CN110373119B - Environment-friendly modified starch adhesive for manufacturing corrugated board, high-performance environment-friendly corrugated board and manufacturing method thereof - Google Patents
Environment-friendly modified starch adhesive for manufacturing corrugated board, high-performance environment-friendly corrugated board and manufacturing method thereof Download PDFInfo
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- CN110373119B CN110373119B CN201910656145.XA CN201910656145A CN110373119B CN 110373119 B CN110373119 B CN 110373119B CN 201910656145 A CN201910656145 A CN 201910656145A CN 110373119 B CN110373119 B CN 110373119B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B29/00—Layered products comprising a layer of paper or cardboard
- B32B29/02—Layered products comprising a layer of paper or cardboard next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B29/00—Layered products comprising a layer of paper or cardboard
- B32B29/08—Corrugated paper or cardboard
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0261—Polyamide fibres
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
Abstract
The invention discloses an environment-friendly modified starch adhesive for manufacturing corrugated boards, a high-performance environment-friendly corrugated board and a manufacturing method thereof, wherein the environment-friendly modified starch adhesive for manufacturing the corrugated boards is prepared from the following raw materials in parts by weight: 60-75 parts of pressure-sensitive adhesive solution, 15-20 parts of hydrogenated rosin resin, 20-27 parts of polyether polyurethane prepolymer, 15-19 parts of glycerol modified starch, 18-23 parts of formamide modified starch, 5-8 parts of methacryloxy silane, 2.5-4 parts of hexamethylene diisocyanate, 3-5 parts of diacetyl tartaric acid monoglyceride and 20-30 parts of acetone. The environment-friendly modified starch adhesive for manufacturing the corrugated board has the advantages that the initial viscosity, the holding viscosity and the 180-degree adhesive force are obviously superior to those of the common starch adhesive, the adhesive force and the bonding strength are higher, the stripping force is large, and the manufacturing requirements of the high-performance environment-friendly corrugated board can be met; no formaldehyde is released, the degradation is easy, and the environment is protected.
Description
Technical Field
The invention relates to the field of adhesive technology and corrugated boards, in particular to an environment-friendly modified starch adhesive for manufacturing corrugated boards, a high-performance environment-friendly corrugated board and a manufacturing method thereof.
Background
The adhesive is used as an organic high molecular compound, is increasingly widely applied in the fields of packaging, printing, building engineering, textile printing and dyeing, shoe making, biological medicine and the like, and becomes an indispensable material in modern industry and national defense industry. With the increasing attention on environmental protection in the world, particularly the domestic green economy is taken as the main direction of future development, and the green environmental protection is the inevitable trend of development of various industries. Adhesives widely applied in printing and packaging materials also inevitably face higher environmental protection requirements, and the environmental protection adhesives become a necessary way for the development of the adhesives.
Corrugated paper boxes are ideal packaging containers, have the characteristics of lightness, firmness, vibration reduction and suitability for mechanized production, and are used for transport packaging and sale packaging for many years. Corrugated boxes have won the market with their elegant appearance and inherently superior quality. It not only protects the goods, is convenient for storage and transportation, but also beautifies the goods and publicizes the goods. Especially, under the condition that environmental protection is very important in all countries in the world at present, the corrugated case has the advantage of recycling, is favorable for environmental protection, is favorable for loading, unloading and transportation, is favorable for saving wood and the like.
Corrugated cardboard is a base material for manufacturing various corrugated cases. Generally, a corrugated cardboard is a plate-like object formed by bonding (bonding or adhering) a cardboard sheet and a corrugated medium sheet with an adhesive.
However, the following problems still exist at present:
1. although the environment-friendly adhesive used for bonding each layer of material of the corrugated board is degradable and has environment-friendly property, the adhesive has low adhesive force and low bonding strength, and can not meet the manufacturing requirements of high-performance environment-friendly corrugated boards;
2. if other solvent-based adhesives are used for bonding materials of each layer of the high-performance environment-friendly corrugated board, the formaldehyde release amount of the adhesives is high, the adhesives are not easy to degrade, and the adhesives are not environment-friendly;
3. the prepared corrugated board has poor mechanical properties such as strength and the like, is easy to damage or tear, and cannot meet the requirements of high-performance packaging corrugated boxes.
Disclosure of Invention
Based on the above situation, the invention aims to provide an environment-friendly modified starch adhesive for manufacturing corrugated boards, a high-performance environment-friendly corrugated board and a manufacturing method thereof, which can effectively solve the above problems.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
an environment-friendly modified starch adhesive for manufacturing corrugated boards is prepared from the following raw materials in parts by weight: 60-75 parts of pressure-sensitive adhesive solution, 15-20 parts of hydrogenated rosin resin, 20-27 parts of polyether polyurethane prepolymer, 15-19 parts of glycerol modified starch, 18-23 parts of formamide modified starch, 5-8 parts of methacryloxy silane, 2.5-4 parts of hexamethylene diisocyanate, 3-5 parts of diacetyl tartaric acid monoglyceride and 20-30 parts of acetone.
The environment-friendly modified starch adhesive for manufacturing the corrugated board disclosed by the invention is prepared by selecting raw materials and optimizing the content of each raw material, so that the advantages of the environment-friendly modified starch adhesive are fully exerted, the raw materials complement each other, promote each other and improve the quality stability of a product, and the initial viscosity, the holding viscosity and the 180-degree adhesive force of the prepared environment-friendly modified starch adhesive for manufacturing the corrugated board are obviously superior to those of a common starch adhesive, so that the environment-friendly modified starch adhesive has higher adhesive force and bonding strength and large stripping force, and can meet the manufacturing requirements of high-performance environment-friendly corrugated boards; no formaldehyde is released, the degradation is easy, and the environment is protected.
