CN110713812A - Adhesive composition for low surface energy and pressure-sensitive adhesive tape - Google Patents

Adhesive composition for low surface energy and pressure-sensitive adhesive tape Download PDF

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Publication number
CN110713812A
CN110713812A CN201911076010.2A CN201911076010A CN110713812A CN 110713812 A CN110713812 A CN 110713812A CN 201911076010 A CN201911076010 A CN 201911076010A CN 110713812 A CN110713812 A CN 110713812A
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copolymer
monomer
resin
adhesive
polar
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檀海维
龙冲
黄得和
高鹏
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XINLUN TECHNOLOGY (CHANGZHOU) Co Ltd
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XINLUN TECHNOLOGY (CHANGZHOU) Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/006—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

Abstract

The invention relates to a low surface energy adhesive composition and a pressure-sensitive adhesive tape, which comprise a copolymer, wherein the copolymer comprises an acrylate monomer, a polar cross-linkable monomer, a non-polar monomer and EVA or SIS, the copolymer has a weight average molecular weight of 500000-1000000 g/mol, and the surface energy of acrylic glue is reduced by selecting monomer raw materials, proportioning different monomers and adjusting a polymerization process; by selecting tackifying resin with proper polarity for matching, the pressure-sensitive adhesive has good overall compatibility, small polarity and low surface energy; the surface energy of the acrylic acid series pressure-sensitive adhesive can be reduced by introducing ethylene-vinyl acetate with small polarity and high ethylene content for graft copolymerization, and the disadvantages of no aging resistance and high temperature resistance can also be avoided.

Description

Adhesive composition for low surface energy and pressure-sensitive adhesive tape
Technical Field
The invention belongs to the technical field of adhesive materials, and relates to a low-surface-energy adhesive composition and a pressure-sensitive adhesive tape.
Background
With the rapid development of polymer material science, polyolefin materials have been used in some industries, such as automobiles, buildings, aerospace and the like. The polyolefin material has the advantages of easy processing, easy coloring, low cost and the like, and the good mechanical property and the lower cost enable the polyolefin material to have obvious advantages and be developed rapidly in global competitiveness and cost oriented markets. Thus, substrates requiring assembly and bonding are moving from traditional metals, paints, wood, and the like, to plastics such as polyethylene, polypropylene, and other poly-alpha-olefin based materials. Such as: conventional traffic signs are typically made of metals or alloys, which have high surface energies. In recent years, some polyethylene materials or materials coated with powder coatings on their surfaces have also begun to be used for the production of traffic signs, which have low surface energy and are difficult to bond. Acrylate adhesives are well known in the art and generally comprise a copolymer of a major proportion of C4 to C14 acrylate monomers and a minor proportion of polar cross-linkable acrylic monomers. The main characteristics of these adhesives are low cost, resistance to aging, good weatherability and good adhesive properties, i.e. a good balance of adhesion, cohesion, ductility and elasticity. However, the acrylic copolymers all contain polar groups, resulting in failure to exhibit sufficient adhesion properties to low surface energy substrates. In contrast, rubber-based adhesives tend to have adequate adhesion to low surface energy substrates, but have the disadvantage of being inherently less resistant to aging and poor low temperature performance. Another preferred low surface energy adhesive is a silicone based adhesive which has excellent overall properties, but is costly, limiting its use.
The application of polymer materials in social life and defense industry is gradually wide, and some non-polar low surface energy materials are used in large quantity, and the materials comprise polyethylene, polypropylene, polytetrafluoroethylene, ethylene propylene diene monomer and the like. Because of the low surface energy, certain difficulties arise in the bonding of these materials, which limits their use. The rubber-based pressure-sensitive adhesives have good adhesion to these low-surface materials, but are sensitive to oxygen and have poor aging resistance due to the residual double bonds. However, the silicone pressure-sensitive adhesive cannot be used in large quantities due to its high price. In the current market, pressure-sensitive adhesive tapes based on acrylate copolymers have poor adhesion to low surface energy materials.
