CN111793449A - UV-curing thermal-viscosity-reducing adhesive layer composition, adhesive and adhesive tape - Google Patents
UV-curing thermal-viscosity-reducing adhesive layer composition, adhesive and adhesive tape Download PDFInfo
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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
- 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
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- 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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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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
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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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
- C09J135/00—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 a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J135/02—Homopolymers or copolymers of esters
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- 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®
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- 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
- C08J2333/04—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 esters
- C08J2333/06—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 esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
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- 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
- C08J2335/00—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 at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2335/02—Characterised by the use of homopolymers or copolymers of esters
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field related to adhesives, and particularly provides a UV-curing thermal-debonding adhesive layer composition, an adhesive and an adhesive tape. The invention provides a UV curing thermal viscosity-reducing adhesive layer composition, which is characterized by comprising the following raw materials: (I) an acrylic resin; (II) thermally expandable microspheres which account for 6.5 to 16.6 wt% of the acrylic resin; preferably 9.2 to 12.1 wt%; (III) a polymerization initiator which accounts for 0.1 to 2.5 wt% of the acrylic resin; preferably 0.45-0.96 wt%; wherein the acrylic resin is formed by raw materials of (c) acrylic monomer without active group with the weight-average molecular weight of 200-800 g/mol, (d) acrylic monomer with active group with the weight-average molecular weight of 150-650 g/mol and (e) diisocyanate, and the active group is a reactive group structure such as amino, hydroxyl, carboxyl, epoxy and the like.
Description
Technical Field
The invention relates to the technical field related to adhesives, and particularly provides a UV-curing thermal-debonding adhesive layer composition, an adhesive and an adhesive tape.
Background
In recent years, semiconductor components have been rapidly developed, electronic devices tend to be small, light, high in performance and multifunctional, and the preparation of electronic devices depends on the size and refinement of chips to a great extent.
The preparation process of the chip involves the processes of cutting, picking and re-pasting, and in the process, the chip is firstly pasted and fixed through an adhesive tape and needs a certain adhesive force, otherwise, the chip is easy to splash in the cutting process to cause the damage of the chip; in addition, after cutting, after curing under thermal condition or illumination condition, use the manipulator arm to carry out high accuracy location to the chip and snatch, otherwise probably the adhesion force is still great after the UV shines, the better pick-up can not be realized to the manipulator, also can cause the damage of chip, chip surface also has the cull simultaneously, influence the quality of chip, it is the gluing agent that uses to influence this greatly to this in-process, consequently, need one kind both can satisfy under the initial condition, the better fixed of chip, also can realize simultaneously can cooperate with the manipulator after the solidification, realize the photocuring composition that high accuracy location snatchs.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the invention provides a UV curing thermal viscosity-reducing adhesive layer composition, which has better adhesive property before curing treatment, and avoids the problem of splashing or loosening in the wafer cutting process due to the influence of thermal expansion microspheres on the adhesive property; meanwhile, the adhesive layer is stable after curing treatment, small molecule migration or overflow is avoided, the bonded object is easy to peel, the pickup property is good, and the phenomenon of wafer pollution or adhesive residue is avoided.
The invention provides a UV curing thermal viscosity-reducing adhesive layer composition, which comprises the following raw materials:
(I) an acrylic resin;
(II) thermally expandable microspheres which account for 6.5 to 16.6 wt% of the acrylic resin; preferably 9.2 to 12.1 wt%;
(III) a polymerization initiator which accounts for 0.1 to 2.5 wt% of the acrylic resin; preferably 0.45-0.96 wt%;
wherein the acrylic resin is formed by raw materials of (c) acrylic monomer without active group with the weight-average molecular weight of 200-800 g/mol, (d) acrylic monomer with active group with the weight-average molecular weight of 150-650 g/mol and (e) diisocyanate, and the active group is a reactive group structure such as amino, hydroxyl, carboxyl, epoxy and the like.
