CN116925679A - Ureido-containing UV (ultraviolet) curing polymer composition, pressure-sensitive adhesive tape and preparation method - Google Patents

Ureido-containing UV (ultraviolet) curing polymer composition, pressure-sensitive adhesive tape and preparation method Download PDF

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Publication number
CN116925679A
CN116925679A CN202310921843.4A CN202310921843A CN116925679A CN 116925679 A CN116925679 A CN 116925679A CN 202310921843 A CN202310921843 A CN 202310921843A CN 116925679 A CN116925679 A CN 116925679A
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parts
monomer
ureido
acrylate
acrylic ester
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李征
朱翰涛
王博
李欣悦
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Beijing Xulun Technology Co ltd
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Beijing Xulun 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
    • C09J133/04—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
    • 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
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (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
    • 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
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or copolymers of ethene
    • C09J2423/046—Presence of homo or copolymers of ethene in the substrate
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention relates to an ureido-containing UV curing polymer composition, a pressure-sensitive adhesive tape and a preparation method, wherein the polymer composition comprises the following raw materials in parts by mass: 100 parts of polyurea acrylic ester pre-polymerized resin, 1-2 parts of photoinitiator, 1-5 parts of curing agent and 1-5 parts of plasticizer; the polyurea acrylic ester pre-polymerized resin is obtained by copolymerizing the following monomers in parts by mass: 6-10 parts of ureido acrylic ester functional monomer, 60-80 parts of soft monomer, 10-20 parts of hard monomer, 1-5 parts of unsaturated carboxylic acid and 10-15 parts of hydroxyl-containing acrylic ester monomer; the ureido acrylate functional monomer contains more than 2 carbon-carbon unsaturated double bonds, more than 2 urea groups and more than 1 functional group, and the functional group is at least one selected from hydroxyl, epoxy, carboxyl and amino. The ureido-containing UV curing polymer composition provided by the invention has excellent UV viscosity reduction performance and high temperature resistance.

Description

Ureido-containing UV (ultraviolet) curing polymer composition, pressure-sensitive adhesive tape and preparation method
Technical Field
The invention belongs to the technical field of chip protection films, and particularly relates to an ureido-containing UV (ultraviolet) curing polymer composition, a pressure-sensitive adhesive tape containing the ureido-containing UV curing polymer composition and a preparation method of the ureido-containing UV curing polymer composition.
Background
The UV adhesive-reducing tape has high adhesive force before UV irradiation, good adhesion, when separation is needed, after short-time UV irradiation, the adhesive force is greatly reduced, and the adhesive-reducing tape is easy to tear off without residual adhesive, is widely applied to the fields of semiconductor wafer cutting, semiconductor wafer grinding and the like, plays roles of fixing, protecting and bonding conveying in the manufacturing process of the semiconductor wafer, but the wafer cutting and grinding process in some processes is subjected to a high-temperature process, and the general UV adhesive-reducing tape is difficult to meet the process requirement.
Most of the UV glue reducing formulas in the current market are uniformly mixed by stirring hydroxyl-containing and carboxyl-containing unsaturated acrylate polymers, multifunctional acrylate low polymers, photoinitiators and curing agents, but the method has limited system compatibility, is easy to remain glue after crosslinking, and is more difficult to apply to the requirements of high-temperature working procedures.
After the first appearance of a patent of a UV-cured strippable pressure-sensitive adhesive tape specially used for chip processing from the end of the 80 th century, most of the currently widely used glue reducing agents are composed of acrylate copolymers, for example, seung-Woo Lee and the like propose that 3-trimethoxysilane propyl acrylate is introduced into the glue reducing agent, silane groups are introduced into the glue reducing agent to improve the adhesion of a glue reducing layer to a wafer, resin creep during wafer grinding is reduced to improve the stability of the glue layer, but the introduction of the silane groups leads to the reduction of the adhesion of the glue layer to a substrate, and the glue is easy to remain after UV irradiation. In the aspect of domestic production and research of UV (ultraviolet) glue reducing agent, the patent No. CN109825200A describes that when glue reducing agent is manufactured, a special side chain is grafted with a photosensitive group on main resin, and quick stripping can be realized after UV illumination, but the side chain of the photosensitive resin chain is introduced with a rigid photosensitive group to improve the hardness of the resin, the wettability is reduced, and after the adhesive force of the resin to a base material is reduced, the UV illumination is easily carried out, the base material is easily separated from the base material to be adhered on the surface of a wafer, so that the processing is influenced.
