CN116987468A - Migration-free rapid UV viscosity-reducing polymer composition and preparation method thereof - Google Patents

Migration-free rapid UV viscosity-reducing polymer composition and preparation method thereof Download PDF

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CN116987468A
CN116987468A CN202311252090.9A CN202311252090A CN116987468A CN 116987468 A CN116987468 A CN 116987468A CN 202311252090 A CN202311252090 A CN 202311252090A CN 116987468 A CN116987468 A CN 116987468A
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parts
polymer composition
migration
viscosity
monomer
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CN116987468B (en
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朱翰涛
王博
李欣悦
李征
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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
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09J133/16—Homopolymers or copolymers of esters containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer

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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)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention relates to a migration-free rapid UV (ultraviolet) viscosity-reducing polymer composition and a preparation method thereof, wherein the UV viscosity-reducing polymer composition comprises the following raw materials: acrylic ester pre-polymerization resin, polymerization inhibitor, photoinitiation active aziridine compound, organic tin and semi-end-capped curing agent; the preparation monomers of the acrylate prepolymer resin comprise a benzophenone unsaturated photoinitiator and an unsaturated cyclic tertiary amine monomer; the semi-blocked curing agent is cardanol compound and isophorone diisocyanate according to the mass ratio of 3.0-3.3:2, reacting to obtain the product. The rapid UV viscosity-reducing polymer composition provided by the invention also has a good UV viscosity-reducing effect under the condition of shortening UV irradiation, and the production efficiency of the UV viscosity-reducing composition as a high-precision semiconductor electronic component is greatly enhanced; and the UV glue reducing agent is high-temperature resistant and can not leave residual glue after high-temperature treatment.

Description

Migration-free rapid UV viscosity-reducing polymer composition and preparation method thereof
Technical Field
The invention belongs to the technical field of chip cutting films and the technical field of polymer compositions, and particularly relates to a migration-free rapid UV (ultraviolet) viscosity-reducing polymer composition and a preparation method thereof.
Background
When the traditional adhesive is detached, the peel strength is high, so that precise electronic components are easy to damage, and particularly, the semiconductor technology is developed to date, the size is smaller and smaller, and the precision degree is higher and higher. UV-curable adhesives are currently used in semiconductor precision chip dicing to achieve precision chip manufacturing processes. The UV-curable adhesive is a special polymer composition, wherein unreacted unsaturated double bonds remain on the resin, after UV irradiation, the adhesive is cured to be reduced, the peeling strength is rapidly reduced, and the resin can be completely peeled. At present, a photoinitiator needs to be added into the UV adhesive for initiating polymerization by UV irradiation, and the small molecular photoinitiator can slowly migrate to the surface of an adhesive layer in the storage and use processes, particularly the migration speed can be accelerated under the heating condition, the peeling strength of a pressure-sensitive adhesive tape is seriously influenced, and the phenomenon of adhesive residue easily occurs, so that the application of the small molecular photoinitiator in the technical field of chip dicing films is limited.
The general function in the prior art is to adopt a macromolecular photoinitiator or a polymerizable photoinitiator to enable the photoinitiator to become a part of the UV anti-adhesion resin, and the defect caused by migration of the photoinitiator is avoided naturally due to the fact that no small molecular photoinitiator exists. Such as XIAO P, et al [ J ]. Prog Org Coat,2009 (64): 510-514 discloses a benzophenone derivative with acrylic acid esters at two ends, which has the following structural formula:
。
for another example, polym Adv Tech,2008 (19): 1305-1310 disclose double bond-containing benzophenone derivatives of the following structure,
。
such photoinitiators containing polymerizable groups have received considerable attention and research in the field of UV curing. However, the current polymerizable photoinitiator cannot be applied to practical application at present in the UV reducing adhesive, because the peeling strength before UV curing cannot be met, or the peeling strength after UV irradiation is not obviously reduced enough, and the phenomenon of adhesive residue is obvious.