In the existing research and development, a single acrylate copolymer is used as a main component, and the method is characterized in that an acrylate monomer with a smaller solubility parameter is introduced, so that the polarity and the surface energy of the whole system are reduced to be close to the surface energy of a base material, the expansion of an adhesive on a bonded surface is promoted, and the bonding strength is improved. However, the decrease in the surface energy of the polar groups inherent in the copolymerization of acrylic esters, including ester groups and carboxyl groups or hydroxyl groups serving as crosslinking sites, has a certain limit, and thus the adhesive strength has a bottleneck and does not always achieve the desired effect. The presence of polar groups in the acrylate copolymer itself limits the reduction of its surface energy, which is still high compared to low surface energy substrates, and does not result in good wetting and intermolecular interactions, and thus the bond strength does not achieve the desired effect. Moreover, since the cost of the fluorine-containing acrylate monomer is high, the method of reducing the surface energy by introducing the fluorine-containing monomer can greatly increase the cost of the product, which is not favorable for popularization of the application.
Therefore, there is a need for a low surface energy adhesive composition and a pressure sensitive adhesive tape.
Disclosure of Invention
The invention aims to invent a low-surface-energy adhesive composition and a pressure-sensitive adhesive tape, and solves the technical problems.
The technical scheme adopted by the invention for solving the technical problems is as follows: provided is a composition for a low surface energy adhesive: comprising a copolymer comprising an acrylate monomer, a polar cross-linkable monomer and a non-polar monomer, said copolymer further comprising EVA or SIS, wherein said copolymer has a weight average molecular weight of 500000 to 1000000 g/mole, 15 to 40 parts of a resin or mixture of resins per 100 parts of said copolymer, and 0.05 to 0.2 parts of a cross-linking agent per 100 parts of said copolymer.
As a preferred embodiment of the invention, a copolymer comprising an acrylate monomer, a polar cross-linkable monomer and a non-polar monomer, and EVA or SIS is included, wherein the copolymer has a weight average molecular weight of 500000 to 1000000 g/mol, 15 to 40 parts of resin or mixture of resins per 100 parts of the copolymer, and 0.05 to 0.2 parts of cross-linking agent per 100 parts of the copolymer.
As a preferred embodiment of the invention, the resin or the mixture of the resins is one or two of rosin resin and C9 petroleum resin, the softening point of the rosin resin is between 80 and 140 ℃, and the softening point of the C9 petroleum resin is between 90 and 115 ℃.
As a preferred embodiment of the present invention, the content of the acrylate monomer is 70 to 90wt%, the content of the polar crosslinkable monomer is 2.5 to 5wt%, the content of the non-polar monomer is 2.5 to 15wt%, and the content of the SIS is 5 to 10 wt%; wherein the copolymer has a weight average molecular weight of 500000 to 1000000 g/mole.
As a preferred embodiment of the present invention, the resin or the mixture of resins is any one or two of terpene resin and terpene phenol resin, the softening point of the terpene resin is between 80 and 120 ℃, and the softening point of the terpene phenol resin is between 115 and 150 ℃.
As a preferred embodiment of the present invention, the acrylate monomer is any one of 2-ethylhexyl acrylate, isooctyl acrylate, or dodecyl methacrylate; the polar crosslinkable monomer is any one of acrylic acid, itaconic acid or beta-acryloxypropionic acid; the nonpolar monomer is any one of isobornyl acrylate, tetrahydrofuran acrylate or a mixture of isobornyl acrylate and vinyl neodecanoate; the cross-linking agent is any one or a combination of more of an epoxy curing agent, an N-propyl pyridine curing agent or a metal chelate.
As a preferred embodiment of the present invention, the copolymer is obtained by thermal polymerization in a solvent comprising a combination of any one or more of ethyl acetate, toluene, methyl ethyl ketone, butyl acetate, n-hexane; the initiator used in the polymerization process is any one of azobisisobutyronitrile, dibenzoyl peroxide or dimethyl azobisisobutyrate.