CN111057474a discloses an adhesive for UV-reducing film, comprising an acrylate resin, a tackifying resin, a polyfunctional monomer, etc., wherein the polyfunctional monomer is a polyfunctional acrylate monomer containing ureido groups, such as triallyl isocyanate, 1, 3-diallyl urea. The acrylic ester monomer containing the urea group is adopted, the polarity of the urea group is high, the bonding strength is improved, meanwhile, the urea group can react with isocyanate, the crosslinking degree is improved, and the residual glue phenomenon is reduced. However, the peel strength of UV irradiation after the high temperature treatment of 100 ℃ or more is remarkably improved, the viscosity reduction performance of UV is reduced, and the method is not suitable for the working procedure with high temperature operation.
Therefore, developing a high-peel force before UV irradiation, a quick-decrease peeling force after irradiation, easy-to-drop, no residual glue and high-temperature resistant adhesive reducing tape is a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a high-temperature resistant ureido-containing UV-cured polymer composition, one or more ureido-containing functional acrylate ultraviolet-cured pressure-sensitive adhesive tapes and a preparation method thereof. The ureido monomer is a functional monomer containing unsaturated double bonds, has the functions of improving the stability of a resin system and enhancing the adhesive force in a polyurea acrylic resin system, and particularly can greatly improve the wettability of the resin due to the existence of the ureido group, thereby improving the adhesive force. In addition, unsaturated double bonds in the functional monomers are self-crosslinked after UV illumination, so that the anti-adhesion effect is achieved, the anti-adhesion adhesive tape is easy to fall off, and the adhesive tape has high peel strength, good fixity and good high temperature resistance before UV illumination.
In a first aspect, the invention provides an ureido-containing UV-curable polymer composition, which comprises the following raw materials in parts by mass: 100 parts of polyurea acrylic ester pre-polymerized resin, 1-2 parts of photoinitiator, 1-5 parts of curing agent and 1-5 parts of plasticizer; the polyurea acrylic ester pre-polymerized resin is obtained by copolymerizing the following monomers in parts by mass: 6-10 parts of ureido acrylic ester functional monomer, 60-80 parts of soft monomer, 10-20 parts of hard monomer, 1-5 parts of unsaturated carboxylic acid and 10-15 parts of hydroxyl-containing acrylic ester monomer; the ureido acrylate functional monomer contains more than 2 carbon-carbon unsaturated double bonds, more than 2 urea groups and more than 1 functional group, and the functional group is at least one selected from hydroxyl, epoxy, carboxyl and amino.
The high temperature resistance is that the high temperature treatment at 120-180 ℃ (such as 120 ℃, 150 ℃ and 180 ℃) still has good UV viscosity reduction performance, namely the high temperature treatment at 120-180 ℃ is carried out for 1-2 hours, and the peeling strength after UV irradiation is less than or equal to 15gf/25 mm).
The raw materials for preparing the polyurea acrylic acid ester prepolymer resin comprise an initiator besides the monomers, wherein the initiator is a peroxy initiator, an azo initiator such as benzoyl peroxide, and the addition amount of the initiator is 0.6-1.5wt% of the total mass of the monomers, preferably 0.9-1.1wt%. The total mass of the monomers is the sum of the mass of the ureido acrylate functional monomer, the soft monomer, the hard monomer, the unsaturated carboxylic acid and the hydroxyl-containing acrylate monomer.
Further, the ultraviolet initiator is at least one of benzoin diethyl ether, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate and phenyl bis (2, 4, 6-trimethylbenzoyl) phosphinate; the curing agent is at least one of aziridine curing agent and isocyanate; the plasticizer is selected from at least one of sebacic acid series, adipic acid series and phthalic acid series, such as at least one of dioctyl sebacate, dioctyl adipate and dioctyl phthalate.