The invention adopts acrylic monomers without active groups and with the weight-average molecular weight of 200-800 g/mol, acrylic monomers with active groups and with the weight-average molecular weight of 150-650 g/mol and diisocyanate to form acrylic prepolymer, namely, the diisocyanate and the acrylic monomers with active groups are utilized to form oligomer with a three-dimensional network structure, so as to be further used for coating the glue line composition; in practical use, in order to control the action of the adhesive layer composition with a base material in the using process, avoid delamination, control the cohesive force of the adhesive layer and the proper adhesive force with a chip or a wafer, and avoid the problems of splashing or adhesive residue, the weight ratio of (c), (d) and (e) needs to be controlled to be 1: (0.65-0.85): (0.55-0.68).
The "weight average molecular weight" in the present invention is a molecular weight obtained by averaging the statistical average molecular weight by mass per unit weight, and is measured by Gel Permeation Chromatography (GPC).
The thermal expansion microsphere is generally a thermoplastic hollow polymer microsphere, and consists of a thermoplastic polymer shell and sealed liquid alkane gas, when the temperature reaches a certain temperature in the process, the liquid alkane gas in the shell is subjected to phase change, and the thermoplastic material of the shell is deformed and enlarged in volume, so that the distance between two phase interfaces of an adhesive system and an adhered object is increased, and the peeling effect is realized, however, the expansion volume multiple and the expansion starting temperature of the thermal expansion microsphere can influence the fixing effect between the adhesive layer composition system and the adhered object and the peeling effect after thermal treatment or curing in the actual use process, so that the diameter of the thermal expansion microsphere is preferably 10-60 um; preferably, the initial temperature of the foaming is 80-200 ℃, and the maximum temperature of the foaming is 120-210 ℃.
Further preferably, the thermal expansion microspheres comprise first thermal expansion microspheres and second thermal expansion microspheres, wherein the diameter of the first thermal expansion microspheres is 10-20 um, the initial foaming temperature is 80-98 ℃, and the maximum foaming temperature is 120-130 ℃; the diameter of the second thermal expansion microspheres is 30-40 um, the initial foaming temperature is 100-115 ℃, and the highest foaming temperature is 150-165 ℃; specifically, for example, the first thermal expansion microspheres have a diameter of 10 to 20 μm, an initial foaming temperature of 85 to 95 ℃ and a maximum foaming temperature of 120 to 130 ℃ and are available from Beijing Shanghai brocade science and technology Co., Ltd 150D; the diameter of the second thermal expansion microsphere is 30-40 um, the initial foaming temperature is 100-110 ℃, the maximum foaming temperature is 150-165 ℃, and the second thermal expansion microsphere is purchased from H65D of Beijing Shanghai brocade technology Limited.
The applicant introduces two-stage expansion microspheres into the system, wherein the two-stage expansion microspheres are respectively small in diameter, low in foaming temperature and relatively large in diameter, the foaming temperature is higher by one step, so that the two-stage expansion microspheres are used coordinately, the harsh heat treatment or curing conditions are avoided, and meanwhile, the two-stage expansion microspheres act together with a glue layer composition system to form a uniform expansion interface, so that the effect of easy peeling is realized, and the problems that the expansion space is not uniform, part of the expansion space has residual glue, and part of the expansion space is loosened in the cutting process are; in order to further effectively achieve the above effects, it is necessary to control the mass ratio of the thermally-expandable microspheres including the first thermally-expandable microspheres and the second thermally-expandable microspheres to be 1: (2.2-3.7); the low foaming temperature is avoided, the cohesive force of a glue layer system is prevented from being collapsed in the synthesis process of the acrylic resin, the high foaming temperature is also avoided, and the cohesive force is large in the curing and heat treatment process or the initial stage of the synthesis of the acrylic resin, so that the defects can also occur.
The "starting temperature of foaming" in the present invention means the glass transition temperature of the outer shell thereof, i.e., the temperature at which the outer shell starts to expand; "maximum temperature of foaming" refers to the temperature at which the spheres shrink or break.
Preferably, the (c) reactive group-free acrylic monomer having a weight average molecular weight of 200 to 800g/mol includes (c1) an acrylic monomer having a number of double bonds as a monofunctional group having a weight average molecular weight of 200 to 350g/mol, (c2) an acrylic monomer having a number of double bonds as a bifunctional group having a weight average molecular weight of 300 to 520g/mol, and (c3) an acrylic monomer having a weight average molecular weight of 250 to 340g/mol and a number of double bonds as a trifunctional group having no cyclic structure of 3.
