CN113528030B - Flame-retardant UV (ultraviolet) photocuring acrylate pressure-sensitive adhesive as well as preparation method and application thereof - Google Patents

Flame-retardant UV (ultraviolet) photocuring acrylate pressure-sensitive adhesive as well as preparation method and application thereof Download PDF

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CN113528030B
CN113528030B CN202010304641.1A CN202010304641A CN113528030B CN 113528030 B CN113528030 B CN 113528030B CN 202010304641 A CN202010304641 A CN 202010304641A CN 113528030 B CN113528030 B CN 113528030B
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acrylate
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sensitive adhesive
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CN113528030A (en
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谢琴妍
林晓丹
刘星
曾诚
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Xintian Derun New Material Industrial Park Co ltd
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J7/385—Acrylic polymers
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a flame-retardant UV (ultraviolet) photocuring acrylate pressure-sensitive adhesive as well as a preparation method and application thereof. The flame-retardant UV-cured acrylate pressure-sensitive adhesive is prepared from the following components in parts by weight: 30-45 parts of an acrylate prepolymer, 0.5-5 parts of a small-molecular acrylate monomer, 50-70 parts of aluminum hydroxide, 0.1-1 part of magnesium oxide whisker and a first photoinitiator, wherein the acrylate prepolymer is prepared from 70-75 parts by weight of isooctyl acrylate, 10-15 parts by weight of butyl acrylate, 10-15 parts by weight of acrylic acid and 1-5 parts by weight of N, N-dimethylacrylamide. The flame-retardant UV-cured acrylate pressure-sensitive adhesive disclosed by the invention has good bonding performance and flame-retardant performance, the flame-retardant grade can reach V-0 grade, the bonding strength can reach 20.1N/25mm, the mechanical strength and toughness are good, the preparation process is simple, the cost is low, and no pollution is caused to the environment.

Description

Flame-retardant UV (ultraviolet) photocuring acrylate pressure-sensitive adhesive as well as preparation method and application thereof
Technical Field
The invention belongs to the technical field of pressure-sensitive adhesives, and particularly relates to a flame-retardant UV (ultraviolet) photocuring acrylate pressure-sensitive adhesive as well as a preparation method and application thereof.
Background
The acrylate adhesive synthesized by taking acrylic acid or acrylate as a main raw material has excellent light stability, weather resistance, good film forming property, adhesion, corrosion resistance, chemical resistance and flexibility, so that the acrylate adhesive can be used for bonding various materials. The UV light-cured acrylate adhesive can serve a plurality of application fields, and is used in the field of photoelectricity in the manufacturing industry of LCD (liquid crystal display), the manufacturing industry of optical products such as cameras and the like, and the manufacturing industry of compact discs (CD, VCD, DVD and DVD-R); in the electronic field, the surface element is used for adhering a Printed Circuit Board (PCB), a coil, a liquid crystal display, watch manufacturing industry and the assembly of mobile phone keys; the adhesive is used for assembling automobile lamps, adhering a rearview mirror and an air bag part, and producing a fuel injection system, an equipment panel, a cylinder gasket, a steering wheel and the like in the automobile field; the glass is used for manufacturing glass furniture, assembling glass artware and assembling toys and jewelry ornaments in the field of daily necessities.
And because the acrylate adhesive is a polymer, the acrylate adhesive can be decomposed into unstable combustible substances under the condition of heat or ignition, thereby causing fire. In order to ensure the safety of the adhesive tape during use and transportation, the adhesive tape needs to be endowed with flame retardance, in the prior art, a sufficient amount of flame retardant is added into the adhesive to meet the flame retardant effect, but the adhesive property of the adhesive is reduced and the toughness is poor along with the increase of the addition amount of the flame retardant.
