阅读说明：本技术 一种复合瓦楞纸及其制备方法 (Composite corrugated paper and preparation method thereof ) 是由 刘伟锋 刘志锋 赖耀康 于 2020-11-23 设计创作，主要内容包括：本发明涉及瓦楞纸技术领域,具体涉及一种复合瓦楞纸及其制备方法,包括依次贴合的第一面纸、抗菌层、加强层、瓦楞芯纸、纤维层、防水层和第二面纸,加强层的上表面和纤维层的下表面均涂布有复合胶粘层,复合胶粘剂包括如下重量份的原料：改性醇酸树脂10-20份、偶氮引发剂0.1-2.0份、酚类化合物1-5份、去离子水10-15份、聚乙烯醇1-5份、稻壳纤维10-20份、环氧树脂20-30份、纳米SiO-21-3份、壳聚糖8-12份、增塑剂1-5份、固化剂0.1-3.0份、抗氧剂0.1-3.0份、柠檬酸0.1-1.0份、填料1-5份和淀粉15-25份。本发明复合瓦楞纸具有很好的强度和防霉抗菌效果,且使用寿命长。(The invention relates to the technical field of corrugated paper, in particular to composite corrugated paper and a preparation method thereof, wherein the composite corrugated paper comprises a first surface paper, an antibacterial layer, a reinforcing layer, corrugated core paper, a fiber layer, a waterproof layer and a second surface paper which are sequentially attached, composite adhesive layers are respectively coated on the upper surface of the reinforcing layer and the lower surface of the fiber layer, and the composite adhesive comprises the following raw materials in parts by weight: 10-20 parts of modified alkyd resin, 0.1-2.0 parts of azo initiator, 1-5 parts of phenolic compound, 10-15 parts of deionized water, 1-5 parts of polyvinyl alcohol, 10-20 parts of rice hull fiber, 20-30 parts of epoxy resin and nano SiO 2 1-3 parts of chitosan, 8-12 parts of plasticizer, 1-5 parts of curing agent, 0.1-3.0 parts of antioxidant, 0.1-1.0 part of citric acid, 1-5 parts of filler and 15-25 parts of starch. The composite corrugated paper has good strength, mould-proof and antibacterial effects and long service life.)

1. The utility model provides a compound corrugated paper, includes corrugated medium paper, its characterized in that: the corrugated medium paper comprises a corrugated medium paper, and is characterized by further comprising a reinforcing layer, an antibacterial layer, a first surface paper layer, a fiber layer, a waterproof layer and a second surface paper layer, wherein the reinforcing layer is attached to the lower surface of the corrugated medium paper, the antibacterial layer is attached to the lower surface of the reinforcing layer, the first surface paper layer is attached to the lower surface of the antibacterial layer, the fiber layer is attached to the upper surface of the corrugated medium paper, the waterproof layer is attached to the upper surface of the fiber layer, the second surface paper layer is attached to the upper surface of the waterproof layer, composite adhesive layers are coated on the upper surface of the reinforcing layer and the lower surface of the fiber:

10-20 parts of modified alkyd resin

0.1 to 2.0 portions of azo initiator

Phenolic compound 1-5 parts

10-15 parts of deionized water

1-5 parts of polyvinyl alcohol

10-20 parts of rice hull fiber

20-30 parts of epoxy resin

Nano SiO₂1-3 parts of

8-12 parts of chitosan

1-5 parts of plasticizer

0.1 to 3.0 portions of curing agent

0.1 to 3.0 portions of antioxidant

0.1 to 1.0 portion of citric acid

1-5 parts of filler

15-25 parts of starch.

2. A composite corrugated paper as claimed in claim 1, wherein: each part of the modified alkyd resin comprises the following raw materials in parts by weight:

1-5 parts of phthalic anhydride

5-10 parts of acrylic resin

Alkyd resin 25-35 parts

8-12 parts of pentaerythritol

1-3 parts of abietic acid

1-5 parts of castor oil

0.1-3 parts of zinc oxide.

3. A composite corrugated paper as claimed in claim 2, wherein: the modified alkyd resin is prepared by the following method:

s1, mixing acrylic resin and alkyd resin according to parts by weight, adding the mixture into a reaction device, heating to 120 ℃ at 100 ℃, stirring for 10-20min, adding zinc oxide, and continuously stirring for 20-40min to obtain a mixture A for later use;

s2, adding abietic acid, phthalic anhydride and castor oil into pentaerythritol according to parts by weight, heating to 60-90 ℃, continuously stirring at the speed of 350r/min for 20-40min, heating to 200 ℃ at 160-;

s3, adding the mixture B obtained in the step S2 into the mixture A obtained in the step S1, heating to 120 ℃, and continuously stirring for 20-40min to obtain the modified alkyd resin.

4. A composite corrugated paper as claimed in claim 1, wherein: each part of the azo initiator is at least one of azodiisopropyl imidazoline hydrochloride, azodiisobutyronitrile and azodiisoheptanonitrile.

5. A composite corrugated paper as claimed in claim 1, wherein: each part of the phenolic compound is at least one of phenol, cresol, resorcinol and cardanol.

6. A composite corrugated paper as claimed in claim 1, wherein: each part of the plasticizer is at least one of urea, di-n-octyl phthalate and glycerol.

7. A composite corrugated paper as claimed in claim 1, wherein: each part of the curing agent is at least one of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride.

8. A composite corrugated paper as claimed in claim 1, wherein: each part of the antioxidant is at least two of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 619, antioxidant 703, antioxidant BHT, antioxidant 2112 and antioxidant 703.

9. A composite corrugated paper according to any one of claims 1 to 8, wherein: the composite adhesive is prepared by the following steps:

e1, mixing the modified alkyd resin, the epoxy resin, the azo initiator, the phenolic compound and the nano SiO₂Adding the filler and the filler into a stirring device for mixing, heating to 80-100 ℃, and continuously stirring at the speed of 350-450r/min for 20-40min to obtain a mixture A for later use;

e2, mixing and fermenting the rice hull fiber, the polyvinyl alcohol, the citric acid and the deionized water according to the parts by weight, filtering, ball-milling, drying and carbonizing to obtain modified fiber for later use;

e3, adding starch, chitosan and an antioxidant into the modified fiber obtained in the step E2 according to the parts by weight, uniformly mixing and stirring, heating to 60-80 ℃, and continuously stirring for 20-40min to obtain a mixture B for later use;

e4, adding the mixture B obtained in the step E3, the plasticizer and the curing agent into the mixture A obtained in the step E1, heating to 60-80 ℃, stirring at the speed of 300-400r/min for 40-60min, and cooling to obtain the composite adhesive.

10. A method of making composite corrugated paper according to any one of claims 1 to 8, wherein: is prepared by the following steps:

uniformly coating the composite adhesive on the upper surface of the reinforcing layer and bonding the composite adhesive with the lower surface of the corrugated medium paper, and putting the corrugated medium paper into a drying device for drying to obtain a semi-finished product A;

coating the antibacterial layer on the lower surface of the semi-finished product A, and putting the semi-finished product A into a drying device for drying to obtain a semi-finished product B;

adhering the upper surface of the first facial tissue to the lower surface of the semi-finished product B through hot melt adhesive, and putting the semi-finished product B into a drying device for drying to obtain a semi-finished product C;

uniformly coating the composite adhesive on the lower surface of the fiber layer, bonding the composite adhesive with the upper surface of the semi-finished product C, and putting the semi-finished product C into a drying device for drying to obtain a semi-finished product D;

coating the waterproof layer on the upper surface of the semi-finished product D, and putting the semi-finished product D into a drying device for drying to obtain a semi-finished product E;

and adhering the lower surface of the second surface paper to the upper surface of the semi-finished product E through hot melt adhesive, flattening and compacting by using a plate press, and putting into a drying device for drying to obtain a finished product of the composite corrugated paper.

Technical Field

The invention relates to the technical field of corrugated paper, in particular to composite corrugated paper and a preparation method thereof.