The invention adopts acrylic monomers with different molecular weights, different double bond numbers and different molecular structures as raw materials of the adhesive layer composition, and the applicant finds that the acrylic monomers with different double bond numbers, molecular weights and molecular structures are favorable for controlling the acting force between the adhesive layer composition and a base material, avoiding the formed adhesive tape from layering, avoiding the adhesive force between the adhesive layer composition and a chip from being larger and the adhesive force between the adhesive layer and the chip from being lower, the acrylic monomer with the monofunctional degree of weight average molecular weight of 200-350 g/mol (c1), namely the double bond number of 1, is favorable for controlling the molecular weights of the formed acrylic prepolymer and the acrylic polymer when the adhesive layer is cured in the actual operation process, and avoiding the molecular weight and the viscosity of the system from being too large, and the acrylic monomer with the bifunctional degree of weight average molecular weight of 300-520 g/mol (c2), namely the double bond number of 2, is favorable for promoting the increasing of the molecular weight of the system, meanwhile, the phenomena of chip pollution and adhesive residue caused by the migration of unreacted monomers are avoided; and (c3) bifunctional acrylic monomers with the weight average molecular weight of 320-500 g/mol, namely the number of double bonds is 2, and the acrylic monomers with the cyclic structure, (c4) trifunctional acrylic monomers with the weight average molecular weight of 250-340 g/mol, namely the number of double bonds is 3, and (c2) are cooperated, so that the cohesion of the system is improved, and the mutual restraint is realized, and the excessive cohesion is controlled.
In order to control the reaction activity and the acting influence of different acrylic monomers in the reaction process, the better viscosity is realized before UV irradiation, and splashing in the wafer cutting process is avoided; the problem of cohesive force dispersion caused by heat absorption expansion of the expanded microspheres in the prepolymerization stage of the acrylic resin is also required to be avoided, easy peeling after curing is realized, the pickup property is good, the phenomenon of wafer pollution or adhesive residue is avoided, and the molar ratio of (c1), (c2) and (c3) is required to be controlled to be 1: (3.1-4.5): (0.55-0.69).
More preferably, (c1) an acid value of an acrylic monomer having a monofunctional group with a weight average molecular weight of 200 to 350g/mol, i.e., the number of double bonds is 1, is not more than 0.5; preferably, the viscosity is 2 to 40cps at 25 ℃; further preferably, the surface tension is 20 to 35; (c1) has relatively low weight average molecular weight and viscosity, and surface tension similar to or in gradient distribution with other acrylic monomers without direct differenceThe size is large, so that better fusion property among monomers in the reaction process is facilitated, the reaction efficiency is improved, and the molecular weight of a system is also facilitated to be controlled; specifically, (c1) is exemplified by, but not limited to:
(Changxing chemical EM-315-LM, weight average molecular weight 254g/mol, acid value less than or equal to 0.5; viscosity 4-8 cps at 25 deg.C; surface tension 28.9).
More preferably, (c2) an acid value of an acrylic monomer having a bifunctional group with a weight average molecular weight of 300 to 520g/mol, i.e., the number of double bonds of 2, of not more than 0.5; preferably, the viscosity is 5 to 85cps at 25 ℃; further preferably, the surface tension is 30 to 43; specifically, (c2) is exemplified by, but not limited to:
(Changxing chemical EM-228, weight average molecular weight 408g/mol, acid value less than or equal to 0.5; viscosity at 25 ℃ of 25-45 cps; surface tension of 39); the invention utilizes low viscosity bifunctional acrylic monomers to facilitate increased viscosity and cohesion during curing.