Further, the soft monomer is at least one selected from isooctyl acrylate, butyl acrylate and hexyl acrylate; the hard monomer is at least one selected from vinyl acetate, methyl (meth) propionate and ethyl (meth) acrylate; the unsaturated carboxylic acid is at least one selected from acrylic acid and maleic acid; the hydroxyl-containing acrylate monomer is at least one selected from hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.
Further, the ureido acrylate functional monomer is prepared by a preparation method comprising the following steps: hydroxyl acrylic ester and isophorone diisocyanate react in the presence of a polymerization inhibitor and a catalyst, and then a polyfunctional group compound is added for continuous reaction to obtain an allophanate functional monomer; the polyfunctional compound has 2 or more functional groups capable of reacting with isocyanate (NCO) groups, such as hydroxyl, amino, carboxyl.
Still further, the hydroxyacrylate is selected from at least one of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; isophorone diisocyanate has two NCO groups, but is different in reactivity, and by taking advantage of this property of isophorone diisocyanate, the hydroxyl acrylate reacts with one NCO group on isophorone diisocyanate, and the resulting product retains one NCO group; the multifunctional compound is at least one of 3-amino-1, 2-propanediol, 1, 3-diamino-2-hydroxy propane, 1, 11-diamino undecan-6-ol, 2, 6-diamino-1-hexanol, 2, 3-diamino-1-butanol, 2-di (aminomethyl) propane-1, 3-diol and 1, 4-diamino-2, 3-butanediol.
The polymerization inhibitor and the catalyst are not particularly limited, and those conventionally used in the art for preventing polymerization of carbon-carbon unsaturated double bonds, for the reaction of NCO and hydroxyl groups, or NCO and amino groups, may be used. For example, the polymerization inhibitor is selected from hydroquinone, and the amount of the polymerization inhibitor is 0.5-1wt% of the mass of the hydroxy acrylic ester; the catalyst is organotin, such as dibutyl tin dilaurate, and the catalyst is used in an amount of 1-2wt% of the mass of the hydroxy acrylate.
Further, the hydroxyl acrylic ester and isophorone diisocyanate react at 0-10 ℃, isophorone diisocyanate is slowly added into the system, for example, after the addition is completed in 1-3 hours, the temperature is kept for 3-5 hours after the addition is completed; the continuous reaction of the polyfunctional group compound is carried out by slowly adding the polyfunctional group compound into the system at 40-50 ℃, for example, after the addition is completed within 1-3 hours, the reaction is carried out for 3-5 hours after the addition is completed.
Still further, the ureido acrylate functional monomer is prepared by a preparation method comprising the following steps: 100 parts by mass of hydroxy acrylic ester is dissolved in a first organic solvent with the mass being 2-4 times that of the hydroxy acrylic ester, a polymerization inhibitor and a catalyst are added, isophorone diisocyanate is dropwise added at the temperature of 0-10 ℃ for 1-3 hours, and the reaction is carried out for 3-5 hours after the completion of dropwise addition; and then controlling the temperature to be 40-50 ℃, slowly adding the multifunctional group compound, after finishing the addition for 1-3 hours, carrying out heat preservation reaction for 3-5 hours, and distilling off the solvent and unreacted monomers by vacuum distillation to obtain the ureido acrylic ester functional monomer. Preferably, the first organic solvent is selected from at least one of acetone, butanone, tetrahydrofuran and ethyl acetate. The molar ratio of the hydroxy acrylate, isophorone diisocyanate and the polyfunctional compound is 1:0.9-1:1-1.1
Further, the polyurea acrylate prepolymer resin is prepared by a preparation method comprising the following steps:
(S1) mixing 60-80 parts of soft monomer, 10-20 parts of hard monomer and 1-5 parts of unsaturated carboxylic acid uniformly to obtain a mixed monomer, taking 25-35wt% of the mixed monomer, and adding an initiator accounting for 0.3-0.35wt% of the total mass of the monomers to obtain an agent A; mixing 30-40wt% of mixed monomer, and adding initiator in 0.4-0.5wt% of total monomer mass as agent B; adding 6-10 parts of ureido acrylic ester functional monomer and 10-15 parts of hydroxyl acrylic ester monomer into the rest mixed monomers, and adding an initiator accounting for 0.2-3wt% of the total mass of the monomers to serve as a C agent;
the total mass of the monomers is the sum of the mass of the ureido acrylic ester functional monomer, the soft monomer, the hard monomer, the unsaturated carboxylic acid and the hydroxyl-containing acrylic ester monomer;
(S2) under protective atmosphere, adding the agent A into a second organic solvent, heating to 65-70 ℃, and carrying out heat preservation reaction for 1-2h; heating to 80-85 ℃, dropwise adding the agent B, and after the dropwise adding is finished within 1-2 hours, carrying out heat preservation reaction for 0.5-1 hour; dropwise adding the agent C within 1-2h, and reacting for 1-2h at a constant temperature;
and (S3) cooling the reaction system to 40-50 ℃, and adding a second organic solvent to adjust the solid content to 30-40% to obtain the polyurea acrylate prepolymer resin solution.
