Environment-friendly water-based paste box adhesive and preparation method thereof

Abstract

The present application relates to a kind of environment-friendly water-based paste box glue and its preparation method, according to percentage by weight, including modified acrylic emulsion 40-50%, glutinous rice glue 20-25%, carboxymethyl cellulose 10-15%, fatty alcohol polyoxyethylene ether 1.0-1.2%, alkyl polyglycoside 0.2-0.25%, polyether modified silicone 0.3-0.4%, chitosan 1.5-2.0%, triethyl citrate 0.3-0.5%, nano silicon dioxide 0.5-1.0%, citric acid 0.5-1.0%, polyvinyl alcohol 0.5-1%, sodium benzoate 0.1-0.3%, and deionized water is the remainder.The present application is optimized by optimizing bonding component, surfactant and its additive, systematically solves the core problems such as permeability, weather resistance, safety of traditional paste box glue in copperplate paper application, has high performance and green attribute, and is a kind of high-end paper product packaging excellent adhesive.

Description

Technical Field

[0001] This invention relates to an environmentally friendly water-based box-gluing adhesive and its preparation method, belonging to the field of adhesives. Background Technology

[0002] Box gluing adhesive, also known as sealing glue or box bonding adhesive, is a fine chemical product mainly used for gluing high-end boxes. Its adhesive properties primarily affect the bond between paper and the laminating material. It includes both oil-based and water-based adhesives. The quality of the gluing directly impacts the overall quality of the box gluing process, and water-based adhesives have largely replaced solvent-based adhesives in this process.

[0003] Coated paper, due to its high gloss, smooth surface, and excellent printability, is widely used in high-end packaging boxes (such as cosmetics, food, pharmaceuticals, and luxury goods). However, the smooth surface and dense coating of coated paper make it difficult for traditional gluing adhesives (mainly acrylic emulsions) to effectively penetrate the fiber pores due to their high molecular weight and viscosity. This results in weak mechanical anchoring, low initial bond strength, and high surface tension, leading to a large contact angle and the tendency to form droplets that easily peel off after drying. Furthermore, traditional water-based adhesives rely on chemical preservatives, making them prone to mold growth during long-term storage and exhibiting weak anti-mold and antibacterial capabilities. Therefore, developing gluing adhesives suitable for coated paper is of great significance. Summary of the Invention

[0004] This invention provides an environmentally friendly water-based box-gluing adhesive and its preparation method, which solves the problems of low adhesion, easy splitting, and poor anti-corrosion effect of existing box-gluing adhesives.

[0005] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows:

[0006] An environmentally friendly water-based box-sealing adhesive, by weight percentage, comprises 40-50% modified acrylic emulsion, 20-25% glutinous rice glue, 10-15% carboxymethyl cellulose, 1.0-1.2% fatty alcohol polyoxyethylene ether, 0.2-0.25% alkyl polysaccharide glycoside, 0.3-0.4% polyether-modified organosilicon, 1.5-2.0% chitosan, 0.3-0.5% triethyl citrate, and nano-silica.

[0007] 0.5-1.0%, citric acid 0.5-1.0%, polyvinyl alcohol 0.5-1%, sodium benzoate 0.1-0.3%, deionized water as the balance.

[0008] Furthermore, a preferred embodiment of the present invention is that the modified acrylic emulsion comprises a silicone-acrylic emulsion and an acetate-acrylic emulsion, wherein the weight ratio of the silicone-acrylic emulsion to the acetate-acrylic emulsion is 6:4.

[0009] Further, a preferred scheme of the present application is that the glutinous rice glue is prepared by grinding and purifying glutinous rice and then adding water to adjust the weight ratio of the glutinous rice to water to 0.9:1.

[0010] Further, a preferred scheme of the present application is that the fatty alcohol polyoxyethylene ether is AEO-9; the alkyl polyglycoside is APG1214 or APG0810; the polyether modified organosilicon is Silok-8000; and the chitosan is chitosan with a deacetylation degree of more than or equal to 90%.

[0011] Further, a preferred scheme of the present application is that the polyvinyl alcohol is PEG1000-2000.

[0012] The preparation method of the environment-friendly water-based paste box glue of the present application comprises the following steps:

[0013] (1) Pre-mixing the fatty alcohol polyoxyethylene ether, the alkyl polyglycoside, the polyether modified organosilicon and deionized water to form a surfactant system;

[0014] (2) Adding the modified acrylic emulsion, the glutinous rice glue and the carboxymethyl cellulose and stirring at high speed until uniform;

[0015] (3) Adding the chitosan, the triethyl citrate, the nano-silicon dioxide and the polyvinyl alcohol in sequence and stirring at low speed until uniform;

[0016] (4) Adjusting the pH to 6-7 with citric acid, adding sodium benzoate for preservation, and finally filtering through a 200-mesh sieve to remove impurities to obtain the product.

