CN115926690A - Viscosity-reducing adhesive composition, viscosity-reducing adhesive tape and preparation method thereof - Google Patents
Viscosity-reducing adhesive composition, viscosity-reducing adhesive tape and preparation method thereof Download PDFInfo
- Publication number
- CN115926690A CN115926690A CN202211518410.6A CN202211518410A CN115926690A CN 115926690 A CN115926690 A CN 115926690A CN 202211518410 A CN202211518410 A CN 202211518410A CN 115926690 A CN115926690 A CN 115926690A
- Authority
- CN
- China
- Prior art keywords
- parts
- viscosity
- hydroxyl
- adhesive composition
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a viscosity-reducing adhesive composition, a viscosity-reducing adhesive tape and a preparation method thereof. The visbreaking adhesive comprises the following components in parts by weight: 65-95 parts of hydroxyl-containing acrylic resin, 1-30 parts of carbon-carbon double bond-containing monomer, 0.2-2 parts of cross-linking agent and 50-200 parts of solvent A. The anti-sticking adhesive composition provided by the invention has excellent performance, so that the prepared anti-sticking adhesive tape has better initial adhesion, lasting adhesion and higher peel strength, and after UV irradiation, the anti-sticking adhesive tape has lower peel strength and no residual adhesive residue after peeling, thereby meeting the use requirements of the market.
Description
Technical Field
The invention belongs to the technical field of viscosity reducing adhesives, and particularly relates to a viscosity reducing adhesive composition, a viscosity reducing adhesive tape and a preparation method thereof.
Background
With the rapid development of science and technology, the electronic industry is updated very rapidly. The demand of UV anti-sticking protective films in various fields such as wafer cutting, semiconductor chips, OCA (optical clear adhesive) bonding and positioning is increasing or decreasing. Such tapes are intended to be stable in position initially, to protect during cutting or etching, and to be easily removed without leaving any residue after UV irradiation, which requires the tape to maintain a high adhesion initially and to have a property of reducing adhesion rapidly after UV irradiation. The principle for realizing the process is that after UV irradiation, double bonds of a large number of oligomers in the adhesive tape are subjected to crosslinking reaction, and Tg is rapidly increased to lose viscosity. With the increase of market demand, the research on the viscosity reducing adhesive and the viscosity reducing adhesive tape is more and more intensive.
CN109294464A discloses a preparation method of a heating and adhesive reducing protective film. The preparation method comprises the step of heating and reducing the viscose, wherein the heating and reducing viscose is prepared by mixing resin, a curing agent, a solvent, a self-expanding microsphere foaming agent, toner and an OBSH foaming agent, and the components are mixed according to the following ratio in parts by mass: 25 to 60 portions of resin, 0.5 to 10 portions of curing agent, 30 to 60 portions of solvent, 4 to 8 portions of self-expanding microsphere foaming agent, 0.5 to 5 portions of toner and 0.5 to 2 portions of OBSH foaming agent. The finished product of the heating and viscosity reducing protective film prepared by the preparation method provided by the technical scheme has stronger bearing capacity, stronger pressure die casting resistance, stronger viscosity reduction after being adhered to the FPC and easier tearing.
CN209352815U discloses a UV visbreaking adhesive tape. The UV anti-sticking adhesive tape comprises a base film, a UV anti-sticking adhesive layer, a release layer and a UV absorption coating; the UV visbreaking adhesive layer is positioned between the base film and the UV absorption coating layer; the release layer is located between the UV visbreaking adhesive layer and the UV absorption coating. Increase one deck UV absorption coating on the release layer through at UV visbreaking sticky tape, can absorb and the external UV radiation of separation, play the effect of protection UV visbreaking sticky layer, consequently need not do the shading packing, just also need not to demolish packaging material during the use, saved the packaging cost on the one hand, on the other hand has also promoted the convenient to use degree of UV visbreaking sticky tape.
CN114085625A discloses a UV visbreaking adhesive tape and a preparation process thereof. The UV visbreaking adhesive tape comprises a release film layer, a UV visbreaking adhesive layer and a base film, wherein a plasticizer precipitation preventing adhesive layer is further arranged between the UV visbreaking adhesive layer and the base film, the plasticizer precipitation preventing adhesive layer is formed by a plasticizer precipitation preventing adhesive, and the plasticizer precipitation preventing adhesive comprises the following raw material components in parts by weight: 30 to 70 parts of solvent type polyacrylate pressure-sensitive adhesive, 1 to 20 parts of tackifying resin, 1 to 20 parts of mixed additive, 0.1 to 5 parts of curing agent and 20 to 50 parts of solvent. The UV visbreaking adhesive tape provided by the technical scheme has the advantages that the anti-plasticizer precipitation adhesive layer is further arranged between the UV visbreaking adhesive layer and the base film, the influence of the plasticizer on the UV visbreaking adhesive film is reduced, and the performance of the UV visbreaking adhesive tape is more stable and reliable.
With the increase of the market demand and the intensive research on the anti-adhesive, how to provide an anti-adhesive composition which can adjust the peel strength after UV irradiation and has a simple preparation method becomes a technical problem to be solved urgently.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a viscosity-reducing adhesive composition, a viscosity-reducing adhesive tape and a preparation method thereof. According to the invention, through designing the components of the viscosity-reducing adhesive composition and further through using the monomer containing the carbon-carbon double bond, the prepared viscosity-reducing adhesive composition has better initial viscosity, and the prepared viscosity-reducing adhesive tape has lower peel strength after being irradiated by UV and has no residual adhesive after being peeled.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a viscosity reducing adhesive composition, which is characterized in that the viscosity reducing adhesive comprises the following components in parts by weight:
65-95 parts of hydroxyl-containing acrylic resin, 1-30 parts of carbon-carbon double bond-containing monomer, 0.2-2 parts of cross-linking agent and 50-200 parts of solvent A.