The invention discloses a phosphorus-containing acrylate elastomer flame retardant and a preparation method thereof, wherein (diethoxyphosphine) methyl acrylate (DEAMP) is used as a flame-retardant monomer, and the phosphorus-containing acrylate elastomer flame retardant is prepared by an emulsion polymerization method, has flame-retardant and toughening functions, can improve the mechanical property of acrylate adhesive, but has insufficient bonding property.
Patent application No. CN110128967A discloses a preparation method of a flame retardant adhesive, which can prepare a flame retardant adhesive tape with good bonding performance and flame retardant effect by mixing acrylate polymer, tackifying resin, flame retardant and cross-linking agent, but according to tests, the situation that the acrylate polymer is incompatible with the tackifying resin can occur along with the addition of the tackifying resin, thereby affecting the uniformity and stability of the adhesive tape.
The patent application with the application number of CN109628029A discloses a preparation method of a halogen-free flame-retardant acrylate pressure-sensitive adhesive, which comprises the following raw materials in parts by weight: 10-15 parts of lauryl acrylate, 10-15 parts of butyl acrylate, 3-5 parts of acrylic acid, 6-9 parts of vinyl acetate, 7-10 parts of methyl methacrylate, 5-10 parts of acrylic polyether phosphate, 7-10 parts of a phosphorus-nitrogen flame retardant, 40-55 parts of a solvent and 0.2-0.5 part of an initiator, wherein the pressure-sensitive adhesive uses a methyl methacrylate monomer with higher glass transition temperature, the temperature resistance of the pressure-sensitive adhesive is improved, the bonding property of the pressure-sensitive adhesive is improved by introducing a hydrogen bond, but the existence and volatilization of the solvent in the preparation process can affect the environment.
Therefore, there is a need to develop a flame retardant acrylate adhesive which has both flame retardant property and adhesive property, and has simple preparation process and no pollution.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the flame-retardant UV (ultraviolet) photocuring acrylate pressure-sensitive adhesive. The acrylate adhesive has good adhesive property and flame retardant property, the flame retardant grade can reach V-0 grade, the adhesive strength can reach 20.1N/25mm, the mechanical strength and the toughness are good, the preparation process is simple, the cost is low, and the environment is not polluted.
The invention also aims to provide a preparation method of the flame-retardant UV light-cured acrylate pressure-sensitive adhesive.
The invention further aims to provide application of the flame-retardant UV light-cured acrylate pressure-sensitive adhesive.
The purpose of the invention is realized by the following technical scheme:
the flame-retardant UV (ultraviolet) photocuring acrylate pressure-sensitive adhesive is prepared from the following components in parts by weight:
30-45 parts of an acrylate prepolymer, 0.5-5 parts of a small molecular acrylate monomer, 50-70 parts of aluminum hydroxide, 0.1-1 part of magnesium oxide whisker and a first photoinitiator;
the acrylate prepolymer is prepared by polymerizing 70-75 parts by weight of isooctyl acrylate, 10-15 parts by weight of butyl acrylate, 10-15 parts by weight of acrylic acid and 1-5 parts by weight of N, N-dimethylacrylamide under the action of 0.01-0.05 part by weight of a second photoinitiator and 0.1-0.5 part by weight of a chain transfer agent dodecyl mercaptan through ultraviolet irradiation;
the addition amount of the first photoinitiator is 1-5 per mill of the mass of the acrylate prepolymer.
Preferably, the flame-retardant UV light-cured acrylate pressure-sensitive adhesive is prepared from the following components in parts by weight: 33-43 parts of acrylate prepolymer, 0.5-5 parts of small molecular acrylate monomer, 52.5-62 parts of aluminum hydroxide, 0.1-1 part of magnesium oxide whisker and a first photoinitiator.
More preferably, the flame-retardant UV light-cured acrylate pressure-sensitive adhesive is prepared from the following components in parts by weight: 33-38.5 parts of acrylate prepolymer, 4 parts of small molecular acrylate monomer, 52.5-57 parts of aluminum hydroxide, 0.5 part of magnesium oxide whisker and a first photoinitiator.