More preferably, (c3) an acrylic monomer having a weight average molecular weight of 250 to 340g/mol and a trifunctional group not containing a cyclic structure, i.e., 3 double bonds, and having an acid value of 0.5 or less; preferably, the viscosity is 50 to 200cps at 25 ℃; further preferably, the surface tension is 30 to 40; specifically, for example, but not limited to:
(Changxing chemical EM 231-TF, weight average molecular weight 296g/mol, acid value less than or equal to 0.5; viscosity at 25 ℃ of 70-110 cps; surface tension of 35); the acrylic monomer with low viscosity and no cyclic structure and three functionality, namely 3 double bonds, is adopted, and the surface tension of the acrylic monomer is close to that of other acrylic monomers, so that the viscosity of a system is favorably reduced, the adhesive force between an adhesive layer and the surface of a base material is improved, the cohesive force of a polymer can be improved in the curing process, the micromolecules are prevented from overflowing, and the cohesive force caused by the heat absorption expansion of expanded microspheres in the prepolymerization reaction stage of acrylic resin is also avoidedThe problem of force dispersion.
Preferably, (d) the reactive group-containing acrylic monomer having a weight average molecular weight of 150 to 650g/mol includes (d1) an acrylic monomer having a reactive group number of 1, (d2) an acrylic monomer having a reactive group number of 2, (d3) an acrylic monomer having a reactive group number of 3 or more; further preferably, the reactive group is a hydroxyl group; the acrylic resin is formed by the synergistic effect of the acrylic monomer containing different active groups, the acrylic monomer without the active groups and diisocyanate, and the density, the cohesion and the bonding capability to a wafer or a chip are influenced by the different active groups; in order to further improve the balance between the cohesive force and the bonding ability to the wafer or the chip, the molar ratio of (d1), (d2), (d3) is controlled to be 1: (2.8-4.1): (0.41-0.55).
As (d1) acrylic monomer having the number of reactive groups of 1, and the reactive groups are hydroxyl, for example but not limited to: hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like.
As (d2) acrylic monomer having the number of reactive groups of 2 and the reactive groups being hydroxyl, there may be mentioned, for example but not limited to: tripropylene glycol diacrylate, 1, 6-ethylene glycol diacrylate, and the like.
As the (d3) acrylic monomer having 3 or more reactive groups and hydroxyl groups, for example, but not limited to: trimethylolpropane triacrylate, pentaerythritol triacrylate, and the like.
The diisocyanate is not particularly limited in the present invention, and examples thereof include, but are not limited to: aromatic diisocyanate: 4, 4' -diphenylmethane diisocyanate, 1, 4-xylylene diisocyanate, 4' -diphenylmethyl diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4' -toluidine diisocyanate, 2, 4, 6-isocyanatotoluene, 1, 3, 5-triisocyanatobenzene, dianisidine isocyanate, 4' -diphenyl ether diisocyanate, 4', 4 ″ -triphenylmethane triisocyanate; alicyclic diisocyanate: 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), 1, 4-bis (isocyanotomethyl) cyclohexane, and the like.
The polymerization initiator is a photoinitiator, and the monomer polymerization is initiated under the UV irradiation to cure the adhesive layer composition, wherein the photoinitiator can be acetophenones, anthraquinones, thioxanthones and the like, wherein the acetophenones include benzoin alkyl ethers, acetophenone, 2-dimethoxy-2-acetophenone, 2-diethoxy-2-acetophenone, 1-dichloroacetophenone and the like; examples of the anthraquinones include 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone; examples of the thioxanthones include 2, 4-dimethylthioxanthone, 2, 4-diisopropylthioxanthone, 2-chlorothioxanthone, and 2, 4-diisopropylthioxanthone; preferably, it accounts for 0.1 to 2.5 wt% of the acrylic prepolymer; when the content of the adhesive is less, the cohesive force of the adhesive layer composition is lower, and the problems of adhesive residue and pollution are easy to occur; when the content of the additive is higher, the cohesive force is higher, and the phenomenon of splashing in the cutting process occurs.
The preparation method of the acrylic prepolymer disclosed by the invention comprises the following steps: mixing c) acrylic monomers without active groups and with the weight-average molecular weight of 200-800 g/mol, (d) acrylic monomers with active groups and with the weight-average molecular weight of 150-650 g/mol, and (e) diisocyanate, heating to react for 2-3 h at 50-60 ℃, adding thermal expansion microspheres, and then reacting for 1.5-3 h to obtain the acrylic resin composition.
