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CN115975558B - Laminating adhesive for INS film and laminating method thereof - Google Patents

Laminating adhesive for INS film and laminating method thereof Download PDF

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Publication number
CN115975558B
CN115975558B CN202310031955.2A CN202310031955A CN115975558B CN 115975558 B CN115975558 B CN 115975558B CN 202310031955 A CN202310031955 A CN 202310031955A CN 115975558 B CN115975558 B CN 115975558B
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component
laminating adhesive
parts
rubber
laminating
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CN115975558A (en
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黄德林
殷廷
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Jinmei Xingcan New Materials Anhui Co ltd
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Jinmei Xingcan New Materials Anhui Co ltd
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy

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Abstract

The application provides laminating adhesive for an INS film and a laminating method thereof, wherein the laminating adhesive comprises a component A, a component B and a component C, wherein: the component A comprises the following components in parts by weight: 30-80 parts of polyacrylate; 10-20 parts of polystyrene; 6-8 parts of calcium silicate; a proper amount of organic solvent; the component B comprises the following components in parts by weight: 50-80 parts of acrylic acid; 40-60 parts of acrylic acid polyethylene glycol diester; 20-40 parts of vinyl ether; 5-12 parts of phosphate; 0.2 to 0.5 part of initiator; 3-8 parts of copper oxide; 100-200 parts of water; the component C comprises the following components in parts by weight: 20-30 parts of organic metal soap; 40-60 parts of rubber; 8-12 parts of a surfactant; 0.3 to 0.5 part of coupling agent; 5-15 parts of a reducing agent; 100-150 parts of water, the laminating adhesive and the laminating method thereof do not need long-time curing treatment, have short delivery cycle, and have the advantages of small volatilization of organic solvents, no need of premixing before using the adhesive and high bonding strength.

Description

Laminating adhesive for INS film and laminating method thereof
Technical Field
The application relates to the technical field of functional films, in particular to laminating adhesive for an INS film and a laminating method thereof.
Background
The INS film technology is Film Insert Molding for short, also called an insert injection molding process, and covers a part surface by prefabricating a film with patterns in the injection molding process, so that different colors, textures and glossiness are formed on the part surface, and the appearance of the part can be quickly adjusted according to the requirement. The membrane prepared by the INS technology has the advantages of high definition, scratch resistance on the surface, various pattern shapes, attractive product appearance and the like, is widely used in the fields of automotive decorative films, household appliance decorative films and the like at present, and can effectively improve the fineness and added value of the product.
Generally, the product structure of an INS film comprises, in order: PMMA layer, printing ink layer, laminating glue layer and ABS layer, wherein, the PMMA layer is located the surface of INS membrane, be used for bearing and protecting the printing ink layer, the ABS layer is for the substrate layer of INS membrane, be used for when moulding plastics with the material fusion cross-linking shaping of spare part together, laminating glue layer is the gluing coating, be used for with PMMA layer and ABS layer link together. Generally, the INS film is made as follows:
(1) Preparing the PMMA layer and the ABS layer respectively;
(2) Printing patterns and colors on the PMMA layer;
(3) Coating laminating glue on the ABS layer, and then laminating and connecting the PMMA layer and the ABS layer together on line;
(4) And (3) placing the INS film product in an oven for curing, and removing solvent residues in the laminating glue.
In the process, the laminating glue is generally double-component polyurethane glue, and the double-component polyurethane glue loses viscosity after being thoroughly dried, so that the PMMA layer and the ABS layer are directly laminated on line after the laminating glue is coated and the surface of the laminating glue layer is dried, and the PMMA layer and the ABS layer can be firmly laminated; meanwhile, the adhesive glue layer is only surface-dried and is not thoroughly dried, so that the solvent in the adhesive glue layer still exists, and at the moment, if the adhesive glue layer is directly used for customers, the quality problems such as bubbles and the like can occur in INS film products, if the residual solvent is to be completely removed, the solvent residues in the products can be removed through curing time of about 450 hours, the production time of the whole INS film products is about 25 days, the delivery period is very long, and a large amount of power loss is caused.
In addition, a large amount of glue and organic solvent are needed in the laminating process, so that the organic solvent volatilizes, RTO pressure is increased, and the performance of the two-component polyurethane glue is changed quickly after mixing, particularly the viscosity is increased quickly, so that the operation difficulty is increased, the residual glue can only be removed each time, and the cost is increased.
Furthermore, the bonding strength of the existing two-component polyurethane glue is very limited, and especially the bonding strength of an INS film product is easy to be greatly reduced at a high temperature in the later injection molding process or after aging for a long time, so that the INS film product is easy to crack and peel.
Disclosure of Invention
The application designs a laminating adhesive for an INS film and a laminating method thereof, which are used for solving the technical problems of long curing time, long delivery period, large volatilization amount of an organic solvent, easy change of the performance of the adhesive after mixing and low bonding strength in the existing laminating process of the INS film.
