CN110938394B - Adhesive, preparation method thereof, adhesive layer prepared from adhesive and thermal de-bonding adhesive tape - Google Patents

Adhesive, preparation method thereof, adhesive layer prepared from adhesive and thermal de-bonding adhesive tape Download PDF

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Publication number
CN110938394B
CN110938394B CN201911302772.XA CN201911302772A CN110938394B CN 110938394 B CN110938394 B CN 110938394B CN 201911302772 A CN201911302772 A CN 201911302772A CN 110938394 B CN110938394 B CN 110938394B
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adhesive
layer
tape
thermal
monomer
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CN110938394A (en
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李阜阳
韩晓航
刘源
陈洪野
吴小平
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Suzhou Cybrid Application Technology Co ltd
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Suzhou Cybrid Application Technology 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • 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
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/22—Expandable microspheres, e.g. Expancel®
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/24—Homopolymers or copolymers of amides or imides
    • C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides an adhesive, a preparation method thereof, an adhesive layer prepared from the adhesive and a thermal de-bonding adhesive tape, wherein the adhesive is prepared from the following raw materials: hard monomer, soft monomer, functional monomer, solvent, initiator, curing agent and foaming microsphere. According to the high-temperature-resistant heat-release adhesive tape, a specific monomer is selected for polymerization, so that the high temperature resistance of an adhesive layer is effectively improved, and then, foaming microspheres are creatively introduced into preparation raw materials, so that after the obtained adhesive layer is compounded with a base material layer, a heavy release layer and a light release layer, the high-temperature-resistant heat-release adhesive tape can be obtained, and the adhesive layer and an object to be pasted can be separated through the expansion effect of the microspheres through the foaming of the microspheres, so that the problem of adhesive residue is radically solved; and under specific temperature, the stripping process used by the adhesive tape is simpler, namely, the purposes of reducing the processing procedures and improving the production efficiency are achieved.

Description

Adhesive, preparation method thereof, adhesive layer prepared from adhesive and thermal de-bonding adhesive tape
Technical Field
The invention relates to the technical field of functional adhesive tapes, in particular to an adhesive, a preparation method thereof, an adhesive layer prepared from the adhesive and a thermal de-bonding adhesive tape.
Background
In the semiconductor manufacturing process, when semiconductor wafers are cut and polished, in order to reduce the defect density of silicon thin layers, wafer cutting anti-sticking protective films are often used. In the prior art, a high-temperature-resistant protective film is adopted for bearing, and the protective film is peeled off after a specific temperature is passed. Because be in under the high temperature condition for a long time, traditional high temperature protection film has the cull risk to viscidity after long-time climbs greatly, is difficult for peeling off in later stage.
CN107163869A discloses a thermal viscosity-reducing adhesive tape and a preparation method thereof, which comprises a release film layer, a bottom surface coating, a heat-sensitive adhesive layer and a PO film layer which are arranged from bottom to top in sequence. The PO film is used as the base material of the thermal viscosity reducing adhesive tape, the application range of the thermal adhesive tape is widened, the structure of the thermal adhesive tape is improved according to the characteristics of the PO film, the bottom surface coating is added between the PO film layer and the thermal adhesive layer, the connection between the PO film layer and the thermal adhesive layer is firmer, the fixing capacity of the thermal adhesive tape is improved, and when the PO plastic film is used as the base material, when the adhesive tape is stretched during stripping, the effect that the viscosity of the adhesive tape disappears after the adhesive tape is pulled can be generated. However, the anti-tack adhesive tape obtained by the invention cannot resist high temperature and cannot be used in a high-temperature working environment for a long time.
CN109266236A discloses a high-temperature viscosity-reducing adhesive tape, which comprises a substrate film and a high-temperature viscosity-reducing polyacrylate pressure-sensitive adhesive coated on the substrate film. The polyacrylate with high-temperature crosslinking functional groups and the multifunctional acrylate in the high-temperature viscosity-reducing adhesive tape can be further crosslinked at high temperature, so that the stripping force is greatly reduced, and the high-temperature process adhesive tape is easier to strip; after the high-temperature anti-sticking adhesive tape is heated to 120-160 ℃ and used for 20-30 min, the peeling force is obviously reduced, so that the adhesive tape is easier to peel, the adhesive residue risk is reduced, and the production efficiency is improved. However, the invention can only bear the temperature below 120-160 ℃ and cannot resist higher temperature.