The special pressure-sensitive adhesive solution is adopted, so that the adhesive force and the stripping force are large, and the environment-friendly modified starch adhesive for manufacturing the corrugated board has good adhesive property; hydrogenated rosin resin with a proper proportion is added for adjusting the solid content and viscosity of the prepared environment-friendly modified starch adhesive for manufacturing corrugated boards and adjusting the stripping force so as to adapt to different use requirements; the polyether polyurethane prepolymer, the glycerol modified starch and the formamide modified starch are added in a proper proportion and used for being crosslinked and cured with a special pressure-sensitive adhesive solution under the action of hexamethylene diisocyanate to form a network structure, in addition, the glycerol modified starch and the formamide modified starch are added to ensure that the prepared environment-friendly modified starch adhesive for manufacturing the corrugated board is degradable, and once the environment-friendly modified starch adhesive is degraded, the structure of the environment-friendly modified starch adhesive for manufacturing the whole cured corrugated board collapses, the degradation is accelerated, and the pollution is reduced; the addition of the methacryloxy silane in a proper proportion improves the bonding strength and the water resistance of the environment-friendly modified starch adhesive for manufacturing the corrugated board; adding diacetyl tartaric acid monoglyceride with a proper proportion as an emulsifying dispersant, and also participating in crosslinking and curing; acetone is dissolved and is easy to volatilize, and almost no residue exists.
Preferably, the adhesive comprises 70 parts of pressure-sensitive adhesive solution, 17.5 parts of hydrogenated rosin resin, 23.5 parts of polyether polyurethane prepolymer, 17.2 parts of glycerol modified starch, 21.5 parts of formamide modified starch, 6.5 parts of methacryloxy silane, 3.7 parts of hexamethylene diisocyanate, 4 parts of diacetyl tartaric acid monoglyceride and 25 parts of acetone.
More preferably, the pressure-sensitive adhesive solution is prepared from the following raw materials in parts by weight: 30-40 parts of hydroxytetradecyl methacrylate, 20-30 parts of acrylamide, 25-35 parts of tripropylene glycol diacrylate, 30-35 parts of butyl acrylate, 95-125 parts of butanone, 2.5-3.5 parts of azobisisobutyronitrile and 1.2-1.6 parts of dodecyl mercaptan.
Most preferably, the pressure-sensitive adhesive solution is prepared from the following raw materials in parts by weight: 35 parts of hydroxytetradecyl methacrylate, 26 parts of acrylamide, 32 parts of tripropylene glycol diacrylate, 33 parts of butyl acrylate, 110 parts of butanone, 3 parts of azobisisobutyronitrile and 1.4 parts of dodecyl mercaptan.
Preferably, the preparation method of the pressure-sensitive adhesive solution is as follows:
s1, weighing the following components in parts by weight: hydroxytetradecyl methacrylate, acrylamide, tripropylene glycol diacrylate, butyl acrylate, butanone, azobisisobutyronitrile and dodecanethiol;
s2, performing prepolymerization reaction by using all hydroxytetradecyl methacrylate as soft monomers, all acrylamide as functional hard monomers, 1/3 of azobisisobutyronitrile as an initiator, half of butanone as a solvent and half of dodecanethiol as a molecular weight regulator to obtain a prepolymer of hydroxytetradecyl methacrylate and acrylamide; the temperature of the prepolymerization reaction is controlled to be 75-77 ℃, the prepolymerization time is 25-30 min, and N is adopted in the prepolymerization process2Protection;
the hydroxyl tetradecyl methacrylate is a soft monomer and is easier to participate in crosslinking and curing under the action of hexamethylene diisocyanate; and polymerizing to obtain a prepolymer of the hydroxytetradecyl methacrylate and the acrylamide, forming a block in a molecular chain of the final pressure-sensitive adhesive solution, and adjusting the hardness of the pressure-sensitive adhesive solution to ensure that the hardness of the pressure-sensitive adhesive solution is moderate and the distribution of the pressure-sensitive adhesive solution is uniform.
S3, taking all butyl acrylate as a soft monomer, all tripropylene glycol diacrylate as a functional hard monomer, 1/3 of azobisisobutyronitrile as an initiator, half of butanone as a solvent and half of dodecanethiol as a molecular weight regulator, and performing prepolymerization reaction to obtain a prepolymer of tripropylene glycol diacrylate and butyl acrylate; the temperature of the prepolymerization reaction is controlled to be 75-77 ℃, the prepolymerization time is 20-30 min, and N is adopted in the prepolymerization process2Protection;
tripropylene glycol diacrylate is a functional hard monomer and is more easily subjected to crosslinking and curing under the action of hexamethylene diisocyanate; and (3) obtaining a prepolymer of tripropylene glycol diacrylate and butyl acrylate after polymerization, forming a block in a molecular chain of the final pressure-sensitive adhesive solution, and adjusting the hardness to ensure that the hardness is moderate and the distribution is uniform.
S4, mixing the prepolymer of the hydroxyl tetradecyl methacrylate and the acrylamide obtained in the step S2, the tripropylene glycol diacrylate and the acrylic acid obtained in the step S3Mixing the butyl ester prepolymer, adding the rest 1/3 azodiisobutyronitrile, carrying out polymerization reaction, refluxing, controlling the polymerization reaction temperature at 78-79 ℃, controlling the polymerization time at 4-6 h, and adopting N in the polymerization process2And protecting to obtain the pressure-sensitive adhesive solution.