The conditions used for UV curing of the photocurable coating composition of the present invention may be well known to those skilled in the art, for example, irradiation with an ultraviolet lamp at an illuminance of 5mW/cm2(ii) a And completely curing the mixture.
The temperature of the adhesive layer composition is 105-115 ℃ when the adhesive layer composition is peeled by heat treatment, and the time is 1-2 h.
In the actual use process, additives such as a softening agent, an aging inhibitor, a filler, a conductive agent, an ultraviolet absorber, a light stabilizer and the like may be added to the adhesive layer composition according to actual needs.
The invention provides an adhesive containing the UV curing thermal viscosity reduction adhesive layer composition in a second aspect.
The third aspect of the present invention provides an adhesive tape containing the UV-curable heat-tack reducing adhesive layer composition; the adhesive tape sequentially comprises a base material layer, an adhesive layer and a release layer from bottom to top, and the adhesive layer is formed by a photocuring adhesive layer composition.
Examples of the material of the substrate layer include polyvinyl chloride, polyethylene terephthalate, ethylene-vinyl acetate copolymer, ethylene acrylic acid-acrylic ester film, ethylene ethyl acrylate copolymer, polyethylene, polypropylene, propylene-based copolymer, ethylene acrylic acid copolymer, and the like; the substrate film may be a single-layer or multi-layer film or sheet composed of the above materials, or may be obtained by laminating films composed of different materials; the thickness of the base material film is 50 to 150 μm, preferably 70 to 120 μm.
Examples of the release layer material include polyvinyl chloride, polyethylene terephthalate, ethylene-vinyl acetate copolymer, ethylene acrylic acid-acrylic ester film, ethylene ethyl acrylate copolymer, polyethylene, polypropylene, propylene-based copolymer, ethylene acrylic acid copolymer, and the like; the substrate film may be a single-layer or multi-layer film or sheet composed of the above materials, or may be obtained by laminating films composed of different materials; the thickness of the base material film is 50 to 200 μm.
Has the advantages that:
(1) the invention can realize the effect of weakening the acting force of the two-phase interface of the adhesive layer composition and the bonded object through heating treatment and UV curing treatment, and overcomes the defect of splashing or loosening of the bonded object caused by the interfacial shrinkage of the film layer of the adhesive layer composition possibly occurring in the UV curing process;
(2) the invention adopts the thermal expansion microspheres with gradient diameters and gradient foaming temperature distribution, avoids harsh heat treatment conditions, and simultaneously avoids the situation that the cohesive force of a glue layer composition is greater than the enlarged inward movement of the thermal expansion microspheres due to uneven single gradient heat absorption or single particle size, thereby influencing the balance of pickup and mechanics and causing the defects of splashing or loosening of an adhered object;
(3) the invention also adopts acrylic monomers with different molecular weights and different viscosities, and utilizes the synergistic effect of the acrylic resin and the thermal expansion microspheres formed by the acrylic monomers to realize better bonding performance before curing treatment, and meanwhile, the phenomenon of wafer pollution or residual glue can not occur.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following raw materials were used as components in the examples:
a: the polymerization initiator is 2, 2-dimethoxy-2-acetophenone;
b: the diisocyanate is 2, 4-tolyl diisocyanate;
c: acrylic monomers free of reactive groups
C1：
Purchased from Changxing chemical EM-315-LM, with weight average molecular weight of 254g/mol and acid value less than or equal to 0.5; the viscosity is 4-8 cps at 25 deg.C; surface tension 28.9;
C2：
purchased from Changxing chemical EM-228, the weight-average molecular weight is 408g/mol, and the acid value is less than or equal to 0.5; the viscosity is 25-45 cps at 25 deg.C; a surface tension of 39;
C3：
purchased from Changxing chemical EM 231-TF, the weight average molecular weight is 296g/mol, and the acid value is less than or equal to 0.5; the viscosity is 70 to 110cps at 25 ℃; a surface tension of 35;