Therefore, it is an urgent need to solve the above-mentioned problems to develop a high temperature resistant adhesive tape which can be easily peeled off and can resist high temperature.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an adhesive, a preparation method thereof, an adhesive layer prepared from the adhesive and a thermal de-bonding adhesive tape. According to the high-temperature-resistant heat-release adhesive tape, specific monomers with different functions are selected for polymerization, so that the high temperature resistance of an adhesive layer is effectively improved, and foaming microspheres are creatively introduced into preparation raw materials of the adhesive, so that after the obtained adhesive layer is compounded with a base material layer, a heavy release layer and a light release layer, the high-temperature-resistant heat-release adhesive tape can be obtained, and the adhesive layer and an object to be pasted can be separated through the expansion effect of the microspheres through the foaming of the microspheres, so that the problem of adhesive residue is radically solved; and under specific temperature, the stripping process used by the adhesive tape is simpler, namely, the purposes of reducing the processing procedures and improving the production efficiency are achieved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an adhesive, wherein the adhesive is prepared from the following raw materials: hard monomer, soft monomer, functional monomer, solvent, initiator, curing agent and foaming microsphere.
According to the high-temperature-resistant heat-release adhesive tape, specific monomers with different functions are selected for polymerization, so that the high temperature resistance of an adhesive layer is effectively improved, and foaming microspheres are creatively introduced into preparation raw materials of the adhesive, so that after the obtained adhesive layer is compounded with a base material layer, a heavy release layer and a light release layer, the high-temperature-resistant heat-release adhesive tape can be obtained, and the adhesive layer and an object to be adhered can be separated through the expansion effect of the microspheres through the foaming of the microspheres, so that the problem of adhesive residue is radically solved; and under specific temperature, the stripping process used by the adhesive tape is simpler, namely, the purposes of reducing the processing procedures and improving the production efficiency are achieved.
Preferably, the adhesive layer is prepared from the following raw materials by taking the total mass of the adhesive as 100 percent: 3-5% of hard monomer, 20-35% of soft monomer, 2-8% of functional monomer, 50-60% of solvent, 0.1-1% of initiator, 0.2-2% of curing agent and 1-5% of foaming microsphere.
According to the invention, the preparation raw materials are preferably reacted in a specific proportion, and the components are matched with each other, so that the obtained adhesive layer can not be subjected to viscosity reduction at a specific high temperature, and has a function of viscosity loss at a higher temperature. Particularly, the invention preferably controls the mass percentage of the foaming microspheres within the range of 1-5%, so that the foaming quality of the foaming microspheres can be ensured, namely the bonding strength and the adhesive losing effect of the high-temperature-resistant heat-reducing adhesive tape are considered. When the mass percentage of the foaming microspheres is less than 1%, that is, the content of the foaming microspheres is too small, the foaming effect is poor, the foaming time is too long, and further, the adhesive tape is long in hot-tack loss time and poor in viscosity reduction effect, and when the mass percentage of the foaming microspheres is more than 5%, that is, the content of the foaming microspheres is too large, the viscosity of the adhesive tape and the base material is obviously reduced, and the adhesive performance of the adhesive tape is reduced.
The hard monomer may be 3 to 5%, for example, 3%, 3.2%, 3.5%, 3.7%, 4%, 4.3%, 4.5%, 4.8%, or 5%.
The soft monomer content is 20 to 35%, and may be, for example, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, or the like.
The functional monomer content may be 2 to 8%, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or the like.
The solvent may be 50 to 60%, for example, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, or 60%.
The initiator may be 0.1 to 1%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%.
The curing agent may be 0.2 to 2%, for example, 0.2%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, or 2%.
The amount of the expanded beads is 1 to 5%, for example, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%.