Preferably, the viscosity of the acrylate adhesive prepolymer is 300-400 mPa.s. The viscosity of the acrylate prepolymer is controlled by controlling the temperature of the prepolymer and the dilution concentration of the monomer in the preparation process of the prepolymer.
Preferably, the small-molecular acrylate monomer is isobornyl acrylate, hydroxyethyl acrylate and isooctyl acrylate according to a mass ratio of (1-5): (0.4-2): (0.6-3) mixing the obtained mixture.
Preferably, the particle size of the aluminum hydroxide is 800-8000 meshes, and the aluminum hydroxide powder is a mixture of particles with different particle sizes.
Preferably, the particle size of the magnesium oxide whisker is 4-10 μm, and the magnesium oxide whisker is a mixture of particles with different particle sizes.
Preferably, the first photoinitiator is 184 photoinitiator and the second photoinitiator is TPO photoinitiator.
The preparation method of the flame-retardant UV photocuring acrylate pressure-sensitive adhesive comprises the following steps:
(1) uniformly mixing 70-75 parts by weight of isooctyl acrylate, 10-15 parts by weight of butyl acrylate, 0.01-0.05 part by weight of a second photoinitiator and 0.1-0.5 part by weight of dodecyl mercaptan, then adding 10-15 parts by weight of acrylic acid and 1-5 parts by weight of N, N-dimethylacrylamide, uniformly mixing, carrying out photopolymerization under the irradiation of UV light, and introducing air to terminate the reaction when the reaction temperature reaches 80-85 ℃ to obtain an acrylate prepolymer;
(2) adding a small molecular acrylate monomer into the acrylate prepolymer, stirring and dissolving, adding a first photoinitiator, stirring and dissolving, adding aluminum hydroxide and magnesium oxide whiskers, and uniformly mixing to obtain an acrylate pressure-sensitive adhesive solution;
(3) and coating the acrylate pressure-sensitive adhesive solution on a polyester film, covering a release film to isolate oxygen, and curing under UV light to obtain the flame-retardant UV-cured acrylate pressure-sensitive adhesive.
Preferably, the energy of the UV light in the step (3) is 150 mJ/cm2~768 mJ/cm2。
Preferably, the curing time in the step (3) is 350-600 s.
The application of the flame-retardant UV photocuring acrylate pressure-sensitive adhesive is provided.
The flame-retardant UV photocuring acrylate pressure-sensitive adhesive has the advantages of flame retardance, bonding property, good surface property and good toughness, and is suitable for the fields of automobiles, electronic devices, electric appliances and the like.
The pressure-sensitive adhesive adopts a specific acrylate prepolymer, a specific flame retardant and a specific micromolecule monomer, and the acrylate prepolymer, the flame retardant, the micromolecule monomer and a photoinitiator are compounded according to a specific proportion, so that the pressure-sensitive adhesive has good flame retardant property and adhesive property through the interaction between the acrylate prepolymer, the flame retardant and the micromolecule monomer.
In the invention, the bonding force is provided by adding the soft monomers of isooctyl acrylate and butyl acrylate, and the long side chain alkyl groups of the monomers moderate the interaction between the main chains of the high polymers, play a role in internal plasticization and reduce the glass transition temperature of the monomers; modified monomers such as acrylic acid, hydroxyethyl acrylate and N, N-dimethylacrylamide are added, and the modified monomers have functional groups such as carboxyl, hydroxyl and amino, so that the cohesive strength and the bonding strength of the pressure-sensitive adhesive can be obviously improved under the action of intermolecular polar force and intermolecular hydrogen bonds.
