CN111234738A - Hot melt adhesive for environment-friendly wax cartons and preparation method thereof - Google Patents
Hot melt adhesive for environment-friendly wax cartons and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
- C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09J131/04—Homopolymers or copolymers of vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses an environment-friendly hot melt adhesive for wax cartons and a preparation method thereof, wherein the hot melt adhesive is obtained by emulsion polymerization of vinyl acetate, methyl methacrylate, butyl acrylate and acrylic acid in paraffin emulsion, and dioctyl phthalate can be optionally added; the melting temperature of the hot melt adhesive for the environment-friendly wax carton is between 58 and 71 ℃, and the characteristic that the temperature of the hot melt adhesive is lower than or close to the temperature of a wax coating can effectively protect the wax coating on the surface of the wax carton from being damaged in the bonding process; the T-shaped peel strength and the single lap joint shear strength of the solid hot melt adhesive are superior to those of common hot melt adhesives sold in the market, the requirement for large bonding strength of a wax layer of a wax paper box is met, the high cohesive strength is achieved, the solid hot melt adhesive is not prone to damage, meanwhile, the hot melt adhesive is good in fluidity and short in bonding time in a molten state, rapid bonding operation can be achieved, and production efficiency is effectively improved.
Description
Technical Field
The invention relates to the technical field of hot melt adhesives, and particularly relates to an environment-friendly hot melt adhesive for wax cartons and a preparation method thereof.
Background
With the improvement of the living quality of modern people, the people improve the understanding of the nutritive value of fresh vegetables, and the requirement on the freshness of melons, fruits and vegetables is also improved. The scientific and technological development of Chinese agriculture, domestic high-grade agricultural products are sold to the world across the ocean and the land. In the field of food, the packaging of fresh food needs to have not only the basic functions of a packaging box, but also the functions of freshness preservation, water resistance, extrusion resistance and the like. Therefore, the wax carton can become an ideal environment-friendly cold chain package.
The wax layer is coated on the surface of the wax carton, so that the requirement on an adhesive is high, firstly, the bonding strength is high, secondly, the wax on the wax carton is melted at about 70 ℃ and possibly separated out, and therefore, the working temperature of a workshop cannot be too high.
The commonly used sealing materials at present are adhesive tapes, starch adhesives and hot melt adhesives. Transport cartons must be able to withstand temperature, humidity variations and rough handling, but this requirement is more difficult to meet with adhesive tape. The starch adhesive used in the paper box production industry at present is mainly prepared from starch, water, sodium hydroxide, an oxidant and other raw materials, has the defects of low drying speed, low bonding strength, poor water resistance, unstable storage performance and the like, and is not firmly bonded to a coated or oily paper board. Although the bonding strength of the box sealing hot melt adhesive is superior to that of a starch adhesive, the bonding strength of some hot melt adhesives is still not enough for adhering wax cartons, and secondly, the service temperature of most hot melt adhesives is higher, so that the service requirements of the adhesives for the wax cartons can not be well met. Moreover, the hot melt adhesives have the problems of complex production process, use of organic solvents, high requirements on production equipment and the like. The existing carton adhesive has limited the application of wax cartons in the packaging production industry to a certain extent.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims at providing the environment-friendly hot melt adhesive for the wax cartons, which has the advantages of excellent bonding performance, simple preparation method, safe production and no environmental pollution, takes water as a medium in the production process, does not use volatile organic solvents, can be widely applied as a bonding agent for various cartons by adopting a low-temperature gluing mode during application, and particularly meets the use requirements of the wax cartons on the bonding agent.
The invention also aims to provide a preparation method of the hot melt adhesive for the environment-friendly wax cartons.
Therefore, the technical scheme of the invention is as follows:
the environment-friendly hot melt adhesive for the wax cartons comprises the following raw materials in parts by weight:
copolymer monomer (b): the acrylic acid-free vinyl acetate emulsion comprises 20-28 parts of vinyl acetate, 3-11 parts of methyl methacrylate, 4-8 parts of butyl acrylate and 2-5 parts of acrylic acid;
1-12 parts of paraffin emulsion;
43-59 parts of deionized water;
and 0.2-0.4% of peroxide initiator, 0.5-2% of emulsifier A, 0.1-0.3% of buffering agent and 0-20% of dioctyl phthalate, wherein the peroxide initiator accounts for the total weight of the copolymer monomer, the paraffin emulsion and the deionized water;
wherein the paraffin emulsion is formed by mixing 10-20 parts of paraffin, 4-10 parts of emulsifier B and 70-80 parts of deionized water; the buffer is sodium bicarbonate; the emulsifier A is a composite emulsifier formed by mixing alkylphenol polyoxyethylene ether and lauryl sodium sulfate in a weight ratio of 3.5: 1; the emulsifier B is a composite emulsifier formed by mixing alkylphenol polyoxyethylene ether and span 80 in a weight ratio of 11: 9.
Among the above-mentioned components, dioctyl phthalate is the optional increase component, and its viscosity that adds and can increase the hot melt adhesive promotes the mobility under its molten state, still has fast curing's effect simultaneously, can effectively save the activity duration, improves production efficiency.
Preferably, the peroxide initiator is potassium persulfate.