Preferably, the initial foaming temperature of the expanded microspheres is 210-300 ℃, and may be, for example, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃ or 300 ℃.
Preferably, the particle size of the expanded beads is 10 to 30 μm, and may be, for example, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, or 30 μm.
Preferably, the hard monomer is selected from any one of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate or vinyl acrylate or a combination of at least two thereof.
Preferably, the soft monomer is selected from any one of isooctyl acrylate, ethyl acrylate or butyl acrylate or a combination of at least two thereof.
Preferably, the functional monomer is selected from any one of acrylic acid, methacrylic acid, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylamide or hydroxyacrylamide or a combination of at least two thereof.
According to the invention, the hard monomer, the soft monomer and the functional monomer are preferably selected from the above substances specifically, so that the obtained acrylic polymer has good high temperature resistance, and the compatibility of the obtained acrylic polymer and the foaming microspheres is good, and the acrylic polymer and the foaming microspheres can be matched with each other, so that the foaming performance is effectively improved, and the high-temperature-resistant heat-resistant adhesive tape has good adhesive strength and anti-adhesive effect.
Preferably, the solvent is a mixture of toluene and ethyl acetate.
Preferably, the mass ratio of the toluene to the ethyl acetate is 1 (2-5), and may be, for example, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, or the like.
Preferably, the initiator is dibenzoyl peroxide and/or azobisisobutyronitrile.
Preferably, the curing agent is selected from any one of toluene diisocyanate, hexamethylene diisocyanate or m-xylylene diamine epoxy resin or a combination of at least two of the above.
In a second aspect, the present invention further provides a preparation method of the adhesive according to the first aspect, including:
1) mixing a hard monomer, a soft monomer, a functional monomer, an initiator and a solvent, and reacting to obtain an acrylic polymer;
2) mixing the acrylic polymer obtained in the step 1), a curing agent and foaming microspheres to obtain the adhesive.
Preferably, the weight average molecular weight of the acrylic polymer in step 1) is 100 to 120 ten thousand, for example, 100, 105, 110, 115 or 120 ten thousand, etc.
Preferably, the glass transition temperature of the acrylic polymer of step 1) is-8 to 10 ℃, and may be, for example, -8 ℃, -7 ℃, -6 ℃, -5 ℃, -4 ℃, -3 ℃, -2 ℃, -1 ℃, 0 ℃, 1 ℃, 2 ℃, 3 ℃, 4 ℃, 5 ℃, 6 ℃, 7 ℃, 8 ℃, 9 ℃ or 10 ℃.
Preferably, the acrylic polymer of step 1) has a crosslinking density of 85 to 98%, for example, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, etc.
Preferably, the temperature of the mixing in step 1) is 18 to 30 ℃, and may be, for example, 18 ℃, 20 ℃, 22 ℃, 25 ℃, 27 ℃, 29 ℃, or 30 ℃.
Preferably, step 1) further comprises: before the reaction, the mixture was warmed to 70-80 ℃ over 0.5-1 h.
The above-mentioned 0.5 to 1 hour may be, for example, 0.5 hour, 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour or 1 hour.
The temperature of 70-80 ℃ may be, for example, 70 ℃, 72 ℃, 75 ℃, 78 ℃, 79 ℃ or 80 ℃.
Preferably, the reaction temperature in step 1) is 80-100 deg.C, such as 80 deg.C, 82 deg.C, 85 deg.C, 88 deg.C, 90 deg.C, 92 deg.C, 95 deg.C, 98 deg.C, 99 deg.C or 100 deg.C.
Preferably, the reaction time in step 1) is 1-3h, for example, 1h, 1.3h, 1.5h, 1.8h, 2h, 2.5h or 3h, etc.
Preferably, step 1) further comprises: after the reaction, the obtained reaction product is cooled to 18-30 ℃, for example, 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃.
Preferably, the mixing in step 2) is performed by shaking.
Preferably, the mixing time in step 2) is 30-60min, such as 30min, 33min, 35min, 38min, 40min, 45min, 48min, 50min, 55min or 60 min.