The flame retardant adopts the aluminum hydroxide, and the aluminum hydroxide serving as the flame retardant not only can retard flame, but also can prevent fuming, does not produce drippings and does not produce toxic gas; however, in the prior art, if the effect of the flame retardant adhesive reaches the V-0 grade, a large amount of aluminum hydroxide powder needs to be added into the acrylate adhesive, which causes the bonding strength of the acrylate adhesive to be reduced. Experiments of the invention show that as the mass part of acrylic acid in the acrylate adhesive is increased, the mass part of aluminum hydroxide required by the acrylate adhesive for reaching the flame retardant grade V-0 grade is reduced compared with that in the prior art, which shows that a neutralizing substance generated under the reaction of the acrylic acid and the aluminum hydroxide is beneficial to the flame retardant effect of the acrylate adhesive, and simultaneously, the cohesive strength and the bonding strength of the flame retardant adhesive can also be increased.
The invention also adds a small amount of magnesium oxide whisker filler to improve the thermal stability of the material, effectively reduces the decomposition rate of the acrylate adhesive material at high temperature by matching with the flame retardant, achieves good flame retardant effect, is beneficial to improving the mechanical strength of the acrylate adhesive and improves the toughness of the acrylate adhesive.
According to the invention, the bonding strength and cohesive strength of the acrylate adhesive material are effectively improved by adjusting the composition structure and the curing mechanism of the acrylate adhesive, and the flame retardant effect is excellent. Compared with the existing flame retardant adhesive material, the UV curing acrylate pressure-sensitive adhesive has the advantages of simple process and low cost when in use, has better bonding strength than the common flame retardant adhesive material, and has better mechanical strength and toughness.
The preparation method has the advantages of simple process, short time consumption, high efficiency, low cost, less volatile components and little influence on the environment.
Compared with the prior art, the invention has the following advantages and beneficial effects:
according to the invention, a specific kind of acrylate prepolymer and a specific kind of small molecular monomer are adopted, and the acrylate prepolymer, the small molecular monomer and a photoinitiator are compounded according to a specific proportion, so that the cohesive strength and the bonding strength of the acrylate adhesive are improved under the action of introducing functional groups such as hydroxyl, carboxyl, amino and the like through the action of hydrogen bonds; then adding a flame retardant aluminum hydroxide, wherein the aluminum hydroxide has excellent flame retardant effect and further enhances the flame retardant effect, cohesive strength and bonding strength of the flame retardant acrylate adhesive under the action of acrylic acid in the original adhesive; and the added magnesia whiskers further enhance the thermal stability and toughness of the material. Compared with the existing flame-retardant adhesive material, the flame-retardant UV-cured acrylate pressure-sensitive adhesive has the advantages of simple process and low cost when in use, the flame-retardant grade can reach V-0 grade, the bonding strength is superior to that of the common flame-retardant adhesive material, and the mechanical strength and the toughness are good.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
The preparation method of the UV-cured acrylate pressure-sensitive adhesive provided by the embodiment of the invention comprises the following steps:
(1) preparation of acrylate prepolymer
Uniformly mixing 75 parts by weight of isooctyl acrylate, 10 parts by weight of butyl acrylate, 0.01 part by weight of second photoinitiator (TPO) and 0.1 part by weight of dodecyl mercaptan, adding 10 parts by weight of acrylic acid and 5 parts by weight of N, N-dimethylacrylamide, fully stirring, introducing nitrogen into a reaction device, carrying out photopolymerization under the irradiation of UV (ultraviolet) light, and introducing air when the temperature of the prepolymer reaches 85 ℃ to terminate the reaction, thereby obtaining an acrylate prepolymer (the viscosity is 350 mPa.s).
(2) Preparation of pressure-sensitive adhesive liquid
Adding 4 parts by weight of small-molecular acrylate monomer mixture into 38.5 parts by weight of acrylate prepolymer, fully stirring, adding a first photoinitiator (184) into the obtained solution, stirring and dissolving (the photoinitiator can be rapidly dissolved by micro-heating assistance), and obtaining an acrylate adhesive solution, wherein the adding amount of a second photoinitiator is five per thousand of the mass of the acrylate prepolymer.