A preparation method of the environment-friendly wax carton hot melt adhesive based on the components comprises the following steps:
s1, preparing paraffin emulsion: placing the sliced paraffin and the composite emulsifier B into a reaction container, heating to 75 ℃, starting stirring after the paraffin is completely melted, stirring for 10min, then dropwise adding 80 parts of deionized water heated to 75 ℃ at the speed of 2.0mL/min, continuing stirring at 75 ℃ for 30-60 min, and then cooling the prepared paraffin emulsion to room temperature for later use;
s2, preparing a composite emulsion: uniformly mixing vinyl acetate, methyl methacrylate, butyl acrylate and acrylic acid, or vinyl acetate, methyl methacrylate, butyl acrylate, acrylic acid and dioctyl phthalate to obtain a monomer mixed solution; dissolving peroxide initiator in partial deionized water to prepare initiator aqueous solution; mixing and stirring the rest deionized water, the compound emulsifier A and the buffer uniformly to obtain a mixed reaction solution; heating the mixed reaction liquid to 40 ℃, adding 1/4 parts by weight of monomer mixed liquid and 1/5 parts by weight of peroxide aqueous solution, stirring and mixing uniformly, continuously heating to 60 ℃, adding 10 parts of paraffin emulsion prepared in the step S1 into the mixed reaction liquid, mixing and stirring uniformly, continuously heating to 75-78 ℃, dropwise adding the rest monomer mixed liquid into the mixed reaction liquid at the speed of 2S/drop, dropwise adding the rest potassium persulfate aqueous solution at the speed of 10S/drop, after dropwise adding is finished, continuously keeping the temperature at 75-78 ℃, stirring and reacting for 1.5 hours, and then cooling the obtained composite emulsion to room temperature;
s3, dropwise adding a saturated sodium chloride solution prepared at room temperature into the composite emulsion obtained in the step S2, violently stirring at the speed of 150-200 r/min, filtering after dropwise adding is completed and obvious polymer precipitation appears in the system, washing the precipitate for 3 times by deionized water, and vacuum-drying at 50 ℃ for 3 hours to obtain the solid hot melt adhesive.
Compared with the prior art, the hot melt adhesive for the environment-friendly wax carton has the following beneficial effects:
1) the melting temperature of the solid hot melt adhesive is between 58 and 71 ℃, and the characteristic that the melting temperature is lower than or close to the temperature of the wax coating can effectively protect the wax coating on the surface of the wax carton from being damaged in the bonding process;
2) the T-shaped peeling strength of the solid hot melt adhesive is 38-55N/25 mm under the test of the standard GB/T2791-1995, the higher T-shaped peeling strength meets the higher bonding strength required by a wax layer of a wax carton, and the solid hot melt adhesive is more suitable for bonding wax cartons compared with the current common hot melt adhesive sold in the market; and the peeling failure mode in the wax carton experiment after manual peeling and bonding in the laboratory is expressed as a glue layer and interface failure mode;
3) the single lap joint shear strength of the solid hot melt adhesive can reach 0.5-2 Mpa under the standard GB/T33334-2016, and the solid hot melt adhesive shows high cohesive strength, namely, the solid hot melt adhesive is not easy to damage;
4) the solid hot melt adhesive has short bonding time, has good fluidity by adding dioctyl phthalate, is convenient to coat, further realizes quick bonding operation in practical application, and effectively improves the production efficiency.
Detailed Description
The present invention will be further described with reference to the following examples, which are not intended to limit the invention in any way. The components used in the following examples are commercially available products, and the parts of the components in the examples are specifically parts by weight.
Example 1
An environment-friendly hot melt adhesive for wax cartons, which comprises the following preparation steps:
s1, preparing paraffin emulsion: placing 16 parts of sliced paraffin and 4 parts of compound emulsifier B in a reaction container, heating to 75 ℃, starting stirring after paraffin is completely melted, stirring for 10min, dropwise adding 80 parts of deionized water heated to 75 ℃ at the speed of 2.0mL/min, continuing stirring at 75 ℃ for 30min, and cooling the prepared paraffin emulsion to room temperature for later use; wherein the composite emulsifier B is a mixed solution of alkylphenol polyoxyethylene ether and span 80 in a weight ratio of 11: 9;
s2, preparing a composite emulsion: uniformly mixing 28 parts of vinyl acetate, 3 parts of methyl methacrylate, 7 parts of butyl acrylate and 2 parts of acrylic acid to obtain a monomer mixed solution; dissolving 0.3 part of potassium persulfate in 15 parts of deionized water to prepare an initiator solution; mixing and stirring the rest 33 parts of deionized water, 1.5 parts of composite emulsifier A and 0.1 part of sodium bicarbonate uniformly to obtain a mixed reaction solution; heating the mixed reaction liquid to 40 ℃, adding 1/4 parts by weight of monomer mixed liquid and 1/5 parts by weight of initiator solution, stirring and mixing uniformly, continuing to heat to 60 ℃, adding 12 parts of paraffin emulsion prepared in the step S1 into the mixed reaction liquid, mixing and stirring uniformly, continuing to heat to 75 ℃, dropwise adding the rest monomer mixed liquid into the mixed reaction liquid at the speed of 2S/drop, dropwise adding the rest initiator solution at the speed of 10S/drop, after dropwise adding, continuing to stir at 75 ℃ for 1.5h, and then cooling the obtained composite emulsion to room temperature; wherein the composite emulsifier A is a mixed solution of alkylphenol polyoxyethylene ether and sodium dodecyl sulfate in a weight ratio of 3.5: 1;
s3, dropwise adding a saturated sodium chloride solution prepared at room temperature into the composite emulsion obtained in the step S2 at a speed of 1S/drop, violently stirring at a speed of 150r/min, filtering after dropwise adding is completed and obvious polymer precipitation appears in the system, washing the precipitate for 3 times by deionized water, and drying in vacuum at 50 ℃ for 3 hours to obtain the solid hot melt adhesive.