In order to solve the problems, the application discloses
A laminating adhesive for an INS film, the laminating adhesive comprising an a component, a B component, and a C component, wherein:
the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
the component C comprises the following components in parts by weight:
further, in the laminating adhesive, the weight ratio of the component A to the component B to the component C is (20-30): (60-100): (30-40).
Further, in the component A, the total weight concentration of polyacrylate and polystyrene in the organic solvent should be controlled to 2 to 6wt%.
Further, the preparation method of the component A comprises the following steps: firstly, respectively dissolving polyacrylate and polystyrene in an organic solvent, and then slowly dripping the obtained polyacrylate solution into the polystyrene solution under stirring or ultrasonic oscillation; then adding calcium silicate, stirring to disperse uniformly.
Further, the preparation method of the component B comprises the following steps: mixing the acrylic acid and the acrylic acid polyethylene glycol diester in a proper amount of water, and taking the mixture as a first solution for standby; mixing the vinyl ether, the phosphate and the initiator in the residual water, and taking the mixture as a second solution for standby; and then the first solution is dripped into the second solution for 2-3 h, and stirring is continued for 1-1.5 h after dripping is finished.
Further, the organic metal soap is zinc-iron organic metal soap.
Further, the rubber is partially oxidized chlorinated butyl rubber or brominated butyl rubber.
Further, the partially oxidized chlorinated butyl rubber or brominated butyl rubber is prepared according to the following method: firstly, mixing the latex of the chlorinated butyl rubber or the brominated butyl rubber with glutaraldehyde solution, standing for 3-5 hours, centrifugally cleaning for 2-3 times after standing, then spray-drying the cleaned solution, adding an organic solvent incompatible with water, and washing for 1-2 times after light-shielding and standing to obtain rubber latex particles which are suspended in water and have swollen surfaces; and then mixing the rubber latex particles with peroxycarboxylic acid, and reacting at 60-100 ℃ to obtain the partially oxidized rubber after the reaction is finished.
Further, the preparation method of the component C comprises the following steps: firstly, shearing and dispersing the organic metal soap in water, then adding the surfactant, and fully stirring to prepare emulsion for later use; dissolving the rubber in a proper amount of organic solvent to form a rubber solution; and then mixing the rubber solution with the emulsion of the organic metal soap, wherein the rubber solution can be coated outside the organic metal soap to form microcapsules coated with the organic metal soap, heating a reaction system to 90-110 ℃, completely evaporating the organic solvent, adding a coupling agent and a reducing agent, and uniformly stirring to obtain the component C.
The laminating method for the INS film uses the laminating adhesive to laminate and connect the PMMA layer and the ABS layer in the INS film together, and comprises the following steps:
s1, uniformly stirring the component A in the laminating adhesive, coating the laminating adhesive on the PMMA layer, and removing a solvent in the component A;
s2, coating the component C in the laminating adhesive on the ABS layer, and removing the solvent in the component C;
s3, heating the component B in the laminating adhesive to 30-40 ℃, preserving heat for 0.3-0.5 h, then heating the component B to 80-100 ℃, and immediately coating the component B on the ABS layer;
s3, bonding and connecting the ABS layer and the PMMA layer together under the condition of drying by hot air at 180-200 ℃;
s4, adding the attached INS film at 60-70 ℃, and preserving heat for 3-5 hours to fully solidify the INS film.
The laminating adhesive for the INS film and the laminating method thereof have the following advantages:
(1) Only the component A contains a certain amount of organic solvent, and the rest of the components B and C use water as the solvent, so that the use amount of the organic solvent in the laminating adhesive can be greatly reduced, and the RTO pressure is reduced;
(2) In the attaching stage, the solvent in the component A is treated independently, so that the concentrated treatment of the organic solvent can be realized, and the recovery and the diffusion prevention are convenient;
(3) The solvent content in the adhesive layer during the lamination is greatly reduced by pre-coating and drying the component A and the component B, and the removal difficulty of the solvent during the lamination is reduced;
(4) When in lamination, the moisture in the component B is rapidly removed through the drying capacity of hot air, so that the subsequent long-time curing treatment is avoided;
(5) In the laminating adhesive, the component A, the component B and the component C are respectively coated, and premixing is not needed before use, so that the problems of performance change, such as viscosity rising and the like, generated after mixing of the traditional multi-component adhesive can be effectively avoided, and the operation difficulty and the use cost are reduced;
(6) The double-layer miniature discontinuous membrane composite formed by the laminating adhesive and the micro-structure filled with the adhesive solution can greatly improve the bonding strength of the laminating adhesive and reduce the curing time.
Detailed Description
In order that the above-recited objects, features and advantages of the present application will become more readily apparent, a more particular description of embodiments of the application will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
A laminating adhesive for an INS film, the laminating adhesive comprising an a component, a B component, and a C component, wherein:
the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
the component C comprises the following components in parts by weight:
further, in the laminating adhesive, the weight ratio of the component A to the component B to the component C is (20-30): (60-100): (30-40).