In the method, the mass ratio of each monomer in the small molecule acrylate monomer mixture is as follows: isobornyl acrylate (IBOA): hydroxyethyl acrylate (HEA): isooctyl acrylate (2-EHA) = 5: 2; 3.
and then, continuously adding 57 parts by mass of aluminum hydroxide powder (with the particle size of 800-8000 meshes) and 0.5 part by mass of magnesium oxide whiskers (with the particle size of 4-10 microns) into the acrylate adhesive solution, and fully stirring to obtain the flame-retardant acrylate adhesive.
(3) Coating film
Coating the flame-retardant acrylate adhesive obtained in the step (2) on a polyester film, covering a release film to isolate oxygen, and curing the polyester film for 600s under an ultraviolet lamp (the illumination energy is 768 mJ/cm)2) And obtaining the solvent-free flame-retardant UV-cured acrylate pressure-sensitive adhesive.
Performance testing
The pressure-sensitive adhesive sample obtained after the coating film in this example was cured was cut and stored, and the 180 ° peel strength of the adhesive tape adhered to a stainless steel sheet was tested according to the GB/T2792-81 standard, with the test results shown in table 1.
The pressure-sensitive adhesive sample obtained after the coating film in the embodiment is cured is cut into strips and stored, and the flame retardant grade of the adhesive tape is tested on a horizontal vertical combustion instrument according to the UL94-2006 standard. The test results are shown in table 1.
Examples 2 to 7
Examples 2 to 7 were prepared in the same manner as in example 1, wherein the mass ratio of isooctyl acrylate (2-EHA) to hydroxyethyl acrylate (HEA) in step (2) was constantly 3: 2, only the mixture ratio of isobornyl acrylate (IBOA) to the total mass of isooctyl acrylate and hydroxyethyl acrylate (HEA + 2-EHA) is changed, and the specific mixture ratio is shown in Table 1.
Performance testing
The pressure-sensitive adhesive samples obtained after the coating films in the embodiments 1-7 are cured are cut into strips and stored, the 180-degree peel strength of the adhesive tape adhered to the stainless steel sheet is tested according to the GB/T2792-81 standard, and the test results are shown in Table 1.
The pressure-sensitive adhesive sample obtained after the coating films in the embodiments 1-7 are cured is cut into strips and stored, and the flame retardant grade of the adhesive tape is tested on a horizontal vertical combustion instrument according to the UL94-2006 standard. The test results are shown in table 1.
TABLE 1 formulation (wt%) of UV-curable acrylate pressure-sensitive adhesive and test results
Figure 231747DEST_PATH_IMAGE001
According to the data of the examples 1-7 in the table 1, when the addition amount of the aluminum hydroxide is 57 parts and the amount of the magnesium oxide whisker is 0.5 part, the flame retardant grade of the flame retardant adhesive can reach V-0, and the flame retardant property is good. Then, with different ratios of the small molecule monomer isobornyl acrylate (IBOA), isooctyl acrylate and hydroxyethyl acrylate (HEA + 2-EHA), the peel strength of the flame retardant adhesive is different, and as can be seen from the data in the table, the peel strength of examples 1, 2, 4, 5 and 7 is all larger than 17N/mm, the peel strength is excellent and exceeds the peel strength of the common flame retardant adhesive in the market, and the peel force of example 5 is the highest, the synergistic effect between each small molecule monomer, the prepolymer and the filler is the best, and the cohesive strength and the peel strength are the best, which is the best example.
Example 8
The preparation method of the UV-cured acrylate pressure-sensitive adhesive provided by the embodiment of the invention comprises the following steps:
(1) preparation of acrylate prepolymer
Uniformly mixing 75 parts by weight of isooctyl acrylate, 10 parts by weight of butyl acrylate, 0.01 part by weight of second photoinitiator (TPO) and 0.1 part by weight of dodecyl mercaptan, adding 10 parts by weight of acrylic acid and 5 parts by weight of N, N-dimethylacrylamide, fully stirring, introducing nitrogen into a reaction device, carrying out photopolymerization under the irradiation of UV (ultraviolet) light, and introducing air when the temperature of the prepolymer reaches 85 ℃ to terminate the reaction, thereby obtaining an acrylate prepolymer (the viscosity is 350 mPa.s).