Background

In various kinds of packing of industrial product, the corrugated paper has good resistance to deformation's characteristic, therefore the packing box that the corrugated paper pasted has the intensity of resistance to deformation, can effectually avoid the damage of corrugated paper to lead to the phenomenon that the object of splendid attire scatters on ground, therefore corrugated container board as most important, the most widely used packaging material, have that the quality is light, with low costs, easy processing, be convenient for store and transport advantages such as, this is that timber packing and metal package do not possess, and its prismatic structure such as U, V, UV has also improved the resistance to compression, the burst ability of carton greatly, but its not enough lies in: traditional corrugated container board is in the use, and its intensity and impact resistance are not high, do not have dampproofing and fungi-proofing effect moreover, and the tear strength is low, and easy layering for can take place the phenomenon of damage by the packing object in the transportation, and traditional corrugated container board life is too short.

Disclosure of Invention

In order to overcome the defects and shortcomings in the prior art, the invention aims to provide composite corrugated paper which adopts a multilayer structure of first surface paper, an antibacterial layer, a reinforcing layer, corrugated core paper, a fiber layer, a waterproof layer and second surface paper which are sequentially attached, so that the composite corrugated paper has good strength, impact resistance and mildew-proof and antibacterial effects, the fiber layer, the reinforcing layer and a composite adhesive provide double guarantee for the corrugated paper, and the corrugated paper has the advantages of good strength, impact resistance and difficulty in glue opening.

The invention also aims to provide a preparation method of the composite corrugated paper, which has the advantages of simple operation, convenient control, high production efficiency and low production cost.

The purpose of the invention is realized by the following technical scheme: the utility model provides a composite corrugated paper, includes corrugated core paper, still include laminate in the enhancement layer of corrugated core paper lower surface, laminate in the antibiotic layer of enhancement layer lower surface, laminate in the first surface paper layer of antibiotic layer lower surface, laminate in the fibrous layer of corrugated core paper upper surface, laminate in the waterproof layer of fibrous layer upper surface, and laminate in the second surface paper layer of waterproof layer upper surface, the upper surface of enhancement layer and the lower surface of fibrous layer all coat and have compound adhesive layer, compound adhesive layer is made through the coating of compound adhesive, compound adhesive includes the raw materials of following parts by weight:

the filler is at least one of silver-loaded zeolite powder, quartz sand, aluminum powder and zinc powder; the starch is preferably corn starch; the epoxy resin is SR-670 epoxy resin produced by Guangdong Shengtu new material science and technology limited.

The composite corrugated paper has a multilayer structure of the first surface paper, the antibacterial layer, the reinforcing layer, the corrugated medium paper, the fiber layer, the waterproof layer and the second surface paper which are sequentially attached, so that the composite corrugated paper has good strength, impact resistance and mildew-proof and antibacterial effects, the fiber layer, the reinforcing layer and the composite adhesive provide double guarantee for the corrugated paper, and the corrugated paper has the advantages of good strength, impact resistance and difficulty in glue opening. The epoxy resin adopted in the composite adhesive has a longer main chain and large intermolecular force, and can effectively improve the performances of hydrophobicity, strength, toughness, impact resistance and the like of the composite adhesive; the adopted chitosan has high deacetylation degree, the antibacterial activity of the chitosan is higher, the positive charge of the chitosan is increased due to the increase of the amino amount, so that the contact with the negative cell bodies of bacteria is improved, the growth of the bacteria is interfered, in addition, the cell walls of the bacteria are firstly separated from the cell membranes by the chitosan, then the cell membranes are destroyed, so that intracellular enzymes and nucleic acids are leaked, meanwhile, amino positive ions and high-molecular-weight chitosan are combined with the bacterial cells in the chitosan acid solution, the cell membrane structure is destroyed, so that the permeation of potassium ions and ATP is caused, and the antibacterial purpose is achieved; the added rice hull fiber has good bonding performance through a series of treatments, so that the bonding strength of the composite adhesive is further improved; the adopted polyvinyl alcohol is a biodegradable high polymer material, the molecular chain of the material contains hydroxyl groups and has good water solubility, the polyvinyl alcohol also has good film forming property, high crystallinity and high barrier property and excellent oil-resistant ester and solvent-resistant properties, the polyvinyl alcohol is used as a water-soluble synthetic adhesive, a solvent volatilizes when being heated, molecules of the polyvinyl alcohol are closely contacted to form a film with certain mechanical strength by virtue of the adsorption effect among the molecules, so that the function of the adhesive is exerted, the citric acid has a polycarboxyl structure and can be esterified with the hydroxyl groups on the starch or the polyvinyl alcohol at high temperature to form crosslinking, esterification and crosslinking in the material, the film forming property of the material can be improved, and the mechanical property of the material can also be improved; in addition, carboxyl on the citric acid and hydroxyl on the starch and the polyvinyl alcohol can form a strong hydrogen bond, so that the intermolecular interaction is increased, and the cured adhesive has good mechanical property and stability; the adopted filler can make up the defects that the interaction force among the molecules of the modified alkyd resin, the epoxy resin and the phenolic compound is weaker and the cohesive energy is low, improves the mechanical property of the prepared composite adhesive, plays a role in reinforcement, avoids the phenomenon that the composite adhesive lacks adhesive due to flowing in the curing process, can improve the thixotropic property of the adhesive solution so as to control the flowability of the composite adhesive, can adjust the curing speed, prolongs the service life and is beneficial to operation and construction.

Preferably, each part of the modified alkyd resin comprises the following raw materials in parts by weight:

the acrylic resin is acrylic resin BR-113 produced by Shenzhen Jitian chemical limited, and the alkyd resin is alkyd resin produced by Wu\38495in Henan province.

The modified alkyd resin is prepared by the following method:

s1, mixing acrylic resin and alkyd resin according to parts by weight, adding the mixture into a reaction device, heating to 120 ℃ at 100 ℃, stirring for 10-20min, adding zinc oxide, and continuously stirring for 20-40min to obtain a mixture A for later use;

s2, adding abietic acid, phthalic anhydride and castor oil into pentaerythritol according to parts by weight, heating to 60-90 ℃, continuously stirring at the speed of 350r/min for 20-40min, heating to 200 ℃ at 160-;

s3, adding the mixture B obtained in the step S2 into the mixture A obtained in the step S1, heating to 120 ℃, and continuously stirring for 20-40min to obtain the modified alkyd resin.

The modified alkyd resin is synthesized into carboxyl-terminated alkyd resin by selecting phthalic anhydride, castor oil and pentaerythritol, carboxyl on the alkyd resin is utilized to react with epoxy groups on the epoxy resin, the epoxy resin is introduced into the alkyd resin, and hydroxyl with high activity is generated at the same time. Epoxy resin is introduced into alkyd resin from a molecular layer to form a macromolecular structure, so that the alkyd resin has both an alkyd structure and an epoxy structure on a molecular chain, the advantages of corrosion resistance and high hardness of the epoxy resin are kept, the adhesive force and the toughness of the alkyd resin are strong, and the impact resistance and the heat resistance of the prepared composite adhesive coating film-forming material can be greatly improved through the modified alkyd resin; compared with the common paint, the composite adhesive prepared by introducing the abietic acid has the characteristics of strong adhesive force, good flexibility, excellent cohesive property, quick drying and the like. The modified alkyd resin prepared by the method has the advantages of strong adhesive force and strong toughness; the heating temperature in step S2 needs to be strictly controlled to be 100-120 ℃ during the preparation process, and if the temperature is too high, the mixing of the components of mixture a and mixture B is not favorable, and if the temperature is too low, the mixing of the components of mixture a and mixture B is also not favorable.

Preferably, each part of the azo initiator is at least one of azodiisopropyl imidazoline hydrochloride, azodiisobutyronitrile and azodiisoheptanonitrile; more preferably, each part of the azo initiator is a mixture of azobisisopropylimidazoline hydrochloride, azobisisobutyronitrile and azobisisoheptonitrile in a weight ratio of 0.8-1.2: 0.4-0.8: 0.1-0.5. Each part of the phenolic compound is one or more of phenol, cresol, resorcinol and cardanol.

