CN108822757B - Low-viscosity PET (polyethylene terephthalate) protective film for foam material - Google Patents
Low-viscosity PET (polyethylene terephthalate) protective film for foam material Download PDFInfo
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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Abstract
The invention provides a low-viscosity PET protective film for a foaming material, which consists of a PET substrate layer, a low-viscosity middle layer and a protective layer, has a simple preparation process, is easy to operate and is suitable for industrial production. Firstly, the chain extender with high performance and low viscose is acidic, and the acidic substance can inhibit the generation reaction of biuret, so as to inhibit the crosslinking reaction and reduce the viscosity; secondly, the catalyst is a mild acidic ionic liquid, the catalytic activity of the catalyst is low, and the nucleophilic attack of the catalyst on isocyanate is effectively inhibited, so that the activity of the reaction of the isocyanate and the hydroxyl of the macromolecular diol is reduced, the catalyst has a good synergistic effect with an emulsifier, the viscosity of a product is reduced, and the storage stability of high-performance low-viscosity adhesive is improved. Therefore, the PET protective film provided by the invention has the characteristics of low viscosity, easiness in tearing, no adhesive residue, good bonding property, good high-temperature resistance and excellent mechanical property.
Description
Technical Field
The invention relates to the technical field of protective films, in particular to a low-viscosity PET protective film for a foaming body material.
Background
The protective film has penetrated into various industries, such as instruments, electronics, machinery, buildings, automobile manufacturing, labels and the like, and the application of the protective film not only improves the appearance quality of products and facilitates material processing, but also improves the utilization rate of materials and reduces the production cost of the products.
The foam material is a microporous material having numerous cells in the interior thereof based on a polymer such as plastic, rubber, elastomer, natural polymer material, etc., and can also be considered as a composite material having a gas as a filler. The foam material has the advantages of sound insulation, heat preservation, operation cost reduction, energy conservation, environmental protection and the like, and is widely applied to the fields of sports goods, electronics, precise instruments, household appliances, automobiles and the like. Along with the development of society and the promotion of people's demand, the demand of foaming body material to the protection film is gradually increased, however protection film on the market generally has some problems such as not high temperature resistant, difficult tear, incomplete glue surplus, laminating nature is poor and the viscidity is unstable.
Therefore, the preparation of the low-viscosity PET protective film for the foaming material, which is low in viscosity, easy to tear, free of adhesive residue, good in laminating property, good in high temperature resistance and excellent in mechanical property, has important significance for the protective film industry.
Disclosure of Invention
The invention mainly aims to provide a low-viscosity PET protective film for a foaming body material, which has the characteristics of low viscosity, easiness in tearing, no adhesive residue, good laminating property, good high-temperature resistance and excellent mechanical property.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows:
the low-viscosity PET protective film for the foaming body material comprises a PET base material layer, a low-viscosity middle layer and a protective layer which are sequentially stacked, wherein the low-viscosity middle layer is formed by high-performance low-viscosity glue, the high-performance low-viscosity glue is formed by 20-80 parts by weight of macromolecular polyol, 3-10 parts by weight of isocyanate, 2-5 parts by weight of a chain extender, 0.5-2 parts by weight of a salt forming agent, 4-10 parts by weight of a catalyst, 10-30 parts by weight of an organic solvent and 100-150 parts by weight of deionized water, the chain extender is a carboxylic acid type ionic liquid 1-acetic acid imidazole cation dimethylolpropionic acid anion salt, and the catalyst is ionic liquid 1-methyl-3-ethyl imidazole bromide.
Preferably, the thickness of the PET substrate layer is 50-200 μm.
Preferably, the protective layer is a PET film with the thickness of 20-100 μm.
Preferably, the high-performance low-viscose glue is prepared according to the following method: dehydrating the macromolecular polyalcohol at the temperature of 100-120 ℃ for 1-5h in vacuum, and cooling to 60-80 ℃; then adding isocyanate, an organic solvent and a catalyst, and reacting at a constant temperature of 500-1500r/min for 2-6 h; adding a chain extender for chain extension reaction for 1-5h, and cooling to 30-50 ℃;
then adding a salt forming agent and deionized water, and carrying out high-speed shearing dispersion for 0.5-2h under the condition of 1000-3000r/min to obtain the high-performance low-viscose glue.
Preferably, the macromolecular polyol is one or more of polyester polyol, polyether polyol and polycarbonate polyol.
Preferably, the isocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate and 4, 4' -diphenylmethane diisocyanate.