Example 2
An environment-friendly hot melt adhesive for wax cartons, which comprises the following preparation steps:
s1, preparing paraffin emulsion: placing 16 parts of sliced paraffin and 10 parts of composite emulsifier B in a reaction container, heating to 75 ℃, starting stirring after paraffin is completely melted, stirring for 10min, dropwise adding 74 parts of deionized water heated to 75 ℃ at the speed of 2.0mL/min, continuing stirring at 75 ℃ for 45min, and cooling the prepared paraffin emulsion to room temperature for later use; wherein the composite emulsifier B is a mixed solution of alkylphenol polyoxyethylene ether and span 80 in a weight ratio of 11: 9;
s2, preparing a composite emulsion: uniformly mixing 28 parts of vinyl acetate, 6 parts of methyl methacrylate, 4 parts of butyl acrylate and 2 parts of acrylic acid to obtain a monomer mixed solution; dissolving 0.2 part of potassium persulfate in 15 parts of deionized water to prepare an initiator solution; mixing and stirring the rest 35 parts of deionized water, 2 parts of compound emulsifier A and 0.1 part of sodium bicarbonate uniformly to obtain a mixed reaction solution; heating the mixed reaction liquid to 40 ℃, adding 1/4 parts by weight of monomer mixed liquid and 1/5 parts by weight of initiator solution, stirring and mixing uniformly, continuing to heat to 60 ℃, adding 10 parts of paraffin emulsion prepared in the step S1 into the mixed reaction liquid, mixing and stirring uniformly, continuing to heat to 78 ℃, dropwise adding the rest monomer mixed liquid into the mixed reaction liquid at the speed of 2S/drop, dropwise adding the rest initiator solution at the speed of 10S/drop, after dropwise adding, continuing to stir at 78 ℃ for 1.5h, and then cooling the obtained composite emulsion to room temperature; wherein the composite emulsifier A is a mixed solution of alkylphenol polyoxyethylene ether and sodium dodecyl sulfate in a weight ratio of 3.5: 1;
s3, dropwise adding a saturated sodium chloride solution prepared at room temperature into the composite emulsion obtained in the step S2 at a speed of 1S/drop, violently stirring at a speed of 200r/min, filtering after dropwise adding is completed and obvious polymer precipitation appears in the system, washing the precipitate for 3 times by deionized water, and drying in vacuum at 50 ℃ for 3 hours to obtain the solid hot melt adhesive.
Example 3
An environment-friendly hot melt adhesive for wax cartons, which comprises the following preparation steps:
s1, preparing paraffin emulsion: placing 12 parts of sliced paraffin and 8 parts of compound emulsifier B in a reaction container, heating to 75 ℃, starting stirring after paraffin is completely melted, stirring for 10min, dropwise adding 80 parts of deionized water heated to 75 ℃ at the speed of 2.0mL/min, continuing stirring at 75 ℃ for 60min, and cooling the prepared paraffin emulsion to room temperature for later use; wherein the composite emulsifier B is a mixed solution of alkylphenol polyoxyethylene ether and span 80 in a weight ratio of 11: 9;
s2, preparing a composite emulsion: uniformly mixing 22 parts of vinyl acetate, 7.2 parts of methyl methacrylate, 5.8 parts of butyl acrylate and 5 parts of acrylic acid to obtain a monomer mixed solution; dissolving 0.2 part of potassium persulfate in 15 parts of deionized water to prepare an initiator solution; mixing and stirring uniformly the rest 37 parts of deionized water, 1 part of composite emulsifier A and 0.3 part of sodium bicarbonate to obtain a mixed reaction solution; heating the mixed reaction liquid to 40 ℃, adding 1/4 parts by weight of monomer mixed liquid and 1/5 parts by weight of initiator solution, stirring and mixing uniformly, continuing to heat to 60 ℃, adding 8 parts of paraffin emulsion prepared in the step S1 into the mixed reaction liquid, mixing and stirring uniformly, continuing to heat to 75 ℃, dropwise adding the rest monomer mixed liquid into the mixed reaction liquid at the speed of 2S/drop, dropwise adding the rest initiator solution at the speed of 10S/drop, after dropwise adding, continuing to stir at 75 ℃ for 1.5h, and then cooling the obtained composite emulsion to room temperature; wherein the composite emulsifier A is a mixed solution of alkylphenol polyoxyethylene ether and sodium dodecyl sulfate in a weight ratio of 3.5: 1;
s3, dropwise adding a saturated sodium chloride solution prepared at room temperature into the composite emulsion obtained in the step S2 at a speed of 1S/drop, violently stirring at a speed of 250r/min, filtering after dropwise adding is completed and obvious polymer precipitation appears in the system, washing the precipitate for 3 times by deionized water, and drying in vacuum at 50 ℃ for 3 hours to obtain the solid hot melt adhesive.