[0017] Further, a preferred scheme of the present application is that the stirring speed at high speed is 800-1000r / min and the stirring time is 0.5-1h.

[0018] Further, a preferred scheme of the present application is that the stirring speed at low speed is 300-500r / min and the stirring time is 1-2h.

[0019] The present application has the following beneficial effects:

[0020] The glutinous rice glue (natural starch glue), the carboxymethyl cellulose and the chitosan used in the present application are all bio-based raw materials and meet the environmental protection requirements; the fatty alcohol polyoxyethylene ether and the alkyl polyglycoside are non-ionic surfactants with excellent biodegradability and no toxic residues; only a small amount of triethyl citrate is contained in the formula as a plasticizer to replace traditional benzene and ketone solvents and reduce VOCs emissions.

[0021] The application adopts modified acrylic emulsion (styrene-acrylic / vinyl-acrylic emulsion) to provide excellent initial adhesion and holding adhesion, stable low-temperature resistance and high-temperature resistance; waxy rice glue and CMC synergistically enhance the permeability of paper-based materials, and improve the bonding strength; nano-silicon dioxide (SiO2) as a filler enhances the wear resistance and anti-aging property of the glue film; polyether modified silicone improves the high-temperature resistance and shear resistance; AEO and APG reduce the surface tension and improve the wettability of the glue solution to the base material; polyvinyl alcohol (PVA) as a film-forming aid adjusts the rheological property of the glue solution and ensures the uniformity of coating.

[0022] The amino group in the chitosan molecule in the application forms a coordinate bond with the calcium carbonate of the coated paper coating, enhancing the interfacial bonding force; the nano-silicon dioxide can improve the hardness, wear resistance and thermal stability, and together with CMC, the colloidal structure is optimized; triethyl citrate can improve the flexibility of the glue film and alleviate the rigidity defect of the acrylic emulsion.

[0023] The application optimizes the combination of the bonding components, surfactants and their additives, systematically solves the core problems of the traditional paste box glue in the application of coated paper, such as permeability, weather resistance and safety, and has high performance and green properties, and is an excellent adhesive for high-end paper product packaging. DETAILED DESCRIPTION

[0024] The technical solutions in the embodiments of the application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the application, not all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor are included.

[0025] The silicone-acrylic emulsion adopts WC-SA108, the solid content is 47±1(%), and the viscosity is 1000-4000(S); the vinyl-acrylic emulsion adopts vinyl-acrylic emulsion DC-7039, the solid content is 52±1(%)%, and the viscosity is 1500(S).

[0026] The waxy rice glue is prepared by grinding and purifying waxy rice and then adding water to adjust the weight ratio of waxy rice to water to 0.9:1. The fatty alcohol polyoxyethylene ether is AEO-9; the alkyl polyglycoside is APG1214; the polyether modified silicone is Silok-8000; the chitosan is chitosan with a degree of deacetylation of not less than 90%, and the chitosan used in the following embodiments is chitosan with a degree of deacetylation of 90%. The polyvinyl alcohol is PEG1500.

[0027] Example 1 investigates the influence of different bonding materials on paste box glue

[0028] An environment-friendly water-based paste box adhesive comprises, by weight percentage, modified acrylic emulsion 40-50%, waxy rice glue 20-25%, carboxymethyl cellulose 10-15%, fatty alcohol polyoxyethylene ether 1.0%, alkyl polyglycoside 0.2%, polyether modified silicone 0.3%, chitosan 1.5%, triethyl citrate 0.3%, nano-silica 0.5%, citric acid 0.5%, polyvinyl alcohol 0.5%, sodium benzoate 0.3%, and deionized water as the balance. The specific ingredient table is shown in Table 1.

[0029] Table 1: Proportion of different bonding materials

[0030] Modified acrylic emulsions Waxy rice gum Carboxymethyl cellulose Example 1 45 20 15 Example 2 80 0 0 Example 3 0 80 0 Example 4 60 20 0 Example 5 65 0 15

[0031] The preparation method comprises the following steps:

[0032] (1) Pre-mixing fatty alcohol polyoxyethylene ether, alkyl polyglycoside, polyether modified silicone and deionized water to form a surfactant system;

[0033] (2) Adding modified acrylic emulsion, waxy rice glue and carboxymethyl cellulose, and stirring at high speed until uniform, at a speed of 800 r / min for 1 h;

[0034] (3) Adding chitosan, triethyl citrate, nano-silica and polyvinyl alcohol in sequence, and stirring at low speed until uniform, at a speed of 300 r / min for 1 h;

[0035] (4) Adjusting pH to 6-7 with citric acid, adding sodium benzoate for preservation, and finally filtering through a 200-mesh sieve to remove impurities.