The azodiisopropyl imidazoline hydrochloride in the azo initiator is a novel azo initiator, does not contain cyano, has nontoxic decomposition products, and can efficiently initiate polymerization at low temperature and low concentration to generate high linear and high molecular mass polymers; in addition, the amount of the initiator needs to be controlled to be 0.1-2.0 parts, if the amount of the initiator is small, the polymerization reaction is not sufficiently initiated, the monomer reaction is incomplete, the molecular weight of the copolymer is large, the viscosity of the composite adhesive is high, heat dissipation is not easy, gel is easy to generate, and the composite adhesive is unstable. In addition, the adopted phenolic compounds are used as a solvent and a degrading agent of the starch, so that the starch is degraded sufficiently and can participate in the synthesis process of the composite adhesive, the crosslinking density of reactants is high, and the strength and the water resistance of the obtained composite adhesive are greatly improved.

Preferably, each part of the plasticizer is at least one of urea, di-n-octyl phthalate and glycerol; more preferably, each part of the plasticizer is a mixture of urea, di-n-octyl phthalate and glycerol in a weight ratio of 0.8-1.2: 0.1-0.5: 0.4-0.8. Each part of the curing agent is at least one of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride; more preferably, each part of the curing agent is a mixture of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride in a weight ratio of 0.4-0.8: 0.1-0.5: 0.8-1.2.

The plasticizer adopted in the invention can ensure that the composite adhesive has good flexibility after being coated into a film. The aluminum ammonium sulfate is an acid salt and contains metal aluminum ions, an acid environment is provided in the curing process of the composite adhesive, and the aluminum ions and modified alkyd resin molecules have flocculation action to accelerate the curing of the composite adhesive; after magnesium sulfate is added, magnesium sulfate absorbs water to become hydrated magnesium sulfate, the crystallization of the hydrated magnesium sulfate accelerates the solidification of the modified alkyd resin, the crosslinking degree of the modified alkyd resin is increased, the adhesiveness and the water resistance of the composite adhesive are improved, and the bonding strength of the composite adhesive can be improved by cooperating with the excellent performances of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride

Preferably, each part of the antioxidant is at least two of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 619, antioxidant 703, antioxidant BHT, antioxidant 2112 and antioxidant 703; more preferably, each part of the antioxidant is a mixture of the antioxidant 1010, the antioxidant 168, the antioxidant 2112 and the antioxidant 703 according to the weight ratio of 0.1-0.5: 0.4-0.8: 0.8-1.2: 0.6-1.0.

The antioxidant 1010 adopted by the invention has excellent oxidation resistance on modified alkyd resin and epoxy resin, and the antioxidant 1010 can effectively prevent the thermal oxidation degradation of the composite adhesive in the long-term aging process, so that the service life of the composite adhesive is prolonged, and in addition, the antioxidant 1010 can be used together with the antioxidant 168 to have a synergistic effect; the antioxidant 168, the antioxidant 2112 and the antioxidant 703 are auxiliary antioxidants of the antioxidant 1010, are compounded with the main antioxidant 1010, have good synergistic effect, can effectively prevent the thermal degradation of the modified alkyd resin and the epoxy resin in basic injection molding, and provide extra long-term protection for the composite adhesive.

Preferably, the composite adhesive is prepared by the following steps:

e1, mixing the modified alkyd resin, the epoxy resin, the azo initiator, the phenolic compound and the nano SiO₂Adding the filler and the filler into a stirring device for mixing, heating to 80-100 ℃, and continuously stirring at the speed of 350-450r/min for 20-40min to obtain a mixture A for later use;

e2, mixing and fermenting the rice hull fiber, the polyvinyl alcohol, the citric acid and the deionized water according to the parts by weight, filtering, ball-milling, drying and carbonizing to obtain modified fiber for later use;

e3, adding starch, chitosan and an antioxidant into the modified fiber obtained in the step E2 according to the parts by weight, uniformly mixing and stirring, heating to 60-80 ℃, and continuously stirring for 20-40min to obtain a mixture B for later use;

e4, adding the mixture B obtained in the step E3, the plasticizer and the curing agent into the mixture A obtained in the step E1, heating to 60-80 ℃, stirring at the speed of 300-400r/min for 40-60min, and cooling to obtain the composite adhesive.

The composite adhesive prepared by the method has good performances such as hydrophobicity, strength, toughness, impact resistance and the like, and bonding performance. The stirring speed in the step E1 is strictly controlled to be 350-450r/min during the preparation process, if the stirring speed is too high, a large amount of foam is contained in the mixture A, the subsequent defoaming treatment is not facilitated, and if the stirring speed is low, the modified alkyd resin, the epoxy resin, the azo initiator, the phenolic compound and the nano SiO are caused to be modified₂The mixture is not fully mixed with the filler six, and then the mixture is mixed with the nano SiO₂The reinforcing effect of the filler on the modified alkyd resin and the epoxy resin is reduced; in addition, the heating temperature in step E3 needs to be controlled to 40-60 ℃, and if the heating temperature is too high, the composite action between starch and chitosan will be reduced, and if the heating temperature is too low, the reaction will not be sufficiently performed, the grafting action between starch and chitosan will be reduced, and the strength, toughness and film-forming property of the prepared composite adhesive will be reduced.

The invention also provides a preparation method of the composite corrugated paper, which comprises the following steps:

1) uniformly coating the composite adhesive on the upper surface of the reinforcing layer and bonding the composite adhesive with the lower surface of the corrugated medium paper, and putting the corrugated medium paper into a drying device for drying to obtain a semi-finished product A;

2) coating the antibacterial layer on the lower surface of the semi-finished product A, and putting the semi-finished product A into a drying device for drying to obtain a semi-finished product B:

3) adhering the upper surface of the first facial tissue to the lower surface of the semi-finished product B through hot melt adhesive, and putting the semi-finished product B into a drying device for drying to obtain a semi-finished product C;

4) uniformly coating the composite adhesive on the lower surface of the fiber layer, bonding the composite adhesive with the upper surface of the semi-finished product C, and putting the semi-finished product C into a drying device for drying to obtain a semi-finished product D;

5) coating the waterproof layer on the upper surface of the semi-finished product D, and putting the semi-finished product D into a drying device for drying to obtain a semi-finished product E:

6) and adhering the lower surface of the second surface paper to the upper surface of the semi-finished product E through hot melt adhesive, flattening and compacting by using a plate press, and putting into a drying device for drying to obtain a finished product of the composite corrugated paper.

The composite corrugated paper prepared by the steps has excellent strength, impact resistance and mildew-proof and antibacterial effects, the fiber layer, the reinforcing layer and the composite adhesive provide double guarantee for the corrugated paper, so that the corrugated paper has the advantages of good strength, impact resistance and difficulty in glue opening.

The invention has the beneficial effects that: the composite corrugated paper has a multilayer structure of the first surface paper, the antibacterial layer, the reinforcing layer, the corrugated medium paper, the fiber layer, the waterproof layer and the second surface paper which are sequentially attached, so that the composite corrugated paper has good strength, impact resistance and mildew-proof and antibacterial effects, the fiber layer, the reinforcing layer and the composite adhesive provide double guarantee for the corrugated paper, and the corrugated paper has the advantages of good strength, impact resistance and difficulty in glue opening.

The preparation method of the composite corrugated paper is simple to operate, convenient to control, high in production efficiency and low in production cost.

Drawings

Fig. 1 is a schematic cross-sectional structure of the composite corrugated paper of the present invention.

The reference signs are: 1-first surface paper, 2-antibacterial layer, 3-reinforcing layer, 4-composite adhesive layer, 5-corrugated medium paper, 6-fiber layer, 7-waterproof layer and 8-second surface paper.

Detailed Description

For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and the accompanying fig. 1, and the description of the embodiments is not intended to limit the present invention.