In a second aspect, the present invention further provides an adhesive layer, wherein the adhesive layer is prepared from the adhesive according to the first aspect.
In a third aspect, the present invention also provides a thermal adhesive reduction tape including the adhesive layer according to the second aspect.
Preferably, the thermal anti-adhesive tape comprises a substrate layer, wherein one side of the substrate layer is covered with a heavy release layer, the substrate layer and the heavy release layer are bonded together through an adhesive layer A, the other side of the substrate layer is covered with a light release layer, and the substrate layer and the light release layer are bonded together through an adhesive layer B;
wherein the adhesive layer A and the adhesive layer B are both composed of the adhesive layer according to the second aspect.
Preferably, the substrate layer is a PI film layer.
The heavy release layer is a release layer with a release force of 20-30g/25mm, and the light release layer is a release layer with a release force of 10-15g/25 mm.
Preferably, the release force of the heavy release layer is 20-30g/25mm, and can be, for example, 20g/25mm, 21g/25mm, 22g/25mm, 23g/25mm, 24g/25mm, 25g/25mm, 26g/25mm, 27g/25mm, 28g/25mm, 29g/25mm, 30g/25mm, or the like.
Preferably, the release force of the light release layer is 10-15g/25mm, for example, 10g/25mm, 11g/25mm, 12g/25mm, 13g/25mm, 14g/25mm or 15g/25mm, etc.
The thickness of the substrate layer is preferably 12 to 100. mu.m, and may be, for example, 12 μm, 15 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm or the like, preferably 20 to 80 μm, and more preferably 40 to 60 μm.
Preferably, the thickness of the heavy release layer is 30-40 μm, and may be 30 μm, 32 μm, 34 μm, 35 μm, 40 μm, or the like, for example.
Preferably, the thickness of the light release layer is 20-30 μm, and may be, for example, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm, or the like.
Preferably, the thickness of the adhesive layer a and the adhesive layer B is 35-50 μm, and may be 35 μm, 36 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 49 μm, 50 μm, or the like, for example.
Compared with the prior art, the invention has the following beneficial effects:
according to the high-temperature-resistant heat-release adhesive tape, specific monomers with different functions are selected for polymerization, so that the high temperature resistance of an adhesive layer is effectively improved, and foaming microspheres are creatively introduced into preparation raw materials, so that after the obtained adhesive layer is compounded with a base material layer, a heavy release layer and a light release layer, the high-temperature-resistant heat-release adhesive tape can be obtained, and can be separated from an adhered object through the expansion effect of the microspheres through the foaming of the microspheres, and the problem of adhesive residue is radically solved; and under specific temperature, the stripping process used by the adhesive tape is simpler, namely, the purposes of reducing the processing procedures and improving the production efficiency are achieved.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides an adhesive and a preparation method thereof.
The adhesive comprises the following raw materials in percentage by mass of 100 percent: 3 percent of methyl methacrylate (hard monomer), 26 percent of isooctyl acrylate (soft monomer), 4 percent of butyl acrylate (soft monomer), 3 percent of methacrylic acid (functional monomer), 3 percent of acrylic acid-2-hydroxyethyl ester (functional monomer), 1 percent of acrylamide (functional monomer), 12 percent of toluene, 43.85 percent of ethyl acetate, 0.2 percent of AIBN, 1.5 percent of toluene diisocyanate, 0.05 percent of m-xylylenediamine epoxy resin and 2.4 percent of foaming microspheres (the initial foaming temperature is 210 ℃).
The preparation method comprises the following steps:
1) mixing methyl methacrylate, isooctyl acrylate, butyl acrylate, methacrylic acid, 2-hydroxyethyl acrylate, acrylamide, toluene and ethyl acetate at 20 ℃, heating to 73 ℃ within 1h, adding AIBN, mixing for 2h, heating to 80 ℃ for reaction for 1h, cooling the obtained reactant to 20 ℃ to obtain an acrylic polymer;
2) mixing the acrylic polymer obtained in the step 1), toluene diisocyanate, m-xylylenediamine epoxy resin and foaming microspheres, and oscillating for 40min to obtain the adhesive.