In addition, UV-curable adhesives used in the chip dicing film technical field are required to be faster in terms of faster UV irradiation due to the rapid operation in addition to suitable pre-irradiation/post-irradiation peel strength. However, if the UV irradiation time is not long enough, the residual glue phenomenon may be caused, and the irradiation time of the UV-reduced glue is more than 5s at present. The addition of the auxiliary initiator in the prior art improves the photoinitiation efficiency and shortens the UV illumination time, but the introduction of the photoinitiation auxiliary agent still has the migration risk. The inventor's prior patent CN202311145816.9 discloses a UV visbreaking polymer composition without a small molecule photoinitiator. The specific formula is adopted, so that the photoinitiator groups are on the polymer chain of the resin, and residual small-molecule photoinitiation active substances are avoided after polymerization, and the defect of VU (vacuum ultraviolet) glue reduction caused by migration of the small-molecule photoinitiator is reduced. But the UV visbreaking speed is not yet fully satisfactory.
Disclosure of Invention
The invention provides a migration-free UV (ultraviolet) viscosity-reducing polymer composition and a preparation method thereof, and aims to overcome the defect that the prior art is lack of the migration-free or low-migration-free UV viscosity-reducing polymer composition capable of meeting the industrial production efficiency. The invention introduces polymerizable tertiary amine based on the prior UV viscosity-reducing polymer composition without a small molecular photoinitiator, and has obvious industrial advantages while keeping excellent UV viscosity-reducing performance and obviously accelerating UV irradiation time. The invention aims at realizing the following technical scheme:
a migration-free rapid UV viscosity-reducing polymer composition comprises the following raw materials: 40-50 parts by mass of acrylate prepolymer resin, 0.1-0.5 part by mass of polymerization inhibitor, 2-3 parts by mass of photoinitiated active aziridine compound, 0.3-0.6 part by mass of organic tin, 3-5 parts by mass of semi-end-capped curing agent and organic solvent; the addition amount of the organic solvent ensures that the solid content of the system is 30-40 percent;
the acrylic ester pre-polymerization resin is prepared by copolymerizing the following monomers in parts by mass: 2-4 parts of a benzophenone unsaturated photoinitiator, 50-70 parts of a soft monomer, 10-15 parts of a hard monomer, 6-10 parts of an unsaturated carboxylic acid monomer, 5-8 parts of a polyfunctional monomer, 10-15 parts of a hydroxyl-containing acrylate monomer and 3-5 parts of an unsaturated cyclic tertiary amine monomer; the semi-blocked curing agent is cardanol compound and isophorone diisocyanate according to the mass ratio of 3.0-3.3:2, reacting to obtain the product.
The rapid UV visbreaking means that the stripping force of the UV visbreaking composition is reduced to below 10gf/25mm after UV irradiation for 2-5 s.
Further, the unsaturated cyclic tertiary amine monomer is at least one selected from 2-morpholinoethyl methacrylate and 4-acryloylmorpholine. In the preparation of the acrylic ester pre-polymerized resin, not only the benzophenone unsaturated photoinitiator but also the unsaturated cyclic tertiary amine monomer are introduced. The unsaturated cyclic tertiary amine can be used as an auxiliary agent of a hydrogen abstraction type photoinitiator and is introduced in the form of an unsaturated monomer, so that the risk of increasing movable small molecules in the component is avoided. The unsaturated cyclic tertiary amine is introduced to polymerize and then the acrylate prepolymer resin is used as the main component of the VU viscosity-reducing polymer composition, so that the UV viscosity-reducing performance can be maintained in a shortened UV irradiation time. Greatly shortens the UV irradiation process time of the UV viscosity-reducing polymer composition as a chip cutting film and improves the manufacturing efficiency. The inventors found that although the tertiary amine can all have the effect of promoting the activity of the photoinitiator in theory, after polymerization, only the structure of introducing unsaturated cyclic tertiary amine monomer into the high molecular chain of the acrylate prepolymer resin has obvious effect, but the chain unsaturated tertiary amine such as 2- (dimethylamino) ethyl methacrylate and dimethylamino propyl methacrylamide has no obvious effect.