Example 1

The utility model provides a composite corrugated paper, includes corrugated medium paper 5, still include laminate in the enhancement layer 3 of 5 lower surfaces of corrugated medium paper, laminate in the antibiotic layer 2 of 3 lower surfaces of enhancement layer, laminate in 1 layer of first facial tissue of antibiotic layer 2 lower surface, laminate in fibrous layer 6 of 5 upper surfaces of corrugated medium paper, laminate in the waterproof layer 7 of 6 upper surfaces of fibrous layer, and laminate in the second facial tissue 8 layer of 7 upper surfaces of waterproof layer, the upper surface of enhancement layer 3 and the lower surface of fibrous layer 6 all coat has composite adhesive layer 4, composite adhesive layer 4 is made through the coating of composite adhesive, composite adhesive includes the raw materials of following parts by weight:

the filler is quartz sand; the starch is preferably corn starch; the epoxy resin is SR-670 epoxy resin produced by Guangdong Shengtu new material science and technology limited.

Each part of the modified alkyd resin comprises the following raw materials in parts by weight:

the acrylic resin is acrylic resin BR-113 produced by Shenzhen Jitian chemical limited, and the alkyd resin is alkyd resin produced by Wu\38495in Henan province.

The modified alkyd resin is prepared by the following method:

s1, mixing acrylic resin and alkyd resin according to parts by weight, adding the mixture into a reaction device, heating to 100 ℃, stirring for 10min, adding zinc oxide, and continuously stirring for 20min to obtain a mixture A for later use;

s2, adding abietic acid, phthalic anhydride and castor oil into pentaerythritol according to parts by weight, heating to 60 ℃, continuously stirring at the speed of 250r/min for 20min, heating to 160 ℃, and continuously stirring at the same speed for 40min to obtain a mixture B for later use;

s3, adding the mixture B obtained in the step S2 into the mixture A obtained in the step S1, heating to 100 ℃, and continuously stirring for 20min to obtain the modified alkyd resin.

Each part of the azo initiator is a mixture of azodiisopropyl imidazoline hydrochloride, azodiisobutyronitrile and azodiisoheptanonitrile according to the weight ratio of 0.8: 0.4: 0.1.

Each of the phenolic compounds is phenol.

Each part of the plasticizer is a mixture of urea, di-n-octyl phthalate and glycerol according to the weight ratio of 0.8: 0.1: 0.4.

Each part of the curing agent is a mixture of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride according to the weight ratio of 0.4: 0.1: 0.8.

Each part of the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant 2112 and an antioxidant 703 in a weight ratio of 0.1: 0.4: 0.8: 0.6.

The composite adhesive is prepared by the following steps:

f1, mixing the modified alkyd resin, the epoxy resin, the azo initiator, the phenolic compound and the nano SiO₂Adding the filler and the filler into a stirring device for mixing, heating to 80 ℃, and continuously stirring for 20min at the speed of 350r/min to obtain a mixture A for later use;

e2, mixing and fermenting the rice hull fiber, the polyvinyl alcohol, the citric acid and the deionized water according to the parts by weight, filtering, ball-milling, drying and carbonizing to obtain modified fiber for later use;

e3, adding starch, chitosan and an antioxidant into the modified fiber obtained in the step E2 according to the parts by weight, uniformly mixing and stirring, heating to 60 ℃, and continuously stirring for 20min to obtain a mixture B for later use;

e4, adding the mixture B obtained in the step E3, a plasticizer and a curing agent into the mixture A obtained in the step E1, heating to 60 ℃, stirring at the speed of 300r/min for 40min, and cooling to obtain the composite adhesive.

The preparation method of the composite corrugated paper comprises the following steps:

1) uniformly coating the composite adhesive on the upper surface of the reinforcing layer 3 and bonding the composite adhesive with the lower surface of the corrugated medium paper 5, and putting the corrugated medium paper into a drying device for drying to obtain a semi-finished product A;

2) coating the antibacterial layer 2 on the lower surface of the semi-finished product A, and putting the semi-finished product A into a drying device for drying to obtain a semi-finished product B;

3) adhering the upper surface of the first facial tissue 1 to the lower surface of the semi-finished product B through hot melt adhesive, and putting the semi-finished product B into a drying device for drying to obtain a semi-finished product C;

4) uniformly coating the composite adhesive on the lower surface of the fiber layer 6, bonding the composite adhesive with the upper surface of the semi-finished product C, and putting the semi-finished product C into a drying device for drying to obtain a semi-finished product D;

5) coating the waterproof layer 7 on the upper surface of the semi-finished product D, and putting the semi-finished product D into a drying device for drying to obtain a semi-finished product E;

6) and adhering the lower surface of the second surface paper 8 to the upper surface of the semi-finished product E through hot melt adhesive, flattening and compacting by using a plate press, and putting into a drying device for drying to obtain a finished product of the composite corrugated paper.

Example 2

The utility model provides a composite corrugated paper, includes corrugated medium paper 5, still include laminate in the enhancement layer 3 of 5 lower surfaces of corrugated medium paper, laminate in the antibiotic layer 2 of 3 lower surfaces of enhancement layer, laminate in 1 layer of first facial tissue of antibiotic layer 2 lower surface, laminate in fibrous layer 6 of 5 upper surfaces of corrugated medium paper, laminate in the waterproof layer 7 of 6 upper surfaces of fibrous layer, and laminate in the second facial tissue 8 layer of 7 upper surfaces of waterproof layer, the upper surface of enhancement layer 3 and the lower surface of fibrous layer 6 all coat has composite adhesive layer 4, composite adhesive layer 4 is made through the coating of composite adhesive, composite adhesive includes the raw materials of following parts by weight:

the filler is silver-loaded zeolite powder; the starch is preferably corn starch; the epoxy resin is SR-670 epoxy resin produced by Guangdong Shengtu new material science and technology limited.

Each part of the modified alkyd resin comprises the following raw materials in parts by weight:

the acrylic resin is acrylic resin BR-113 produced by Shenzhen Jitian chemical limited, and the alkyd resin is alkyd resin produced by Wu\38495in Henan province.

The modified alkyd resin is prepared by the following method:

s1, mixing acrylic resin and alkyd resin according to parts by weight, adding the mixture into a reaction device, heating to 105 ℃, stirring for 13min, adding zinc oxide, and continuously stirring for 25min to obtain a mixture A for later use;

s2, adding abietic acid, phthalic anhydride and castor oil into pentaerythritol according to parts by weight, heating to 68 ℃, continuously stirring at 275r/min for 25min, heating to 190 ℃, and continuously stirring at the same speed for 45min to obtain a mixture B for later use;

s3, adding the mixture B obtained in the step S2 into the mixture A obtained in the step S1, heating to 105 ℃, and continuously stirring for 25min to obtain the modified alkyd resin.

Each part of the azo initiator is a mixture of azodiisopropyl imidazoline hydrochloride, azodiisobutyronitrile and azodiisoheptanonitrile according to the weight ratio of 0.9: 0.5: 0.2.

The phenolic compound is cresol for each portion.

Each part of the plasticizer is a mixture of urea, di-n-octyl phthalate and glycerol according to the weight ratio of 0.9: 0.2: 0.5.

Each part of the curing agent is a mixture of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride according to the weight ratio of 0.5: 0.2: 0.9.

Each part of the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant 2112 and an antioxidant 703 in a weight ratio of 0.2: 0.5: 0.9: 0.7.

The composite adhesive is prepared by the following steps:

e1, mixing the modified alkyd resin, the epoxy resin, the azo initiator, the phenolic compound and the nano SiO₂Adding the filler and the filler into a stirring device for mixing, heating to 85 ℃, and continuously stirring at the speed of 375r/min for 25min to obtain a mixture A for later use;

e2, mixing and fermenting the rice hull fiber, the polyvinyl alcohol, the citric acid and the deionized water according to the parts by weight, filtering, ball-milling, drying and carbonizing to obtain modified fiber for later use;

e3, adding starch, chitosan and an antioxidant into the modified fiber obtained in the step E2 according to the parts by weight, uniformly mixing and stirring, heating to 65 ℃, and continuously stirring for 25min to obtain a mixture B for later use;

e4, adding the mixture B obtained in the step E3, a plasticizer and a curing agent into the mixture A obtained in the step E1, heating to 65 ℃, stirring at the speed of 325r/min for 45min, and cooling to obtain the composite adhesive.