[0036] Determine the indexes, and the specific method is as follows:

[0037] I. Viscosity determination

[0038] Examples 1-5 are determined according to the determination method in GB / T 2794-2013 "Determination of Adhesive Viscosity", and the test environment is: temperature 25℃, speed 6r / min.

[0039] II. Determination of peel strength

[0040] The paste box adhesive final product prepared in Examples 1-5 is tested according to the provisions of GB / T 30778-2014, and the glue application amount is set to 5g / m 2 , 10g / m 2 and 15g / m 2 , and the test results are shown in Table 2.

[0041] III. Determination of high and low temperature resistance

[0042] The paste box glue prepared by using the paste box glue prepared in Examples 1-5 is used to bond two pieces of light type superior 90g standard double-sided copper plate paper, and after the bonded paper is placed in an environment with a temperature of 25±5℃ and a humidity of 50±5% for 24 hours, it is placed in a 70℃ oven for 8 hours, and then the interface of the bonded paper box is observed to be free of bubbles and glue opening, and then the paper fibers are peeled off along the interface to observe whether the paper fibers are damaged; if the paper fibers are damaged, it indicates that the prepared paste box glue has qualified high temperature resistance; if the paper fibers are not damaged, it indicates that the prepared paste box glue has unqualified high temperature resistance.

[0043] The paste box glue prepared by using the paste box glue prepared in Examples 1-5 is used to bond two pieces of light type superior 90g standard double-sided copper plate paper, and after the bonded paper is placed in an environment with a temperature of 25±5℃ and a humidity of 50±5% for 24 hours, it is placed in a 70℃ oven for 8 hours, and then the interface of the bonded paper box is observed to be free of bubbles and glue opening, and then the paper fibers are peeled off along the interface to observe whether the paper fibers are damaged; if the paper fibers are damaged, it indicates that the prepared paste box glue has qualified high temperature resistance; if the paper fibers are not damaged, it indicates that the prepared paste box glue has unqualified high temperature resistance.

[0044] The test results are shown in Table 2.

[0045] Table 2 Results of the influence of different bonding materials on paste box glue

[0046]

[0047] As shown in Table 2, the paste box glue of the present application has good performance. In the present embodiment, the interaction of the silicone-acrylic emulsion and the vinyl-acrylic emulsion forms an interpenetrating network structure, reduces the water absorption of the glue film, and improves the temperature resistance: the Si-O bond in the silicone-acrylic emulsion endows high temperature stability, and the branched structure of the vinyl-acrylic emulsion enhances the low temperature toughness.

[0048] The branched starch of waxy maize glue is embedded into the copper plate paper fibers through hydrogen bonds; the hydrophobic groups of the modified acrylic emulsion and the hydrophilic groups of the starch form a gradient structure, reducing the water molecule penetration path, so that the peel strength is maintained high after water immersion for 24 hours. The rapid crystallization characteristics of waxy maize glue and the viscous rheology of vinyl-acrylic emulsion are synergistic, so that physical anchoring is formed in the glue layer after contacting the copper plate paper; the crosslinking network of the vinyl-acrylic emulsion and the hydrogen bond network of the waxy maize glue form a gradient structure, so that the glue layer remains intact under continuous stress; the CMC adjusts the thixotropy of the glue solution, preventing glue shedding during high speed coating, and at the same time, the carboxyl groups and the hydroxyl groups form ionic bonds, enhancing the glue film anti-sagging property.

[0049] The modified acrylic emulsion, waxy maize glue and CMC of the present application are synergistic through interface wetting, rheological regulation and chemical-physical crosslinking, systematically solving the core problems of poor permeability and insufficient water resistance of copper plate paper paste box glue. The scheme has high peel strength, low cost and environmental friendliness, and provides an innovative bonding solution for high-end color box, cold chain packaging and other scenarios.

[0050] Example 2 investigates the influence of different surfactants on the paste box paste

[0051] An environmentally friendly water-based paste box paste, according to the percentage by weight, including modified acrylic emulsion 45%, glutinous rice glue 20%, carboxymethyl cellulose 15%, fatty alcohol polyoxyethylene ether 1.0-1.2%; alkyl polyglycoside 0.2-0.25%, polyether modified silicone 0.3-0.4%, chitosan 1.5%, triethyl citrate 0.3%, nano silicon dioxide 0.5%, citric acid 0.5%, polyvinyl alcohol 0.5%, sodium benzoate 0.3%, deionized water for the rest. The specific ingredient table is shown in Table 3.