The application also provides a pressure-sensitive adhesive tape: the adhesive film comprises a PET (polyethylene terephthalate) base material and an adhesive film, wherein the surface tension of the PET base material is less than 50mN/cm, the adhesive film is composed of a composition for a low-surface-energy adhesive, and the preparation method comprises the following steps:
(1) adding EVA into a reaction kettle provided with a reflux device, introducing nitrogen, a thermometer and a stirring device, adding a solvent to dissolve the EVA, adding an acrylate monomer, a polar crosslinkable monomer and a non-polar monomer, heating to 65 ℃, introducing nitrogen for 30 minutes, adding an initiator accounting for 0.15 to 0.4wt% of the total amount of the monomers, reacting for 12 hours, and cooling to room temperature to obtain a copolymer, wherein the solid content of the copolymer is 45 to 50 wt%;
(2) and mixing the copolymer with resin or a mixture of the resin, a cross-linking agent and a solvent, standing for defoaming, coating the mixture on a release film by using a coating shaft, baking for 10min at 120 ℃, then adhering the release film to a PET (polyethylene terephthalate) substrate with the thickness of 50 microns and subjected to corona surface treatment, and standing for 7 days at normal temperature to obtain the pressure-sensitive adhesive tape.
The present application also provides another pressure sensitive adhesive tape: the adhesive film comprises a PET (polyethylene terephthalate) base material and an adhesive film, wherein the surface tension of the PET base material is less than 50mN/cm, the adhesive film is composed of a composition for a low-surface-energy adhesive, and the preparation method comprises the following steps:
(1) adding SIS into a reaction kettle provided with a reflux device, nitrogen, a thermometer and a stirring device, adding a solvent to dissolve the SIS, adding an acrylate monomer, a polar crosslinkable monomer and a non-polar monomer, heating to 65 ℃, introducing nitrogen for 30 minutes, adding an initiator accounting for 0.15 to 0.4wt% of the total amount of the monomers, reacting for 12 hours, and cooling to room temperature to obtain a copolymer, wherein the solid content of the copolymer is 45 to 50 wt%;
(2) and mixing the copolymer with resin or a mixture of the resin, a cross-linking agent and a solvent, standing for defoaming, coating the mixture on a release film by using a coating shaft, baking for 10min at 120 ℃, then adhering the release film to a PET (polyethylene terephthalate) substrate with the thickness of 25 micrometers and subjected to corona surface treatment, and standing for 7 days at normal temperature to obtain the pressure-sensitive adhesive tape.
The invention discloses a low surface energy adhesive composition and a pressure-sensitive adhesive tape, which have the advantages that: the surface energy of the acrylic glue is reduced by selecting monomer raw materials, proportioning different monomers and adjusting a polymerization process; by selecting tackifying resin with proper polarity for matching, the pressure-sensitive adhesive has good overall compatibility, small polarity and low surface energy; the surface energy of the acrylic acid series pressure-sensitive adhesive can be reduced by introducing ethylene-vinyl acetate with small polarity and high ethylene content for graft copolymerization, and the disadvantages of no aging resistance and high temperature resistance can also be avoided.
Detailed Description
The invention provides a composition for a low surface energy adhesive, which comprises a copolymer of the following materials: 60 to 85wt% of an acrylate, 2.5 to 5wt% of a polar crosslinkable monomer, 2.5 to 15wt% of a non-polar monomer and 10 to 20wt% of EVA; wherein the copolymer has a weight average molecular weight of 600000 to 900000 g/mole, 15 to 40 parts of a rosin or a C9 petroleum resin, or a mixture thereof, per 100 parts of the copolymer, and 0.05 to 0.2 parts (solid/solid) of a crosslinking agent per 100 parts of the copolymer.
The acrylate monomer is one of 2-ethylhexyl acrylate, isooctyl acrylate or dodecyl methacrylate; the polar cross-linkable monomer is one of acrylic acid, itaconic acid or beta-acryloxypropionic acid; the nonpolar monomer is isobornyl acrylate, tetrahydrofuran acrylate or a mixture of isobornyl acrylate and vinyl neodecanoate; the softening point of the rosin resin is between 80 and 140 ℃, and the available sources are Arizona, Keteng and Missaging chemical; c9 Petroleum resins have a softening point of 90 to 115 deg.C and are available from Arizona, Keteng and Mikan Chemicals; the cross-linking agent is one of an epoxy curing agent, an N-propyl pyridine curing agent or a metal chelate and a combination thereof. The copolymer is obtained by thermal polymerization in a solvent, wherein the solvent comprises one of ethyl acetate, toluene, butanone, butyl acetate, n-hexane and the combination of the ethyl acetate, the toluene, the butanone, the butyl acetate and the n-hexane; the initiator used in the polymerization process is one of azobisisobutyronitrile or dibenzoyl peroxide or dimethyl azobisisobutyrate.