Example 2
The embodiment provides an adhesive and a preparation method thereof.
The adhesive comprises the following raw materials in percentage by mass of 100 percent: 2% of methyl methacrylate, 3% of n-butyl methacrylate (hard monomer), 15% of isooctyl acrylate (soft monomer), 15% of ethyl acrylate (soft monomer), 2% of acrylic acid (functional monomer), 2% of acrylic acid-2-hydroxyethyl acrylate (functional monomer), 4% of acrylamide (functional monomer), 10% of toluene, 45% of ethyl acetate, 0.8% of AIBN, 0.1% of toluene diisocyanate, 0.1% of m-xylylenediamine epoxy resin and 1% of foaming microspheres (initial foaming temperature is 210 ℃).
The preparation method comprises the following steps:
1) mixing methyl methacrylate, n-butyl methacrylate, isooctyl acrylate, ethyl acrylate, acrylic acid, 2-hydroxyethyl acrylate, acrylamide, toluene and ethyl acetate at 25 ℃, heating to 75 ℃ within 1h, adding AIBN, mixing for 2h, heating to 85 ℃ for reaction for 1h, and cooling the obtained reactant to 23 ℃ to obtain an acrylic polymer;
2) mixing the acrylic polymer obtained in the step 1), toluene diisocyanate, m-xylylenediamine epoxy resin and foaming microspheres, and oscillating for 60min to obtain the adhesive.
Example 3
The embodiment provides an adhesive and a preparation method thereof.
The adhesive comprises the following raw materials in percentage by mass of 100 percent: 2% of methyl methacrylate, 2% of ethyl methacrylate (hard monomer), 30% of ethyl acrylate (soft monomer), 5% of butyl acrylate (soft monomer), 1% of acrylic acid (functional monomer), 2% of acrylic acid-2-hydroxyethyl acrylate (functional monomer), 2% of acrylamide (functional monomer), 16% of toluene, 34.5% of ethyl acetate, 0.5% of dibenzoyl peroxide, 1% of toluene diisocyanate, 1% of hexamethylene diisocyanate and 3% of foaming microspheres (the initial foaming temperature is 210 ℃).
The preparation method comprises the following steps:
1) mixing methyl methacrylate, ethyl acrylate, butyl acrylate, acrylic acid, 2-hydroxyethyl acrylate, acrylamide, toluene and ethyl acetate at 25 ℃, heating to 75 ℃ within 1h, adding dibenzoyl peroxide, mixing for 2h, heating to 85 ℃, reacting for 1h, cooling the obtained reactant to 23 ℃, and obtaining an acrylic polymer;
2) mixing the acrylic polymer obtained in the step 1), toluene diisocyanate, m-xylylenediamine epoxy resin and foaming microspheres, and oscillating for 60min to obtain the adhesive.
Example 4
The only difference from example 1 is that the amount of expanded microspheres was 5%.
Example 5
The only difference from example 1 is that the amount used between the toluene diisocyanates is 0.9%.
Example 6
The only difference from example 1 is that m-xylylenediamine epoxy resin was not contained.
Example 7
The only difference from example 1 is that the initial foaming temperature of the expanded microspheres was 100 ℃.
Example 8
The only difference from example 1 is that the amount of expanded microspheres was 8%.
Example 9
The only difference from example 1 is that the amount of expanded microspheres was 0.5%.
Example 10
The only difference from example 1 is that the particle size of the expanded microspheres was 40 μm.
Example 11
The only difference from example 1 is that the particle size of the expanded microspheres is 5 μm.
Example 12
The difference from example 1 is that m-xylylenediamine epoxy resin was used in an amount of 1.5%, i.e., the total amount of the curing agent was 3%.
Example 13
The difference from example 1 is that toluene diisocyanate was used in an amount of 0.05%, i.e., the total amount of the curing agent was 0.1%.
Comparative example 1
The difference from example 1 is that the expanded microspheres are not contained.