Preferably, in the laminating adhesive, the dosage of the component B is more than or equal to 1.2 to 1.45 times of the sum of the dosages of the component A and the component C. Thus, the component B can be well filled and connected between the component A and the component C, and the adhesive obtained by the method has higher bonding strength.
Further, in the component A, the addition ratio of the polyacrylate to the polystyrene should be controlled to be (8-5): 1.
Further, in the component a, the total weight concentration of the polyacrylate and the polystyrene in the organic solvent should be controlled to be 2-6wt%, and if the total weight concentration of the polyacrylate and the polystyrene is too high, a continuous film layer will be formed on the PMMA layer, and at this time, the adhesive strength of the adhesive is reduced and the usage amount is increased.
As some embodiments of the present application, the organic solvent in the a component is one or more of acetone, chloroform, tetrahydrofuran, ethyl acetate, dichloromethane, and the like.
Preferably, the calcium silicate is nano calcium silicate particles, and the nano calcium silicate particles are dispersed in the component A in a suspension state.
Further, the preparation method of the component A comprises the following steps: firstly, respectively dissolving polyacrylate and polystyrene in an organic solvent, and then slowly dripping the obtained polyacrylate solution into the polystyrene solution under stirring or ultrasonic oscillation; then adding calcium silicate, stirring to disperse uniformly.
Preferably, in the organic solvent in the component A, the organic solvent in the polyacrylate solution accounts for 60-70% of the total organic solvent.
Preferably, the polyacrylate solution is controlled to be added dropwise within 20-30 min.
As some examples of the present application, a proper amount of dispersant may be added to the A component to improve the dispersing ability of the calcium silicate particles and reduce agglomeration. In addition, before using, the component A can be stirred again, and then coated on the PMMA layer after being uniformly mixed.
Preferably, in the component B, the vinyl ether is methyl allyl polyoxyethylene ether.
Preferably, the phosphate is an acrylic phosphate.
Preferably, the initiator is one or more of ammonium persulfate, potassium persulfate and sodium persulfate.
Preferably, the copper oxide is nano copper oxide particles, and the nano copper oxide particles are dispersed in the component B in a suspension state.
In the component B, the vinyl ether is nontoxic and non-irritating, has good water solubility, can adopt water as a solvent of the component B when being used for laminating adhesive of INS films, avoids the use of an organic solvent, and is beneficial to environmental protection; meanwhile, the acrylic acid is used as the simplest unsaturated carboxylic acid, raw materials are easy to obtain, esterification reaction can be carried out between the acrylic acid and the vinyl ether to form a macromolecular monomer, and the bonding strength of the laminating adhesive can be improved.
In addition, the acrylic acid polyethylene glycol diester contains two carbon-carbon double bonds, and after the acrylic acid polyethylene glycol diester is mixed with vinyl ether, the carbon-carbon double bonds can generate copolymerization reaction with free radicals, so that a netlike macromolecular structure can be formed among the acrylic acid, the acrylic acid polyethylene glycol diester and the vinyl ether, and the bonding strength of the laminating adhesive can be further improved.
Meanwhile, phosphate groups in the phosphate have two negative charges, phosphate monomer branched chains can be introduced into a reticular macromolecular structure formed among the acrylic acid, the acrylic acid polyethylene glycol diester and the vinyl ether by using the phosphate, the phosphate branched chains in the reticular macromolecular structure can be stretched in an aqueous solution, and a hydrophilic membrane layer is formed on the surface of a macromolecule of the reticular structure, so that the diffusion capacity and the fluidity of the reticular structure are improved; in addition, in the application, when the B component system is regulated to be in a weak alkaline environment, part of polymers and phosphate monomers in the reticular macromolecular structure can be subjected to ester bond hydrolysis to generate free phosphate ions, the free phosphate ions have extremely strong hydrophilicity and can be combined with water molecules to form a stable solvated water film with lubricating effect, and the diffusivity and flowability of the reticular macromolecular structure can be further improved, so that the reticular macromolecular structure is easy to coat.
Further, a proper amount of pH regulator can be added to regulate the pH value of the component B to be between 8 and 9.
Further, the preparation method of the component B comprises the following steps:
mixing the acrylic acid and the acrylic acid polyethylene glycol diester in a proper amount of water, and taking the mixture as a first solution for standby; mixing the vinyl ether, the phosphate and the initiator in the residual water, and taking the mixture as a second solution for standby; and then the first solution is dripped into the second solution for 2-3 h, and stirring is continued for 1-1.5 h after dripping is finished.
Further, the component B further comprises: 10 to 30 parts by weight of an acrylic acid ester such as one or more of methyl methacrylate, hexyl acrylate and the like.
Further, the component B further comprises: 0.5 to 1 weight portion of mildew inhibitor and 0.5 to 1 weight portion of defoaming agent.
Further, the component C further comprises: 1 to 2 parts by weight of iron powder, 2 to 3 parts by weight of citric acid and 1 to 3 parts by weight of chitosan.