Further, in the preparation of the semi-blocked curing agent, the reactivity of two isocyanate groups on isophorone diisocyanate is different, and the molar ratio of the cardanol compound to isophorone diisocyanate is controlled to be close to 1:1, cardanol can be slightly excessive to ensure that semi-end capping is complete and small molecule residues are avoided. The isocyanate on isophorone diisocyanate reacts with the phenolic hydroxyl of cardanol, and an isocyanate group remains on the product, so that the reaction can be continued. The invention adopts semi-end-capped curing agent, cardanol is used as sealing agent, the deblocking temperature is 120-130 ℃, and isocyanate groups are released to participate in the reaction in the subsequent drying process of the drying tunnel.
Further, the semi-end-capped curing agent is prepared by a preparation method comprising the following steps: uniformly mixing 30-33 parts by mass of cardanol, 200-300 parts by mass of an organic solvent, 0.5-1 part of a polymerization inhibitor and 1.5-3 parts of organic tin, dropwise adding 20 parts by mass of isophorone diisocyanate at a temperature of 0-10 ℃, after 2-3 hours of dropwise adding, carrying out heat preservation reaction for 2-3 hours, tracking the reaction degree, and removing acetone by vacuum distillation when the isocyanate content is unchanged, thereby obtaining the semi-end-capped curing agent. The organic solvent is at least one selected from acetone, butanone and cyclohexanone.
Further, in the preparation of the acrylate prepolymer resin, the benzophenone unsaturated photoinitiator is at least one selected from the following compounds of formula (I) and formula (II):
；
further, the hard monomer is at least one selected from vinyl acetate, methyl methacrylate and ethyl methacrylate; the soft monomer is at least one selected from isooctyl acrylate and butyl acrylate; the unsaturated carboxylic acid monomer is at least one selected from (methyl) acrylic acid and fumaric acid; the hydroxyl-containing acrylate monomer is at least one selected from hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; the polyfunctional monomer is at least one selected from 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate and tripropylene glycol diacrylate.
The preparation method of the acrylic ester pre-polymerized resin comprises the following steps:
under inert atmosphere and light-shielding condition, adding a benzophenone unsaturated photoinitiator, a soft monomer, a hard monomer, an unsaturated carboxylic acid monomer, a hydroxyl-containing acrylate monomer and an unsaturated cyclic tertiary amine monomer into a solvent, heating to 50-70 ℃, adding 30-50 wt% of an initiator for heat preservation reaction, adding the rest initiator and a polyfunctional monomer after reaction for 1-2 hours, and continuing heat preservation reaction for 3-5 hours to complete polymerization, thus obtaining a dispersion liquid of acrylate prepolymer resin; preferably, after the polymerization is finished, an organic solvent is also added to ensure that the solid content of the dispersion liquid of the acrylate prepolymer resin is 30-40%; the organic solvent is at least one selected from ethyl acetate, propyl acetate and butyl acetate.
The initiator is at least one of AIBN and BPO, and the amount of the initiator is 1-2wt% of the total monomer.
The initiator is added in batches, and finally the polyfunctional monomer is added for the purpose of preparing the acrylic ester pre-polymerized resin with better quality.
Further, the photoinitiated active aziridine compound is selected from at least one of the following compounds of formula (III) and formula (IV):
。
the functional group with photoinitiation activity is grafted and modified to the acrylic ester pre-polymer resin by the reaction of the aziridine group on the photoinitiation activity aziridine compound and the carboxyl, and the acrylic ester pre-polymer resin has photoinitiation functional groups brought by unsaturated photoinitiators on the acrylic ester pre-polymer resin due to the existence of the unsaturated photoinitiators, also contains photoinitiation functional groups brought by the reaction of the photoinitiation activity aziridine compound, and the two photoinitiation functional groups interact and cooperate with each other, so that the UV viscosity-reducing polymer composition provided by the invention is used as a pressure-sensitive adhesive of a chip cutting film, has excellent UV viscosity-reducing performance and high temperature resistance, thoroughly eliminates the potential hazards of residual glue easily caused by the decrease of peel strength generated by the migration of the photoinitiators due to the absence of small molecular photoinitiators, and is particularly suitable for being used in pressure-sensitive adhesives for semiconductor fine processing.