Comparative example 2
The difference from example 1 is that a commercially available acrylic polymer (available from Anglo Chemicals under the trade name Y-1510, weight average molecular weight 20-40 ten thousand, glass transition temperature-30 ℃ C., crosslink density 78%) was used instead of the acrylic polymer obtained in example step 1).
Comparative example 3
The difference from example 1 is that a single methyl methacrylate was used instead of all the acrylic monomers in example 1, i.e., the amount of methyl methacrylate used in this comparative example was 40%.
Comparative example 4
The difference from example 1 is that isooctyl acrylate alone is used instead of all the acrylic monomers of example 1, i.e., the amount of isooctyl acrylate used in this comparative example is 40%.
Comparative example 5
The difference from example 1 is that a single methacrylic acid was used instead of all the acrylic monomers in example 1, i.e., the amount of methacrylic acid used in this comparative example was 40%.
Application example 1
The application example provides a high-temperature-resistant heat-resisting adhesive reducing tape and a preparation method thereof.
The adhesive comprises a base material layer, a heavy release layer, a light release layer and a bonding layer, wherein the heavy release layer covers one side of the base material layer, the base material layer and the heavy release layer are bonded together through an adhesive layer A, the light release layer covers the other side of the base material layer, and the base material layer and the light release layer are bonded together through an adhesive layer B; wherein the adhesive layer A and the adhesive layer B are both composed of the adhesive layer of claim 7.
Wherein the substrate layer is brown PI with the thickness of 50um, the heavy release layer is 36 μm in thickness, and the release force is 25g/25 mm; the thickness of the light release layer is 25um, the release force is 10g/25mm, the composition of the adhesive layer a is the same as that of the adhesive layer B, the light release layer and the adhesive layer B are both the composition of the adhesive layer prepared from the adhesive of embodiment 1, and the thickness of the light release layer is 38 um.
The preparation method comprises the following steps:
1) coating the adhesive prepared in the embodiment 1 on a substrate layer, wherein the thickness of the adhesive is 38 microns, so as to obtain an adhesive B, baking the adhesive B for 3min at 100 ℃, and compounding the adhesive B with a light release film;
2) coating the adhesive prepared in the embodiment 1 on a heavy release film, wherein the thickness of the adhesive is 38 micrometers, so as to obtain an adhesive A, baking the adhesive A at 100 ℃ for 3min, then attaching the adhesive A to a substrate layer, and curing the adhesive A at 45 ℃ for 72h, so as to obtain the thermal de-bonding adhesive tape.
Application examples 2 to 15
Application examples 2 to 15 correspond to the adhesives prepared in the application examples 2 to 15, respectively, the other structures are the same as in application example 1, and the preparation method is the same as in application example 1.
Comparative application examples 1 to 5
Application examples 1 to 5 correspond to the adhesives prepared in comparative examples 1 to 5, respectively, and the other structures are the same as in application example 1, and the preparation method is also the same as in application example 1.
And (3) performance testing:
1. and (3) viscosity test:
the heat-tack-reducing tapes prepared in application examples 1 to 15 and comparative application examples 1 to 5 were subjected to tack tests in accordance with GB/T2792-1998.
The test method is as follows:
the adhesive tape was attached to the PI substrate and tested for initial peel force (180 ℃ peel) for 20min at ambient temperature and ambient humidity (23. + -. 2 ℃ C., 50%. + -. 5% RH); the adhesive tape is attached to the PI base material, placed at 180 ℃ for 2h, tested for the peeling force (180-degree peeling) of the adhesive tape, and observed for the attaching effect; the tape was attached to a PI substrate, left at 240 ℃ for 10min, tested for peel force (180 ℃ peel) and observed for attachment.
Specific test results are shown in table 1:
TABLE 1
Figure BDA0002322284370000131
Figure BDA0002322284370000141
From the examples and the performance tests, it can be seen that after the adhesive prepared in the examples 1 to 3 is applied to the anti-adhesive tape, the viscosity of the adhesive at 180 ℃ can be as high as 800g/25mm, and the viscosity of the adhesive at 240 ℃ is 0 without adhesive residue, which indicates that the high-temperature-resistant adhesive-reducing tape prepared in the examples of the invention not only realizes non-anti-adhesive at a specific high temperature, but also has the function of being capable of losing adhesive when subjected to a higher temperature.