Example 4
An environment-friendly hot melt adhesive for wax cartons, which comprises the following preparation steps:
s1, preparing paraffin emulsion: placing 20 parts of sliced paraffin and 4 parts of compound emulsifier B into a reaction container, heating to 75 ℃, starting stirring after paraffin is completely melted, stirring for 10min, dropwise adding 76 parts of deionized water heated to 75 ℃ at the speed of 2.0mL/min, continuing stirring at 75 ℃ for 50min, and cooling the prepared paraffin emulsion to room temperature for later use; wherein the composite emulsifier B is a mixed solution of alkylphenol polyoxyethylene ether and span 80 in a weight ratio of 11: 9;
s2, preparing a composite emulsion: uniformly mixing 20 parts of vinyl acetate, 11 parts of methyl methacrylate, 5.6 parts of butyl acrylate and 3.2 parts of acrylic acid to obtain a monomer mixed solution; dissolving 0.3 part of potassium persulfate in 15 parts of deionized water to prepare an initiator solution; mixing and stirring the rest 44 parts of deionized water, 0.7 part of composite emulsifier A and 0.3 part of sodium bicarbonate uniformly to obtain a mixed reaction solution; heating the mixed reaction liquid to 40 ℃, adding 1/4 parts by weight of monomer mixed liquid and 1/5 parts by weight of initiator solution, stirring and mixing uniformly, continuing to heat to 60 ℃, adding 1 part of paraffin emulsion prepared in the step S1 into the mixed reaction liquid, mixing and stirring uniformly, continuing to heat to 75 ℃, dropwise adding the rest monomer mixed liquid into the mixed reaction liquid at the speed of 2S/drop, dropwise adding the rest initiator solution at the speed of 10S/drop, after dropwise adding, continuing to stir at 75 ℃ for 1.5h, and then cooling the obtained composite emulsion to room temperature; wherein the composite emulsifier A is a mixed solution of alkylphenol polyoxyethylene ether and sodium dodecyl sulfate in a weight ratio of 3.5: 1;
s3, dropwise adding a saturated sodium chloride solution prepared at room temperature into the composite emulsion obtained in the step S2 at a speed of 1S/drop, violently stirring at a speed of 150r/min, filtering after dropwise adding is completed and obvious polymer precipitation appears in the system, washing the precipitate for 3 times by deionized water, and drying in vacuum at 50 ℃ for 3 hours to obtain the solid hot melt adhesive.
Example 5
An environment-friendly hot melt adhesive for wax cartons, which comprises the following preparation steps:
s1, preparing paraffin emulsion: placing 20 parts of sliced paraffin and 10 parts of compound emulsifier B into a reaction container, heating to 75 ℃, starting stirring after paraffin is completely melted, stirring for 10min, dropwise adding 70 parts of deionized water heated to 75 ℃ at the speed of 2.0mL/min, continuing stirring at 75 ℃ for 35min, and cooling the prepared paraffin emulsion to room temperature for later use; wherein the composite emulsifier B is a mixed solution of alkylphenol polyoxyethylene ether and span 80 in a weight ratio of 11: 9;
s2, preparing a composite emulsion: uniformly mixing 22 parts of vinyl acetate, 5.2 parts of methyl methacrylate, 8 parts of butyl acrylate and 4.8 parts of acrylic acid to obtain a monomer mixed solution; dissolving 0.4 part of potassium persulfate in 15 parts of deionized water to prepare an initiator solution; mixing and stirring the rest 41 parts of deionized water, 1.2 parts of composite emulsifier A and 0.1 part of sodium bicarbonate uniformly to obtain a mixed reaction solution; heating the mixed reaction liquid to 40 ℃, adding 1/4 parts by weight of monomer mixed liquid and 1/5 parts by weight of initiator solution, stirring and mixing uniformly, continuing to heat to 60 ℃, adding 4 parts of paraffin emulsion prepared in the step S1 into the mixed reaction liquid, mixing and stirring uniformly, continuing to heat to 75 ℃, dropwise adding the rest monomer mixed liquid into the mixed reaction liquid at the speed of 2S/drop, dropwise adding the rest initiator solution at the speed of 10S/drop, after dropwise adding, continuing to stir at 75 ℃ for 1.5h, and then cooling the obtained composite emulsion to room temperature; wherein the composite emulsifier A is a mixed solution of alkylphenol polyoxyethylene ether and sodium dodecyl sulfate in a weight ratio of 3.5: 1;
s3, dropwise adding a saturated sodium chloride solution prepared at room temperature into the composite emulsion obtained in the step S2 at a speed of 1S/drop, violently stirring at a speed of 150r/min, filtering after dropwise adding is completed and obvious polymer precipitation appears in the system, washing the precipitate for 3 times by deionized water, and drying in vacuum at 50 ℃ for 3 hours to obtain the solid hot melt adhesive.
Example 6
An environment-friendly hot melt adhesive for wax cartons, which comprises the following preparation steps:
s1, preparing paraffin emulsion: placing 12 parts of sliced paraffin and 6 parts of compound emulsifier B in a reaction container, heating to 75 ℃, starting stirring after paraffin is completely melted, stirring for 10min, dropwise adding 80 parts of deionized water heated to 75 ℃ at the speed of 2.0mL/min, continuing stirring at 75 ℃ for 55min, and cooling the prepared paraffin emulsion to room temperature for later use; wherein the composite emulsifier B is a mixed solution of alkylphenol polyoxyethylene ether and span 80 in a weight ratio of 11: 9;
s2, preparing a composite emulsion: uniformly mixing 26 parts of vinyl acetate, 5.2 parts of methyl methacrylate, 5.6 parts of butyl acrylate and 3.2 parts of acrylic acid to obtain a monomer mixed solution; dissolving 0.2 part of potassium persulfate in 15 parts of water to prepare an initiator solution; mixing and stirring 28 parts of deionized water, 0.5 part of composite emulsifier A and 0.1 part of sodium bicarbonate uniformly to obtain a mixed reaction solution; heating the mixed reaction liquid to 40 ℃, adding 1/4 parts by weight of monomer mixed liquid and 1/5 parts by weight of initiator solution, stirring and mixing uniformly, continuing to heat to 60 ℃, adding 12 parts of paraffin emulsion prepared in the step S1 into the mixed reaction liquid, mixing and stirring uniformly, continuing to heat to 75 ℃, dropwise adding the rest monomer mixed liquid into the mixed reaction liquid at the speed of 2S/drop, dropwise adding the rest initiator solution at the speed of 10S/drop, after dropwise adding, continuing to stir at 75 ℃ for 1.5h, and then cooling the obtained composite emulsion to room temperature; wherein the composite emulsifier A is a mixed solution of alkylphenol polyoxyethylene ether and sodium dodecyl sulfate in a weight ratio of 3.5: 1;
s3, dropwise adding a saturated sodium chloride solution prepared at room temperature into the composite emulsion obtained in the step S2 at a speed of 1S/drop, violently stirring at a speed of 200r/min, filtering after dropwise adding is completed and obvious polymer precipitation appears in the system, washing the precipitate for 3 times by deionized water, and drying in vacuum at 50 ℃ for 3 hours to obtain the solid hot melt adhesive.