Further, the second organic solvent is at least one selected from ethyl acetate, propyl acetate and butyl acetate. The addition amount of the second organic solvent is 50-60wt% of the total mass of the agent A, the agent B and the agent C
The invention also provides an ultraviolet curing pressure-sensitive adhesive tape which sequentially comprises a polyester release film, a coating of the ureido-containing UV curing polymer composition layer and a base film.
Further, the polyester release film is a PET polyester release film; the base film is selected from polyvinyl chloride films, polyolefin films (polyethylene films, polypropylene films). The thickness of the polyester release film is 35-45 mu m, the thickness of the urea-group-containing UV viscosity-reducing adhesive is 10-20 mu m, and the thickness of the base film is 80-120 mu m.
The invention also provides a preparation method of the ultraviolet light curing pressure-sensitive adhesive tape, which comprises the following steps: uniformly coating the urea-containing UV curing polymer composition solution on a polyester release film, and carrying out prepolymerization and solvent removal through temperature gradient heating; and then compounding the polyester release film coated with the ureido-containing UV-cured polymer composition coating with the base film, and curing to obtain the ultraviolet-cured pressure-sensitive adhesive tape.
Further, a mode of coating the solution of the ureido-containing UV-curable polymer composition is not particularly limited, such as coating, roll coating, spray coating, spin coating. In one embodiment of the invention, a roller coating mode is adopted, and the linear speed is 5-30m/min.
Further, the temperature gradient is baking with 3-5 baking channels, such as 4 baking channels, wherein the temperature of the first stage is 75-85 ℃, the temperature of the second stage is 90-100 ℃, the temperature of the third stage is 105-120 ℃, and the temperature of the fourth stage is 90-100 ℃.
Further, the compounding is carried out under the pressure of 0.3-0.8MPa, and the curing is carried out in a drying room at the temperature of 45-60 ℃ for 48-72h.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
1. the ultraviolet-curable pressure-sensitive adhesive is prepared by adopting the polyurea acrylate pre-polymerized resin, and the urea-based monomer is a functional monomer containing unsaturated double bonds, so that the ultraviolet-curable pressure-sensitive adhesive has the functions of improving the stability of a resin system and enhancing the adhesive force in an acrylic resin system, and particularly the existence of urea groups can greatly improve the wettability of the resin, thereby improving the adhesive force. Compared with the traditional ultraviolet light curing acrylate monomer and low molecular weight ureido monomer mixed or polyurethane double-component ultraviolet light curing pressure-sensitive adhesive, the adhesive layer has good cohesive force, good adhesiveness on the surface of a base material and no pollution to the surface of a wafer cutting product before and after ultraviolet light irradiation. The urea-based UV adhesive-reducing composition has the advantages that the stripping strength of materials is high, the viscosity is rapidly reduced after UV illumination, no additional UV active monomer or oligomer is needed, the risk of adhesive residue is avoided, the adhesive force of the materials to a substrate can be improved due to the urea-based unsaturated acrylate adhesive, and meanwhile, the urea-based UV adhesive-reducing composition has high temperature resistance and creep resistance.
2. The polyurea acrylate pre-polymerized resin provided by the invention has the advantages that the double bond is reserved in the polymerization process and more hydroxyl and amino groups are reserved in the polymerization process due to the doping of the strong polar monomer, and the cross-linking point is provided as a matrix resin in the ultraviolet curing pressure-sensitive adhesive, so that the initial adhesive force of the dicing tape is strong, a good fixing effect can be achieved on a wafer, when the ultraviolet is irradiated, the adhesive layer is cross-linked and cured, the adhesive force of the adhesive tape is reduced to a small value (the peeling force is within 10gf/25 mm), the adhesive is easy to peel, and the diced wafer can be picked up well.