The preparation method of the composite corrugated paper comprises the following steps:

1) uniformly coating the composite adhesive on the upper surface of the reinforcing layer 3 and bonding the composite adhesive with the lower surface of the corrugated medium paper 5, and putting the corrugated medium paper into a drying device for drying to obtain a semi-finished product A;

2) coating the antibacterial layer 2 on the lower surface of the semi-finished product A, and putting the semi-finished product A into a drying device for drying to obtain a semi-finished product B;

3) adhering the upper surface of the first facial tissue 1 to the lower surface of the semi-finished product B through hot melt adhesive, and putting the semi-finished product B into a drying device for drying to obtain a semi-finished product C;

4) uniformly coating the composite adhesive on the lower surface of the fiber layer 6, bonding the composite adhesive with the upper surface of the semi-finished product C, and putting the semi-finished product C into a drying device for drying to obtain a semi-finished product D;

5) coating the waterproof layer 7 on the upper surface of the semi-finished product D, and putting the semi-finished product D into a drying device for drying to obtain a semi-finished product E;

6) and adhering the lower surface of the second surface paper 8 to the upper surface of the semi-finished product E through hot melt adhesive, flattening and compacting by using a plate press, and putting into a drying device for drying to obtain a finished product of the composite corrugated paper.

Example 3

The utility model provides a composite corrugated paper, includes corrugated medium paper 5, still include laminate in the enhancement layer 3 of 5 lower surfaces of corrugated medium paper, laminate in the antibiotic layer 2 of 3 lower surfaces of enhancement layer, laminate in 1 layer of first facial tissue of antibiotic layer 2 lower surface, laminate in fibrous layer 6 of 5 upper surfaces of corrugated medium paper, laminate in the waterproof layer 7 of 6 upper surfaces of fibrous layer, and laminate in the second facial tissue 8 layer of 7 upper surfaces of waterproof layer, the upper surface of enhancement layer 3 and the lower surface of fibrous layer 6 all coat has composite adhesive layer 4, composite adhesive layer 4 is made through the coating of composite adhesive, composite adhesive includes the raw materials of following parts by weight:

the filler is aluminum powder; the starch is preferably corn starch; the epoxy resin is SR-670 epoxy resin produced by Guangdong Shengtu new material science and technology limited.

Each part of the modified alkyd resin comprises the following raw materials in parts by weight:

the acrylic resin is acrylic resin BR-113 produced by Shenzhen Jitian chemical limited, and the alkyd resin is alkyd resin produced by Wu\38495in Henan province.

The modified alkyd resin is prepared by the following method:

s1, mixing acrylic resin and alkyd resin according to parts by weight, adding the mixture into a reaction device, heating to 110 ℃, stirring for 15min, adding zinc oxide, and continuously stirring for 30min to obtain a mixture A for later use;

s2, adding abietic acid, phthalic anhydride and castor oil into pentaerythritol according to parts by weight, heating to 75 ℃, continuously stirring at the speed of 300r/min for 30min, heating to 180 ℃, and continuously stirring at the same speed for 50min to obtain a mixture B for later use;

s3, adding the mixture B obtained in the step S2 into the mixture A obtained in the step S1, heating to 110 ℃, and continuously stirring for 30min to obtain the modified alkyd resin.

Each part of the azo initiator is a mixture of azodiisopropyl imidazoline hydrochloride, azodiisobutyronitrile and azodiisoheptanonitrile according to the weight ratio of 1.0: 0.6: 0.3.

Each portion of the phenolic compound is resorcinol.

Each part of the plasticizer is a mixture of urea, di-n-octyl phthalate and glycerol according to the weight ratio of 1.0: 0.3: 0.6.

Each part of the curing agent is a mixture of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride according to the weight ratio of 0.6: 0.3: 1.0.

Each part of the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant 2112 and an antioxidant 703 according to the weight ratio of 0.3: 0.6: 1.0: 0.8.

The composite adhesive is prepared by the following steps:

e1, mixing the modified alkyd resin, the epoxy resin, the azo initiator, the phenolic compound and the nano SiO₂Adding the filler into a stirring device for mixingHeating to 90 ℃, and continuously stirring for 30min at the speed of 400r/min to obtain a mixture A for later use;

e2, mixing and fermenting the rice hull fiber, the polyvinyl alcohol, the citric acid and the deionized water according to the parts by weight, filtering, ball-milling, drying and carbonizing to obtain modified fiber for later use;

e3, adding starch, chitosan and an antioxidant into the modified fiber obtained in the step E2 according to the parts by weight, uniformly mixing and stirring, heating to 70 ℃, and continuously stirring for 30min to obtain a mixture B for later use;

e4, adding the mixture B obtained in the step E3, a plasticizer and a curing agent into the mixture A obtained in the step E1, heating to 70 ℃, stirring at the speed of 350r/min for 50min, and cooling to obtain the composite adhesive.

The preparation method of the composite corrugated paper comprises the following steps:

1) uniformly coating the composite adhesive on the upper surface of the reinforcing layer 3 and bonding the composite adhesive with the lower surface of the corrugated medium paper 5, and putting the corrugated medium paper into a drying device for drying to obtain a semi-finished product A;

2) coating the antibacterial layer 2 on the lower surface of the semi-finished product A, and putting the semi-finished product A into a drying device for drying to obtain a semi-finished product B;

3) adhering the upper surface of the first facial tissue 1 to the lower surface of the semi-finished product B through hot melt adhesive, and putting the semi-finished product B into a drying device for drying to obtain a semi-finished product C;

4) uniformly coating the composite adhesive on the lower surface of the fiber layer 6, bonding the composite adhesive with the upper surface of the semi-finished product C, and putting the semi-finished product C into a drying device for drying to obtain a semi-finished product D;

5) coating the waterproof layer 7 on the upper surface of the semi-finished product D, and putting the semi-finished product D into a drying device for drying to obtain a semi-finished product E;

6) and adhering the lower surface of the second surface paper 8 to the upper surface of the semi-finished product E through hot melt adhesive, flattening and compacting by using a plate press, and putting into a drying device for drying to obtain a finished product of the composite corrugated paper.

Example 4

The utility model provides a composite corrugated paper, includes corrugated medium paper 5, still include laminate in the enhancement layer 3 of 5 lower surfaces of corrugated medium paper, laminate in the antibiotic layer 2 of 3 lower surfaces of enhancement layer, laminate in 1 layer of first facial tissue of antibiotic layer 2 lower surface, laminate in fibrous layer 6 of 5 upper surfaces of corrugated medium paper, laminate in the waterproof layer 7 of 6 upper surfaces of fibrous layer, and laminate in the second facial tissue 8 layer of 7 upper surfaces of waterproof layer, the upper surface of enhancement layer 3 and the lower surface of fibrous layer 6 all coat has composite adhesive layer 4, composite adhesive layer 4 is made through the coating of composite adhesive, composite adhesive includes the raw materials of following parts by weight:

the filler is zinc powder; the starch is preferably corn starch; the epoxy resin is SR-670 epoxy resin produced by Guangdong Shengtu new material science and technology limited.

Each part of the modified alkyd resin comprises the following raw materials in parts by weight:

the acrylic resin is acrylic resin BR-113 produced by Shenzhen Jitian chemical limited, and the alkyd resin is alkyd resin produced by Wu\38495in Henan province.

The modified alkyd resin is prepared by the following method:

s1, mixing acrylic resin and alkyd resin according to parts by weight, adding the mixture into a reaction device, heating to 115 ℃, stirring for 18min, adding zinc oxide, and continuously stirring for 35min to obtain a mixture A for later use;

s2, adding abietic acid, phthalic anhydride and castor oil into pentaerythritol according to parts by weight, heating to 83 ℃, continuously stirring at the speed of 325r/min for 35min, heating to 190 ℃, and continuously stirring at the same speed for 55min to obtain a mixture B for later use;

s3, adding the mixture B obtained in the step S2 into the mixture A obtained in the step S1, heating to 115 ℃, and continuously stirring for 35min to obtain the modified alkyd resin.

Each part of the azo initiator is a mixture of azodiisopropyl imidazoline hydrochloride, azodiisobutyronitrile and azodiisoheptanonitrile according to the weight ratio of 1.1: 0.7: 0.4.

Each part of the phenolic compound is a mixture of resorcinol and cardanol according to the weight ratio of 1: 1.