The preparation method of the composition comprises the following steps: adding EVA into a reaction kettle provided with a reflux device, nitrogen, a thermometer and a stirring device, adding a solvent to dissolve the EVA, heating an acrylate monomer to 65 ℃, introducing nitrogen for 30 minutes, adding an initiator accounting for 0.15 to 0.4wt% of the total amount of the monomer, reacting for 12 hours, and cooling to room temperature, wherein the solid content of the glue is 45 to 50 wt%.
The pressure-sensitive adhesive tape comprises the following components: the surface tension of the adhesive composition is less than 50mN/cm PET substrate, and the adhesive composition is used for a low surface energy adhesive film, and the preparation method comprises the following steps: mixing the copolymer with tackifying resin, a cross-linking agent and a solvent, standing for defoaming, coating the mixture on a release film by using a coating shaft, baking the release film for 10min at 120 ℃, then adhering the release film to a PET film with the thickness of 50 microns and processed by a corona surface treatment mode, and standing the release film for 7 days at normal temperature to prepare the pressure-sensitive adhesive tape.
The invention provides a composition for a low surface energy adhesive, which comprises a copolymer of the following materials: 70 to 90wt% of an acrylate, 2.5 to 5wt% of a polar crosslinkable monomer, 2.5 to 15wt% of a non-polar monomer and 5 to 10wt% of SIS; wherein the copolymer has a weight average molecular weight of 500000 to 1000000 g/mol, 15 to 40 parts of terpene resin or terpene phenol resin or a mixture of terpene resin and terpene phenol resin are added per 100 parts of the copolymer; 0.05 to 0.2 parts (solid/solid) of a crosslinking agent per 100 parts of copolymer.
The acrylate monomer is one of 2-ethylhexyl acrylate, isooctyl acrylate or dodecyl methacrylate; the polar cross-linkable monomer is one of acrylic acid or beta-acryloxypropionic acid; the nonpolar monomer is isobornyl acrylate or a mixture of isobornyl acrylate and vinyl neodecanoate; the terpene resin has a softening point of 80-120 deg.C, and can be obtained from Arizona, Keteng and Missakawa; terpene phenol resins have softening points between 115 and 150 ℃ and are available from arizona, anyuan, hamari, and the like; the cross-linking agent is one of an epoxy curing agent, an N-propyl pyridine curing agent or a metal chelate and a combination thereof. The copolymer is obtained by thermal polymerization in a solvent, wherein the solvent comprises one of ethyl acetate, toluene, butanone, butyl acetate, n-hexane and the combination of the ethyl acetate, the toluene, the butanone, the butyl acetate and the n-hexane; the initiator used in the polymerization process is one of azobisisobutyronitrile or dibenzoyl peroxide or dimethyl azobisisobutyrate.
The preparation method of the composition comprises the following steps: adding SIS into a reaction kettle provided with a reflux device, nitrogen, a thermometer and a stirring device, adding a solvent to dissolve the SIS, heating an acrylate monomer to 65 ℃, introducing nitrogen for 30 minutes, adding an initiator accounting for 0.15 to 0.4wt percent of the total amount of the monomers, reacting for 12 hours, and cooling to room temperature, wherein the solid content of the glue is 45 to 50wt percent.
The pressure-sensitive adhesive tape comprises the following components: the PET base material with the surface tension less than 50mN/cm and the adhesive film for the low-surface-energy adhesive composition have the preparation method that: mixing the copolymer with tackifying resin, a cross-linking agent and a solvent, standing for defoaming, coating the mixture on a release film by using a coating shaft, baking the release film for 10min at 120 ℃, then adhering the release film to a PET film with the thickness of 25 mu m and processed by a corona surface treatment mode, and standing the release film for 7 days at normal temperature to prepare the pressure-sensitive adhesive tape.
The monomers, initiators, solvents, tackifying resins and curing agents used in the present invention are shown in Table 1 for short:
Figure BDA0002262468130000071
Figure BDA0002262468130000081
TABLE 1 raw materials and reagents
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited to these examples.