Further, the organic metal soap is zinc-iron organic metal soap.
Preferably, the organic metal soap is organic metal soap generated by the action of zinc-iron salt and naphthenic acid, such as zinc naphthenate and iron naphthenate.
More preferably, the organic metal soap is a mixture of zinc organic metal soap and iron organic metal soap according to the weight ratio of (2-3): 1, and the addition of the zinc organic metal soap can keep the film layer formed by the laminating adhesive to have longer opening time and delay the surface drying rate, so that the film layer formed by the laminating adhesive is promoted to be dried rapidly and thoroughly; the iron organic metal soap can promote the polymerization and crosslinking of the membrane formed by the component B and the component C respectively, improve the connection speed and connection strength between different components in the laminating adhesive and improve the drying speed of the laminating adhesive.
Further, the rubber is one or more of natural rubber, nitrile rubber, polyurethane rubber, chlorinated butyl rubber, brominated butyl rubber and the like.
Preferably, the rubber is chlorinated butyl rubber or brominated butyl rubber.
More preferably, the rubber is partially oxidized chlorinated butyl rubber or brominated butyl rubber.
Specifically, the partially oxidized chlorinated butyl rubber or brominated butyl rubber is prepared according to the following method: firstly, mixing the latex of the chlorinated butyl rubber or the brominated butyl rubber with glutaraldehyde solution, standing for 3-5 hours, centrifugally cleaning for 2-3 times after standing, then spray-drying the cleaned solution, adding an organic solvent incompatible with water, and washing for 1-2 times after light-shielding and standing to obtain rubber latex particles which are suspended in water and have swollen surfaces; and then mixing the rubber latex particles with peroxycarboxylic acid, and reacting at 60-100 ℃ to obtain the partially oxidized rubber after the reaction is finished.
Preferably, the partially oxidized chlorinated or brominated butyl rubber has an oxidation level of 10 to 30%.
Preferably, the surfactant is a reactive non-migration surfactant, and may be one or more of a cationic surfactant, an anionic surfactant, and a nonionic surfactant, such as 3969, 3300B, G5000, and the like.
Preferably, the coupling agent is a silane coupling agent.
Further, the preparation method of the component C comprises the following steps:
firstly, shearing and dispersing the organic metal soap in water, then adding the surfactant, and fully stirring to prepare emulsion for later use; dissolving the rubber in a proper amount of organic solvent to form a rubber solution; and then mixing the rubber solution with the emulsion of the organic metal soap, wherein the rubber solution can be coated outside the organic metal soap to form microcapsules coated with the organic metal soap, heating a reaction system to 90-110 ℃, completely evaporating the organic solvent, adding a coupling agent and a reducing agent, and uniformly stirring to obtain the component C.
As some embodiments of the application, the rubber may be dissolved in an appropriate amount of toluene or chloroform. Preferably, the weight ratio of the rubber to the organic solvent dissolving the rubber is 1:20-100.
In the component C, a microcapsule of rubber coated organic metal soap is formed, and a surfactant attached in the microcapsule forms a protective layer positioned on the inner surface of the microcapsule, and the arrangement of the protective layer can not only reduce the particle size of the microcapsule, but also improve the shell strength of the microcapsule, so that the microcapsule is not easy to crack in the storage process. Meanwhile, in the component C, the water-in-oil-in-water system has good fluidity and stability, so that the system is easy to cast or uniformly coat.
When the component C is coated on the PMMA layer or the ABS layer, the microcapsules spontaneously break along with the evaporation of moisture, so that the organometallic soap in the microcapsules is released, and the organometallic soap can promote crosslinking and oxidation and improve the drying speed of the laminating adhesive; meanwhile, in the broken microcapsule, the capsule wall formed by rubber is unfolded from a spherical structure to form a sheet, then the sheet is dried to form a film, another discontinuous latex film is formed on the PMMA layer or the ABS layer, the latex film is staggered and overlapped with the film formed by the polyacrylate and the polystyrene, the glue solution formed by the component B is filled in the film, and the composite and glue solution filled microstructure of the double-layer miniature discontinuous film can greatly improve the bonding strength of the laminating glue.
Furthermore, the latex film formed by the rubber can form a hydroxyl group with reactivity with calcium silicate and water in the component A, so that the moisture in the laminating adhesive is consumed, meanwhile, the hydroxyl group with reactivity can further react with the hydroxyl group in Si-OH on the surface of the calcium silicate to form an ether bond, and the bonding strength between the latex film and the membrane formed by the polyacrylate and the polystyrene is further improved by using the formed ether bond between the calcium silicate and the latex film.