Each part of the plasticizer is a mixture of urea, di-n-octyl phthalate and glycerol according to the weight ratio of 1.1: 0.4: 0.7.

Each part of the curing agent is a mixture of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride according to the weight ratio of 0.7: 0.4: 1.1.

Each part of the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant 2112 and an antioxidant 703 in a weight ratio of 0.4: 0.7: 1.1: 0.9.

The composite adhesive is prepared by the following steps:

e1, mixing the modified alkyd resin, the epoxy resin, the azo initiator, the phenolic compound and the nano SiO₂Adding the filler and the filler into a stirring device for mixing, heating to 95 ℃, and continuously stirring at the speed of 425r/min for 35min to obtain a mixture A for later use;

e2, mixing and fermenting the rice hull fiber, the polyvinyl alcohol, the citric acid and the deionized water according to the parts by weight, filtering, ball-milling, drying and carbonizing to obtain modified fiber for later use;

e3, adding starch, chitosan and an antioxidant into the modified fiber obtained in the step E2 according to the parts by weight, uniformly mixing and stirring, heating to 75 ℃, and continuously stirring for 35min to obtain a mixture B for later use;

e4, adding the mixture B obtained in the step E3, a plasticizer and a curing agent into the mixture A obtained in the step E1, heating to 75 ℃, stirring at the speed of 375r/min for 55min, and cooling to obtain the composite adhesive.

The preparation method of the composite corrugated paper comprises the following steps:

1) uniformly coating the composite adhesive on the upper surface of the reinforcing layer 3 and bonding the composite adhesive with the lower surface of the corrugated medium paper 5, and putting the corrugated medium paper into a drying device for drying to obtain a semi-finished product A;

2) coating the antibacterial layer 2 on the lower surface of the semi-finished product A, and putting the semi-finished product A into a drying device for drying to obtain a semi-finished product B;

3) adhering the upper surface of the first facial tissue 1 to the lower surface of the semi-finished product B through hot melt adhesive, and putting the semi-finished product B into a drying device for drying to obtain a semi-finished product C;

4) uniformly coating the composite adhesive on the lower surface of the fiber layer 6, bonding the composite adhesive with the upper surface of the semi-finished product C, and putting the semi-finished product C into a drying device for drying to obtain a semi-finished product D;

5) coating the waterproof layer 7 on the upper surface of the semi-finished product D, and putting the semi-finished product D into a drying device for drying to obtain a semi-finished product E;

6) and adhering the lower surface of the second surface paper 8 to the upper surface of the semi-finished product E through hot melt adhesive, flattening and compacting by using a plate press, and putting into a drying device for drying to obtain a finished product of the composite corrugated paper.

Example 5

The utility model provides a composite corrugated paper, includes corrugated medium paper 5, still include laminate in the enhancement layer 3 of 5 lower surfaces of corrugated medium paper, laminate in the antibiotic layer 2 of 3 lower surfaces of enhancement layer, laminate in 1 layer of first facial tissue of antibiotic layer 2 lower surface, laminate in fibrous layer 6 of 5 upper surfaces of corrugated medium paper, laminate in the waterproof layer 7 of 6 upper surfaces of fibrous layer, and laminate in the second facial tissue 8 layer of 7 upper surfaces of waterproof layer, the upper surface of enhancement layer 3 and the lower surface of fibrous layer 6 all coat has composite adhesive layer 4, composite adhesive layer 4 is made through the coating of composite adhesive, composite adhesive includes the raw materials of following parts by weight:

the filler is a mixture of silver-loaded zeolite powder and quartz sand according to the weight ratio of 0.5: 0.8; the starch is preferably corn starch; the epoxy resin is SR-670 epoxy resin produced by Guangdong Shengtu new material science and technology limited.

Each part of the modified alkyd resin comprises the following raw materials in parts by weight:

the acrylic resin is acrylic resin BR-113 produced by Shenzhen Jitian chemical limited, and the alkyd resin is alkyd resin produced by Wu\38495in Henan province.

The modified alkyd resin is prepared by the following method:

s1, mixing acrylic resin and alkyd resin according to parts by weight, adding the mixture into a reaction device, heating to 120 ℃, stirring for 20min, adding zinc oxide, and continuously stirring for 40min to obtain a mixture A for later use;

s2, adding abietic acid, phthalic anhydride and castor oil into pentaerythritol according to parts by weight, heating to 90 ℃, continuously stirring at the speed of 350r/min for 40min, heating to 200 ℃, and continuously stirring at the same speed for 60min to obtain a mixture B for later use;

s3, adding the mixture B obtained in the step S2 into the mixture A obtained in the step S1, heating to 120 ℃, and continuously stirring for 40min to obtain the modified alkyd resin.

Each part of the azo initiator is a mixture of azodiisopropyl imidazoline hydrochloride, azodiisobutyronitrile and azodiisoheptanonitrile according to the weight ratio of 1.2: 0.8: 0.5.

Each part of the phenolic compound is a mixture of phenol and cardanol according to the weight ratio of 1.2: 0.8.

Each part of the plasticizer is a mixture of urea, di-n-octyl phthalate and glycerol according to the weight ratio of 1.2: 0.5: 0.8.

Each part of the curing agent is a mixture of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride according to the weight ratio of 0.8: 0.5: 1.2.

Each part of the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant 2112 and an antioxidant 703 according to the weight ratio of 0.5: 0.8: 1.2: 1.0.

The composite adhesive is prepared by the following steps:

e1, mixing the modified alkyd resin, the epoxy resin, the azo initiator, the phenolic compound and the nano SiO₂Adding the filler and the filler into a stirring device for mixing, heating to 100 ℃, and continuously stirring at the speed of 450r/min for 40min to obtain a mixture A for later use;

e2, mixing and fermenting the rice hull fiber, the polyvinyl alcohol, the citric acid and the deionized water according to the parts by weight, filtering, ball-milling, drying and carbonizing to obtain modified fiber for later use;

e3, adding starch, chitosan and an antioxidant into the modified fiber obtained in the step E2 according to the parts by weight, uniformly mixing and stirring, heating to 80 ℃, and continuously stirring for 40min to obtain a mixture B for later use;

e4, adding the mixture B obtained in the step E3, a plasticizer and a curing agent into the mixture A obtained in the step E1, heating to 80 ℃, stirring at the speed of 400r/min for 60min, and cooling to obtain the composite adhesive.

The preparation method of the composite corrugated paper comprises the following steps:

1) uniformly coating the composite adhesive on the upper surface of the reinforcing layer 3 and bonding the composite adhesive with the lower surface of the corrugated medium paper 5, and putting the corrugated medium paper into a drying device for drying to obtain a semi-finished product A;

2) coating the antibacterial layer 2 on the lower surface of the semi-finished product A, and putting the semi-finished product A into a drying device for drying to obtain a semi-finished product B;

3) adhering the upper surface of the first facial tissue 1 to the lower surface of the semi-finished product B through hot melt adhesive, and putting the semi-finished product B into a drying device for drying to obtain a semi-finished product C;

4) uniformly coating the composite adhesive on the lower surface of the fiber layer 6, bonding the composite adhesive with the upper surface of the semi-finished product C, and putting the semi-finished product C into a drying device for drying to obtain a semi-finished product D;

5) coating the waterproof layer 7 on the upper surface of the semi-finished product D, and putting the semi-finished product D into a drying device for drying to obtain a semi-finished product E;

6) and adhering the lower surface of the second surface paper 8 to the upper surface of the semi-finished product E through hot melt adhesive, flattening and compacting by using a plate press, and putting into a drying device for drying to obtain a finished product of the composite corrugated paper.