(2) Preparation of pressure-sensitive adhesive liquid
Adding 4 parts by weight of acrylate small-molecular monomer mixture into 43 parts by weight of acrylate prepolymer, fully stirring, adding a first photoinitiator (184) into the obtained solution, stirring and dissolving (the photoinitiator can be rapidly dissolved by slight heating assistance), and obtaining an acrylate adhesive solution, wherein the adding amount of a second photoinitiator is five per thousand of the mass of the acrylate prepolymer.
In the method, the mass ratio of each monomer in the small molecule acrylate monomer mixture is as follows: hydroxyethyl acrylate (HEA): isooctyl acrylate (2-EHA) = 2; isobornyl acrylate (IBOA), a mixture of hydroxyethyl acrylate and isooctyl acrylate (HEA + 2-EHA) = 5: 3.
and then, continuously adding 52.5 parts by mass of aluminum hydroxide powder (with the particle size of 800-800 meshes) and 0.5 part by mass of magnesium oxide whiskers (with the particle size of 4-10 microns) into the acrylate adhesive solution, and fully stirring to obtain the flame-retardant acrylate adhesive.
(3) Coating film
Coating the flame-retardant acrylate adhesive obtained in the step (2) on a polyester film, covering a release film to isolate oxygen, and curing the polyester film for 600s under an ultraviolet lamp (the illumination energy is 768 mJ/cm)2) And obtaining the solvent-free flame-retardant UV-cured acrylate pressure-sensitive adhesive.
Performance testing
The pressure-sensitive adhesive sample obtained after curing the coating film in this example 8 was cut and stored, and the 180 ° peel strength of the adhesive tape adhered to a stainless steel sheet was tested according to the GB/T2792-81 standard, with the test results shown in table 2.
The pressure-sensitive adhesive sample obtained after the coating film in the example 8 is cured is cut into strips and stored, and the flame retardant rating of the adhesive tape is tested on a horizontal vertical combustion instrument according to the UL94-2006 standard. The test results are shown in table 2.
Examples 9 to 10
The preparation methods of the embodiments 9-10 are the same as those of the embodiment 8, and only the mixture ratio of the aluminum hydroxide and the acrylate prepolymer in the step (2) is changed, wherein the total weight part of the aluminum hydroxide and the acrylate prepolymer is 95.5 parts, and the specific mixture ratio is shown in table 2.
Comparative example 1
Comparative example 1 the preparation method was the same as in example 8 except that the ratio of aluminum hydroxide to the acrylate prepolymer in step (2) was changed, wherein the total weight of the aluminum hydroxide and the acrylate prepolymer was 95.5 parts, and the specific ratio is shown in table 2.
Performance testing
The pressure-sensitive adhesive samples obtained after curing the coatings in the examples 9-10 and the comparative example 1 were cut and stored, and the 180 ° peel strength of the adhesive tape adhered to the stainless steel sheet was tested according to the GB/T2792-81 standard, with the test results shown in table 2.
The pressure-sensitive adhesive samples obtained after the coatings in the examples 9-10 and the comparative example 1 are cured are cut into strips and stored, and the flame retardant rating of the adhesive tape is tested on a horizontal and vertical combustor according to the UL94-2006 standard. The test results are shown in table 2.