Further, the reducing agent is a compound of ferrous sulfate, vitamin E, vitamin C, sodium bisulfite and the like. The reducing agent is used for reducing copper oxide in the component B into cuprous oxide, the forbidden bandwidth of the cuprous oxide is about 2.0eV, the conduction band position is-1.4V, electrons can be transited from the valence band of the cuprous oxide to the conduction band under the irradiation of visible light, at the moment, electrons generated by excitation of the cuprous oxide have strong reducing capability due to the fact that the conduction band position of the cuprous oxide is very negative, oxygen adsorbed on the surface of the cuprous oxide can be reduced into hydrogen peroxide, ferrous ions in the reducing agent can react with hydrogen peroxide to generate chain oxidation of hydroxyl radicals, and when the hydroxyl radicals are thermally activated, polymerization can be promoted, the connection strength between polymers can be improved, and meanwhile solidification is accelerated.
In addition, the application also provides a bonding method for the INS film, which uses the bonding adhesive to bond and connect the PMMA layer and the ABS layer in the INS film together, and comprises the following steps:
s1, uniformly stirring the component A in the laminating adhesive, coating the laminating adhesive on the PMMA layer, and removing a solvent in the component A;
s2, coating the component C in the laminating adhesive on the ABS layer, and removing the solvent in the component C;
s3, heating the component B in the laminating adhesive to 30-40 ℃, preserving heat for 0.3-0.5 h, then heating the component B to 80-100 ℃, and immediately coating the component B on the ABS layer;
s3, bonding and connecting the ABS layer and the PMMA layer together under the condition of drying by hot air at 180-200 ℃;
s4, adding the attached INS film at 60-70 ℃, and preserving heat for 3-5 hours to fully solidify the INS film.
As some embodiments of the present application, in the step S1, the a component of the laminating adhesive may be coated on the PMMA layer by a spin coating method, and at this time, the solvent in the a component may be directly removed by continuing to spin or heat.
As still other embodiments of the present application, in the step S1, the a component of the laminating adhesive may be coated on the PMMA layer by a spraying method or a printing method, and at this time, the solvent in the a component may be removed by heating or decompressing.
By means of the step S1, the PMMA layer can be coated with the non-fused polyacrylate and polystyrene, and by removing the solvent, a discontinuous film layer can be formed on the PMMA layer, and the thickness of the film layer is extremely thin and is about 5-200 nm. The discontinuous film layer comprises micro-films formed by polyacrylate and polystyrene, and the formation of the discontinuous micro-films can improve the surface morphology of the PMMA layer on one hand, so that the PMMA layer is roughened, has active crosslinking points, is easy to adhere to the laminating adhesive of the component B and the component C, and improves the adhesive capacity of the laminating adhesive; on the other hand, a filling space of the B-component laminating adhesive can be formed in a gap between adjacent films, so that the filling quantity of the B-component laminating adhesive is reduced, the quantity of residual solvent is further reduced, and the curing time is shortened; meanwhile, the adhesive capacity of the laminating adhesive is further improved through the inlaying and biting actions between the discontinuous film layer and the rest components.
In addition, copper oxide or cuprous oxide particles can play roles in pinning and blocking, and the membrane in the membrane layer is prevented from sliding and deforming.
Further, in the step S2, the manner of coating the C component in the laminating adhesive on the ABS layer is a spraying method, and then the solvent in the C component is removed by heating.
In the step S2, the component C in the laminating adhesive is sprayed on the ABS layer, and the microcapsules in the component C are spontaneously broken along with the evaporation of water, so that the organometallic soap in the microcapsules is released, the crosslinking and the oxidation are promoted, and the drying speed of the laminating adhesive is improved; more importantly, in the ruptured microcapsule, the capsule wall formed by rubber is unfolded from a spherical structure to form a sheet, then the sheet is dried to form a film, another discontinuous latex film is formed on the ABS layer, the latex film is staggered and overlapped with the micro film formed by the polyacrylate and the polystyrene, the glue solution formed by the component B is filled in the micro film, and the double-layer micro discontinuous film composite and glue solution filled microstructure can greatly improve the bonding strength of the laminating glue and reduce curing time.
In the step S3, the aim of heat preservation of the component B at the temperature of 30-40 ℃ is to improve the integrity of the surface water-based film with a macromolecular network structure and improve the fluidity, the extension and the permeability of the surface water-based film; the purpose of the coating by heating to 80 to 100 ℃ is to increase the reactivity of copper oxide, macromolecular chains and the like in the B component with the remaining components.
Further, in the step S4, the flow rate of the dry hot air at 180 to 200 ℃ is adjusted according to the water content in the B component, so that 80% or more of the water in the B component can be taken away.
In addition, in the laminating adhesive, after the component B and the component C are mixed, when hydroxyl radicals are thermally activated at high temperature, polymerization can be rapidly promoted, the connection strength between polymers is improved, and meanwhile, solidification is accelerated, at the moment, under the drying action of dry hot air at 180-200 ℃, glue solution in the component B can be rapidly solidified and dried, and meanwhile, high-strength connection action is formed between the glue solution and the component A and the component C and between the PMMA layer and the ABS layer.
Further, in the step S5, the bonding strength of the laminating adhesive can be further improved by curing at a low temperature of 60-70 ℃, the solvent content in the laminating adhesive can be reduced, and the quality problems such as bubbles and the like of the obtained INS film product are ensured not to easily occur.