C4：
purchased from Changxing chemical EM 2107, with weight average molecular weight of 310g/mol and acid value less than or equal to 0.5; the viscosity is 130 to 170cps at 25 ℃;
C5：
purchased from changxing chemical EM 235; the viscosity is 400-550 cps at 25 ℃;
C6：
purchased from Changxing chemical EM 320, with the weight-average molecular weight of 198g/mol and the acid value less than or equal to 0.5; the viscosity is 100 to 300cps at 25 ℃;
d acrylic monomer containing reactive group:
d1: hydroxybutyl methacrylate;
d2: tripropylene glycol diacrylate;
d3: pentaerythritol triacrylate;
e: thermally expandable microspheres
E1: the diameter is 10-20 um, the initial foaming temperature is 85-95 ℃, the maximum foaming temperature is 120-130 ℃, and the foaming agent is purchased from 150D of Beijing Hujin technology Limited;
e2: the diameter is 30-40 um, the initial foaming temperature is 100-110 ℃, the maximum foaming temperature is 150-165 ℃, and the foaming agent is purchased from H65D of Beijing Hujin scientific and technological Limited;
e3: the diameter is 10-30 um, the initial foaming temperature is 100-110 ℃, the maximum foaming temperature is 150-165 ℃, and the foaming agent is purchased from 150D of Beijing Hujin technology Limited;
e4: the diameter is 25-35 um, the initial temperature of foaming is 130-140 ℃, the maximum temperature of foaming is 175-185 ℃, and the foaming is purchased from 180D of Shanghai brocade technology Limited, Beijing.
Example 1
Embodiment 1 of the present invention provides a UV-curable thermal-detackifying adhesive layer composition, which comprises a component a, an acrylic resin and a component E, wherein the component a accounts for 2.5 wt% of the acrylic resin; the acrylic resin is formed by a component B, a component C and a component D, wherein the weight ratio of the component C to the component D to the component B is 1: 0.85: 0.68;
the component C comprises C1, C2 and C3; the molar ratio of C1 to C2 to C3 is 1: 4.5: 0.69;
the component D comprises D1, D2 and D3; the molar ratio of D1, D2 and D3 is 1: 4.1: 0.55;
component E comprises 10.8 wt% of the acrylic resin; component E comprises E1 and E2; the mass ratio of E1 to E2 is 1: 3.7.
example 2
Embodiment 2 of the present invention provides a UV-curable thermal-detackifying adhesive layer composition, which comprises a component a, an acrylic resin and a component E, wherein the component a accounts for 0.15 wt% of the acrylic resin; the acrylic resin is formed by a component B, a component C and a component D, wherein the weight ratio of the component C to the component D to the component B is 1: 0.65: 0.55;
the component C comprises C1, C2 and C3; the molar ratio of C1 to C2 to C3 is 1: 3.1: 0.55;
the component D comprises D1, D2 and D3; the molar ratio of D1, D2 and D3 is 1: 2.8: 0.41;
component E comprises 10.8 wt% of the acrylic resin; component E comprises E1 and E2; the mass ratio of E1 to E2 is 1: 2.2.
example 3
Embodiment 3 of the present invention provides a UV-curable thermal-detackifying adhesive layer composition, which comprises a component a, an acrylic resin and a component E, wherein the component a accounts for 0.72 wt% of the acrylic resin; the acrylic resin is formed by a component B, a component C and a component D, wherein the weight ratio of the component C to the component D to the component B is 1: 0.75: 0.62;
the component C comprises C1, C2 and C3; the molar ratio of C1 to C2 to C3 is 1: 3.7: 0.63;
the component D comprises D1, D2 and D3; the molar ratio of D1, D2 and D3 is 1: 3.6: 0.59;
component E comprises 10.8 wt% of the acrylic resin; component E comprises E1 and E2; the mass ratio of E1 to E2 is 1: 3.3.
example 4
Example 4 of the present invention provides a UV curable thermal debinding composition, which is similar to example 3 except that E1 is replaced with E3.
Example 5
Example 5 of the present invention provides a UV curable thermal debinding layer composition, which is similar to example 3 except that E2 is replaced with E4.
Example 6
Example 6 of the present invention provides a UV curable thermal debinding adhesive layer composition, which is similar to example 3 except that the content of E2 is replaced with 0.
Example 7
Example 7 of the present invention provides a UV curable thermal debinding composition, which is similar to example 3 except that C1 is replaced with C4.