TABLE 2 formulation (wt%) of UV-curable acrylate pressure-sensitive adhesive and test results
Figure DEST_PATH_IMAGE002
As can be seen from the data of examples 8 to 10 and comparative example 1 in Table 2, when the ratio of aluminum hydroxide to prepolymer was 55: 45 hours later, the flame retardant grade of the flame retardant adhesive can reach V-1 grade, and the flame retardant property is good; when the ratio of the aluminum hydroxide to the prepolymer is more than or equal to 55: 45 hours later, the flame retardant grade of the flame retardant adhesive can reach V-0 grade, and the flame retardant property is excellent.
Meanwhile, as can be seen from the data in the table, the flame retardant effect is better as the addition amount of the aluminum hydroxide is increased, but the peel strength is reduced due to the decrease of the fluidity caused by the addition of a large amount of the filler, and the wetting effect of the adhesive and the adherend is weakened, so that the peel force is gradually reduced, and the peel force of the examples 8 and 9 is greater than 17N/mm and exceeds the peel strength of common flame retardant adhesives in the market; the best example is selected when the flame retardant rating of example 9 reaches V-0 rating and the peel force of 20.1N/25mm is the highest.
Comparative examples 2 to 5
The preparation methods of comparative examples 2 to 5 are the same as those of example 1, the specific ratio of the acrylic acid in the acrylate prepolymer in step (1) is changed to table 3, and the mass ratio of the acrylate prepolymer to the aluminum hydroxide in step (2) is changed to 45: 55.
performance testing
The pressure-sensitive adhesive samples obtained after the coatings in comparative examples 2-5 were cured were cut and stored, and the 180 ° peel strength of the adhesive tape adhered to the stainless steel sheet was tested according to the GB/T2792-81 standard, with the test results shown in table 3.
And (3) cutting and storing the pressure-sensitive adhesive sample obtained after the coating is cured in the comparative examples 2-5, and testing the flame retardant grade of the adhesive tape on a horizontal and vertical combustor according to the UL94-2006 standard. The test results are shown in table 3.
TABLE 3 formulation (wt%) of UV-curable acrylate pressure-sensitive adhesive and test results
Figure 758674DEST_PATH_IMAGE003
Comparing the data of comparative examples 2-5 and example 10 in table 3, it can be seen that when the amount of aluminum hydroxide is 55 parts, if no acrylic acid is added to the flame retardant adhesive, the flame retardant effect is not good, and the flame retardant rating is only V-2; when the addition amount of the acrylic acid is less, the flame retardant effect is not obviously affected, but the flame retardant effect is better and better along with the increase of the proportion of the acrylic acid in the flame retardant adhesive, even the flame retardant adhesive can reach V-0 level, but the stripping force is reduced. Therefore, the influence of acrylic acid on the flame-retardant effect of the flame-retardant adhesive is analyzed: when the flame-retardant acrylate adhesive is burnt, the flame-retardant effect of the flame-retardant acrylate adhesive can be obviously improved under the synergistic action of acrylic acid and a flame retardant aluminum hydroxide.
Comparative example 6
Comparative example 6 was prepared in the same manner as in example 1 except that the amount of magnesium oxide whiskers added in step (2) was changed to 0.
