial fixation Good Good Good Excellent Excellent Peel strength Not bad Weak Weaker Not bad Weak Dry release A N F / T N F / T N F / T N F / T N F / T B L F / T N F / T N F / T L F / T N F / T Surface Remains (Marks) No No No No No

<Examples 16 to 20>

Except for adding the SBR latex, ammonium stearate dispersant or rosin derivative in the amount described in Table 5 in the composition of Example 2, was prepared in the same manner as in Example 2, and the physical properties were tested (Example 2 and Agitate for about 30 minutes under the same stirring conditions).

Furtherance Solid content Example 16 Example 17 Example 18 Example 19 Example 20 water 0% 97.7 97.2 96.7 97.4 97.1 HPMC 100% 0.5 0.5 0.5 0.5 0.5 Acrylic thickener 25% 1.0 1.0 1.0 1.0 1.0 NaOH (25%) 25% 0.2 0.2 0.2 0.2 0.2 SBR latex 50% - - - - 0.3 Ammonium stearate dispersion 30% - - - 0.3 0.3 Modified rosin 25% 0.5 1.0 1.5 0.5 0.5 Bubble inhibitor - 0.1 0.1 0.1 0.1 0.1 Total 100 100 100 100 100 Solid content (%) 0.8 1.0 1.1 1.0 1.1 Nozzle Coating Characteristics Good Good Good Good Good Initial fixation Good Good Excellent Excellent Excellent Peel strength Not bad Good Excellent Not bad Excellent Dry release A N F / T N F / T N F / T N F / T N F / T B N F / T N F / T L F / T N F / T L F / T Surface Remains (Marks) No No No No No

<Examples 21 to 23>

Experiment to determine the solids threshold of the final product was prepared in the same manner as in Example 2 except that only hydroxypropylmethylcellulose was used alone and the ammonium stearate dispersant was used as the physical property modifier in the amount described in Table 6. And the physical property was experimented (stirring for about 30 minutes on the same stirring conditions as Example 2).

Furtherance Solid content Example 21 Example 22 Example 23 Example 24 water 0% 99.2 69.4 49.5 30.6 HPMC 100% 0.5 0.4 0.3 0.25 NaOH (25%) 25% 0.2 0.1 0.1 0.05 Ammonium stearate dispersion 30% - 30 50 69 Bubble inhibitor - 0.1 0.1 0.1 0.1 Total 100 100 100 100 Solid content (%) 0.5 9.4 15.3 21.0 Nozzle Coating Characteristics Good Good Good Good Initial fixation Good Good Good Good Peel strength Good Good Good Good Dry release A N F / T N F / T N F / T N F / T B L F / T N F / T N F / T N F / T Surface Remains (Marks) No Yes Yes Yes

<Examples 24 to 27>

Experiment to measure the solids threshold of the final product was prepared in the same manner as in Example 2, except that only the acrylic thickener was used alone and the ammonium stearate dispersant was used as the physical property modifier. Experiment was carried out (stirring for about 30 minutes under the same stirring conditions as in Example 2).

Furtherance Solid content Example 24 Example 25 Example 26 Example 27 water 0% 97.7 87.9 78.7 62.5 Acrylic thickener 25% 2 10 11 12 NaOH (25%) 25% 0.2 2 2.2 2.4 Ammonium stearate dispersion 30% - - 8 23 Bubble inhibitor - 0.1 0.1 0.1 0.1 Total 100 100 100 100 Solid content (%) 0.5 2.5 5.1 9.9 Nozzle Coating Characteristics Splashing Splashing Splashing Splashing Initial fixation Good Good Good Good Peel strength Good Good Good Good Dry release A N F / T N F / T N F / T N F / T B N F / T N F / T N F / T N F / T Surface Remains (Marks) No No Yes Yes

From the above results, when a composition having a total solid content of 20% by weight or less using a rubber latex, a wax dispersant, and a rosin derivative is used as a cellulose or a cellulose derivative, an acrylic thickener including a carboxyl group, and a physical property modifier, the antislip agent meets the properties required. The anti-slip agent could be prepared, but as the solid content increased, the stability and the production cost were increased. The total solid content of the anti-slip agent having the most desirable physical properties was 0.2 to 2 wt%.

The anti-slip agent produced in the present invention is applied between paper packaging materials during palletizing of the paper packaging material to prevent slippage due to slip between layers during transportation and transportation after loading, and at the time of separating the paper packaging material at the time of separation from the loading. Not only does it destroy or become extremely weak, which facilitates separation, but it can also be used as an environmentally friendly alternative to the currently commercially available vinyl wrapping.

Claims (10)

delete delete delete delete Antislip comprising cellulose derivatives and acrylic thickeners in which cellulose or cellulose is introduced with methyl group, hydroxyethyl group, hydroxypropyl group or hydroxypropylmethyl group, and the total solid content is 0.2 to 2.0% by weight. My. 6. The anti-slip agent according to claim 5, wherein the cellulose derivative is hydroxypropylmethylcellulose, and the acrylic thickener is an emulsion polymer of acrylic acid or methacrylic acid. Cellulose derivatives in which a methyl group, a hydroxyethyl group, a hydroxypropyl group or a hydroxypropylmethyl group is introduced into cellulose or cellulose; Acrylic thickeners; And at least one selected from rubber latex, wax dispersant or tackifier, wherein the total solid content is 0.2 to 20% by weight. 8. The antislip agent according to claim 7, wherein the rubber latex is chloroprene rubber latex, natural rubber latex, nitro butadiene rubber latex or styrene butadiene rubber latex. 8. The antislip agent according to claim 7, wherein the wax dispersant is a polyethylene dispersant, an ammonium stearate dispersant or a potassium stearate dispersant. The anti-slip agent according to claim 7, wherein the tackifier is a rosin or a rosin derivative.