The polymerization inhibitor is not particularly limited, and a polymerization inhibitor conventionally used in the art for inhibiting polymerization of a carbon-carbon unsaturated double bond, such as hydroquinone, may be used. The organotin is not particularly limited, and organotin catalysts commonly used in the art may be used, such as at least one of dibutyltin dilaurate, stannous octoate, and dibutyltin dichloride.
The second object of the present invention is to provide a preparation method of the migration-free rapid UV viscosity-reducing polymer composition, comprising the following steps: uniformly mixing acrylate pre-polymerization resin, polymerization inhibitor and organic tin, heating to 40-50 ℃, slowly adding a semi-end-capped curing agent and a photoinitiated active aziridine compound, after 2-4 hours of addition, continuing to perform heat preservation reaction for 2-3 hours, cooling to room temperature, and adding an organic solvent to adjust the solid content, thereby obtaining the migration-free rapid UV viscosity-reducing polymer composition.
The third object of the invention is to provide a UV (ultraviolet) visbreaking pressure-sensitive adhesive tape suitable for chip cutting, which comprises a polyester release film, the migration-free rapid UV visbreaking high polymer composition coating and a base film which are sequentially attached.
Further, the polyester release film is a PET polyester release film with the thickness of 30-45 mu m; the thickness of the migration-free rapid UV viscosity-reducing polymer composition coating is 10-20 mu m; the base film is polyvinyl chloride film or polyolefin film (polyethylene film, polypropylene film) with thickness of 80-120 μm.
The fourth object of the present invention is to provide a method for preparing the above UV-tack-reducing pressure-sensitive adhesive tape suitable for chip dicing, comprising the steps of: uniformly coating a dispersion liquid of the migration-free rapid UV viscosity-reducing polymer composition 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 viscosity-reducing high polymer composition with a base film, and curing to obtain the UV viscosity-reducing photosensitive adhesive tape.
Further, the manner of coating uniformly on the polyester release film is not particularly limited, such as hanging 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 that 3-5 drying channels are adopted for baking treatment for 2-5min, such as 4 drying channels, the temperature of the I section is 75-85 ℃, the temperature of the II section is 90-100 ℃, the temperature of the III section is 105-130 ℃, and the temperature of the IV section is 90-100 ℃; 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.
The invention has the excellent effects that the semi-blocked curing agent prepared by adding the unsaturated photoinitiator during the polymerization of the acrylate prepolymer resin and simultaneously matching with the cardanol and the isophorone diisocyanate and the photoinitiated active aziridine compound are matched to obtain the high polymer composition which can finish UV viscosity reduction without adding the small molecular photoinitiator. And the unsaturated cyclic tertiary amine monomer with a promoting effect on photoinitiation is also added during the preparation of the acrylic ester prepolymer resin, so that the UV irradiation effect is enhanced, a good UV viscosity reduction effect is also obtained under the condition of shortening the UV irradiation, and the production efficiency of the UV viscosity reduction composition as a high-precision semiconductor electronic component is greatly enhanced. And the UV glue reducing agent is high-temperature resistant and can not leave residual glue after high-temperature treatment.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. The following examples facilitate a better understanding of the present invention, but are not intended to limit the same. The experimental methods in the following examples are conventional methods unless otherwise specified.
In the embodiment of the invention, cardanol is carded cardanol NX-2025.
The parts in the embodiments of the present invention are parts by mass unless otherwise specified; the "%" is mass percent unless otherwise specified.