Example 1
The polymer formulation is shown in Table 2, and the synthesis is illustrated below by example C-1 and comparative example CE-1:
Figure BDA0002262468130000082
Figure BDA0002262468130000101
table 2 polymerization formulation example C-1: in the presence of mechanical stirring, N2Through port, thermometer and condensed water in a 2L reactor, 20 parts of EVA, 60 parts of 2-EHA, 5 parts of beta-CEA, 5 parts of Veova10, 5 parts of IBOA and 62 parts of EtAc are added, fully stirred, heated to 65 ℃ and N2The flow rate was 0.5/min and N was applied for 30 minutes2Then, 0.15 part of AIBN was added, the mixture was reacted at 65 ℃ under N2 for 12 hours, cooled to room temperature, and diluted with 60 parts of Hex.
CE-1: in the presence of mechanical stirring, N285 parts of 2-EHA, 5 parts of beta-CEA, 5 parts of Veova10, 5 parts of IBOA and 62 parts of EtAc were added to a 2L reactor with a port, a thermometer and condensed water, and the mixture was stirred sufficiently, heated to 65 ℃ and N was added2The flow rate was 0.5/min and N was applied for 30 minutes2Then adding 0.3 part of BPO, and maintaining the temperature at 65 ℃ and N2After 12 hours of ambient reaction, cool to room temperature and dilute by adding 60 parts of Hex.
Preparing the pressure-sensitive adhesive tape:
Figure BDA0002262468130000102
Figure BDA0002262468130000111
table 3 examples of adhesive formulations
The adhesive tape was prepared from the formulation given in Table 3, mixed, coated and cured, as exemplified in example A, by the following procedure:
weighing 100 parts of copolymer 1, 30 parts of TP96 and 1 part of GA240, fully mixing, standing for defoaming, coating the copolymer on a release film by using a coating shaft, heating at 120 ℃ for 5 minutes, then laminating the release film with a PET film which is 50um thick and is subjected to a corona surface treatment mode, ensuring that the thickness of the adhesive film is 50um, and standing at normal temperature for 7 days to obtain the adhesive film.
The sample was cut into a 2.5cm wide strip and tested as follows.
180 ° peel adhesion test: test methods were performed as described in ASTM international standard D3330 method a, test panels including stainless steel (SUS), polypropylene (PP), Polyethylene (PE), Polycarbonate (PC), and Acrylonitrile Butadiene Styrene (ABS). After application, the average adhesion required to tear the bar from the panel is expressed in gf/25mm after 20min of standing under humidity conditions of the test thermometer.
90 ° peel adhesion test: the test method was performed as described in ASTM international standard D3330 method F, and the test panels included stainless steel (SUS) and Polyethylene (PE). After application, the average adhesion required to tear the bar from the panel is expressed in gf/25mm after 20min of standing under humidity conditions of the test thermometer.
Static shear holding force test at 85 ℃: the static shear holding capacity test was carried out as described in procedure A of ASTM International Standard D3654, with a test area of 25 x 25mm, a load of 1000g, an oven temperature of 85 ℃, a test plate of stainless steel (SUS) and a test result expressed as a sliding distance in mm in 1 hour.
Figure BDA0002262468130000121
TABLE 4 test of adhesive tape Properties
When stainless steel panels were used, all samples had better shear resistance at 85 ℃, no failure and no falling occurred, and the cohesion was significantly improved after grafting EVA. As summarized in Table 4, CE-1 and CE-2 contained only acrylate polymer, without grafted EVA. Although having higher adhesion on SUS, PC and ABS panels of high surface energy, the adhesion to low surface energy substrates such as PP and PE is less. In contrast, by grafting of EVA, adhesion to low surface energy substrates PP and PE can be significantly improved while maintaining good adhesion to high surface energy substrates.
Figure BDA0002262468130000122
Figure BDA0002262468130000131
Table 5 compares the adhesive properties of commercially available adhesives and tapes
Table 5 shows the performance test results for example J compared to various commercially available low surface energy adhesive tapes, and in comparison, example J provides adequate adhesion to low surface energy substrates, as well as good adhesion to various other substrates, while having adequate cohesive strength.