Preferably, the polyether polyurethane prepolymer comprises the following raw materials in parts by weight: 45-50 parts of aromatic diisocyanate and 50-55 parts of polyoxyethylene polyol with the number average molecular weight of 1500-2500.
Preferably, the hexamethylene diisocyanate is MFA-75X manufactured by Asahi Kasei corporation.
The invention also provides the high-performance environment-friendly corrugated board, and all the layers of the high-performance environment-friendly corrugated board are bonded by the environment-friendly modified starch adhesive for manufacturing the corrugated board.
The corrugated board has firm bonding among all layers, and the bonding agent has good ageing resistance and waterproof effect; not easy to absorb moisture and can well keep the mechanical property.
Preferably, the high-performance environment-friendly corrugated board sequentially comprises a first cardboard layer, a first nylon non-woven fabric layer, a corrugated core paper layer, a second nylon non-woven fabric layer and a second cardboard layer; the first nylon non-woven fabric layer and the second nylon non-woven fabric layer are both needle-punched non-woven fabrics.
The first nylon non-woven fabric layer and the second nylon non-woven fabric layer are introduced, so that the edge pressure strength and the puncture strength of the high-performance environment-friendly corrugated board are greatly improved, and the high performance is ensured.
The invention also provides a manufacturing method of the high-performance environment-friendly corrugated board, which comprises the following steps:
A. preparing an environment-friendly modified starch adhesive for manufacturing corrugated boards: respectively weighing pressure-sensitive adhesive solution, hydrogenated rosin resin, polyether type polyurethane prepolymer, glycerol modified starch, formamide modified starch, methacryloxy silane, hexamethylene diisocyanate, diacetyl tartaric acid monoglyceride and acetone according to parts by weight; firstly, uniformly stirring and mixing a pressure-sensitive adhesive solution, hydrogenated rosin resin, polyether type polyurethane prepolymer, glycerol modified starch, formamide modified starch, methacryloxy silane, diacetyl tartaric acid monoglyceride and acetone in a container, adding hexamethylene diisocyanate before use, and uniformly stirring and mixing to obtain the environment-friendly modified starch adhesive for manufacturing corrugated boards;
B. and uniformly coating the environment-friendly modified starch adhesive for manufacturing the corrugated board on the bonding surfaces among the first box paperboard layer, the first nylon non-woven fabric layer, the corrugated core paper layer, the second nylon non-woven fabric layer and the second box paperboard layer, sequentially pressing and bonding, standing at room temperature for 6-24 hours until the environment-friendly modified starch adhesive for manufacturing the corrugated board is completely crosslinked and cured, and thus obtaining the high-performance environment-friendly corrugated board.
Drawings
Fig. 1 is a schematic structural diagram of a high-performance environment-friendly corrugated board according to an embodiment of the present invention.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present patent.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods.
Example 1:
an environment-friendly modified starch adhesive for manufacturing corrugated boards is prepared from the following raw materials in parts by weight: 60-75 parts of pressure-sensitive adhesive solution, 15-20 parts of hydrogenated rosin resin, 20-27 parts of polyether polyurethane prepolymer, 15-19 parts of glycerol modified starch, 18-23 parts of formamide modified starch, 5-8 parts of methacryloxy silane, 2.5-4 parts of hexamethylene diisocyanate, 3-5 parts of diacetyl tartaric acid monoglyceride and 20-30 parts of acetone.
Preferably, the adhesive comprises 70 parts of pressure-sensitive adhesive solution, 17.5 parts of hydrogenated rosin resin, 23.5 parts of polyether polyurethane prepolymer, 17.2 parts of glycerol modified starch, 21.5 parts of formamide modified starch, 6.5 parts of methacryloxy silane, 3.7 parts of hexamethylene diisocyanate, 4 parts of diacetyl tartaric acid monoglyceride and 25 parts of acetone.
More preferably, the pressure-sensitive adhesive solution is prepared from the following raw materials in parts by weight: 30-40 parts of hydroxytetradecyl methacrylate, 20-30 parts of acrylamide, 25-35 parts of tripropylene glycol diacrylate, 30-35 parts of butyl acrylate, 95-125 parts of butanone, 2.5-3.5 parts of azobisisobutyronitrile and 1.2-1.6 parts of dodecyl mercaptan.
Most preferably, the pressure-sensitive adhesive solution is prepared from the following raw materials in parts by weight: 35 parts of hydroxytetradecyl methacrylate, 26 parts of acrylamide, 32 parts of tripropylene glycol diacrylate, 33 parts of butyl acrylate, 110 parts of butanone, 3 parts of azobisisobutyronitrile and 1.4 parts of dodecyl mercaptan.