Preferably, the chain extender is prepared according to the following method: mixing imidazole-1-acetic acid and ethyl acetate to prepare a solution with the mass fraction of 30-50%, then adding bromoethane with the same mole as the imidazole-1-acetic acid, stirring and heating to 50-80 ℃ under the condition of 450-750r/min, and reacting for 6-18h to obtain an intermediate; adding dimethylolpropionic acid with the same mole as the imidazole-1-acetic acid into the intermediate, stirring and heating to 60-90 ℃ under the condition of 300-500r/min, reacting for 8-24h, and centrifugally washing to obtain the chain extender.
Preferably, the salt forming agent is one or more of triethylamine, NaOH, KOH and ammonia water.
Preferably, the organic solvent is one or more of acetone, butanone, N-methylpyrrolidone and N, N-dimethylformamide.
Preferably, the catalyst is prepared according to the following method: methylimidazole and bromoethane with the molar ratio of 1:1 are stirred and heated to 50-80 ℃ under the condition of 750r/min at 450-.
The invention provides a low-viscosity PET protective film for a foaming material, which consists of a PET substrate layer, a low-viscosity middle layer and a protective layer, has a simple preparation process, is easy to operate and is suitable for industrial production. Firstly, the chain extender with high performance and low viscose is acidic, and the acidic substance can inhibit the generation reaction of biuret so as to inhibit the crosslinking reaction, thereby reducing the crosslinking degree and viscosity; secondly, the catalyst with high performance and low viscosity is a mild acidic ionic liquid, the catalytic activity of the catalyst is low, and the nucleophilic attack of the catalyst on isocyanate is effectively inhibited, so that the activity of the reaction of the isocyanate and the hydroxyl of the macromolecular diol is reduced, the catalyst has a good synergistic effect with an emulsifier, and the viscosity of the product is reduced; meanwhile, the viscosity of the reaction system is controlled, the generation of implosion or gel is avoided, and the storage stability of the high-performance low-viscosity adhesive is improved. Therefore, the PET protective film provided by the invention has the characteristics of low viscosity, easiness in tearing, no adhesive residue, good laminating property, good high-temperature resistance and excellent mechanical property, and meanwhile, the PET film also has excellent heat resistance, cold resistance, chemical resistance and oil resistance.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
The invention provides a low-viscosity PET protective film for a foaming body material, which consists of a PET substrate layer, a low-viscosity middle layer and a protective layer which are sequentially laminated, wherein the low-viscosity middle layer is formed by high-performance low-viscosity glue, the high-performance low-viscosity glue consists of 20-80 parts by weight of macromolecular polyol, 3-10 parts by weight of isocyanate, 2-5 parts by weight of a chain extender, 0.5-2 parts by weight of a salt forming agent, 4-10 parts by weight of a catalyst, 10-30 parts by weight of an organic solvent and 100-150 parts by weight of deionized water, the chain extender is a carboxylic acid type ionic liquid 1-acetic acid imidazole cation dimethylolpropionic acid anion salt, and the catalyst is ionic liquid 1-methyl-3-ethyl imidazole bromide salt.
Preferably, the thickness of the PET base material layer is 50-200 μm; the protective layer is a PET film with the thickness of 20-100 μm.
Preferably, the high-performance low-viscose glue is prepared by the following method: dehydrating the macromolecular polyalcohol at the temperature of 100-120 ℃ for 1-5h in vacuum, and cooling to 60-80 ℃; then adding isocyanate, an organic solvent and a catalyst, and reacting at a constant temperature of 500-1500r/min for 2-6 h; adding a chain extender for chain extension reaction for 1-5h, and cooling to 30-50 ℃; then adding a salt forming agent and deionized water, and carrying out high-speed shearing dispersion for 0.5-2h under the condition of 1000-3000r/min to obtain the high-performance low-viscose glue.
Preferably, the macromolecular polyol is one or more of polyester polyol, polyether polyol and polycarbonate polyol. The isocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate and 4, 4' -diphenylmethane diisocyanate.
Preferably, the chain extender is prepared according to the following method: mixing imidazole-1-acetic acid and ethyl acetate to prepare a solution with the mass fraction of 30-50%, then adding bromoethane with the same mole as the imidazole-1-acetic acid, stirring and heating to 50-80 ℃ under the condition of 450-750r/min, and reacting for 6-18h to obtain an intermediate; adding dimethylolpropionic acid with the same mole as the imidazole-1-acetic acid into the intermediate, stirring and heating to 60-90 ℃ under the condition of 300-500r/min, reacting for 8-24h, and centrifugally washing to obtain the chain extender.