In summary, the laminating adhesive and the laminating method thereof of the application are available:
(1) Only the component A contains a certain amount of organic solvent, and the rest of the components B and C use water as the solvent, so that the use amount of the organic solvent in the laminating adhesive can be greatly reduced, and the RTO pressure is reduced;
(2) In the attaching stage, the solvent in the component A is treated independently, so that the concentrated treatment of the organic solvent can be realized, and the recovery and the diffusion prevention are convenient;
(3) The solvent content in the adhesive layer during the lamination is greatly reduced by pre-coating and drying the component A and the component B, and the removal difficulty of the solvent during the lamination is reduced;
(4) When in lamination, the moisture in the component B is rapidly removed through the drying capacity of hot air, so that the subsequent long-time curing treatment is avoided;
(5) In the laminating adhesive, the component A, the component B and the component C are respectively coated, and premixing is not needed before use, so that the problems of performance change, such as viscosity rising and the like, generated after mixing of the traditional multi-component adhesive can be effectively avoided, and the operation difficulty and the use cost are reduced;
(6) The double-layer miniature discontinuous membrane composite formed by the laminating adhesive and the micro-structure filled with the adhesive solution can greatly improve the bonding strength of the laminating adhesive and reduce the curing time.
The laminating adhesive for the INS film and the laminating method thereof according to the present application are illustrated by the following specific examples:
example 1
A laminating adhesive for an INS film, the laminating adhesive comprising an a component, a B component, and a C component, wherein:
the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
the component C comprises the following components in parts by weight:
in the laminating adhesive, the weight ratio of the component A to the component B to the component C is 20:60:30.
Example 2
A laminating adhesive for an INS film, the laminating adhesive comprising an a component, a B component, and a C component, wherein:
the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
the component C comprises the following components in parts by weight:
in the laminating adhesive, the weight ratio of the component A to the component B to the component C is 20:70:35, the rubber is chlorinated butyl rubber with the oxidation degree of 20%, and the reducing agent is a compound prepared by mixing ferrous sulfate and vitamin E according to the weight ratio of 1:1.
Example 3
A laminating adhesive for an INS film, the laminating adhesive comprising an a component, a B component, and a C component, wherein:
the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
the component C comprises the following components in parts by weight:
in the laminating adhesive, the weight ratio of the component A to the component B to the component C is 30:100:40.
Example 4
A bonding method for an INS film, the bonding method bonding a PMMA layer and an ABS layer in the INS film together using the bonding adhesive in the above embodiment 1, the bonding method comprising the steps of:
s1, uniformly stirring the component A in the laminating adhesive, coating the laminating adhesive on the PMMA layer, and removing a solvent in the component A;
s2, coating the component C in the laminating adhesive on the ABS layer, and removing the solvent in the component C;
s3, heating the component B in the laminating adhesive to 30 ℃, preserving heat for 0.5h, heating the laminating adhesive to 80 ℃, and immediately coating the laminating adhesive on the ABS layer;
s3, bonding and connecting the ABS layer and the PMMA layer together under the condition of drying by hot air at 180 ℃;
s4, adding the INS film after the lamination connection to the temperature of 60 ℃, and preserving the heat for 5 hours to fully solidify the INS film.
Example 5
A bonding method for an INS film, the bonding method bonding a PMMA layer and an ABS layer in the INS film together using the bonding adhesive in the above-described example 2, the bonding method comprising the steps of:
s1, uniformly stirring the component A in the laminating adhesive, coating the laminating adhesive on the PMMA layer, and removing a solvent in the component A;
s2, coating the component C in the laminating adhesive on the ABS layer, and removing the solvent in the component C;
s3, heating the component B in the laminating adhesive to 36 ℃, preserving heat for 0.4h, heating to 90 ℃, and immediately coating on the ABS layer;
s3, bonding and connecting the ABS layer and the PMMA layer together under the condition of drying by hot air at 190 ℃;
s4, adding the INS film after the lamination connection to 63 ℃, and preserving heat for 4 hours to fully solidify the INS film.
Example 6
A bonding method for an INS film, the bonding method bonding and connecting a PMMA layer and an ABS layer in the INS film together using the bonding adhesive of the above embodiment 3, the bonding method comprising the steps of:
s1, uniformly stirring the component A in the laminating adhesive, coating the laminating adhesive on the PMMA layer, and removing a solvent in the component A;
s2, coating the component C in the laminating adhesive on the ABS layer, and removing the solvent in the component C;
s3, heating the component B in the laminating adhesive to 40 ℃, preserving heat for 0.3h, heating the laminating adhesive to 100 ℃, and immediately coating the laminating adhesive on the ABS layer;
s3, bonding and connecting the ABS layer and the PMMA layer together under the condition of drying by hot air at 200 ℃;
s4, adding the INS film after the lamination connection to the temperature of 70 ℃, and preserving the heat for 3 hours to fully solidify the INS film.