Preferably, the preparation method of the pressure-sensitive adhesive solution is as follows:
s1, weighing the following components in parts by weight: hydroxytetradecyl methacrylate, acrylamide, tripropylene glycol diacrylate, butyl acrylate, butanone, azobisisobutyronitrile and dodecanethiol;
s2, performing prepolymerization reaction by using all hydroxytetradecyl methacrylate as soft monomers, all acrylamide as functional hard monomers, 1/3 of azobisisobutyronitrile as an initiator, half of butanone as a solvent and half of dodecanethiol as a molecular weight regulator to obtain a prepolymer of hydroxytetradecyl methacrylate and acrylamide; the temperature of the prepolymerization reaction is controlled to be 75-77 ℃, the prepolymerization time is 25-30 min, and N is adopted in the prepolymerization process2Protection;
s3, taking all butyl acrylate as a soft monomer, all tripropylene glycol diacrylate as a functional hard monomer, 1/3 of azobisisobutyronitrile as an initiator, half of butanone as a solvent and half of dodecanethiol as a molecular weight regulator, and performing prepolymerization reaction to obtain a prepolymer of tripropylene glycol diacrylate and butyl acrylate; the temperature of the prepolymerization reaction is controlled to be 75-77 ℃, the prepolymerization time is 20-30 min, and N is adopted in the prepolymerization process2Protection;
s4, prepolymer of the hydroxyl tetradecyl methacrylate and the acrylamide obtained in the step S2 and the stepMixing the tripropylene glycol diacrylate and butyl acrylate prepolymer obtained in the step S3, adding the rest 1/3 of azodiisobutyronitrile, carrying out polymerization reaction, refluxing, controlling the polymerization reaction temperature at 78-79 ℃, controlling the polymerization time at 4-6 h, and adopting N in the polymerization process2And protecting to obtain the pressure-sensitive adhesive solution.
Preferably, the polyether polyurethane prepolymer comprises the following raw materials in parts by weight: 45-50 parts of aromatic diisocyanate and 50-55 parts of polyoxyethylene polyol with the number average molecular weight of 1500-2500.
Preferably, the hexamethylene diisocyanate is MFA-75X manufactured by Asahi Kasei corporation.
As shown in fig. 1, the invention also provides a high-performance environment-friendly corrugated board, wherein all the layers of the high-performance environment-friendly corrugated board are bonded by the environment-friendly modified starch adhesive for manufacturing the corrugated board.
Preferably, the high-performance environment-friendly corrugated board sequentially comprises a first cardboard layer (1), a first nylon non-woven fabric layer (2), a corrugated core paper layer (3), a second nylon non-woven fabric layer (4) and a second cardboard layer (5); the first nylon non-woven fabric layer (2) and the second nylon non-woven fabric layer (4) are both needle-punched non-woven fabrics.
The invention also provides a manufacturing method of the high-performance environment-friendly corrugated board, which comprises the following steps:
A. preparing an environment-friendly modified starch adhesive for manufacturing corrugated boards: respectively weighing pressure-sensitive adhesive solution, hydrogenated rosin resin, polyether type polyurethane prepolymer, glycerol modified starch, formamide modified starch, methacryloxy silane, hexamethylene diisocyanate, diacetyl tartaric acid monoglyceride and acetone according to parts by weight; firstly, uniformly stirring and mixing a pressure-sensitive adhesive solution, hydrogenated rosin resin, polyether type polyurethane prepolymer, glycerol modified starch, formamide modified starch, methacryloxy silane, diacetyl tartaric acid monoglyceride and acetone in a container, adding hexamethylene diisocyanate before use, and uniformly stirring and mixing to obtain the environment-friendly modified starch adhesive for manufacturing corrugated boards;
B. uniformly coating the environment-friendly modified starch adhesive for manufacturing the corrugated board on the bonding surface between the first box paperboard layer (1), the first nylon non-woven fabric layer (2), the corrugated core paper layer (3), the second nylon non-woven fabric layer (4) and the second box paperboard layer (5), sequentially pressing and bonding, standing at room temperature for 6-24 hours until the environment-friendly modified starch adhesive for manufacturing the corrugated board is completely crosslinked and cured, and thus obtaining the high-performance environment-friendly corrugated board.
Example 2:
an environment-friendly modified starch adhesive for manufacturing corrugated boards is prepared from the following raw materials in parts by weight: 60 parts of pressure-sensitive adhesive solution, 15 parts of hydrogenated rosin resin, 20 parts of polyether type polyurethane prepolymer, 15 parts of glycerol modified starch, 18 parts of formamide modified starch, 5 parts of methacryloxy silane, 2.5 parts of hexamethylene diisocyanate, 3 parts of diacetyl tartaric acid monoglyceride and 20 parts of acetone.
Preferably, the pressure-sensitive adhesive solution is prepared from the following raw materials in parts by weight: 30 parts of hydroxytetradecyl methacrylate, 20 parts of acrylamide, 25 parts of tripropylene glycol diacrylate, 30 parts of butyl acrylate, 95 parts of butanone, 2.5 parts of azobisisobutyronitrile and 1.2 parts of dodecyl mercaptan.
In this embodiment, the preparation method of the pressure-sensitive adhesive solution is as follows:
s1, weighing the following components in parts by weight: hydroxytetradecyl methacrylate, acrylamide, tripropylene glycol diacrylate, butyl acrylate, butanone, azobisisobutyronitrile and dodecanethiol;
s2, performing prepolymerization reaction by using all hydroxytetradecyl methacrylate as soft monomers, all acrylamide as functional hard monomers, 1/3 of azobisisobutyronitrile as an initiator, half of butanone as a solvent and half of dodecanethiol as a molecular weight regulator to obtain a prepolymer of hydroxytetradecyl methacrylate and acrylamide; the temperature of the prepolymerization reaction is controlled at 75 ℃, the prepolymerization time is 30min, and N is adopted in the prepolymerization process2Protection;
s3, taking all butyl acrylate as soft monomer, all tripropylene glycol diacrylate as functional hard monomer, 1/3 azodiisobutyronitrile as initiator and half butanoneTaking solvent and half of dodecyl mercaptan as molecular weight regulator, and carrying out prepolymerization reaction to obtain a prepolymer of tripropylene glycol diacrylate and butyl acrylate; the temperature of the prepolymerization reaction is controlled at 75 ℃, the prepolymerization time is 30min, and N is adopted in the prepolymerization process2Protection;
s4, mixing the prepolymer of the hydroxytetradecyl methacrylate and the acrylamide obtained in the step S2 and the prepolymer of the tripropylene glycol diacrylate and the butyl acrylate obtained in the step S3, adding the rest 1/3 of azobisisobutyronitrile, carrying out polymerization reaction, refluxing, controlling the polymerization reaction temperature at 78 ℃, controlling the polymerization time at 6h, wherein N is adopted in the polymerization process2And protecting to obtain the pressure-sensitive adhesive solution.