The chain extender plays an important role in the preparation of the high-performance low-viscose glue, the chain extender is acidic, and the acidic substances can inhibit the generation reaction of biuret so as to inhibit the crosslinking reaction, so that the crosslinking degree is reduced, and the viscosity is reduced.
Preferably, the salt forming agent is one or more of triethylamine, NaOH, KOH and ammonia water. The organic solvent is preferably one or more of acetone, butanone, N-methylpyrrolidone and N, N-dimethylformamide.
Preferably, the catalyst is prepared according to the following method: methylimidazole and bromoethane with the molar ratio of 1:1 are stirred and heated to 50-80 ℃ under the condition of 750r/min at 450-.
The catalyst plays a role in promoting the preparation of high-performance low-viscosity glue, is a mild acidic ionic liquid, has low catalytic activity, and effectively inhibits the nucleophilic attack of the catalyst on isocyanate, so that the activity of the reaction of the isocyanate and the hydroxyl of macromolecular dihydric alcohol is reduced, and the viscosity of the product is reduced; meanwhile, the viscosity of the reaction system is controlled, the generation of implosion or gel is avoided, and the storage stability of the high-performance low-viscosity adhesive is improved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the low-viscosity PET protective film for the foaming material consists of a PET substrate layer, a low-viscosity middle layer and a protective layer, has a simple preparation process, is easy to operate, and is suitable for industrial production;
(2) the low-viscosity PET protective film for the foaming body material has the characteristics of low viscosity, easiness in tearing, no adhesive residue, good laminating property, good high-temperature resistance and excellent mechanical property, and meanwhile, the PET film also has excellent heat resistance, cold resistance, chemical resistance and oil resistance;
(3) the chain extender with high performance and low viscose is acidic, and the acidic substance can inhibit the generation reaction of biuret so as to inhibit the crosslinking reaction, thereby reducing the crosslinking degree and viscosity;
(4) the catalyst with high performance and low viscose is a mild acidic ionic liquid, the catalytic activity of the catalyst is low, and the nucleophilic attack of the catalyst on isocyanate is effectively inhibited, so that the activity of the reaction of the isocyanate and the hydroxyl of macromolecular diol is reduced, the catalyst has a good synergistic effect with an emulsifier, and the viscosity of a product is reduced; meanwhile, the viscosity of the reaction system is controlled, the generation of implosion or gel is avoided, and the storage stability of the high-performance low-viscosity adhesive is improved.
For further understanding of the present invention, the following embodiments are provided to illustrate the technical solutions of the present invention in detail, and the scope of the present invention is not limited by the following embodiments.
The chemical reagents adopted in the embodiment of the invention are all purchased from the market: the macromolecular polyol is purchased from Qingdao Ruinoo chemical Co., Ltd; isocyanate is available from Jiubang chemical Co., Ltd, Shanghai; the salt forming agent and the organic solvent are purchased from enlightening chemical industry Co., Ltd, Changzhou city; PET films were purchased from Zhejiang south ocean science, Inc.
Example 1:
the low-viscosity PET protective film for the foam material consists of a PET base material layer with the thickness of 50 mu m, a low-viscosity middle layer with the thickness of 5 mu m and a protective layer with the thickness of 20 mu m.
The low-viscosity middle layer is formed by high-performance low-viscosity glue, the high-performance low-viscosity glue is composed of 20 parts by weight of macromolecular polyol polyether polyol, 3 parts by weight of isocyanate toluene diisocyanate, 2 parts by weight of chain extender, 0.5 part by weight of salt forming agent triethylamine, 4 parts by weight of catalyst, 10 parts by weight of organic solvent acetone and 100 parts by weight of deionized water, and the specific preparation method is as follows:
(1) dehydrating the macromolecular polyol at 100 ℃ for 5h in vacuum, and cooling to 60 ℃;
(2) adding isocyanate, an organic solvent and a catalyst, and reacting for 6 hours at a constant temperature of 500 r/min;
(3) adding a chain extender for chain extension reaction for 1 hour, and cooling the reaction product to about 30 ℃;
(4) adding a salt forming agent and deionized water, and performing high-speed shearing dispersion for 2 hours under the condition of 1000r/min to obtain the high-performance low-viscosity adhesive for later use.