Drawings
From left to right in FIG. 1, the residual glue peeled off after UV irradiation after 150℃treatment was used in example 1, example 2, comparative example 1 and comparative example 2, respectively.
Detailed Description
The following examples are intended to further illustrate the present invention but are not to be construed as limiting its scope, as many insubstantial modifications and adaptations of the invention that are within the scope of the invention as described above would be within the skill of the art.
Curing agent L-75 is purchased from Bayer Material science (China); the polyester plasticizer W-1040-S was purchased from Dietson Corp.
The polyester release film is purchased from the Yangzhou Wanchun phototechnology Co., ltd, and has the product name CT-2, the thickness of 36 mu m and the peeling force of 10gf/25 mm.
PREPARATION EXAMPLE 1-1
Adding 100 parts by mass of hydroxyethyl acrylate into 250 parts by mass of acetone at room temperature, adding 0.5 part by mass of hydroquinone, 1.25 parts by mass of dibutyltin dilaurate, dropwise adding isophorone diisocyanate at a temperature of 0-10 ℃, keeping the temperature for 0-10 ℃ for 3 hours after the completion of dropwise adding the isophorone diisocyanate and the hydroxyethyl acrylate in a molar ratio of 1:1; heating to 40 ℃, dropwise adding 1, 3-diamino-2-hydroxy propane, wherein the molar ratio of the 1, 3-diamino-2-hydroxy propane to the hydroxyethyl acrylate is 1:1, continuously reacting for 3 hours after the completion of dropwise adding, and then distilling off acetone in vacuum to obtain the ureido functional monomer 1.
PREPARATION EXAMPLES 1-2
Other conditions and operations were the same as in preparation example 1-1 except that 1, 3-diamino-2-hydroxypropane was replaced by an equimolar amount of 1, 11-diaminoundec-6-ol to give ureido functional monomer 2.
Preparation examples 1 to 3
Other conditions and operations were the same as in preparation example 1-1 except that 1, 3-diamino-2-hydroxypropane was replaced with an equimolar amount of 2, 3-diamino-1-butanol to give ureido functional monomer 3.
Preparation examples 1 to 4
Other conditions and operations were the same as in preparation example 1-1 except that 1, 3-diamino-2-hydroxypropane was replaced by an equimolar amount of 1, 4-diamino-2, 3-butanediol to give ureido functional monomer 4.
PREPARATION EXAMPLE 2-1
(S1) mixing and stirring 25 parts by mass of isooctyl acrylate, 45 parts by mass of n-butyl acrylate, 3.2 parts by mass of acrylic acid and 10 parts by mass of methyl methacrylate uniformly to obtain a mixed monomer; taking 25% of mixture monomer, and adding BPO with the total mass of 0.3% of the monomer as an agent A; taking 30% of mixed monomer, and adding BPO accounting for 0.4% of the total mass of the monomer as a B agent; adding 10 parts by mass of hydroxyethyl acrylate and 6 parts by mass of the ureido functional monomer 1 prepared in the preparation example 1-1 and BPO accounting for 0.25 weight percent of the total mass of the monomers into the residual mixed monomers to serve as a C agent;
(S2) under the nitrogen atmosphere, adding the agent A into 100 parts by mass of ethyl acetate, heating to 65 ℃, and carrying out heat preservation reaction for 2 hours; heating to 80 ℃, dropwise adding the agent B, and reacting for 1h after the dropwise adding is finished within 1h; dropwise adding the agent C, and after the dropwise adding is finished within 1h, carrying out heat preservation reaction for 2h;
and (S3) cooling the reaction system to 40 ℃, and adding ethyl acetate to adjust the solid content to 40% to obtain the polyurea acrylate prepolymer resin solution 1.
PREPARATION EXAMPLE 2-2
Other conditions and operations are the same as those of preparation example 2-1 except that in step (S1), the ureido functional monomer 1 is replaced with the ureido functional monomer 2 prepared in preparation example 1-2 of equal mass, and finally the polyurea acrylate prepolymer resin solution 2 is obtained.