Example 2
The polymer formulation is shown in Table 6, and the synthesis is illustrated below by example C-1 and comparative example CE-1:
Figure BDA0002262468130000132
Figure BDA0002262468130000141
table 6 polymerization formulation example C-1: in the presence of mechanical stirring, N210 parts of SIS, 70 parts of 2-EHA, 5 parts of beta-CEA, 5 parts of Veova10, 5 parts of IBOA and 62 parts of EtAc were added to a 2L reactor with a port, a thermometer and condensed water, and the mixture was stirred sufficiently and heated to 65 deg.CNitrogen flow of 0.5/min, and 30 minutes of nitrogen, adding 0.15 part of AIBN, maintaining 65 ℃ and nitrogen environment for 12 hours, cooling to room temperature, and adding 60 parts of Hex for dilution.
CE-1: in the presence of mechanical stirring, N285 parts of 2-EHA, 5 parts of β -CEA, 5 parts of Veova10, 5 parts of IBOA and 62 parts of EtAc were added to a 2L reactor equipped with a port, a thermometer and condensed water, and the mixture was stirred sufficiently, heated to 65 ℃ under nitrogen flow at 0.5/min, and then 0.3 parts of BPO was added thereto after 30 minutes of nitrogen gas introduction, and the mixture was cooled to room temperature after maintaining 65 ℃ under nitrogen atmosphere for 12 hours, and then diluted with 60 parts of Hex.
Preparing the pressure-sensitive adhesive tape:
examples of the invention Copolymer TP96 B115 GA240 CX-100 AAA
A C-1 30 / 0.2 / /
B C-2 / 15 / 0.1 /
C C-3 35 / / / 0.15
D C-4 / 40 / 0.2 /
E C-5 20 / 0.05 / /
F C-6 / 30 / / 0.2
G C-7 15 / / 0.05 /
H C-8 15 15 / / 0.09
I C-9 10 30 0.12 / /
J C-10 20 5 / 0.16 /
K CE-1 25 5 0.1 / /
L CE-2 15 10 / 0.12 /
M CE-3 5 20 / / 0.14
Table 7 examples of adhesive formulations
The adhesive tape was prepared from the formulation given in Table 7, mixed, coated and cured, using example A as an example, by the following procedure:
weighing 100 parts of copolymer 1, 30 parts of TP96 and 1 part of GA240, fully mixing, standing for defoaming, coating the copolymer on a release film by using a coating shaft, heating at 120 ℃ for 5 minutes, then laminating the release film with a PET film which is 25um thick and is subjected to a corona surface treatment mode, ensuring that the thickness of the adhesive film is 50um, and standing at normal temperature for 7 days to obtain the adhesive film.
The sample was cut into a 2.5cm wide strip and tested as follows.
90 ° peel adhesion test: test methods were performed as described in ASTM international standard D3330 method F, test panels including stainless steel (SUS), polypropylene (PP), Polyethylene (PE), Polycarbonate (PC), and Acrylonitrile Butadiene Styrene (ABS). After application, the average adhesion required to tear the bar from the panel is expressed in gf/25mm after 20min of standing under humidity conditions of the test thermometer.
180 ° peel adhesion test: test methods were performed as described in ASTM international standard D3330 method a, test panels including stainless steel (SUS), polypropylene (PP), Polyethylene (PE), Polycarbonate (PC), and Acrylonitrile Butadiene Styrene (ABS). After application, the average adhesion required to tear the bar from the panel is expressed in gf/25mm after 20min of standing under humidity conditions of the test thermometer.
Static shear holding force test at 85 ℃: the static shear holding capacity test was carried out as described in procedure A of ASTM International Standard D3654, with a test area of 25 x 25mm, a load of 1000g, an oven temperature of 85 ℃, a test plate of stainless steel (SUS) and a test result expressed as a sliding distance in mm in 1 hour.
Figure BDA0002262468130000161
TABLE 8 test of adhesive tape Properties
All samples had better shear resistance at 85 ℃ with no drop out due to failure when stainless steel faceplates were used, and the cohesion was significantly improved after grafting of the SIS. As summarized in Table 8, CE-1 and CE-2 contained only acrylate polymer, without grafted SIS. Although having higher adhesion on SUS, PC and ABS panels of high surface energy, the adhesion to low surface energy substrates such as PP and PE is less. In contrast, by grafting of SIS, adhesion to low surface energy substrates PP and PE can be significantly improved while maintaining good adhesion to high surface energy substrates.