The preparation method of the chain extender carboxylic acid type ionic liquid 1-acetic acid imidazole cation dimethylolpropionic acid anion salt comprises the following steps:
(1) mixing imidazole-1-acetic acid and ethyl acetate to prepare a solution with the mass fraction of 30%, adding bromoethane with the same mole as the imidazole-1-acetic acid, stirring and heating under the condition of 450r/min to 50 ℃, and reacting for 18h to obtain an intermediate;
(2) and adding dimethylolpropionic acid with the same mole as the imidazole-1-acetic acid, stirring and heating to 60 ℃ under the condition of 300r/min, reacting for 24h, and centrifugally washing to obtain the chain extender for later use.
The catalyst is ionic liquid 1-methyl-3-ethylimidazole bromine salt, and the preparation method comprises the following steps:
the method comprises the steps of stirring and heating methylimidazole and bromoethane with the same mole under the condition of 450r/min to 50 ℃, reacting for 18h, and washing with ethyl acetate for multiple times to obtain the catalyst for later use.
Example 2:
the low-viscosity PET protective film for the foam material consists of a PET base material layer with the thickness of 100 mu m, a low-viscosity middle layer with the thickness of 10 mu m and a protective layer with the thickness of 50 mu m.
The low-viscosity middle layer is formed by high-performance low-viscosity glue, the high-performance low-viscosity glue is composed of 80 parts by weight of macromolecular polyol polyester polyol, 5 parts by weight of isocyanate 4, 4' -diphenylmethane diisocyanate, 3 parts by weight of chain extender, 0.5-2 parts by weight of salt forming agent ammonia water, 4-10 parts by weight of catalyst, 10 parts by weight of organic solvent N-methyl pyrrolidone and 100 parts by weight of deionized water, and the specific preparation method is as follows:
(1) dehydrating the macromolecular polyol at 120 ℃ for 2h in vacuum, and cooling to 80 ℃;
(2) adding isocyanate, an organic solvent and a catalyst, and reacting at a constant temperature of 1500r/min for 2 h;
(3) adding a chain extender for chain extension reaction for 2 hours, and cooling the reaction product to about 50 ℃;
(4) adding a salt forming agent and deionized water, and carrying out high-speed shearing dispersion for 0.5h under the condition of 3000r/min to obtain the high-performance low-viscosity adhesive for later use.
The preparation method of the chain extender carboxylic acid type ionic liquid 1-acetic acid imidazole cation dimethylolpropionic acid anion salt comprises the following steps:
(1) mixing imidazole-1-acetic acid and ethyl acetate to prepare a solution with the mass fraction of 50%, then adding bromoethane with the same mole as the imidazole-1-acetic acid, stirring and heating to 80 ℃ under the condition of 750r/min, and reacting for 6 hours to obtain an intermediate;
(2) and adding dimethylolpropionic acid with the same mole as the imidazole-1-acetic acid, stirring and heating to 90 ℃ under the condition of 500r/min, reacting for 8h, and centrifugally washing to obtain the chain extender for later use.
The catalyst is ionic liquid 1-methyl-3-ethylimidazole bromine salt, and the preparation method comprises the following steps:
and (2) stirring and heating the methyl imidazole and bromoethane with equal moles to 80 ℃ under the condition of 750r/min, reacting for 6h, and washing with ethyl acetate for multiple times to obtain the catalyst for later use.
Example 3:
the low-viscosity PET protective film for the foam material consists of a PET base material layer with the thickness of 200 mu m, a low-viscosity middle layer with the thickness of 20 mu m and a protective layer with the thickness of 50 mu m.
The low-viscosity interlayer is formed by high-performance low-viscosity glue, the high-performance low-viscosity glue is composed of 80 parts by weight of macromolecular polyol polycarbonate polyol, 10 parts by weight of diphenylmethane diisocyanate, 5 parts by weight of chain extender, 2 parts by weight of salt forming agent KOH, 10 parts by weight of catalyst, 30 parts by weight of organic solvent N, N-dimethylformamide and 150 parts by weight of deionized water, and the specific preparation method is as follows:
(1) dehydrating the macromolecular polyol at 120 ℃ for 1h in vacuum, and cooling to 80 ℃;
(2) adding isocyanate, an organic solvent and a catalyst, and reacting at a constant temperature of 1500r/min for 2 h;
(3) adding a chain extender for chain extension reaction for 5 hours, and cooling the reaction product to about 50 ℃;
(4) adding a salt forming agent and deionized water, and carrying out high-speed shearing dispersion for 0.5h under the condition of 3000r/min to obtain the high-performance low-viscosity adhesive for later use.