Example 7
An environment-friendly hot melt adhesive for wax cartons, which comprises the following preparation steps:
s1, preparing paraffin emulsion: placing 20 parts of sliced paraffin and 6 parts of compound emulsifier B into a reaction container, heating to 75 ℃, starting stirring after paraffin is completely melted, stirring for 10min, dropwise adding 74 parts of deionized water heated to 75 ℃ at the speed of 2.0mL/min, continuing stirring at 75 ℃ for 60min, and cooling the prepared paraffin emulsion to room temperature for later use; wherein the composite emulsifier B is a mixed solution of alkylphenol polyoxyethylene ether and span 80 in a weight ratio of 11: 9;
s2, preparing a composite emulsion: uniformly mixing 26 parts of vinyl acetate, 5 parts of methyl methacrylate, 6 parts of butyl acrylate and 3 parts of acrylic acid to obtain a monomer mixed solution; dissolving 0.3 part of potassium persulfate in 15 parts of water to prepare an initiator solution; mixing 35 parts of deionized water, 1 part of composite emulsifier A and 0.1 part of sodium bicarbonate, and uniformly stirring to obtain a mixed reaction solution; heating the mixed reaction liquid to 40 ℃, adding 1/4 parts by weight of monomer mixed liquid and 1/5 parts by weight of initiator solution, stirring and mixing uniformly, continuing to heat to 60 ℃, adding 10 parts of paraffin emulsion prepared in the step S1 into the mixed reaction liquid, mixing and stirring uniformly, continuing to heat to 75 ℃, dropwise adding the rest monomer mixed liquid into the mixed reaction liquid at the speed of 2S/drop, dropwise adding the rest initiator solution at the speed of 10S/drop, after dropwise adding, continuing to stir at 75 ℃ for 1.5h, and then cooling the obtained composite emulsion to room temperature; wherein the composite emulsifier A is a mixed solution of alkylphenol polyoxyethylene ether and sodium dodecyl sulfate in a weight ratio of 3.5: 1;
s3, dropwise adding a saturated sodium chloride solution prepared at room temperature into the composite emulsion obtained in the step S2 at a speed of 1S/drop, violently stirring at a speed of 200r/min, filtering after dropwise adding is completed and obvious polymer precipitation appears in the system, washing the precipitate for 3 times by deionized water, and drying in vacuum at 50 ℃ for 3 hours to obtain the solid hot melt adhesive.
Example 8
An environment-friendly hot melt adhesive for wax cartons, which comprises the following preparation steps:
s1, preparing paraffin emulsion: placing 20 parts of sliced paraffin and 6 parts of compound emulsifier B into a reaction container, heating to 75 ℃, starting stirring after paraffin is completely melted, stirring for 10min, dropwise adding 74 parts of deionized water heated to 75 ℃ at the speed of 2.0mL/min, continuing stirring at 75 ℃ for 60min, and cooling the prepared paraffin emulsion to room temperature for later use; wherein the composite emulsifier B is a mixed solution of alkylphenol polyoxyethylene ether and span 80 in a weight ratio of 11: 9;
s2, preparing a composite emulsion: mixing 26 parts of vinyl acetate, 5 parts of methyl methacrylate, 6 parts of butyl acrylate, 3 parts of acrylic acid and 5 parts of dioctyl phthalate uniformly to obtain a monomer mixed solution; dissolving 0.3 part of potassium persulfate in 15 parts of water to prepare an initiator solution; mixing 35 parts of deionized water, 1 part of composite emulsifier A and 0.1 part of sodium bicarbonate, and uniformly stirring to obtain a mixed reaction solution; heating the mixed reaction liquid to 40 ℃, adding 1/4 parts by weight of monomer mixed liquid and 1/5 parts by weight of initiator solution, stirring and mixing uniformly, continuing to heat to 60 ℃, adding 10 parts of paraffin emulsion prepared in the step S1 into the mixed reaction liquid, mixing and stirring uniformly, continuing to heat to 75 ℃, dropwise adding the rest monomer mixed liquid into the mixed reaction liquid at the speed of 2S/drop, dropwise adding the rest initiator solution at the speed of 10S/drop, after dropwise adding, continuing to stir at 75 ℃ for 1.5h, and then cooling the obtained composite emulsion to room temperature; wherein the composite emulsifier A is a mixed solution of alkylphenol polyoxyethylene ether and sodium dodecyl sulfate in a weight ratio of 3.5: 1;
s3, dropwise adding a saturated sodium chloride solution prepared at room temperature into the composite emulsion obtained in the step S2 at a speed of 1S/drop, violently stirring at a speed of 200r/min, filtering after dropwise adding is completed and obvious polymer precipitation appears in the system, washing the precipitate for 3 times by deionized water, and drying in vacuum at 50 ℃ for 3 hours to obtain the solid hot melt adhesive.