In this embodiment, the polyether polyurethane prepolymer includes the following raw materials in parts by weight: 45 parts of aromatic diisocyanate and 50 parts of polyoxyethylene polyol with the number average molecular weight of 1500.
In this example, the hexamethylene diisocyanate was MFA-75X manufactured by Asahi Kasei corporation.
As shown in fig. 1, the present embodiment further provides a high-performance environment-friendly corrugated cardboard, wherein the layers of the high-performance environment-friendly corrugated cardboard are bonded by the environment-friendly modified starch adhesive for manufacturing corrugated cardboard.
In this embodiment, the high-performance environment-friendly corrugated board sequentially comprises a first cardboard layer (1), a first nylon nonwoven fabric layer (2), a corrugated medium paper layer (3), a second nylon nonwoven fabric layer (4) and a second cardboard layer (5); the first nylon non-woven fabric layer (2) and the second nylon non-woven fabric layer (4) are both needle-punched non-woven fabrics.
In this embodiment, the method for manufacturing the high-performance environment-friendly corrugated board includes the following steps:
A. preparing an environment-friendly modified starch adhesive for manufacturing corrugated boards: respectively weighing pressure-sensitive adhesive solution, hydrogenated rosin resin, polyether type polyurethane prepolymer, glycerol modified starch, formamide modified starch, methacryloxy silane, hexamethylene diisocyanate, diacetyl tartaric acid monoglyceride and acetone according to parts by weight; firstly, uniformly stirring and mixing a pressure-sensitive adhesive solution, hydrogenated rosin resin, polyether type polyurethane prepolymer, glycerol modified starch, formamide modified starch, methacryloxy silane, diacetyl tartaric acid monoglyceride and acetone in a container, adding hexamethylene diisocyanate before use, and uniformly stirring and mixing to obtain the environment-friendly modified starch adhesive for manufacturing corrugated boards;
B. uniformly coating the environment-friendly modified starch adhesive for manufacturing the corrugated board on the bonding surface between the first box paperboard layer (1), the first nylon non-woven fabric layer (2), the corrugated core paper layer (3), the second nylon non-woven fabric layer (4) and the second box paperboard layer (5), sequentially pressing and bonding, standing for 6 hours at room temperature until the environment-friendly modified starch adhesive for manufacturing the corrugated board is completely crosslinked and cured, and thus obtaining the high-performance environment-friendly corrugated board.
Example 3:
an environment-friendly modified starch adhesive for manufacturing corrugated boards is prepared from the following raw materials in parts by weight: 75 parts of pressure-sensitive adhesive solution, 20 parts of hydrogenated rosin resin, 27 parts of polyether type polyurethane prepolymer, 19 parts of glycerol modified starch, 23 parts of formamide modified starch, 8 parts of methacryloxy silane, 4 parts of hexamethylene diisocyanate, 5 parts of diacetyl tartaric acid monoglyceride and 30 parts of acetone.
In this embodiment, the pressure-sensitive adhesive solution is prepared from the following raw materials in parts by weight: 40 parts of hydroxytetradecyl methacrylate, 30 parts of acrylamide, 35 parts of tripropylene glycol diacrylate, 35 parts of butyl acrylate, 125 parts of butanone, 3.5 parts of azobisisobutyronitrile and 1.6 parts of dodecyl mercaptan.
In this embodiment, the preparation method of the pressure-sensitive adhesive solution is as follows:
s1, weighing the following components in parts by weight: hydroxytetradecyl methacrylate, acrylamide, tripropylene glycol diacrylate, butyl acrylate, butanone, azobisisobutyronitrile and dodecanethiol;
s2, taking all hydroxytetradecyl methacrylate as soft monomer, all acrylamide as functional hard monomer, 1/3 azodiisobutyronitrile as initiator, half butanone as solvent and half dodecanethiol as molecular weight regulator, and pre-treatingPerforming polymerization reaction to obtain a prepolymer of the hydroxytetradecyl methacrylate and the acrylamide; the prepolymerization temperature is controlled at 77 deg.C, the prepolymerization time is 25min, and N is adopted in the prepolymerization process2Protection;
s3, taking all butyl acrylate as a soft monomer, all tripropylene glycol diacrylate as a functional hard monomer, 1/3 of azobisisobutyronitrile as an initiator, half of butanone as a solvent and half of dodecanethiol as a molecular weight regulator, and performing prepolymerization reaction to obtain a prepolymer of tripropylene glycol diacrylate and butyl acrylate; the prepolymerization temperature is controlled at 77 deg.C, the prepolymerization time is 20min, and N is adopted in the prepolymerization process2Protection;
s4, mixing the prepolymer of the hydroxytetradecyl methacrylate and the acrylamide obtained in the step S2 and the prepolymer of the tripropylene glycol diacrylate and the butyl acrylate obtained in the step S3, adding the rest 1/3 of azobisisobutyronitrile, carrying out polymerization reaction, refluxing, controlling the polymerization reaction temperature at 79 ℃ and the polymerization time at 4h, wherein N is adopted in the polymerization process2And protecting to obtain the pressure-sensitive adhesive solution.