PREPARATION EXAMPLES 2-3
Other conditions and operations are the same as those of preparation example 2-1 except that in step (S1), the ureido functional monomer 1 is replaced with the ureido functional monomer 3 prepared in preparation examples 1-3 of equal mass, and finally polyurea acrylate prepolymer resin solution 3 is obtained.
PREPARATION EXAMPLES 2 to 4
Other conditions and operations are the same as those of preparation example 2-1 except that in step (S1), the ureido functional monomer 1 is replaced with the ureido functional monomer 4 prepared in preparation examples 1-4 of equal mass, and finally the polyurea acrylate prepolymer resin solution 4 is obtained.
PREPARATION EXAMPLES 2 to 5
Other conditions and operations were the same as in preparation example 2-1 except that in step (S1), the amount of ureido functional monomer 1 was 10 parts by mass, and finally polyurea acrylate prepolymer resin solution 5 was obtained.
Comparative preparation example 1
Other conditions and operations were the same as in preparation example 2-1 except that in step (S1), the ureido functional monomer was not added. Finally obtaining the polyacrylate prepolymer resin solution.
Comparative preparation example 2
Other conditions and operations are the same as in preparation example 2-1 except that in step (S1), the ureido functional monomer 1 is replaced with 1, 3-diallyl urea, and finally polyurea acrylate pre-polymerization resin solution 6 is obtained.
Example 1
(1) 250 parts by mass of a pre-polymerized resin solution 1 of polyurea acrylic acid ester of preparation example 2-1 (the solid content is 40 percent, 100 parts by mass of the pre-polymerized resin of polyurea acrylic acid ester is contained), 1 part by mass of a photoinitiator TPO-L (diphenyl- (2, 4, 6-trimethyl benzoyl) phosphorus oxide), 1.5 parts by mass of an L-75 curing agent and 2 parts by mass of a plasticizer W-1040-S are stirred and mixed uniformly to prepare a solution of an ureido-containing UV-cured polymer composition;
(2) On a coater, the solution of the ureido-containing UV curing polymer composition is divided into 4 drying channels by a roller coating mode at a linear speed of 5m/min through a total length of 10 m: the temperature of the first section is 80 ℃, the temperature of the second section is 100 ℃, the temperature of the third section is 120 ℃, the temperature of the fourth section is 100 ℃, further prepolymerization is carried out, and the solvent in the ultraviolet curing pressure sensitive adhesive is removed; and then compounding the film coated with the ultraviolet curing pressure-sensitive adhesive with a PO film (PE material) with the thickness of 110 mu m at the pressure of 0.3MPa of a pressing roller and the temperature of room temperature, and finally placing the film into a drying room at 50 ℃ for curing for 72 hours to obtain the ultraviolet curing pressure-sensitive adhesive tape. Wherein the thickness of the polyester release film substrate is 36 mu m, the thickness of the urea-group-containing UV anti-adhesive layer is 20 mu m, and the thickness of the PO film substrate is 110 mu m. The properties are shown in Table 1 below.
Examples 2 to 5
Other conditions and operations are the same as in example 1 except that in step (1), the polyurea acrylate prepolymer resin solution 1 of preparation example 2-1 is replaced with the polyurea acrylate prepolymer resin solutions 2 to 5 prepared in preparation examples 2-2 to 2-5, respectively.
Comparative example 1
Other conditions and operations were the same as in preparation example 2-1 except that in step (1), the polyurea acrylate prepolymer resin solution 1 was replaced with the polyacrylate prepolymer resin solution prepared in comparative preparation example 1.
Comparative example 2
Other conditions and operations were the same as in preparation example 2-1 except that in step (1), the polyurea acrylate prepolymer resin solution 1 was replaced with the polyurea acrylate prepolymer resin solution 6 prepared in comparative preparation example 2.