Example 9
An environment-friendly hot melt adhesive for wax cartons, which comprises the following preparation steps:
s1, preparing paraffin emulsion: placing 20 parts of sliced paraffin and 6 parts of compound emulsifier B into a reaction container, heating to 75 ℃, starting stirring after paraffin is completely melted, stirring for 10min, dropwise adding 74 parts of deionized water heated to 75 ℃ at the speed of 2.0mL/min, continuing stirring at 75 ℃ for 60min, and cooling the prepared paraffin emulsion to room temperature for later use; wherein the composite emulsifier B is a mixed solution of alkylphenol polyoxyethylene ether and span 80 in a weight ratio of 11: 9;
s2, preparing a composite emulsion: mixing 26 parts of vinyl acetate, 5 parts of methyl methacrylate, 6 parts of butyl acrylate, 3 parts of acrylic acid and 10 parts of dioctyl phthalate uniformly to obtain a monomer mixed solution; dissolving 0.3 part of potassium persulfate in 15 parts of water to prepare an initiator solution; mixing 35 parts of deionized water, 1 part of composite emulsifier A and 0.1 part of sodium bicarbonate, and uniformly stirring to obtain a mixed reaction solution; heating the mixed reaction liquid to 40 ℃, adding 1/4 parts by weight of monomer mixed liquid and 1/5 parts by weight of initiator solution, stirring and mixing uniformly, continuing to heat to 60 ℃, adding 10 parts of paraffin emulsion prepared in the step S1 into the mixed reaction liquid, mixing and stirring uniformly, continuing to heat to 75 ℃, dropwise adding the rest monomer mixed liquid into the mixed reaction liquid at the speed of 2S/drop, dropwise adding the rest initiator solution at the speed of 10S/drop, after dropwise adding, continuing to stir at 75 ℃ for 1.5h, and then cooling the obtained composite emulsion to room temperature; wherein the composite emulsifier A is a mixed solution of alkylphenol polyoxyethylene ether and sodium dodecyl sulfate in a weight ratio of 3.5: 1;
s3, dropwise adding a saturated sodium chloride solution prepared at room temperature into the composite emulsion obtained in the step S2 at a speed of 1S/drop, violently stirring at a speed of 200r/min, filtering after dropwise adding is completed and obvious polymer precipitation appears in the system, washing the precipitate for 3 times by deionized water, and drying in vacuum at 50 ℃ for 3 hours to obtain the solid hot melt adhesive.
Example 10
An environment-friendly hot melt adhesive for wax cartons, which comprises the following preparation steps:
s1, preparing paraffin emulsion: placing 20 parts of sliced paraffin and 6 parts of compound emulsifier B into a reaction container, heating to 75 ℃, starting stirring after paraffin is completely melted, stirring for 10min, dropwise adding 74 parts of deionized water heated to 75 ℃ at the speed of 2.0mL/min, continuing stirring at 75 ℃ for 60min, and cooling the prepared paraffin emulsion to room temperature for later use; wherein the composite emulsifier B is a mixed solution of alkylphenol polyoxyethylene ether and span 80 in a weight ratio of 11: 9;
s2, preparing a composite emulsion: mixing 26 parts of vinyl acetate, 5 parts of methyl methacrylate, 6 parts of butyl acrylate, 3 parts of acrylic acid and 15 parts of dioctyl phthalate uniformly to obtain a monomer mixed solution; dissolving 0.3 part of potassium persulfate in 15 parts of water to prepare an initiator solution; mixing 35 parts of deionized water, 1 part of composite emulsifier A and 0.1 part of sodium bicarbonate, and uniformly stirring to obtain a mixed reaction solution; heating the mixed reaction liquid to 40 ℃, adding 1/4 parts by weight of monomer mixed liquid and 1/5 parts by weight of initiator solution, stirring and mixing uniformly, continuing to heat to 60 ℃, adding 10 parts of paraffin emulsion prepared in the step S1 into the mixed reaction liquid, mixing and stirring uniformly, continuing to heat to 75 ℃, dropwise adding the rest monomer mixed liquid into the mixed reaction liquid at the speed of 2S/drop, dropwise adding the rest initiator solution at the speed of 10S/drop, after dropwise adding, continuing to stir at 75 ℃ for 1.5h, and then cooling the obtained composite emulsion to room temperature; wherein the composite emulsifier A is a mixed solution of alkylphenol polyoxyethylene ether and sodium dodecyl sulfate in a weight ratio of 3.5: 1;
s3, dropwise adding a saturated sodium chloride solution prepared at room temperature into the composite emulsion obtained in the step S2 at a speed of 1S/drop, violently stirring at a speed of 200r/min, filtering after dropwise adding is completed and obvious polymer precipitation appears in the system, washing the precipitate for 3 times by deionized water, and drying in vacuum at 50 ℃ for 3 hours to obtain the solid hot melt adhesive.