In this embodiment, the polyether polyurethane prepolymer includes the following raw materials in parts by weight: 50 parts of aromatic diisocyanate and 55 parts of polyoxyethylene polyol with the number average molecular weight of 2500.
In this example, the hexamethylene diisocyanate was MFA-75X manufactured by Asahi Kasei corporation.
As shown in fig. 1, the present embodiment further provides a high-performance environment-friendly corrugated cardboard, wherein the layers of the high-performance environment-friendly corrugated cardboard are bonded by the environment-friendly modified starch adhesive for manufacturing corrugated cardboard.
In this embodiment, the high-performance environment-friendly corrugated board sequentially comprises a first cardboard layer (1), a first nylon nonwoven fabric layer (2), a corrugated medium paper layer (3), a second nylon nonwoven fabric layer (4) and a second cardboard layer (5); the first nylon non-woven fabric layer (2) and the second nylon non-woven fabric layer (4) are both needle-punched non-woven fabrics.
In this embodiment, the method for manufacturing the high-performance environment-friendly corrugated board includes the following steps:
A. preparing an environment-friendly modified starch adhesive for manufacturing corrugated boards: respectively weighing pressure-sensitive adhesive solution, hydrogenated rosin resin, polyether type polyurethane prepolymer, glycerol modified starch, formamide modified starch, methacryloxy silane, hexamethylene diisocyanate, diacetyl tartaric acid monoglyceride and acetone according to parts by weight; firstly, uniformly stirring and mixing a pressure-sensitive adhesive solution, hydrogenated rosin resin, polyether type polyurethane prepolymer, glycerol modified starch, formamide modified starch, methacryloxy silane, diacetyl tartaric acid monoglyceride and acetone in a container, adding hexamethylene diisocyanate before use, and uniformly stirring and mixing to obtain the environment-friendly modified starch adhesive for manufacturing corrugated boards;
B. uniformly coating the environment-friendly modified starch adhesive for manufacturing the corrugated board on the bonding surface between the first box paperboard layer (1), the first nylon non-woven fabric layer (2), the corrugated core paper layer (3), the second nylon non-woven fabric layer (4) and the second box paperboard layer (5), sequentially pressing and bonding, standing for 24 hours at room temperature until the environment-friendly modified starch adhesive for manufacturing the corrugated board is completely crosslinked and cured, and thus obtaining the high-performance environment-friendly corrugated board.
Example 4:
an environment-friendly modified starch adhesive for manufacturing corrugated boards is prepared from the following raw materials in parts by weight: 70 parts of pressure-sensitive adhesive solution, 17.5 parts of hydrogenated rosin resin, 23.5 parts of polyether type polyurethane prepolymer, 17.2 parts of glycerol modified starch, 21.5 parts of formamide modified starch, 6.5 parts of methacryloxy silane, 3.7 parts of hexamethylene diisocyanate, 4 parts of diacetyl tartaric acid monoglyceride and 25 parts of acetone.
In this embodiment, the pressure-sensitive adhesive solution is prepared from the following raw materials in parts by weight: 35 parts of hydroxytetradecyl methacrylate, 26 parts of acrylamide, 32 parts of tripropylene glycol diacrylate, 33 parts of butyl acrylate, 110 parts of butanone, 3 parts of azobisisobutyronitrile and 1.4 parts of dodecyl mercaptan.
In this embodiment, the preparation method of the pressure-sensitive adhesive solution is as follows:
s1, weighing the following components in parts by weight: hydroxytetradecyl methacrylate, acrylamide, tripropylene glycol diacrylate, butyl acrylate, butanone, azobisisobutyronitrile and dodecanethiol;
s2, performing prepolymerization reaction by using all hydroxytetradecyl methacrylate as soft monomers, all acrylamide as functional hard monomers, 1/3 of azobisisobutyronitrile as an initiator, half of butanone as a solvent and half of dodecanethiol as a molecular weight regulator to obtain a prepolymer of hydroxytetradecyl methacrylate and acrylamide; the prepolymerization temperature is controlled at 76 deg.C, the prepolymerization time is 28min, and N is adopted in the prepolymerization process2Protection;
s3, taking all butyl acrylate as a soft monomer, all tripropylene glycol diacrylate as a functional hard monomer, 1/3 of azobisisobutyronitrile as an initiator, half of butanone as a solvent and half of dodecanethiol as a molecular weight regulator, and performing prepolymerization reaction to obtain a prepolymer of tripropylene glycol diacrylate and butyl acrylate; the temperature of the prepolymerization reaction is controlled at 76 ℃, the prepolymerization time is 26min, and N is adopted in the prepolymerization process2Protection;
s4, mixing the prepolymer of the hydroxytetradecyl methacrylate and the acrylamide obtained in the step S2 and the prepolymer of the tripropylene glycol diacrylate and the butyl acrylate obtained in the step S3, adding the rest 1/3 of azobisisobutyronitrile, carrying out polymerization reaction, refluxing, controlling the polymerization reaction temperature at 78.5 ℃, controlling the polymerization time at 5h, wherein N is adopted in the polymerization process2And protecting to obtain the pressure-sensitive adhesive solution.
In this embodiment, the polyether polyurethane prepolymer includes the following raw materials in parts by weight: 47.5 parts of aromatic diisocyanate and 52.5 parts of polyoxyethylene polyol with the number average molecular weight of 2000.
In this example, the hexamethylene diisocyanate was MFA-75X manufactured by Asahi Kasei corporation.