Comparative example 1

The utility model provides a composite corrugated paper, includes corrugated medium paper 5, still include laminate in the enhancement layer 3 of 5 lower surfaces of corrugated medium paper, laminate in the antibiotic layer 2 of 3 lower surfaces of enhancement layer, laminate in 1 layer of first facial tissue of antibiotic layer 2 lower surface, laminate in fibrous layer 6 of 5 upper surfaces of corrugated medium paper, laminate in the waterproof layer 7 of 6 upper surfaces of fibrous layer, and laminate in the second facial tissue 8 layer of 7 upper surfaces of waterproof layer, the upper surface of enhancement layer 3 and the lower surface of fibrous layer 6 all coat has composite adhesive layer 4, composite adhesive layer 4 is made through the coating of composite adhesive, composite adhesive includes the raw materials of following parts by weight:

the filler is quartz sand; the starch is preferably corn starch; the epoxy resin is SR-670 epoxy resin produced by Guangdong Shengtu new material science and technology limited.

Each part of the azo initiator is a mixture of azodiisopropyl imidazoline hydrochloride, azodiisobutyronitrile and azodiisoheptanonitrile according to the weight ratio of 0.8: 0.4: 0.1.

Each of the phenolic compounds is phenol.

Each part of the plasticizer is a mixture of urea, di-n-octyl phthalate and glycerol according to the weight ratio of 0.8: 0.1: 0.4.

Each part of the curing agent is a mixture of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride according to the weight ratio of 0.4: 0.1: 0.8.

Each part of the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant 2112 and an antioxidant 703 in a weight ratio of 0.1: 0.4: 0.8: 0.6.

The composite adhesive is prepared by the following steps:

e1, mixing the modified alkyd resin, the epoxy resin, the azo initiator, the phenolic compound and the nano SiO₂Adding the filler and the filler into a stirring device for mixing, heating to 80 ℃, and continuously stirring for 20min at the speed of 350r/min to obtain a mixture A for later use;

e2, mixing and fermenting the rice hull fiber, the polyvinyl alcohol, the citric acid and the deionized water according to the parts by weight, filtering, ball-milling, drying and carbonizing to obtain modified fiber for later use;

e3, adding starch, chitosan and an antioxidant into the modified fiber obtained in the step E2 according to the parts by weight, uniformly mixing and stirring, heating to 60 ℃, and continuously stirring for 20min to obtain a mixture B for later use;

e4, adding the mixture B obtained in the step E3, a plasticizer and a curing agent into the mixture A obtained in the step E1, heating to 60 ℃, stirring at the speed of 300r/min for 40min, and cooling to obtain the composite adhesive.

The preparation method of the composite corrugated paper comprises the following steps:

1) uniformly coating the composite adhesive on the upper surface of the reinforcing layer 3 and bonding the composite adhesive with the lower surface of the corrugated medium paper 5, and putting the corrugated medium paper into a drying device for drying to obtain a semi-finished product A;

2) coating the antibacterial layer 2 on the lower surface of the semi-finished product A, and putting the semi-finished product A into a drying device for drying to obtain a semi-finished product B;

3) adhering the upper surface of the first facial tissue 1 to the lower surface of the semi-finished product B through hot melt adhesive, and putting the semi-finished product B into a drying device for drying to obtain a semi-finished product C;

4) uniformly coating the composite adhesive on the lower surface of the fiber layer 6, bonding the composite adhesive with the upper surface of the semi-finished product C, and putting the semi-finished product C into a drying device for drying to obtain a semi-finished product D;

5) coating the waterproof layer 7 on the upper surface of the semi-finished product D, and putting the semi-finished product D into a drying device for drying to obtain a semi-finished product E;

6) and adhering the lower surface of the second surface paper 8 to the upper surface of the semi-finished product E through hot melt adhesive, flattening and compacting by using a plate press, and putting into a drying device for drying to obtain a finished product of the composite corrugated paper.

Comparative example 2

The utility model provides a composite corrugated paper, includes corrugated medium paper 5, still include laminate in the enhancement layer 3 of 5 lower surfaces of corrugated medium paper, laminate in the antibiotic layer 2 of 3 lower surfaces of enhancement layer, laminate in 1 layer of first facial tissue of antibiotic layer 2 lower surface, laminate in fibrous layer 6 of 5 upper surfaces of corrugated medium paper, laminate in the waterproof layer 7 of 6 upper surfaces of fibrous layer, and laminate in the second facial tissue 8 layer of 7 upper surfaces of waterproof layer, the upper surface of enhancement layer 3 and the lower surface of fibrous layer 6 all coat has composite adhesive layer 4, composite adhesive layer 4 is made through the coating of composite adhesive, composite adhesive includes the raw materials of following parts by weight:

the filler is aluminum powder; the starch is preferably corn starch; the epoxy resin is SR-670 epoxy resin produced by Guangdong Shengtu new material science and technology limited.

Each part of the modified alkyd resin comprises the following raw materials in parts by weight:

the acrylic resin is acrylic resin BR-113 produced by Shenzhen Jitian chemical limited, and the alkyd resin is alkyd resin produced by Wu\38495in Henan province.

The modified alkyd resin is prepared by the following method:

s1, mixing acrylic resin and alkyd resin according to parts by weight, adding the mixture into a reaction device, heating to 110 ℃, stirring for 15min, adding zinc oxide, and continuously stirring for 30min to obtain a mixture A for later use;

s2, adding abietic acid, phthalic anhydride and castor oil into pentaerythritol according to parts by weight, heating to 75 ℃, continuously stirring at the speed of 300r/min for 30min, heating to 180 ℃, and continuously stirring at the same speed for 50min to obtain a mixture B for later use;

s3, adding the mixture B obtained in the step S2 into the mixture A obtained in the step S1, heating to 110 ℃, and continuously stirring for 30min to obtain the modified alkyd resin.

Each part of the azo initiator is a mixture of azodiisopropyl imidazoline hydrochloride, azodiisobutyronitrile and azodiisoheptanonitrile according to the weight ratio of 1.0: 0.6: 0.3.

Each part of the plasticizer is a mixture of urea, di-n-octyl phthalate and glycerol according to the weight ratio of 1.0: 0.3: 0.6.

Each part of the curing agent is a mixture of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride according to the weight ratio of 0.6: 0.3: 1.0.

Each part of the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant 2112 and an antioxidant 703 according to the weight ratio of 0.3: 0.6: 1.0: 0.8.

The composite adhesive is prepared by the following steps:

e1, mixing the modified alkyd resin, the epoxy resin, the azo initiator and the nano SiO₂Adding the filler and the filler into a stirring device for mixing, heating to 90 ℃, and continuously stirring for 30min at the speed of 400r/min to obtain a mixture A for later use;

e2, mixing and stirring uniformly polyvinyl alcohol, citric acid, deionized water, starch and chitosan according to the parts by weight, heating to 70 ℃, and continuously stirring for 30min to obtain a mixture B for later use;

e3, adding the mixture B obtained in the step E2, a plasticizer and a curing agent into the mixture A obtained in the step E1, heating to 70 ℃, stirring at the speed of 350r/min for 50min, and cooling to obtain the composite adhesive.

The preparation method of the composite corrugated paper comprises the following steps:

1) uniformly coating the composite adhesive on the upper surface of the reinforcing layer 3 and bonding the composite adhesive with the lower surface of the corrugated medium paper 5, and putting the corrugated medium paper into a drying device for drying to obtain a semi-finished product A;

2) coating the antibacterial layer 2 on the lower surface of the semi-finished product A, and putting the semi-finished product A into a drying device for drying to obtain a semi-finished product B;

3) adhering the upper surface of the first facial tissue 1 to the lower surface of the semi-finished product B through hot melt adhesive, and putting the semi-finished product B into a drying device for drying to obtain a semi-finished product C;

4) uniformly coating the composite adhesive on the lower surface of the fiber layer 6, bonding the composite adhesive with the upper surface of the semi-finished product C, and putting the semi-finished product C into a drying device for drying to obtain a semi-finished product D;

5) coating the waterproof layer 7 on the upper surface of the semi-finished product D, and putting the semi-finished product D into a drying device for drying to obtain a semi-finished product E;

6) and adhering the lower surface of the second surface paper 8 to the upper surface of the semi-finished product E through hot melt adhesive, flattening and compacting by using a plate press, and putting into a drying device for drying to obtain a finished product of the composite corrugated paper.