Example 11
An environment-friendly hot melt adhesive for wax cartons, which comprises the following preparation steps:
s1, preparing paraffin emulsion: placing 20 parts of sliced paraffin and 6 parts of compound emulsifier B into a reaction container, heating to 75 ℃, starting stirring after paraffin is completely melted, stirring for 10min, dropwise adding 74 parts of deionized water heated to 75 ℃ at the speed of 2.0mL/min, continuing stirring at 75 ℃ for 60min, and cooling the prepared paraffin emulsion to room temperature for later use; wherein the composite emulsifier B is a mixed solution of alkylphenol polyoxyethylene ether and span 80 in a weight ratio of 11: 9;
s2, preparing a composite emulsion: mixing 26 parts of vinyl acetate, 5 parts of methyl methacrylate, 6 parts of butyl acrylate and 3 parts of acrylic acid, and uniformly mixing with 20 parts of dioctyl phthalate to obtain a monomer mixed solution; dissolving 0.3 part of potassium persulfate in 15 parts of water to prepare an initiator solution; mixing 35 parts of deionized water, 1 part of composite emulsifier A and 0.1 part of sodium bicarbonate, and uniformly stirring to obtain a mixed reaction solution; heating the mixed reaction liquid to 40 ℃, adding 1/4 parts by weight of monomer mixed liquid and 1/5 parts by weight of initiator solution, stirring and mixing uniformly, continuing to heat to 60 ℃, adding 10 parts of paraffin emulsion prepared in the step S1 into the mixed reaction liquid, mixing and stirring uniformly, continuing to heat to 75 ℃, dropwise adding the rest monomer mixed liquid into the mixed reaction liquid at the speed of 2S/drop, dropwise adding the rest initiator solution at the speed of 10S/drop, after dropwise adding, continuing to stir at 75 ℃ for 1.5h, and then cooling the obtained composite emulsion to room temperature; wherein the composite emulsifier A is a mixed solution of alkylphenol polyoxyethylene ether and sodium dodecyl sulfate in a weight ratio of 3.5: 1;
s3, dropwise adding a saturated sodium chloride solution prepared at room temperature into the composite emulsion obtained in the step S2 at a speed of 1S/drop, violently stirring at a speed of 200r/min, filtering after dropwise adding is completed and obvious polymer precipitation appears in the system, washing the precipitate for 3 times by deionized water, and drying in vacuum at 50 ℃ for 3 hours to obtain the solid hot melt adhesive.
And (3) performance testing:
the solid hot melt adhesives prepared in examples 1 to 11 were subjected to a melting temperature test, a T-type peel strength test, and a single lap shear strength test in this order.
Melting temperature test:
the test method comprises the following steps: the melting temperatures of the eleven solid hot melt adhesives prepared in examples 1 to 11 were measured using a melting temperature meter, 3 parallel experiments were performed for each solid hot melt adhesive, and the average value of the melting temperatures was taken as the final measured value.
The specific test results are shown in table 1 below.
Table 1:
from the test results in table 1, it can be seen that the melting temperature of the eleven solid hot melt adhesives prepared in examples 1 to 11 is between 58 ℃ and 71 ℃, and the melting temperature is significantly lower than or close to the temperature of the wax coating layer relative to the wax coating layer on the surface of the wax carton with the melting temperature between 70 ℃ and 75 ℃, so that the requirements of adhering the wax carton without damaging the wax coating layer can be met; the melting temperature of the current common box sealing hot melt adhesive sold in the market is generally between 108 ℃ and 115 ℃, so that the wax coating on the surface of the wax paper box is easily damaged.
(II) T-type peel strength test:
the test method comprises the following steps: the T-type peel strength of the eleven solid hot melt adhesives prepared in examples 1 to 11 was tested according to the standard GB/T2791-1995. The specific test results are shown in table 2 below.
Table 2:
as can be seen from the test results in Table 2, the T-type peel strength of the eleven solid hot melt adhesives prepared in examples 1 to 11 is 38 to 55N/25mm on average; although the national standard of the T-shaped peel strength test is not tested for wax cartons, the T-shaped peel strength of the eleven solid-state hot melt adhesives of the present application is superior to that of the common hot melt adhesives sold in the market at present, and for the characteristics of the wax layers of the wax cartons, the greater the T-shaped peel strength of the hot melt adhesives is, the stronger the bonding strength between the wax layers is, so that the solid-state hot melt adhesives of the present application are more suitable for bonding of the wax cartons than the common hot melt adhesives sold in the market at present.
Meanwhile, the applicant also adopts eleven solid hot melt adhesives of the application in a laboratory to bond a plurality of wax cartons respectively, and peel tests are carried out on bonding positions through manpower; through tests, after the wax paper box bonded by the eleven solid-state hot melt adhesives is peeled, the peeling failure modes are adhesive layers and interface failure modes, and the test result also shows that the eleven solid-state hot melt adhesives have higher bonding strength to the wax paper box.
(III) single lap shear strength test:
the test method comprises the following steps: the eleven solid hot melt adhesives prepared in examples 1 to 11 were tested for their single lap shear strength with reference to the standard GB/T33334-2016.
The specific test results are shown in table 3 below.
Table 3:
as can be seen from the test results in Table 3, the single lap shear strength of the eleven solid hot melt adhesives prepared in examples 1 to 11 can reach 0.5 to 2 MPa. The experimental result can show that the eleven solid hot melt adhesives have high cohesive strength and are not easy to damage.
(IV) Experimental discussion of the bond time after addition of dioctyl phthalate:
the bonding time between the wax layers of the five solid hot melt adhesives prepared in examples 7 to 11 was tested, and the difference in fluidity at the melting temperature of the solid hot melt adhesives prepared after adding dioctyl phthalate was observed. The difference between the five examples is that the content of dioctyl phthalate is increased.
The specific test results are shown in table 4 below.