Comparative example 1
Laminating adhesive for INS film and laminating method thereof:
the only difference between the laminating adhesive used in comparative example 1 and example 2 described above is: the component A is not added with calcium silicate;
the bonding method used in comparative example 1 was the same as in example 5 above.
Comparative example 2
Laminating adhesive for INS film and laminating method thereof:
the only difference between the laminating adhesive used in comparative example 2 and example 2 described above is: the component B is not added with phosphate;
the bonding method used in comparative example 2 was the same as in example 5 above.
Comparative example 3
Laminating adhesive for INS film and laminating method thereof:
the only difference between the laminating adhesive used in comparative example 3 and example 2 described above is: copper oxide is not added in the component B;
the lamination method used in comparative example 3 was the same as in example 5 described above.
Comparative example 4
Laminating adhesive for INS film and laminating method thereof:
the only difference between the laminating adhesive used in comparative example 4 and example 2 described above is: no organic metal soap is added in the component C; when the component C is prepared, the surfactant is directly dispersed in water, then the rubber solution is added, the reaction system is heated to 90 ℃, the organic solvent is completely distilled out, the coupling agent and the reducing agent are added, and the component C is obtained after uniform stirring.
The lamination method used in comparative example 4 was the same as in example 5 described above.
Comparative example 5
Laminating adhesive for INS film and laminating method thereof:
the only difference between the laminating adhesive used in comparative example 5 and example 2 described above is: the component C is not added with rubber; and in the preparation of the component C, shearing and dispersing the organic metal soap in water, adding the surfactant, fully stirring to prepare emulsion, adding the coupling agent and the reducing agent, and uniformly stirring to obtain the component C.
The lamination method used in comparative example 5 was the same as that used in example 5.
Comparative example 6
Laminating adhesive for INS film and laminating method thereof:
the only difference between the laminating adhesive used in comparative example 6 and example 2 described above is: the rubber used in the component C is unoxidized chlorinated butyl rubber.
Comparative example 7
Laminating adhesive for INS film and laminating method thereof:
the only difference between the laminating adhesive used in comparative example 7 and example 2 described above is: the C component is not added with a reducing agent;
the lamination method used in comparative example 7 was the same as in example 5 described above.
Comparative example 8
Laminating adhesive for INS film and laminating method thereof:
the only difference between the laminating adhesive used in comparative example 8 and example 2 described above is: the reducing agent in the component C is vitamin E;
the lamination method used in comparative example 8 was the same as in example 5 described above.
Comparative example 9
Laminating adhesive for INS film and laminating method thereof:
the laminating adhesive used in comparative example 9 was the same as that used in example 2 above;
the lamination method adopted in comparative example 9 differs from that of example 5 described above only in that: in step S3, the B component at room temperature is directly heated to 90 ℃ and immediately coated on the ABS layer.
Test example 1
The INS film products prepared in examples 4 to 6 and comparative examples 1 to 9 were tested and the results are shown in table 1 below:
wherein:
the high temperature test conditions are as follows: 105 ℃ x 168H, the qualification requirements are: no foaming, tilting, delamination and other defects, no obvious change of appearance and touch characteristics, and OK of the hundred-cell test;
the humidity test conditions were: 38 ℃,100rh 144h; the qualification requirements are as follows: no foaming, tilting, delamination and other defects, no obvious change of appearance and touch characteristics, and OK of the hundred-cell test;
the cold and hot impact test conditions are as follows: GMW14124 Grade1 (95% rh40C,24H- >25C1H- >95C24H- >25C1H- > 30C4H- >251H 2 cycles); the qualification requirements are as follows: no foaming, tilting, delamination and other defects, no obvious change of appearance and touch characteristics, and OK of the hundred-cell test;
the conditions of the xenon lamp accelerated aging test are as follows: SAE J2412 1240.8kJ/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The qualification requirements are as follows: no foaming, tilting, delamination and other defects, no obvious change of appearance and touch characteristics, and OK of the hundred-cell test;
the chemical solvent resistance test conditions were: 60C 0.5H of lead-free gasoline; diesel 25c 0.5h; engine oil 25c 0.5h; antifreeze fluid 25C 0.5h; brake fluid 25c 0.5h; ethanol 60c 0.5h; artificial sweat 60c 0.5h; sunscreen/hand cream (mass PV 3964) 80c 24h; the qualification requirements are as follows: no foaming and no obvious change in appearance and touch characteristics.
TABLE 1INS film product Performance test results
Although the present application is disclosed above, the present application is not limited thereto. In the description of the present specification, reference to the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the application, and the scope of the application should be assessed accordingly to that of the appended claims.

Claims (9)

1. Laminating adhesive for INS films, which is characterized by comprising an A component, a B component and a C component, wherein:
the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
wherein the phosphate is acrylic acid phosphate;
the component C comprises the following components in parts by weight:
the preparation method of the component C comprises the following steps: firstly, shearing and dispersing the organic metal soap in water, then adding the surfactant, and fully stirring to prepare emulsion for later use; dissolving the rubber in a proper amount of organic solvent to form a rubber solution; and then mixing the rubber solution with the emulsion of the organic metal soap, coating the rubber solution outside the organic metal soap to form microcapsules coated with the organic metal soap, heating a reaction system to 90-110 ℃, completely evaporating the organic solvent, adding a coupling agent and a reducing agent, and stirring uniformly to obtain the component C.