Effect example
The UV pressure-sensitive adhesive tapes of examples 1-5 above were cut to 25mmBroad strips were used (GB/T2792-2014 method for testing adhesive tape peel Strength, adhesive target is silicon wafer) to test UV front and rear peel force (UV treatment device is LED debonder, wavelength of 365nm, UV radiation intensity of 170 mW/cm) 2 UV radiation energy 300mJ/cm 2 ). Similarly, after the silicon wafer to which the tape was attached was placed in an oven at 150℃for 4 hours, the post-UV peel force was also measured. The peeling interface was observed with a microscope, and the presence or absence of residual glue and adhesive/base failure was observed. The test results are shown in table 1 below.
TABLE 1 pressure sensitive adhesive tape Performance test
In FIG. 1, the adhesive residues at the interfaces are peeled off after the treatment at 150℃for 4 hours in example 1, example 2, comparative example 1 and comparative example 2, respectively, from left to right. It can be seen that the invention has reasonable compatibility and optimization of the formula, can resist high temperature, has excellent UV viscosity reduction performance after high temperature treatment, and does not have residual glue.
The UV pressure-sensitive adhesive tape prepared by the invention has excellent UV viscosity reduction performance, particularly has good UV viscosity reduction performance after being subjected to high-temperature treatment at 150 ℃, has low peel strength after UV irradiation and does not have residual adhesive, so that the UV-curable pressure-sensitive adhesive tape is particularly suitable for the fields of semiconductor wafer cutting, semiconductor wafer grinding and the like with high-temperature working procedures.

Claims (10)

1. The ureido-containing UV curing polymer composition is characterized by comprising the following raw materials in parts by mass: 100 parts of polyurea acrylic ester pre-polymerized resin, 1-2 parts of photoinitiator, 1-5 parts of curing agent and 1-5 parts of plasticizer; the polyurea acrylic ester pre-polymerized resin is obtained by copolymerizing the following monomers in parts by mass: 6-10 parts of ureido acrylic ester functional monomer, 60-80 parts of soft monomer, 10-20 parts of hard monomer, 1-5 parts of unsaturated carboxylic acid and 10-15 parts of hydroxyl-containing acrylic ester monomer; the ureido acrylate functional monomer contains more than 2 carbon-carbon unsaturated double bonds, more than 2 urea groups and more than 1 functional group, wherein the functional group is at least one of hydroxyl, epoxy, carboxyl and amino;
the ureido acrylic ester functional monomer is prepared by a preparation method comprising the following steps: hydroxyl acrylic ester reacts with isophorone diisocyanate in the presence of a polymerization inhibitor and a catalyst, and then a polyfunctional group compound is added for continuous reaction to obtain an allophanate functional monomer; the polyfunctional compound has 2 or more functional groups capable of reacting with isocyanate groups.
2. The ureido group-containing UV curable polymer composition according to claim 1, wherein the functional group capable of reacting with an isocyanate group is one or more selected from the group consisting of a hydroxyl group, an amino group and a carboxyl group.
3. The ureido-containing UV-curable polymer composition according to claim 1, wherein the UV initiator is at least one of benzoin diethyl ether, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphinate; the curing agent is at least one of aziridine curing agent and isocyanate; the plasticizer is selected from at least one of sebacic acid series, adipic acid series and phthalic acid series.
4. The ureido-containing UV-curable polymer composition according to claim 1, wherein the soft monomer is at least one selected from the group consisting of isooctyl acrylate, butyl acrylate, and hexyl acrylate; the hard monomer is at least one selected from vinyl acetate, methyl (meth) propionate and ethyl (meth) acrylate; the unsaturated carboxylic acid is at least one selected from acrylic acid and maleic acid; the hydroxyl-containing acrylate monomer is at least one selected from hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate;
the hydroxy acrylic ester is at least one selected from hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate;
the multifunctional compound is at least one of 3-amino-1, 2-propanediol, 1, 3-diamino-2-hydroxy propane, 1, 11-diamino undecan-6-ol, 2, 6-diamino-1-hexanol, 2, 3-diamino-1-butanol, 2-di (aminomethyl) propane-1, 3-diol and 1, 4-diamino-2, 3-butanediol;
the molar ratio of the hydroxy acrylate, isophorone diisocyanate and the polyfunctional compound is 1:0.9-1:1-1.1.