Preparation example 1
Under the condition of nitrogen atmosphere and light shielding, adding 2 parts of a benzophenone unsaturated photoinitiator with the formula (I), 30 parts of isooctyl acrylate, 15 parts of butyl acrylate, 12 parts of methyl methacrylate, 8 parts of acrylic acid, 12 parts of hydroxyl-containing acrylate monomer and 5 parts of 2-morpholinoethyl methacrylate into 80 parts of ethyl acetate, heating to 65 ℃, adding 0.4 part of AIBN, carrying out heat preservation reaction for 1h, adding 0.6 part of AIBN and 8 parts of 1, 6-hexanediol diacrylate, continuing heat preservation reaction for 3h, completing polymerization, and adding ethyl acetate to adjust the system solid content to 40%, thus obtaining the dispersion liquid of the acrylate prepolymer resin.
Preparation example 2
Other conditions and operations were the same as in preparation example 1 except that 2 parts of the benzophenone unsaturated photoinitiator of formula (I) was replaced with 4 parts of the unsaturated photoinitiator of formula (II), and 5 parts by mass of 2-morpholinoethyl methacrylate was replaced with 3 parts by mass of 4-acryloylmorpholine.
Comparative preparation example 1
Other conditions and operations were the same as in preparation example 1 except that the benzophenone unsaturated photoinitiator of formula (I) was not added.
Comparative preparation example 2
Other conditions and operations were the same as in preparation example 1 except that 2-morpholinoethyl methacrylate was not added.
Preparation example 3
Adding 33 parts by mass of cardanol, 1 part of polymerization inhibitor hydroquinone and 2 parts of dibutyltin dilaurate into 300 parts of acetone, uniformly mixing, controlling the temperature to be 5 ℃, dropwise adding 20 parts by mass of isophorone diisocyanate, after 3 hours of dropwise adding, carrying out heat preservation reaction for 3 hours, tracking the reaction degree, and removing the acetone by vacuum distillation when the isocyanate content is unchanged, thereby obtaining the semi-blocked curing agent.
Comparative preparation example 3
Other conditions and operations were the same as in preparation example 3 except that isophorone diisocyanate was replaced with an equimolar amount of dicyclohexylmethane-4, 4' -diisocyanate.
Example 1
100 parts of the acrylic acid ester prepolymer resin dispersion liquid prepared in preparation example 1 (the solid content of which is 40 percent by weight and contains 40 parts of acrylic acid ester prepolymer resin), 0.3 part of hydroquinone and 0.5 part of dibutyltin dilaurate are uniformly mixed, the temperature is raised to 40 ℃,2 parts of compound of formula (III) and 3 parts of semi-end-capped curing agent prepared in preparation example 3 are slowly added in 3 hours, the heat preservation reaction is continued for 3 hours, the mixture is cooled to room temperature, and ethyl acetate is added to ensure that the solid content of the system is 30 percent, so that the dispersion liquid of the migration-free rapid UV viscosity-reducing polymer composition is obtained.
Example 2
125 parts of the acrylic acid ester prepolymer resin dispersion liquid prepared in preparation example 2 (the solid content of which is 40 percent by weight and contains 50 parts of acrylic acid ester prepolymer resin), 0.35 part of hydroquinone and 0.4 part of dibutyltin dilaurate are uniformly mixed, the temperature is raised to 40 ℃,2 parts of compound of formula (IV) and 4 parts of semi-end-capped curing agent prepared in preparation example 3 are slowly added in 3 hours, the heat preservation reaction is continued for 3 hours, the mixture is cooled to room temperature, and ethyl acetate is added to ensure that the solid content of the system is 30 percent, so that the dispersion liquid of the migration-free rapid UV viscosity-reducing polymer composition is obtained.
Example 3
110 parts of the acrylic acid ester prepolymer resin dispersion liquid prepared in preparation example 1 (the solid content of which is 40 percent by weight and contains 50 parts of acrylic acid ester prepolymer resin), 0.4 part of hydroquinone and 0.5 part of dibutyltin dilaurate are uniformly mixed, the temperature is raised to 40 ℃,3 parts of compound of formula (IV) and 5 parts of semi-end-capped curing agent prepared in preparation example 3 are slowly added in 3 hours, the heat preservation reaction is continued for 3 hours, the mixture is cooled to room temperature, and ethyl acetate is added, so that the solid content of the system is 30 percent, and the dispersion liquid of the migration-free rapid UV viscosity-reducing polymer composition is obtained.