As shown in fig. 1, the present embodiment further provides a high-performance environment-friendly corrugated cardboard, wherein the layers of the high-performance environment-friendly corrugated cardboard are bonded by the environment-friendly modified starch adhesive for manufacturing corrugated cardboard.
In this embodiment, the high-performance environment-friendly corrugated board sequentially comprises a first cardboard layer (1), a first nylon nonwoven fabric layer (2), a corrugated medium paper layer (3), a second nylon nonwoven fabric layer (4) and a second cardboard layer (5); the first nylon non-woven fabric layer (2) and the second nylon non-woven fabric layer (4) are both needle-punched non-woven fabrics.
In this embodiment, the method for manufacturing the high-performance environment-friendly corrugated board includes the following steps:
A. preparing an environment-friendly modified starch adhesive for manufacturing corrugated boards: respectively weighing pressure-sensitive adhesive solution, hydrogenated rosin resin, polyether type polyurethane prepolymer, glycerol modified starch, formamide modified starch, methacryloxy silane, hexamethylene diisocyanate, diacetyl tartaric acid monoglyceride and acetone according to parts by weight; firstly, uniformly stirring and mixing a pressure-sensitive adhesive solution, hydrogenated rosin resin, polyether type polyurethane prepolymer, glycerol modified starch, formamide modified starch, methacryloxy silane, diacetyl tartaric acid monoglyceride and acetone in a container, adding hexamethylene diisocyanate before use, and uniformly stirring and mixing to obtain the environment-friendly modified starch adhesive for manufacturing corrugated boards;
B. uniformly coating the environment-friendly modified starch adhesive for manufacturing the corrugated board on the bonding surface between the first box paperboard layer (1), the first nylon non-woven fabric layer (2), the corrugated core paper layer (3), the second nylon non-woven fabric layer (4) and the second box paperboard layer (5), sequentially pressing and bonding, standing for 18 hours at room temperature until the environment-friendly modified starch adhesive for manufacturing the corrugated board is completely crosslinked and cured, and thus obtaining the high-performance environment-friendly corrugated board.
The following performance tests were performed on the environment-friendly modified starch adhesive and the common starch adhesive for manufacturing corrugated boards obtained in examples 2 to 4 of the present invention, and the test results are shown in table 1:
wherein, when the initial viscosity (ball), the holding viscosity (h) and the 180-degree adhesive force (N/25mm) are tested, the thickness of the coating of the environment-friendly modified starch adhesive for manufacturing the corrugated board is 50um, and a 50um aluminum foil is used as a back material for testing.
TABLE 1
As can be seen from the above table, the environment-friendly modified starch adhesive for manufacturing corrugated boards of the present invention has the following advantages compared with the common starch adhesive: the initial adhesion, the lasting adhesion and the 180-degree adhesion are obviously superior to those of the common starch adhesive, and the adhesive has higher adhesion and bonding strength and can meet the manufacturing requirements of high-performance environment-friendly corrugated boards.
In addition, through tests, the high-performance environment-friendly corrugated boards obtained by bonding the environment-friendly modified starch adhesive for manufacturing the corrugated boards obtained in the embodiments 2 to 4 cannot be peeled off among the layers, and peeling damage is caused by damage of materials of the bonding surfaces, so that the environment-friendly modified starch adhesive for manufacturing the corrugated boards obtained in the embodiments 2 to 4 has the advantages of large peeling force, high peeling strength, large adhesive force and high bonding strength.
The following high-performance environment-friendly corrugated boards obtained in examples 2 to 4 of the present invention and comparative examples: a corrugated board is obtained by bonding with a common starch adhesive (the structure is completely the same as that of the embodiment 4 except that the adhesive is different from that of the embodiment 4); the performance test was performed, and the test results are shown in table 2:
TABLE 2
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (9)
1. The environment-friendly modified starch adhesive for manufacturing the corrugated board is characterized by being prepared from the following raw materials in parts by weight: 60-75 parts of pressure-sensitive adhesive solution, 15-20 parts of hydrogenated rosin resin, 20-27 parts of polyether type polyurethane prepolymer, 15-19 parts of glycerol modified starch, 18-23 parts of formamide modified starch, 5-8 parts of methacryloxy silane, 2.5-4 parts of hexamethylene diisocyanate, 3-5 parts of diacetyl tartaric acid monoglyceride and 20-30 parts of acetone; the pressure-sensitive adhesive solution is prepared from the following raw materials in parts by weight: 30-40 parts of hydroxytetradecyl methacrylate, 20-30 parts of acrylamide, 25-35 parts of tripropylene glycol diacrylate, 30-35 parts of butyl acrylate, 95-125 parts of butanone, 2.5-3.5 parts of azobisisobutyronitrile and 1.2-1.6 parts of dodecyl mercaptan.
2. The environment-friendly modified starch adhesive for manufacturing corrugated boards according to claim 1, wherein the adhesive comprises 70 parts of a pressure-sensitive adhesive solution, 17.5 parts of hydrogenated rosin resin, 23.5 parts of a polyether polyurethane prepolymer, 17.2 parts of glycerol modified starch, 21.5 parts of formamide modified starch, 6.5 parts of methacryloxy silane, 3.7 parts of hexamethylene diisocyanate, 4 parts of diacetyl tartaric acid monoglyceride and 25 parts of acetone.