The preparation method of the chain extender carboxylic acid type ionic liquid 1-acetic acid imidazole cation dimethylolpropionic acid anion salt comprises the following steps:
(1) mixing imidazole-1-acetic acid and ethyl acetate to prepare a solution with the mass fraction of 50%, then adding bromoethane with the same mole as the imidazole-1-acetic acid, stirring and heating to 50 ℃ under the condition of 750r/min, and reacting for 18h to obtain an intermediate;
(2) and adding dimethylolpropionic acid with the same mole as the imidazole-1-acetic acid, stirring and heating to 90 ℃ under the condition of 500r/min, reacting for 8h, and centrifugally washing to obtain the chain extender for later use.
The catalyst is ionic liquid 1-methyl-3-ethylimidazole bromine salt, and the preparation method comprises the following steps:
and (2) stirring and heating the methyl imidazole and bromoethane with equal moles to 80 ℃ under the condition of 750r/min, reacting for 6h, and washing with ethyl acetate for multiple times to obtain the catalyst for later use.
Example 4:
the foam was prepared using a low-tack PET protective film in the same manner as in example 2 except that a commercially available low-tack adhesive was used.
Example 5:
the foam material was prepared using a low viscosity PET protective film in the same manner as in example 2 except that a commercially available chain extender and catalyst were used.
Example 6:
the foam material was prepared using a low-viscosity PET protective film in the same manner as in example 2 except that a commercially available chain extender was used.
Example 7:
the foam was prepared by using a low-viscosity PET protective film in the same manner as in example 2 except that a commercially available catalyst was used.
The bonding performance test of the low-viscosity PET protective film for the foaming material refers to national standard GB/T2792-1995; the high temperature resistance is that the sample is pasted on a 304SUS plate and is kept for 60min at 120 ℃; the mechanical property test refers to the national standard GB/T3398.2-2008.
The performance test results of the low-viscosity PET protective film for the foam material prepared in the embodiment of the invention are shown in Table 1.
TABLE 1 Main Performance indices of Low-viscosity PET protective films for foam materials prepared in examples 1 to 6
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. The low-viscosity PET protective film for the foaming material is characterized by comprising a PET substrate layer, a low-viscosity middle layer and a protective layer which are sequentially laminated, wherein the low-viscosity middle layer is formed by high-performance low-viscosity glue, the high-performance low-viscosity glue is formed by 20-80 parts by weight of macromolecular polyol, 3-10 parts by weight of isocyanate, 2-5 parts by weight of chain extender, 0.5-2 parts by weight of salt forming agent, 4-10 parts by weight of catalyst, 10-30 parts by weight of organic solvent and 100-150 parts by weight of deionized water,
the chain extender is carboxylic acid type ionic liquid 1-acetic acid imidazole cation dimethylolpropionic acid anion salt, the catalyst is ionic liquid 1-ethyl-3-methylimidazole bromine salt,
the thickness of the PET base material layer is 50-200 μm,
the protective layer is a PET film with the thickness of 20-100 μm,
the high-performance low-viscose glue is prepared according to the following method:
dehydrating the macromolecular polyol for 1-5h at the temperature of 100-120 ℃, and then cooling to 60-80 ℃;
then adding isocyanate, an organic solvent and a catalyst, and reacting at a constant temperature of 500-1500r/min for 2-6 h;
adding a chain extender for chain extension reaction for 1-5h, and cooling to 30-50 ℃;
then adding a salt forming agent and deionized water, and carrying out high-speed shearing dispersion for 0.5-2h under the condition of 1000-3000r/min to obtain the high-performance low-viscose glue,
the isocyanate is one or more of toluene diisocyanate and diphenylmethane diisocyanate,
the organic solvent is one or more of acetone, butanone, N-methyl pyrrolidone and N, N-dimethylformamide.
2. The low viscosity PET protective film for foam material according to claim 1, wherein the macromolecular polyol is one or more of polyester polyol, polyether polyol and polycarbonate polyol.
3. The low-viscosity PET protective film for the foaming material as claimed in claim 1, wherein the salt forming agent is one or more of triethylamine, NaOH, KOH and ammonia water.
4. The low viscosity PET protective film for foam material according to claim 1, wherein the catalyst is prepared by the following method:
methylimidazole and bromoethane with the molar ratio of 1:1 are stirred and heated to 50-80 ℃ under the condition of 750r/min at 450-.
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