Meanwhile, the acrylate pressure-sensitive adhesive sample strips prepared in the comparative example 6 and the example 1 are combusted, and compared with the acrylate pressure-sensitive adhesive sample strip without the magnesium oxide whisker, the acrylate pressure-sensitive adhesive sample strip with the magnesium oxide whisker is more difficult to ignite, which shows that under the assistance of the magnesium oxide whisker, a polymer in the acrylate adhesive is more difficult to decompose at high temperature, so that the flame retardant effect of the acrylate pressure-sensitive adhesive is better; and the toughness and the strength of the pressure-sensitive adhesive can be obviously improved by adding a small amount of magnesium oxide whiskers.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. The flame-retardant UV (ultraviolet) photocuring acrylate pressure-sensitive adhesive is characterized by being prepared from the following components in parts by weight:
30-45 parts of an acrylate prepolymer, 0.5-5 parts of a small molecular acrylate monomer, 50-70 parts of aluminum hydroxide, 0.1-1 part of magnesium oxide whisker and a first photoinitiator;
the acrylate prepolymer is prepared by carrying out photopolymerization under the irradiation of UV (ultraviolet) under the action of 70-75 parts by weight of isooctyl acrylate, 10-15 parts by weight of butyl acrylate, 10-15 parts by weight of acrylic acid and 1-5 parts by weight of N, N-dimethylacrylamide, 0.01-0.05 part by weight of a second photoinitiator and 0.1-0.5 part by weight of a chain transfer agent dodecyl mercaptan, and introducing air to stop the reaction when the reaction temperature reaches 80-85 ℃;
the adding amount of the first photoinitiator is 1-5 per mill of the mass of the acrylate prepolymer;
the viscosity of the acrylate prepolymer is 300-400 mPa.s;
the small-molecular acrylate monomer is prepared from isobornyl acrylate, hydroxyethyl acrylate and isooctyl acrylate according to the mass ratio (1-5): (0.4-2): (0.6-3) mixing the obtained mixture.
2. The flame-retardant UV light-cured acrylate pressure-sensitive adhesive according to claim 1, which is prepared from the following components in parts by weight: 33-43 parts of acrylate prepolymer, 0.5-5 parts of small molecular acrylate monomer, 52.5-62 parts of aluminum hydroxide, 0.1-1 part of magnesium oxide whisker and a first photoinitiator.
3. The flame-retardant UV light-cured acrylate pressure-sensitive adhesive according to claim 2, which is prepared from the following components in parts by weight: 33-38.5 parts of acrylate prepolymer, 4 parts of small molecular acrylate monomer, 52.5-57 parts of aluminum hydroxide, 0.5 part of magnesium oxide whisker and a first photoinitiator.
4. The flame-retardant UV light-cured acrylate pressure-sensitive adhesive according to claim 1, 2 or 3, wherein the particle size of the aluminum hydroxide is 800-8000 meshes; the particle size of the magnesium oxide whisker is 4-10 mu m.
5. The flame retardant UV light curable acrylate pressure sensitive adhesive according to claim 1, 2 or 3, wherein the first photoinitiator is 184 photoinitiator and the second photoinitiator is TPO photoinitiator.
6. The preparation method of the flame-retardant UV light-cured acrylate pressure-sensitive adhesive according to any one of claims 1 to 5, characterized by comprising the following steps:
(1) uniformly mixing 70-75 parts by weight of isooctyl acrylate, 10-15 parts by weight of butyl acrylate, 0.01-0.05 part by weight of a second photoinitiator and 0.1-0.5 part by weight of dodecyl mercaptan, then adding 10-15 parts by weight of acrylic acid and 1-5 parts by weight of N, N-dimethylacrylamide, uniformly mixing, carrying out photopolymerization under the irradiation of UV light, and introducing air to terminate the reaction when the reaction temperature reaches 80-85 ℃ to obtain an acrylate prepolymer;
(2) adding a small molecular acrylate monomer into the acrylate prepolymer, stirring and dissolving, adding a first photoinitiator, stirring and dissolving, adding aluminum hydroxide and magnesium oxide whiskers, and uniformly mixing to obtain an acrylate pressure-sensitive adhesive solution;
(3) and coating the acrylate pressure-sensitive adhesive solution on a polyester film, covering a release film to isolate oxygen, and curing under UV light to obtain the flame-retardant UV-cured acrylate pressure-sensitive adhesive.
7. The method for preparing the flame-retardant UV light-cured acrylate pressure-sensitive adhesive according to claim 6, wherein the energy of the UV light in the step (3) is 150 mJ/cm2~768 mJ/cm2(ii) a The curing time is 350-600 s.
8. The use of the flame-retardant UV light-curable acrylate pressure-sensitive adhesive according to any one of claims 1 to 5 in the fields of automobiles, electronic devices and electric appliances.
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