Comparative example 3

The utility model provides a composite corrugated paper, includes corrugated medium paper 5, still include laminate in the enhancement layer 3 of 5 lower surfaces of corrugated medium paper, laminate in the antibiotic layer 2 of 3 lower surfaces of enhancement layer, laminate in 1 layer of first facial tissue of antibiotic layer 2 lower surface, laminate in fibrous layer 6 of 5 upper surfaces of corrugated medium paper, laminate in the waterproof layer 7 of 6 upper surfaces of fibrous layer, and laminate in the second facial tissue 8 layer of 7 upper surfaces of waterproof layer, the upper surface of enhancement layer 3 and the lower surface of fibrous layer 6 all coat has composite adhesive layer 4, composite adhesive layer 4 is made through the coating of composite adhesive, composite adhesive includes the raw materials of following parts by weight:

the starch is preferably corn starch; the epoxy resin is SR-670 epoxy resin produced by Guangdong Shengtu new material science and technology limited.

Each part of the modified alkyd resin comprises the following raw materials in parts by weight:

the acrylic resin is acrylic resin BR-113 produced by Shenzhen Jitian chemical limited, and the alkyd resin is alkyd resin produced by Wu\38495in Henan province.

The modified alkyd resin is prepared by the following method:

s1, mixing acrylic resin and alkyd resin according to parts by weight, adding the mixture into a reaction device, heating to 120 ℃, stirring for 20min, adding zinc oxide, and continuously stirring for 40min to obtain a mixture A for later use;

s2, adding abietic acid, phthalic anhydride and castor oil into pentaerythritol according to parts by weight, heating to 90 ℃, continuously stirring at the speed of 350r/min for 40min, heating to 200 ℃, and continuously stirring at the same speed for 60min to obtain a mixture B for later use;

s3, adding the mixture B obtained in the step S2 into the mixture A obtained in the step S1, heating to 120 ℃, and continuously stirring for 40min to obtain the modified alkyd resin.

Each part of the azo initiator is a mixture of azodiisopropyl imidazoline hydrochloride, azodiisobutyronitrile and azodiisoheptanonitrile according to the weight ratio of 1.2: 0.8: 0.5.

Each part of the phenolic compound is a mixture of phenol and cardanol according to the weight ratio of 1.2: 0.8.

Each part of the plasticizer is a mixture of urea, di-n-octyl phthalate and glycerol according to the weight ratio of 1.2: 0.5: 0.8.

Each part of the curing agent is a mixture of aluminum ammonium sulfate, magnesium sulfate and ammonium chloride according to the weight ratio of 0.8: 0.5: 1.2.

Each part of the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant 2112 and an antioxidant 703 according to the weight ratio of 0.5: 0.8: 1.2: 1.0.

The composite adhesive is prepared by the following steps:

e1, mixing the modified alkyd resin, the epoxy resin, the azo initiator, the phenolic compound and the nano SiO₂Adding the filler and the filler into a stirring device for mixing, heating to 100 ℃, and continuously stirring at the speed of 450r/min for 40min to obtain a mixture A for later use;

e2, mixing and fermenting the rice hull fiber, the polyvinyl alcohol, the citric acid and the deionized water according to the parts by weight, filtering, ball-milling, drying and carbonizing to obtain modified fiber for later use;

e3, adding starch, chitosan and an antioxidant into the modified fiber obtained in the step E2 according to the parts by weight, uniformly mixing and stirring, heating to 80 ℃, and continuously stirring for 40min to obtain a mixture B for later use;

e4, adding the mixture B obtained in the step E3, a plasticizer and a curing agent into the mixture A obtained in the step E1, heating to 80 ℃, stirring at the speed of 400r/min for 60min, and cooling to obtain the composite adhesive.

The preparation method of the composite corrugated paper comprises the following steps:

1) uniformly coating the composite adhesive on the upper surface of the reinforcing layer 3 and bonding the composite adhesive with the lower surface of the corrugated medium paper 5, and putting the corrugated medium paper into a drying device for drying to obtain a semi-finished product A;

2) coating the antibacterial layer 2 on the lower surface of the semi-finished product A, and putting the semi-finished product A into a drying device for drying to obtain a semi-finished product B;

3) adhering the upper surface of the first facial tissue 1 to the lower surface of the semi-finished product B through hot melt adhesive, and putting the semi-finished product B into a drying device for drying to obtain a semi-finished product C;

4) uniformly coating the composite adhesive on the lower surface of the fiber layer 6, bonding the composite adhesive with the upper surface of the semi-finished product C, and putting the semi-finished product C into a drying device for drying to obtain a semi-finished product D;

5) coating the waterproof layer 7 on the upper surface of the semi-finished product D, and putting the semi-finished product D into a drying device for drying to obtain a semi-finished product E;

6) and adhering the lower surface of the second surface paper 8 to the upper surface of the semi-finished product E through hot melt adhesive, flattening and compacting by using a plate press, and putting into a drying device for drying to obtain a finished product of the composite corrugated paper.

The composite corrugated papers obtained in examples 1 to 5 and comparative examples 1 to 3 were tested for antibacterial ratio, water vapor transmission rate, moisture regain test and water absorption rate, and the results are shown in the following table:

the antibacterial property test is based on JISZ 2801: 2010 antimicrobial properties were tested.

Testing the water vapor transmission rate: test standards: astm f 372; test equipment: an automatic multi-head moisture permeability tester; test ring

Environment: at 37 ℃ and RH 100%.

And (3) moisture regain testing: the method comprises the following steps: the composite corrugated paper is placed for 24 hours at the high humidity of 40 ℃ and 95 percent of humidity, the moisture regain of the paper product is measured by using a DM200P nondestructive induction type paper moisture meter, the moisture content of the composite corrugated paper which implements 1-5 and the composite corrugated paper which implements 1-3 is measured respectively, the instrument adopts the high-frequency principle, the simple contact instantaneous reading can be realized, and the moisture regain of the paper can be obtained. And then the tensile strength meter and the tearing strength meter are used for detecting the paper indexes.

As can be seen from the above table, the composite corrugated paper prepared in embodiments 1 to 5 of the present invention has excellent properties, the moisture regain test and the water absorption rate of the composite corrugated paper are significantly reduced, and the antibacterial rate and the edge pressure strength are significantly improved, such that the prepared composite corrugated paper has good strength, anti-mold and antibacterial effects, and also has the advantages of super-strong impact resistance, good mechanical properties, long service life, and good environmental protection properties.

Compared with the embodiment 1, in the comparative example 1, the alkyd resin is not modified when the composite adhesive for the composite corrugated paper is prepared, and various physical property tests are carried out on the prepared composite corrugated paper, and analysis shows that the water vapor transmission rate and the water absorption rate of the composite corrugated paper are slightly increased, and the pressure intensity and the antibacterial rate are reduced; the modified alkyd resin is added when the composite adhesive is prepared, so that the prepared composite corrugated paper has good strength, mildew-proof antibacterial effect, moisture resistance, strength, mildew-proof antibacterial effect, long service life, good environmental protection performance and suitability for large-scale production.

Compared with the embodiment 3, in the comparative example 2, the rice hull fiber and the phenolic compound are not added when the composite adhesive for the composite corrugated paper is prepared, and the physical property tests of the prepared composite corrugated paper show that the water vapor transmission rate of the composite corrugated paper is slightly increased, and the pressure intensity and the antibacterial rate are reduced; the rice hull fiber and the phenolic compound are added during the preparation of the composite adhesive, so that the prepared composite corrugated paper has good strength, mildew-proof and antibacterial effects, moisture resistance, strength and mildew-proof and antibacterial effects, and is long in service life, good in environmental protection performance and suitable for large-scale production.

Compared with the embodiment 5, in the comparative example 3, no filler or epoxy resin is added when the composite adhesive for composite corrugated paper is prepared, and the prepared composite corrugated paper is subjected to various physical property tests, and analysis shows that the water vapor transmission rate of the composite corrugated paper is slightly increased, and the pressure intensity and the antibacterial rate are obviously reduced; the filler and the epoxy resin are added when the composite adhesive is prepared, so that the prepared composite corrugated paper has good strength, mildew-proof antibacterial effect, moisture resistance, strength, mildew-proof antibacterial effect, long service life, good environmental protection performance and suitability for large-scale production.

The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.