Table 4:
| examples | 7 | 8 | 9 | 10 | 11 |
| Bonding time | 15s | 18s | 20s | 22s | 25s |
As can be seen from the test results in Table 4, the bonding time of the eleven solid hot melt adhesives prepared in examples 7 to 11 is 15 to 25 seconds, which is compared with the current common box sealing hot melt adhesive sold in the market, the bonding time of which is 20 to 40 seconds generally; and from the observation of the fluidity at the melting temperature, the fluidity is obviously increased along with the increase of the addition of the dioctyl phthalate, so that the molten hot melt adhesive can be rapidly coated on the bonding area of the wax layer. Therefore, the solid hot melt adhesive is convenient to coat and short in bonding time, can realize rapid bonding operation, and can effectively improve the production efficiency in practical application.
Claims (3)
1. The utility model provides an environment-friendly wax is hot melt adhesive for carton, its characterized in that, the raw materials composition of hot melt adhesive is as follows:
copolymer monomer (b): the acrylic acid-free vinyl acetate emulsion comprises 20-28 parts of vinyl acetate, 3-11 parts of methyl methacrylate, 4-8 parts of butyl acrylate and 2-5 parts of acrylic acid;
1-12 parts of paraffin emulsion;
43-59 parts of deionized water;
and 0.2-0.4% of peroxide initiator, 0.5-2% of emulsifier A, 0.1-0.3% of buffering agent and 0-20% of dioctyl phthalate, wherein the peroxide initiator accounts for the total weight of the copolymer monomer, the paraffin emulsion and the deionized water;
wherein the paraffin emulsion is formed by mixing 10-20 parts of paraffin, 4-10 parts of emulsifier B and 70-80 parts of deionized water; the buffer is sodium bicarbonate; the emulsifier A is a composite emulsifier formed by mixing alkylphenol polyoxyethylene ether and lauryl sodium sulfate in a weight ratio of 3.5: 1; the emulsifier B is a composite emulsifier formed by mixing alkylphenol polyoxyethylene ether and span 80 in a weight ratio of 11: 9.
2. The hot melt adhesive for environment-friendly wax cartons as claimed in claim 1, wherein the peroxide initiator is potassium persulfate.
3. The preparation method of the hot melt adhesive for the environment-friendly wax cartons as claimed in claim 1, which is characterized by comprising the following steps:
s1, preparing paraffin emulsion: placing the sliced paraffin and the composite emulsifier B into a reaction container, heating to 75 ℃, starting stirring after the paraffin is completely melted, stirring for 10min, then dropwise adding 80 parts of deionized water heated to 75 ℃ at the speed of 2.0mL/min, continuing stirring at 75 ℃ for 30-60 min, and then cooling the prepared paraffin emulsion to room temperature for later use;
s2, preparing a composite emulsion: uniformly mixing vinyl acetate, methyl methacrylate, butyl acrylate and acrylic acid, or vinyl acetate, methyl methacrylate, butyl acrylate, acrylic acid and dioctyl phthalate to obtain a monomer mixed solution; dissolving peroxide initiator in partial deionized water to prepare initiator aqueous solution; mixing and stirring the rest deionized water, the compound emulsifier A and the buffer uniformly to obtain a mixed reaction solution; heating the mixed reaction liquid to 40 ℃, adding 1/4 parts by weight of monomer mixed liquid and 1/5 parts by weight of peroxide aqueous solution, stirring and mixing uniformly, continuously heating to 60 ℃, adding 10 parts of paraffin emulsion prepared in the step S1 into the mixed reaction liquid, mixing and stirring uniformly, continuously heating to 75-78 ℃, dropwise adding the rest monomer mixed liquid into the mixed reaction liquid at the speed of 2S/drop, dropwise adding the rest potassium persulfate aqueous solution at the speed of 10S/drop, after dropwise adding is finished, continuously keeping the temperature at 75-78 ℃, stirring and reacting for 1.5 hours, and then cooling the obtained composite emulsion to room temperature;
s3, dropwise adding a saturated sodium chloride solution prepared at room temperature into the composite emulsion obtained in the step S2, violently stirring at the speed of 150-200 r/min, filtering after dropwise adding is completed and obvious polymer precipitation appears in the system, washing the precipitate for 3 times by deionized water, and vacuum-drying at 50 ℃ for 3 hours to obtain the solid hot melt adhesive.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111849395A (en) * | 2020-07-23 | 2020-10-30 | 天津德奥赛恩生物科技有限公司 | Redispersible acrylate hot melt adhesive for paper products and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0781216A (en) * | 1993-09-14 | 1995-03-28 | New Oji Paper Co Ltd | Pressure-sensitive recording body |
| CN107722876A (en) * | 2017-11-17 | 2018-02-23 | 东莞市中凌包装材料有限公司 | A kind of water-based Dispoable medical packing hot-fusible glue and manufacture craft |
| CN110791236A (en) * | 2019-10-29 | 2020-02-14 | 上海保立佳新材料有限公司 | Water-based acrylate adhesive |
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2020
- 2020-03-26 CN CN202010221717.4A patent/CN111234738B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0781216A (en) * | 1993-09-14 | 1995-03-28 | New Oji Paper Co Ltd | Pressure-sensitive recording body |
| CN107722876A (en) * | 2017-11-17 | 2018-02-23 | 东莞市中凌包装材料有限公司 | A kind of water-based Dispoable medical packing hot-fusible glue and manufacture craft |
| CN110791236A (en) * | 2019-10-29 | 2020-02-14 | 上海保立佳新材料有限公司 | Water-based acrylate adhesive |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111849395A (en) * | 2020-07-23 | 2020-10-30 | 天津德奥赛恩生物科技有限公司 | Redispersible acrylate hot melt adhesive for paper products and preparation method thereof |
| CN111849395B (en) * | 2020-07-23 | 2022-03-29 | 天津德奥赛恩生物科技有限公司 | Redispersible acrylate hot melt adhesive for paper products and preparation method thereof |
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