Example 8
Example 8 of the present invention provides a UV curable thermal debinding layer composition, which is similar to example 3 except that C2 is replaced with C6.
Example 9
Example 9 of the present invention provides a UV curable thermal debinding layer composition, which is similar to example 3 except that C3 is replaced with C5.
Example 10
Example 10 of the present invention provides a UV curable thermal debinding adhesive layer composition, which is similar to example 3 except that the content of C3 is replaced with 0.
The preparation method of the acrylic resin in the embodiments 1 to 10 is as follows: mixing the component B, C, D, heating and reacting for 2.5h at 50-60 ℃, then adding the component E, and reacting for 2h to obtain the final product.
Performance evaluation
Coating the photo-curing adhesive layer composition obtained in the embodiment 1-10 on a base material film of polyethylene terephthalate for coating work to dry the adhesive layer to a thickness of 20 μm, and drying the adhesive layer for 5min at 75 ℃; then attaching a release film of polyethylene terephthalate on the surface of the adhesive layer composition, and curing for 48 hours at 60 ℃ to obtain the adhesive tape; wherein the thickness of the base film is 110 μm, and the thickness of the release film is 90 μm.
The conditions adopted by the photo-curing glue layer composition during UV curing are as follows: irradiating under ultraviolet lamp at illuminance of 5mW/cm2(ii) a And completely curing the mixture.
The temperature of the adhesive layer composition is 105-115 ℃ when the adhesive layer composition is peeled off through heat treatment.
The adhesive tapes obtained in examples 1 to 10 were used to bond a ceramic having a length of 80mm, a width of 80mm and a thickness of 0.6mm to an annular frame, and then, each of the cutting and picking-up steps was performed, and the state of the chip in the cutting and picking-up steps was observed:
1. chip splash: the residual ratio of the ceramic chip held on the adhesive sheet after the dicing step was evaluated according to the following criteria:
excellent: the chip flying is less than 5%;
o (good): the chip flying is more than 5% and less than 10%;
x (not): the chip scattering is 10% or more.
2. Pickup property: the evaluation was made according to the following criteria based on the proportion of the ceramic chips that could be picked up in the picking-up step:
excellent: the success rate of picking up the chip is more than 95%;
o (good): the success rate of picking up the chip is more than 80% and less than 95%;
x (not): the success rate of chip pick-up is lower than 80%.
3. Loosening the chip: based on the loosening ratio of the semiconductor chip adjacent to the semiconductor chip to be picked up in the picking-up process due to the impact of the pin projection, evaluation was performed according to the following criteria:
excellent: chip looseness is less than 1%;
o (good): the chip looseness is more than 1% and less than 3%;
x (not): the chip looseness is more than 3%.
4. The phenomenon of adhesive residue: the adhesive scraping was performed by selecting 50 picked up chips at random, observing the side surfaces of the chips with a 500-fold microscope, and evaluating whether or not the adhesive was adhered to the side surfaces of the chips according to the following criteria:
excellent: the adhesive did not adhere on the chip side;
o (good): adhesion of the adhesive on the chip side is less than 5%;
x (not): the adhesion of the adhesive to the chip side is 5% or more.
Table 1 results of performance testing
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. The UV-cured thermal viscosity-reducing adhesive layer composition is characterized by comprising the following raw materials:
(I) an acrylic resin;
(II) thermally expandable microspheres which account for 6.5 to 16.6 wt% of the acrylic resin;
(III) a polymerization initiator which accounts for 0.1 to 2.5 wt% of the acrylic resin;
wherein the acrylic resin is formed by raw materials of (c) acrylic monomer without active group with the weight-average molecular weight of 200-800 g/mol, (d) acrylic monomer with active group with the weight-average molecular weight of 150-650 g/mol and (e) diisocyanate, and the active group is a reactive group structure.
2. The UV-curable thermal debinding adhesive layer composition according to claim 1, wherein the thermally expandable microspheres have a diameter of 10-60 um; preferably, the initial temperature of the foaming is 80-200 ℃, and the maximum temperature of the foaming is 120-210 ℃.