Figure BDA0002262468130000162
Figure BDA0002262468130000171
Table 9 comparison with commercially available Adhesives and tape Performance testing
Table 9 shows the performance test results for example J compared to various commercially available low surface energy adhesive tapes, and in comparison, example J provides adequate adhesion to low surface energy substrates, as well as good adhesion to various other substrates, while having adequate cohesive strength.
In summary, the low surface energy adhesive composition and the pressure sensitive adhesive tape prepared by the invention have the following beneficial effects: the surface energy of the acrylic glue is reduced by selecting monomer raw materials, proportioning different monomers and adjusting a polymerization process; by selecting tackifying resin with proper polarity for matching, the pressure-sensitive adhesive has good overall compatibility, small polarity and low surface energy; the surface energy of the acrylic acid series pressure-sensitive adhesive can be reduced by introducing ethylene-vinyl acetate with small polarity and high ethylene content for graft copolymerization, and the disadvantages of no aging resistance and high temperature resistance can also be avoided.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (9)

1. A composition for a low surface energy adhesive, characterized in that: comprising a copolymer comprising an acrylate monomer, a polar cross-linkable monomer and a non-polar monomer, said copolymer further comprising EVA or SIS, wherein said copolymer has a weight average molecular weight of 500000 to 1000000 g/mole, 15 to 40 parts of a resin or mixture of resins per 100 parts of said copolymer, and 0.05 to 0.2 parts of a cross-linking agent per 100 parts of said copolymer.
2. The composition of claim 1, wherein the adhesive composition comprises: the acrylate monomer is present in an amount of 60 to 85wt%, the polar crosslinkable monomer is present in an amount of 2.5 to 5wt%, the non-polar monomer is present in an amount of 2.5 to 15wt%, and the EVA is present in an amount of 10 to 20wt%, wherein the copolymer has a weight average molecular weight of 600000 to 900000 g/mol.
3. A composition for a low surface energy adhesive as defined in claim 2, wherein: the resin or the mixture of the resins is one or two of rosin resin and C9 petroleum resin, the softening point of the rosin resin is between 80 and 140 ℃, and the softening point of the C9 petroleum resin is between 90 and 115 ℃.
4. The composition of claim 1, wherein the adhesive composition comprises: the acrylate monomer content is 70 to 90wt%, the polar crosslinkable monomer content is 2.5 to 5wt%, the non-polar monomer content is 2.5 to 15wt%, and the SIS content is 5 to 10 wt%; wherein the copolymer has a weight average molecular weight of 500000 to 1000000 g/mole.
5. The composition of claim 4, wherein the adhesive composition comprises: the resin or the mixture of the resins is one or two of terpene resin and terpene phenol resin, the softening point of the terpene resin is between 80 and 120 ℃, and the softening point of the terpene phenol resin is between 115 and 150 ℃.
6. The composition of claim 1, wherein the adhesive composition comprises: the acrylate monomer is any one of 2-ethylhexyl acrylate, isooctyl acrylate or dodecyl methacrylate; the polar crosslinkable monomer is any one of acrylic acid, itaconic acid or beta-acryloxypropionic acid; the nonpolar monomer is any one of isobornyl acrylate, tetrahydrofuran acrylate or a mixture of isobornyl acrylate and vinyl neodecanoate; the cross-linking agent is any one or a combination of more of an epoxy curing agent, an N-propyl pyridine curing agent or a metal chelate.
7. The composition of claim 1, wherein the adhesive composition comprises: the copolymer is obtained by thermal polymerization in a solvent, wherein the solvent comprises any one or more of ethyl acetate, toluene, butanone, butyl acetate and n-hexane; the initiator used in the polymerization process is any one of azobisisobutyronitrile, dibenzoyl peroxide or dimethyl azobisisobutyrate.