Comparative example 1
Other conditions and operations were the same as in example 1 except that 100 parts of the acrylic acid ester pre-polymer resin dispersion prepared in preparation example 1 was replaced with 100 parts of the acrylic acid ester pre-polymer resin dispersion prepared in comparative preparation example 1, and 0.8 part of the photoinitiator benzophenone was added.
Comparative example 2
Other conditions and operations were the same as in example 1 except that 100 parts of the acrylic acid ester pre-polymer resin dispersion prepared in preparation example 1 was replaced with 100 parts of the acrylic acid ester pre-polymer resin dispersion prepared in comparative preparation example 2.
Comparative example 3
Other conditions and operations were the same as in example 1 except that the semi-blocked curing agent prepared in preparation example 3 was replaced with the curing agent prepared in comparative preparation example 3 of equal mass.
Application example
The polymer composition dispersions of examples and comparative examples were coated on a PET polyester release film by roll coating at a line speed of 5m/min on a coater, and divided into 4 drying tunnels by a total length of 10 m: further prepolymerizing at 80℃in stage I, at 100℃in stage II, at 125℃in stage III and at 100℃in stage IV to remove the solvent from the polymer composition; and then compounding the film coated with the polymer composition 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 UV viscosity-reducing polymer composition coating is 20 mu m, and the thickness of the PO film substrate is 110 mu m, so that the pressure-sensitive adhesive tape with different UV viscosity-reducing polymer composition coatings is prepared. The pressure-sensitive adhesive tape was cut into 25mm wide strips, and the UV front-back peel force (UV treatment equipment was an LED debonder, 365nm wavelength, UV radiation intensity 170 mW/cm) was tested using (GB/T2792-2014 test method for adhesive tape peel Strength, adhesive object was silicon wafer) 2 Irradiation time 2 s). Similarly, the pressure-sensitive adhesive tape-attached silicon wafer was placed in an oven at 150℃for 4 hours, and after the high temperature treatment at 150℃was tested for peel force before and after UV irradiation. The residual glue rate is calculated by dividing the spline into 100 blocks with the same shape after the spline is contacted and attached with glass, peeling after being treated for 4 hours at 150 ℃, observing through a microscope, recording the number of the residual glue, and calculating the residual glue rate according to the residual glue rate = the number of the residual glue/100. The properties of the UV-curable polymer composition of the present invention are shown in Table 1.
TABLE 1 pressure sensitive adhesive tape Performance test
。
As can be seen from the data in Table 1, the UV viscosity-reducing polymer composition prepared by the invention introduces the functional group with photoinitiation function and the unsaturated cyclic tertiary amine with function of promoting UV photoinitiation into the acrylic acid prepolymer resin in a copolymerization mode, and meanwhile, the UV viscosity-reducing polymer composition is also added with photoinitiation active aziridine compound, so that the reduction of the performance of the UV viscosity-reducing pressure-sensitive adhesive caused by migration and precipitation of small molecular photoinitiator is avoided, and the phenomenon that the small molecular photoinitiator is accelerated to migrate to the surface in heat treatment, thereby causing adhesive residue is avoided. And the UV irradiation time is greatly shortened.