5. The ureido-containing UV-curable polymer composition according to claim 1, wherein the hydroxyl acrylic ester reacts with isophorone diisocyanate at 0-10 ℃, isophorone diisocyanate is slowly added into the system within 1-3 hours, and the temperature is kept for 3-5 hours after the addition; the polyfunctional group compound is added for continuous reaction, namely, the polyfunctional group compound is slowly added into the system within 1-3h at the temperature of 40-50 ℃, and the temperature is kept for reaction for 3-5h after the addition is finished.
6. The ureido UV curable polymer composition according to claim 5, wherein the ureido acrylate functional monomer is prepared by a preparation method comprising the steps of: 100 parts by mass of hydroxy acrylic ester is dissolved in a first organic solvent with the mass being 2-4 times that of the hydroxy acrylic ester, a polymerization inhibitor and a catalyst are added, isophorone diisocyanate is dropwise added at the temperature of 0-10 ℃ for 1-3 hours, and the reaction is carried out for 3-5 hours after the completion of dropwise addition; then controlling the temperature to be 40-50 ℃, slowly adding the multifunctional group compound, after finishing the addition for 1-3 hours, carrying out heat preservation reaction for 3-5 hours, and distilling off the solvent and unreacted monomers by vacuum distillation to obtain the ureido acrylic ester functional monomer; the molar ratio of the hydroxy acrylate, isophorone diisocyanate and the polyfunctional compound is 1:0.9-1:1-1.1.
7. The ureido-containing UV-curable polymer composition according to claim 1, wherein the polyurea acrylate prepolymer resin is prepared by a preparation method comprising the steps of:
(S1) mixing 60-80 parts of soft monomer, 10-20 parts of hard monomer and 1-5 parts of unsaturated carboxylic acid uniformly to obtain a mixed monomer, taking 25-35wt% of the mixed monomer, and adding an initiator accounting for 0.3-0.35wt% of the total mass of the monomers to obtain an agent A; mixing 30-40wt% of mixed monomer, and adding initiator in 0.4-0.5wt% of total monomer mass as agent B; adding 6-10 parts of ureido acrylic ester functional monomer and 10-15 parts of hydroxyl acrylic ester monomer into the rest mixed monomers, and adding an initiator accounting for 0.2-3wt% of the total mass of the monomers to serve as a C agent;
the total mass of the monomers is the sum of the mass of the ureido acrylic ester functional monomer, the soft monomer, the hard monomer, the unsaturated carboxylic acid and the hydroxyl-containing acrylic ester monomer;
(S2) under protective atmosphere, adding the agent A into a second organic solvent, heating to 65-70 ℃, and carrying out heat preservation reaction for 1-2h; heating to 80-85 ℃, dropwise adding the agent B, and after the dropwise adding is finished within 1-2 hours, carrying out heat preservation reaction for 0.5-1 hour; dropwise adding the agent C within 1-2h, and reacting for 1-2h at a constant temperature;
and (S3) cooling the reaction system to 40-50 ℃, and adding a second organic solvent to adjust the solid content to 30-40% to obtain the polyurea acrylate prepolymer resin solution.
8. An ultraviolet light curing pressure-sensitive adhesive tape, which sequentially comprises a polyester release film, a coating layer of the ureido-containing UV curing polymer composition according to any one of claims 1 to 7 and a base film.
9. The uv curable pressure sensitive adhesive tape of claim 8, wherein the polyester release film is a PET polyester release film; the base film is selected from a polyvinyl chloride film, a polyethylene film or a polypropylene film; the thickness of the polyester release film is 35-45 mu m, the thickness of the urea-group-containing UV viscosity-reducing adhesive is 10-20 mu m, and the thickness of the base film is 80-120 mu m.
10. The method for preparing the ultraviolet light-curable pressure-sensitive adhesive tape as claimed in claim 8 or 9, comprising the steps of: uniformly coating the urea-containing UV curing polymer composition solution on a polyester release film, and carrying out prepolymerization and solvent removal through temperature gradient heating; and then compounding the polyester release film coated with the UV visbreaking adhesive containing the ureido with a base film, and curing to obtain the ultraviolet curing pressure-sensitive adhesive tape.
CN202310921843.4A 2023-07-26 2023-07-26 Ureido-containing UV (ultraviolet) curing polymer composition, pressure-sensitive adhesive tape and preparation method Pending CN116925679A (en)

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