3. The environment-friendly modified starch adhesive for manufacturing corrugated boards as claimed in claim 2, wherein the pressure-sensitive adhesive solution is prepared from the following raw materials in parts by weight: 35 parts of hydroxytetradecyl methacrylate, 26 parts of acrylamide, 32 parts of tripropylene glycol diacrylate, 33 parts of butyl acrylate, 110 parts of butanone, 3 parts of azobisisobutyronitrile and 1.4 parts of dodecyl mercaptan.
4. The environment-friendly modified starch adhesive for manufacturing corrugated boards according to claim 1, wherein the manufacturing method of the pressure-sensitive adhesive solution comprises the following steps:
s1, weighing the following components in parts by weight: hydroxytetradecyl methacrylate, acrylamide, tripropylene glycol diacrylate, butyl acrylate, butanone, azobisisobutyronitrile and dodecanethiol;
s2 Total hydroxyl methacrylatePerforming prepolymerization reaction on tetra-ester which is a soft monomer, all acrylamide which is a functional hard monomer, 1/3 azodiisobutyronitrile which is an initiator, half butanone which is a solvent and half dodecanethiol which is a molecular weight regulator to obtain a prepolymer of hydroxytetradecyl methacrylate and acrylamide; the temperature of the prepolymerization reaction is controlled to be 75-77 ℃, the prepolymerization time is 25-30 min, and N is adopted in the prepolymerization process2Protection;
s3, taking all butyl acrylate as a soft monomer, all tripropylene glycol diacrylate as a functional hard monomer, 1/3 of azobisisobutyronitrile as an initiator, half of butanone as a solvent and half of dodecanethiol as a molecular weight regulator, and performing prepolymerization reaction to obtain a prepolymer of tripropylene glycol diacrylate and butyl acrylate; the temperature of the prepolymerization reaction is controlled to be 75-77 ℃, the prepolymerization time is 20-30 min, and N is adopted in the prepolymerization process2Protection;
s4, mixing the prepolymer of the hydroxytetradecyl methacrylate and the acrylamide obtained in the step S2 and the prepolymer of the tripropylene glycol diacrylate and the butyl acrylate obtained in the step S3, adding the rest 1/3 of azobisisobutyronitrile, carrying out polymerization reaction, refluxing, controlling the polymerization reaction temperature at 78-79 ℃, and the polymerization time at 4-6 h, wherein N is adopted in the polymerization process2And protecting to obtain the pressure-sensitive adhesive solution.
5. The environment-friendly modified starch adhesive for manufacturing corrugated boards as claimed in claim 4, wherein the polyether polyurethane prepolymer comprises the following raw materials in parts by weight: 45-50 parts of aromatic diisocyanate and 50-55 parts of polyoxyethylene polyol with the number average molecular weight of 1500-2500.
6. The environmentally friendly modified starch adhesive for corrugated cardboard production according to claim 5, wherein the hexamethylene diisocyanate is MFA-75X manufactured by Asahi Kasei corporation.
7. The high-performance environment-friendly corrugated cardboard is characterized in that all layers of the high-performance environment-friendly corrugated cardboard are bonded by the environment-friendly modified starch adhesive for manufacturing the corrugated cardboard as claimed in claim 5.
8. The high-performance environment-friendly corrugated cardboard as claimed in claim 7, which comprises a first cardboard layer (1), a first nylon nonwoven layer (2), a corrugated core paper layer (3), a second nylon nonwoven layer (4) and a second cardboard layer (5) in this order; the first nylon non-woven fabric layer (2) and the second nylon non-woven fabric layer (4) are both needle-punched non-woven fabrics.
9. A method for manufacturing high-performance environment-friendly corrugated cardboard as claimed in claim 8, comprising the steps of:
A. preparing an environment-friendly modified starch adhesive for manufacturing corrugated boards: respectively weighing pressure-sensitive adhesive solution, hydrogenated rosin resin, polyether type polyurethane prepolymer, glycerol modified starch, formamide modified starch, methacryloxy silane, hexamethylene diisocyanate, diacetyl tartaric acid monoglyceride and acetone according to parts by weight; firstly, uniformly stirring and mixing a pressure-sensitive adhesive solution, hydrogenated rosin resin, polyether type polyurethane prepolymer, glycerol modified starch, formamide modified starch, methacryloxy silane, diacetyl tartaric acid monoglyceride and acetone in a container, adding hexamethylene diisocyanate before use, and uniformly stirring and mixing to obtain the environment-friendly modified starch adhesive for manufacturing corrugated boards;
uniformly coating the environment-friendly modified starch adhesive for manufacturing the corrugated board on the bonding surface between the first box paperboard layer (1), the first nylon non-woven fabric layer (2), the corrugated core paper layer (3), the second nylon non-woven fabric layer (4) and the second box paperboard layer (5), sequentially pressing and bonding, standing at room temperature for 6-24 hours until the environment-friendly modified starch adhesive for manufacturing the corrugated board is completely crosslinked and cured, and thus obtaining the high-performance environment-friendly corrugated board.
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| CN112195008A (en) * | 2020-09-24 | 2021-01-08 | 晋江市顺力纸箱有限公司 | Environment-friendly adhesive, high-performance shock-absorbing environment-friendly carton and manufacturing method thereof |
| CN113150717A (en) * | 2021-04-09 | 2021-07-23 | 湖北银河彩印包装有限公司 | Preparation method of adhesive for corrugated board |
| CN113621322A (en) * | 2021-07-19 | 2021-11-09 | 宁波卓越印务有限公司 | Multifunctional adhesive label and preparation method thereof |
| CN114148635B (en) * | 2021-12-27 | 2022-07-01 | 广东赞誉防霉科技有限公司 | Degradable mildew-proof bag and application thereof |
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