Claims (10)

1. The migration-free rapid UV viscosity-reducing polymer composition is characterized by comprising the following raw materials: 40-50 parts by mass of acrylate prepolymer resin, 0.1-0.5 part by mass of polymerization inhibitor, 2-3 parts by mass of photoinitiated active aziridine compound, 0.3-0.6 part by mass of organic tin, 3-5 parts by mass of semi-end-capped curing agent and organic solvent; the addition amount of the organic solvent ensures that the solid content of the system is 30-40 percent;
the acrylic ester pre-polymerization resin is prepared by copolymerizing the following monomers in parts by mass: 2-4 parts of a benzophenone unsaturated photoinitiator, 50-70 parts of a soft monomer, 10-15 parts of a hard monomer, 6-10 parts of an unsaturated carboxylic acid monomer, 5-8 parts of a polyfunctional monomer, 10-15 parts of a hydroxyl-containing acrylate monomer and 3-5 parts of an unsaturated cyclic tertiary amine monomer; the semi-blocked curing agent is cardanol compound and isophorone diisocyanate according to the mass ratio of 3.0-3.3:2, reacting to obtain the product.
2. The migration-free fast UV-curable polymer composition according to claim 1, wherein the unsaturated cyclic tertiary amine monomer is at least one selected from the group consisting of 2-morpholinoethyl methacrylate and 4-acryloylmorpholine.
3. The migration-free fast UV curable polymer composition according to claim 1, wherein the semi-blocked curing agent is prepared by a preparation method comprising the steps of: uniformly mixing 30-33 parts by mass of cardanol, 200-300 parts by mass of an organic solvent, 0.5-1 part of a polymerization inhibitor and 1.5-3 parts of organic tin, dropwise adding 20 parts by mass of isophorone diisocyanate at a temperature of 0-10 ℃, after 2-3 hours of dropwise adding, carrying out heat preservation reaction for 2-3 hours, tracking the reaction degree, and removing acetone by vacuum distillation when the isocyanate content is unchanged, thereby obtaining a semi-end-capped curing agent; the organic solvent is at least one selected from acetone, butanone and cyclohexanone.
4. The migration-free fast UV-curable polymer composition according to claim 1, wherein in the preparation of the acrylate prepolymer resin, the benzophenone-type unsaturated photoinitiator is at least one selected from the group consisting of the following compounds of formula (I) and formula (II):
。
5. the migration-free fast UV-curable polymer composition according to claim 1, wherein the hard monomer is at least one selected from the group consisting of vinyl acetate, methyl methacrylate, ethyl methacrylate; the soft monomer is at least one selected from isooctyl acrylate and butyl acrylate; the unsaturated carboxylic acid monomer is at least one selected from (methyl) acrylic acid and fumaric acid; the hydroxyl-containing acrylate monomer is at least one selected from hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; the polyfunctional monomer is at least one selected from 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate and tripropylene glycol diacrylate.
6. The migration-free fast UV-curable polymer composition according to claim 1, wherein the photoinitiated active aziridine compound is at least one selected from the group consisting of the following compounds of formula (III) and formula (IV):
。
7. the migration-free fast UV-viscosity reducing polymer composition according to claim 1, wherein the polymerization inhibitor is hydroquinone; the organic tin is at least one selected from dibutyl tin dilaurate, stannous octoate and dibutyl tin dichloride.
8. A process for preparing a migration-free fast UV-visbreaking polymeric composition according to any one of claims 1 to 7, characterized in that it comprises the following steps: uniformly mixing acrylate pre-polymerization resin, polymerization inhibitor and organic tin, heating to 40-50 ℃, slowly adding a semi-end-capped curing agent and a photoinitiated active aziridine compound, after 2-4 hours of addition, continuing to perform heat preservation reaction for 2-3 hours, cooling to room temperature, and adding an organic solvent to adjust the solid content, thereby obtaining the migration-free rapid UV viscosity-reducing polymer composition.
9. A UV-curable pressure-sensitive adhesive tape suitable for dicing a chip, comprising a polyester release film, a migration-free rapid UV-curable polymer composition coating according to any one of claims 1 to 7, and a base film, which are sequentially bonded.
10. The UV-reduced pressure-sensitive adhesive tape suitable for chip dicing according to claim 9, wherein the polyester release film is a PET polyester release film having a thickness of 30 to 45 μm; the thickness of the migration-free rapid UV viscosity-reducing polymer composition coating is 10-20 mu m; the base film is a polyvinyl chloride film or a polyolefin film, and the thickness is 80-120 mu m.
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