3. The UV-curable thermal viscosity-reducing adhesive layer composition according to claim 1 or 2, wherein the thermally-expandable microspheres comprise first thermally-expandable microspheres and second thermally-expandable microspheres, wherein the diameter of the first thermally-expandable microspheres is 10-20 μm, the foaming starting temperature is 80-98 ℃, and the foaming maximum temperature is 120-130 ℃; the diameter of the second thermal expansion microspheres is 30-10 um, the initial foaming temperature is 100-115 ℃, and the maximum foaming temperature is 150-165 ℃.
4. The UV-curable thermal debinding glue layer composition according to claim 3, wherein the thermally expandable microspheres comprise a first thermally expandable microsphere and a second thermally expandable microsphere in a mass ratio of 1: (2.2-3.7).
5. The UV-curable thermal visbreaker composition according to any one of claims 1 to 4, wherein the (c) reactive group-free acrylic monomer having a weight average molecular weight of 200 to 800g/mol comprises (c1) a monofunctional acrylic monomer having a double bond number of 1 having a weight average molecular weight of 200 to 350g/mol, (c2) a bifunctional acrylic monomer having a weight average molecular weight of 300 to 520g/mol, a double bond number of 2, and (c3) a trifunctional acrylic monomer having a weight average molecular weight of 250 to 340g/mol and containing no cyclic structure, a double bond number of 3.
6. The UV-curable thermal debinding glue layer composition according to claim 5, wherein (c1) an acid value of a monofunctional acrylic monomer having a weight average molecular weight of 200 to 350g/mol, i.e., the number of double bonds is 1, is not more than 0.5; preferably, the viscosity is 2 to 40cps at 25 ℃; further preferably, the surface tension is 20 to 35.
7. The UV-curable heat-curable pressure-sensitive adhesive layer composition according to claim 5 or 6, wherein (c2) an acrylic monomer having a bifunctional group with a weight average molecular weight of 300 to 520g/mol, i.e., having 2 double bonds, has an acid value of 0.5 or less; preferably, the viscosity is 5 to 85cps at 25 ℃; further preferably, the surface tension is 30 to 43.
8. The UV-curable thermal debinding glue layer composition according to any one of claims 5 to 7, wherein (c3) an acrylic monomer having a weight average molecular weight of 250 to 340g/mol and a trifunctional, i.e., 3, double bonds excluding a cyclic structure has an acid value of 0.5 or less; preferably, the viscosity is 50 to 200cps at 25 ℃; further preferably, the surface tension is 30 to 40.
9. An adhesive comprising the UV-curable thermal debinding adhesive layer composition according to any one of claims 1 to 8.
10. An adhesive tape comprising the UV curable heat-tack reducing adhesive layer composition of any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010714895.0A CN111793449A (en) | 2020-07-23 | 2020-07-23 | UV-curing thermal-viscosity-reducing adhesive layer composition, adhesive and adhesive tape |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010714895.0A CN111793449A (en) | 2020-07-23 | 2020-07-23 | UV-curing thermal-viscosity-reducing adhesive layer composition, adhesive and adhesive tape |
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| Publication Number | Publication Date |
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| CN111793449A true CN111793449A (en) | 2020-10-20 |
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|---|---|---|---|
| CN202010714895.0A Withdrawn CN111793449A (en) | 2020-07-23 | 2020-07-23 | UV-curing thermal-viscosity-reducing adhesive layer composition, adhesive and adhesive tape |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022194241A1 (en) * | 2021-03-19 | 2022-09-22 | 立铠精密科技(盐城)有限公司 | Protective colloid and use method therefor |
| CN115926663A (en) * | 2022-12-21 | 2023-04-07 | 上海固柯胶带科技有限公司 | Photo-thermal dual-debonding adhesive and preparation method thereof |
-
2020
- 2020-07-23 CN CN202010714895.0A patent/CN111793449A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022194241A1 (en) * | 2021-03-19 | 2022-09-22 | 立铠精密科技(盐城)有限公司 | Protective colloid and use method therefor |
| CN115926663A (en) * | 2022-12-21 | 2023-04-07 | 上海固柯胶带科技有限公司 | Photo-thermal dual-debonding adhesive and preparation method thereof |
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