Compared with example 1, the viscosity of the high temperature resistant thermal adhesive reducing tape prepared by using the foaming microspheres in example 8 in an amount higher than that in example 1 is obviously reduced, the viscosity of the high temperature resistant thermal adhesive reducing tape prepared by using the foaming microspheres in example 9 in an amount lower than that in example 1 is higher than 0 at 240 ℃, namely, the anti-adhesive effect of the high temperature resistant thermal adhesive reducing tape is reduced at high temperature, which shows that the viscosity at high temperature and the anti-adhesive property at higher temperature can be considered only by controlling the amount of the foaming microspheres in the range of the application.
Compared with example 1, the particle size of the expanded microspheres in example 10 is larger than that in example 1, the viscosity of the prepared high temperature resistant thermal adhesive reduction tape is obviously poor, the appearance is uneven, the particle size of the expanded microspheres in example 11 is smaller than that in example 1, the viscosity of the prepared high temperature resistant thermal adhesive reduction tape at 240 ℃ is higher than 0, namely the anti-adhesive effect of the prepared high temperature resistant thermal adhesive reduction tape at high temperature is poor, and this shows that the viscosity at high temperature and the anti-adhesive property at higher temperature can be ensured only by controlling the particle size of the expanded microspheres within the range of the application.
Compared with example 1, the curing agent in example 12 is used in an amount higher than that in example 1, and the viscosity of the prepared high temperature resistant and heat resistant adhesive tape is obviously poor, because when the content of the curing agent is too much, the crosslinking density in the adhesive film is too large, and the viscosity of the prepared high temperature resistant and heat resistant adhesive tape is obviously reduced, and the curing agent in example 13 is less than that in example 1, the viscosity of the prepared high temperature resistant and heat resistant adhesive tape at 240 ℃ is higher than 0, namely the adhesive losing effect of the prepared high temperature resistant and heat resistant adhesive tape at high temperature is poor, which shows that the viscosity at high temperature and the adhesive losing property at higher temperature can be ensured only by controlling the amount of the curing agent within the range of the application.
Compared with the example 1, the anti-adhesive tape prepared in the comparative example 1 does not contain the foaming microspheres, and the anti-adhesive tape prepared in the comparative example has the advantages of no tearing at 240 ℃ and more residual glue, so that the high-temperature anti-adhesive effect cannot be achieved.
Compared with the example 1, the acrylic polymer prepared by the invention is replaced by the commercially available acrylic polymer in the comparative example 2, the viscosity of the prepared visbreaking adhesive tape at 240 ℃ reaches 783, and the residual adhesive is left, so that the effect of complete high-temperature visbreaking cannot be achieved, because the resin synthesized by the specific acrylic monomer of the invention has good compatibility with the foaming microspheres, and the good bonding strength and the visbreaking effect are further ensured.
Compared with the embodiment 1, the compound monomer system of the three monomers in the embodiment 1 is replaced by the single hard monomer, the single soft monomer or the single functional monomer in the comparative examples 3 to 5, the film forming property of the anti-adhesive tape prepared by the application examples is poor, the viscosity is more than 0 at 240 ℃, and the residual glue is remained, so that the resin synthesized by the specific acrylic monomer can have good compatibility with the foaming microspheres, and the good bonding strength and the good anti-adhesive effect of the resin are ensured.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (30)

1. The adhesive is characterized in that the raw materials for preparing the adhesive comprise the following components by the total mass of 100 percent: 3-5% of hard monomer, 20-35% of soft monomer, 2-8% of functional monomer, 50-60% of solvent, 0.1-1% of initiator, 0.2-2% of curing agent and 1-5% of foaming microsphere;
the initial foaming temperature of the foaming microspheres is 210-300 ℃;
the particle size of the foaming microsphere is 10-30 μm;
the curing agent is selected from the combination of at least two of toluene diisocyanate, hexamethylene diisocyanate or m-xylylenediamine epoxy resin.