8. A pressure-sensitive adhesive tape characterized in that: the adhesive comprises a PET substrate and an adhesive film, wherein the surface tension of the PET substrate is less than 50mN/cm, the adhesive film consists of the adhesive composition for low surface energy in any one of claims 1 to 3 and 6 to 7, and the preparation method comprises the following steps:
(1) adding EVA into a reaction kettle provided with a reflux device, introducing nitrogen, a thermometer and a stirring device, adding a solvent to dissolve the EVA, adding an acrylate monomer, a polar crosslinkable monomer and a non-polar monomer, heating to 65 ℃, introducing nitrogen for 30 minutes, adding an initiator accounting for 0.15 to 0.4wt% of the total amount of the monomers, reacting for 12 hours, and cooling to room temperature to obtain a copolymer, wherein the solid content of the copolymer is 45 to 50 wt%;
(2) and mixing the copolymer with resin or a mixture of the resin, a cross-linking agent and a solvent, standing for defoaming, coating the mixture on a release film by using a coating shaft, baking for 10min at 120 ℃, then adhering the release film to a PET (polyethylene terephthalate) substrate with the thickness of 50 mu m and subjected to corona surface treatment, and standing at normal temperature for 7 days to obtain the pressure-sensitive adhesive tape.
9. A pressure-sensitive adhesive tape characterized in that: the adhesive comprises a PET substrate and an adhesive film, wherein the surface tension of the PET substrate is less than 50mN/cm, the adhesive film consists of the composition for the low-surface-energy adhesive disclosed by any one of claims 1 and 4-7, and the preparation method comprises the following steps:
(1) adding SIS into a reaction kettle provided with a reflux device, nitrogen, a thermometer and a stirring device, adding a solvent to dissolve the SIS, adding an acrylate monomer, a polar crosslinkable monomer and a non-polar monomer, heating to 65 ℃, introducing nitrogen for 30 minutes, adding an initiator accounting for 0.15 to 0.4wt% of the total amount of the monomers, reacting for 12 hours, and cooling to room temperature to obtain a copolymer, wherein the solid content of the copolymer is 45 to 50 wt%;
(2) and mixing the copolymer with resin or a mixture of the resin, a cross-linking agent and a solvent, standing for defoaming, coating the mixture on a release film by using a coating shaft, baking for 10min at 120 ℃, then adhering the release film to a PET (polyethylene terephthalate) substrate with the thickness of 25 mu m and subjected to corona surface treatment, and standing at normal temperature for 7 days to obtain the pressure-sensitive adhesive tape.
CN201911076010.2A 2019-11-06 2019-11-06 Adhesive composition for low surface energy and pressure-sensitive adhesive tape Pending CN110713812A (en)

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CN101698783A (en) * 2009-04-30 2010-04-28 北京高盟化工有限公司 Dry-type compound aqueous paper/plastic laminating emulsion adhesive and preparation method thereof
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CN103351833A (en) * 2013-08-01 2013-10-16 烟台德邦科技有限公司 Preparation method of liquid strippable glue for surface protection film
CN104559857A (en) * 2014-12-31 2015-04-29 东莞市澳中电子材料有限公司 Acrylic acid modified hot-melt pressure-sensitive adhesive for bearing adhesive tape and preparation method of acrylic acid modified hot-melt pressure-sensitive adhesive
CN106753087A (en) * 2017-03-15 2017-05-31 怀化大自然化工有限公司 A kind of aqueous, environmental protective all-purpose adhesive and preparation method thereof
CN109852268A (en) * 2019-03-13 2019-06-07 新纶科技（常州）有限公司 One kind gluing dead type without substrate double faced adhesive tape and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090035594A1 (en) * 2007-08-01 2009-02-05 Lee Chun D Rheology-modified grafts and adhesive blends
CN101698783A (en) * 2009-04-30 2010-04-28 北京高盟化工有限公司 Dry-type compound aqueous paper/plastic laminating emulsion adhesive and preparation method thereof
CN101775263A (en) * 2010-03-15 2010-07-14 日邦树脂(无锡)有限公司 Moisture cured multi-constituties grafting solvent-based adhesive
CN102433094A (en) * 2011-10-19 2012-05-02 常州市宝丽胶粘剂有限公司 Preparation of novel adhesive for low-surface-energy substrate
CN103351833A (en) * 2013-08-01 2013-10-16 烟台德邦科技有限公司 Preparation method of liquid strippable glue for surface protection film
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CN109852268A (en) * 2019-03-13 2019-06-07 新纶科技（常州）有限公司 One kind gluing dead type without substrate double faced adhesive tape and preparation method thereof

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