[0052] Table 3 Different surfactant ratio

[0053] Fatty alcohol polyoxyethylene ether Alkyl polyglycoside Polyether-modified silicone Example 6 1.0 0.2 0.3 Example 7 1.5 0 0 Example 8 0 1.5 0 Example 9 0 0 1.5 Example 10 1.1 0 0.4 Example 11 0 0.7 1.0 Example 12 1.1 0.4 0

[0054] The preparation method and determination method are the same as example 1, and the specific results are shown in table 4.

[0055] Table 4 The results of the influence of different surfactants on the paste box paste

[0056]

[0057] The present application can effectively improve the performance of the paste box paste by optimizing the composition of the surfactant.

[0058] Fatty alcohol polyoxyethylene ether can reduce the surface tension of the system, promote the wetting of hydrophobic substrate (such as coated paperboard), form mixed micelles with APG, improve the emulsification efficiency, and reduce the span of acrylic emulsion particle size distribution. Alkyl polyglycoside can enhance the interfacial compatibility of glutinous rice glue and acrylic emulsion, and the glycoside head group forms hydrogen bond with chitosan molecule, which helps to build three-dimensional network structure and inhibit phase separation. Polyether modified silicone is a dynamic surfactant, which has defoaming and leveling functions, and the siloxane segment migrates to the surface of the film to form a hydrophobic layer, which cooperates with nano SiO2 to improve water resistance.

[0059] Examples 13-15

[0060] An environmentally friendly water-based paste box paste, according to the percentage by weight, including modified acrylic emulsion 45%, glutinous rice glue 20%, carboxymethyl cellulose 15%, fatty alcohol polyoxyethylene ether 1.0-1.2%; alkyl polyglycoside 0.2-0.25%, polyether modified silicone 0.3-0.4%, chitosan 1.5%, triethyl citrate 0.3%, nano silicon dioxide 0.5%, citric acid 0.5%, polyvinyl alcohol 0.5%, sodium benzoate 0.3%, deionized water for the rest. The specific ingredient table is shown in Table 3.

[0061] The procedure was the same as in Example 1. The performance data of the product are shown in Table 6.

[0062] Table 5 Raw material ratio of different examples

[0063]

[0064] Table 6 Performance test results of different examples

[0065]

[0066] The above only describes the preferred embodiments of the present application and is not used to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. An environmentally friendly water-based paste box glue, characterized in that: According to the weight percentage, including modified acrylic emulsion 40-50%, waxy rice gum 20-25%, carboxymethyl cellulose 10-15%, fatty alcohol polyoxyethylene ether 1.0-1.2%; alkyl polyglycoside 0.2-0.25%, polyether modified silicone 0.3-0.4%, chitosan 1.5-2.0%, triethyl citrate 0.3-0.5%, nano silicon dioxide 0.5-1.0%, citric acid 0.5-1.0%, polyvinyl alcohol 0.5-1%, sodium benzoate 0.1-0.3%, deionized water for the remainder; The modified acrylic emulsion includes silicone acrylic emulsion and vinyl acrylic emulsion, and the weight ratio of the silicone acrylic emulsion and the vinyl acrylic emulsion is 6:

4.

2. The environment-friendly water-based carton sealing adhesive according to claim 1, characterized in that: The waxy rice gum is prepared by grinding and purifying waxy rice and then adding water, and the weight ratio of the waxy rice to water is 0.9:

1.

3. The environment-friendly water-based carton sealing adhesive according to claim 1, characterized in that: The fatty alcohol polyoxyethylene ether is AEO-9; the alkyl polyglycoside is APG1214 or APG0810; the polyether modified silicone is Silok-8000; and the chitosan is chitosan with a deacetylation degree of ≥90%.

4. The environment-friendly water-based carton sealing adhesive according to claim 1, characterized in that: The polyvinyl alcohol is PEG3000-6000.

5. The preparation method of the environment-friendly water-based carton glue according to any one of claims 1-4, characterized in that, The method comprises the following steps: (1) Pre-mixing fatty alcohol polyoxyethylene ether, alkyl polyglycoside, polyether modified silicone and deionized water to form a surfactant system; (2) Adding modified acrylic emulsion, waxy rice gum and carboxymethyl cellulose, and stirring at high speed until uniform; (3) Adding chitosan, triethyl citrate, nano silicon dioxide and polyvinyl alcohol in sequence, and stirring at low speed until uniform; (4) Adjusting pH to 6-7 with citric acid, adding sodium benzoate for preservation, and finally filtering through a 200-mesh sieve to remove impurities.

6. The method of claim 5, wherein: The stirring speed of the high-speed stirring is 800-1000r / min, and the stirring time is 0.5-1h.

7. The method of claim 5, wherein: The stirring speed of the low-speed stirring is 300-500r / min, and the stirring time is 1-2h.

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