2. The adhesive of claim 1 wherein the hard monomer is selected from any one of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate or vinyl acrylate or a combination of at least two thereof.
3. The adhesive of claim 1, wherein the soft monomer is selected from any one of isooctyl acrylate, ethyl acrylate or butyl acrylate or a combination of at least two of the above.
4. The adhesive of claim 1, wherein the functional monomer is selected from any one of acrylic acid, methacrylic acid, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylamide, or hydroxyacrylamide, or a combination of at least two thereof.
5. The adhesive of claim 1 wherein the solvent is a mixture of toluene and ethyl acetate.
6. The adhesive according to claim 5, wherein the mass ratio of the toluene to the ethyl acetate is 1 (2-5).
7. The adhesive of claim 1 wherein the initiator is dibenzoyl peroxide and/or azobisisobutyronitrile.
8. A method for preparing the adhesive according to any one of claims 1-7, wherein the method comprises the following steps:
1) mixing a hard monomer, a soft monomer, a functional monomer, an initiator and a solvent, and reacting to obtain an acrylic polymer;
2) mixing the acrylic polymer obtained in the step 1), a curing agent and foaming microspheres to obtain the adhesive.
9. The method of claim 8, wherein the acrylic polymer of step 1) has a weight average molecular weight of 100 to 120 ten thousand.
10. The method according to claim 8, wherein the acrylic polymer of step 1) has a glass transition temperature of-8 to 10 ℃.
11. The method according to claim 8, wherein the acrylic polymer of step 1) has a degree of crosslinking of 85 to 98%.
12. The method of claim 8, wherein the temperature of the mixing in step 1) is 18 to 30 ℃.
13. The method of claim 8, wherein step 1) further comprises: before the reaction, the mixture was warmed to 70-80 ℃ over 0.5-1 h.
14. The method according to claim 8, wherein the temperature of the reaction in step 1) is 80 to 100 ℃.
15. The method according to claim 8, wherein the reaction time in step 1) is 1 to 3 hours.
16. The method of claim 8, wherein step 1) further comprises: after the reaction, the resulting reaction was cooled to 18-30 ℃.
17. The method according to claim 8, wherein the mixing in step 2) is performed by shaking.
18. The method of claim 8, wherein the mixing of step 2) is performed for 30-60 min.
19. An adhesive layer, characterized in that the adhesive layer is prepared from the adhesive according to any one of claims 1 to 7.
20. A heat-tack reducing tape comprising the adhesive layer of claim 19.
21. The thermal de-bonding adhesive tape according to claim 20, wherein the thermal de-bonding adhesive tape comprises a substrate layer, one side of the substrate layer is covered with a heavy release layer, the substrate layer and the heavy release layer are bonded together through an adhesive layer a, the other side of the substrate layer is covered with a light release layer, and the substrate layer and the light release layer are bonded together through an adhesive layer B;
wherein the adhesive layer A and the adhesive layer B are both composed of the adhesive layer of claim 19.
22. The thermal de-bonding tape of claim 21, wherein the substrate layer is a PI film layer.
23. The thermal adhesive tape of claim 21, wherein the heavy release layer has a release force of 20-30g/25 mm.
24. The thermal adhesive tape of claim 21, wherein the light release layer has a release force of 10-15g/25 mm.
25. A heat-detackifying tape according to claim 21 wherein the substrate layer has a thickness of 12-100 μm.
26. A heat-tack free tape according to claim 21 wherein the substrate layer has a thickness of 20 to 80 μm.
27. A heat-tack free tape according to claim 21 wherein the substrate layer has a thickness of 40 to 60 μm.
28. The thermal adhesive tape of claim 21, wherein the heavy release layer has a thickness of 30-40 μm.
29. The thermal adhesive tape of claim 21, wherein the light release layer has a thickness of 20 to 30 μm.
30. The thermal adhesive tape according to claim 21, wherein the thickness of the adhesive layer a and the adhesive layer B is 35 to 50 μm, independently of each other.
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