2. The laminating adhesive according to claim 1, wherein in the laminating adhesive, the weight ratio of the component a, the component B and the component C is (20 to 30): (60-100): (30-40).
3. Laminating adhesive according to claim 1 or 2, wherein in the component a the total concentration of polyacrylate and polystyrene in the organic solvent is controlled to be 2-6 wt%.
4. The laminating adhesive according to claim 1, wherein the preparation method of the component a comprises the following steps: firstly, respectively dissolving polyacrylate and polystyrene in an organic solvent, and then slowly dripping the obtained polyacrylate solution into the polystyrene solution under stirring or ultrasonic oscillation; then adding calcium silicate, stirring to disperse uniformly.
5. The laminating adhesive according to claim 1, wherein the preparation method of the component B comprises the following steps: mixing the acrylic acid and the acrylic acid polyethylene glycol diester in a proper amount of water, and taking the mixture as a first solution for standby; mixing the vinyl ether, the phosphate and the initiator in the residual water, and taking the mixture as a second solution for standby; then the first solution is dripped into the second solution for 2-3 h, and stirring is continued for 1-1.5 h after dripping is finished; the copper oxide is nano copper oxide particles, and the nano copper oxide particles are dispersed in the component B in a suspension state.
6. The laminating adhesive of claim 1, wherein the organometallic soap is a zinc-iron organometallic soap.
7. The laminating adhesive of claim 1, wherein the rubber is a partially oxidized chlorinated butyl rubber or brominated butyl rubber.
8. The laminating adhesive of claim 7, wherein the partially oxidized chlorinated butyl rubber or brominated butyl rubber is prepared according to the following method: firstly, mixing the latex of the chlorinated butyl rubber or the brominated butyl rubber with glutaraldehyde solution, standing for 3-5 hours, centrifugally cleaning for 2-3 times after standing, then spray-drying the cleaned solution, adding an organic solvent incompatible with water, and washing for 1-2 times after light-shielding and standing to obtain rubber latex particles which are suspended in water and have swollen surfaces; and then mixing the rubber latex particles with peroxycarboxylic acid, and reacting at 60-100 ℃ to obtain the partially oxidized rubber after the reaction is finished.
9. A bonding method for an INS film, wherein the bonding method uses the bonding adhesive according to any one of claims 1 to 8 to bond together a PMMA layer and an ABS layer in the INS film, the bonding method comprising the steps of:
s1, uniformly stirring the component A in the laminating adhesive, coating the laminating adhesive on the PMMA layer, and removing a solvent in the component A;
s2, coating the component C in the laminating adhesive on the ABS layer, and removing the solvent in the component C;
s3, heating the component B in the laminating adhesive to 30-40 ℃, preserving heat for 0.3-0.5 h, then heating the component B to 80-100 ℃, and immediately coating the component B on the ABS layer;
s3, bonding and connecting the ABS layer and the PMMA layer together under the condition of drying by hot air at 180-200 ℃;
s4, preserving the temperature of the laminated and connected INS film at 60-70 ℃ for 3-5 hours to fully solidify the INS film.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1138736A1 (en) * 2000-03-30 2001-10-04 Beiersdorf AG Production of acrylate hot melt adhesives from aqueous disperse systems
CN114231005A (en) * 2021-12-13 2022-03-25 上海长伟锦磁工程塑料有限公司 PC/ABS alloy material suitable for INS membrane substrate and preparation method thereof
CN114292619A (en) * 2021-12-07 2022-04-08 深圳市摩码克来沃化学科技有限公司 Adhesive, adhesive film and bonding method
CN114806465A (en) * 2022-04-14 2022-07-29 汤臣(江苏)材料科技股份有限公司 Acrylic body high-strength polymer adhesive

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Publication number Priority date Publication date Assignee Title
JP5725760B2 (en) * 2010-08-19 2015-05-27 大同化成工業株式会社 Acrylic polymer compounds used in pressure-sensitive adhesive compositions for touch panels

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1138736A1 (en) * 2000-03-30 2001-10-04 Beiersdorf AG Production of acrylate hot melt adhesives from aqueous disperse systems
CN114292619A (en) * 2021-12-07 2022-04-08 深圳市摩码克来沃化学科技有限公司 Adhesive, adhesive film and bonding method
CN114231005A (en) * 2021-12-13 2022-03-25 上海长伟锦磁工程塑料有限公司 PC/ABS alloy material suitable for INS membrane substrate and preparation method thereof
CN114806465A (en) * 2022-04-14 2022-07-29 汤臣(江苏)材料科技股份有限公司 Acrylic body high-strength polymer adhesive

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