According to the invention, through designing the components of the anti-adhesive composition, and further through using the monomer containing the carbon-carbon double bond and controlling the content of the monomer containing the carbon-carbon double bond within a specific range, the anti-adhesive composition which has strong initial adhesion and is adjustable in peel strength after UV irradiation can be prepared, and different application requirements can be met. Meanwhile, the molecular weight of the monomer containing the carbon-carbon double bond is small, so that the viscosity-reducing adhesive composition is diluted, and the use of an additional diluent is avoided.
According to the invention, the carbon-carbon double bond can be introduced into the anti-adhesive tape through the reaction between the hydroxyl-containing acrylic resin and the carbon-carbon double bond-containing monomer, so that the prepared anti-adhesive tape has good initial viscosity and high peel strength and permanent viscosity before UV irradiation, after UV irradiation, the carbon-carbon double bond in the carbon-carbon double bond-containing monomer in the anti-adhesive tape is polymerized, and the anti-adhesive tape after UV irradiation has low peel strength and no residual gum residue. Meanwhile, according to the invention, the peeling strength of the anti-sticking adhesive tape after UV irradiation can be regulated and controlled by regulating and controlling the content of the monomer containing the carbon-carbon double bond, so as to meet different use requirements.
In the invention, the content of the carbon-carbon double bond monomer is further controlled within a specific range, so that the prepared anti-adhesive tape has lower peel strength and no adhesive residue after UV irradiation, and can meet the use requirement. If the content of the carbon-carbon double bond-containing monomer is too much, micromolecule migration is easy to occur in the prepared viscosity-reducing adhesive tape, and finally adhesive residue is caused; if the content of the carbon-carbon double bond-containing monomer is too low, the prepared anti-adhesive tape still has higher peel strength after being irradiated by UV, and does not meet the use requirement.
In the present invention, the hydroxyl-containing acrylic resin may be 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, or the like.
The weight portion of the monomer containing the carbon-carbon double bond can be 1 portion, 5 portions, 10 portions, 15 portions, 20 portions, 25 portions or 30 portions, etc.
The crosslinking agent may be present in an amount of 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, or 2 parts by weight.
The weight portion of the solvent A can be 50 portions, 70 portions, 80 portions, 100 portions, 120 portions, 150 portions, 180 portions, 200 portions, and the like.
The following are preferred embodiments of the present invention, but not limiting the technical solutions provided by the present invention, and the objects and advantages of the present invention can be better achieved and achieved by the following preferred embodiments.
In a preferred embodiment of the present invention, the hydroxyl group-containing acrylic resin has a glass transition temperature of-60 to 20 ℃ and may be, for example, -60 ℃, -50 ℃, -40 ℃, -30 ℃, -20 ℃, -10 ℃, 0 ℃, 10 ℃ or 20 ℃.
Preferably, the weight average molecular weight of the hydroxyl group-containing acrylic resin is 20 to 80 ten thousand, and may be, for example, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80 ten thousand.
The hydroxyl group content of the hydroxyl group-containing acrylic resin is preferably 0.1 to 2mmol/g, and may be, for example, 0.1mmol/g, 0.2mmol/g, 0.5mmol/g, 0.7mmol/g, 1mmol/g, 1.3mmol/g, 1.5mmol/g, 1.8mmol/g or 2mmol/g.
As a preferred technical scheme of the invention, the hydroxyl-containing acrylic resin comprises the following raw materials in parts by weight:
40-80 parts of soft monomer, 5-10 parts of hard monomer, 1-20 parts of functional monomer and 1-30 parts of functional monomer containing active hydroxyl.
The weight portion of the soft monomer may be 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, or the like.
The hard monomer may be present in an amount of 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, or the like.
The weight portion of the functional monomer can be 1 part, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 17 parts or 20 parts and the like.
The weight portion of the functional monomer containing active hydroxyl can be 1 portion, 3 portions, 5 portions, 8 portions, 10 portions, 15 portions, 18 portions, 20 portions, 24 portions, 28 portions or 30 portions, etc.
In a preferred embodiment of the present invention, the soft monomer is an alkyl acrylate, and the number of carbon atoms in the alkyl group is an integer of 1 to 12, and may be, for example, 1, 2,4,6, 8, 10 or 12.
Preferably, the soft monomer is selected from any one of methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate or lauryl acrylate or a combination of at least two of the same.
Preferably, the hard monomer is an alkyl methacrylate, and the number of carbon atoms of the alkyl group is an integer of 1 to 6, and may be, for example, 1, 2, 3, 4, 5, or 6.
Preferably, the hard monomer is selected from any one of methyl methacrylate, ethyl methacrylate, butyl methacrylate or cyclohexyl methacrylate or a combination of at least two thereof.
The functional monomer is selected from any one of acrylic acid, methacrylic acid, N-hydroxymethyl acrylamide, glycidyl acrylate or N, N-dimethylacrylamide or the combination of at least two of the acrylic acid, the methacrylic acid, the N-hydroxymethyl acrylamide and the glycidyl acrylate.
The functional monomer containing active hydroxyl is selected from any one or the combination of at least two of hydroxyethyl acrylate, hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate or diethylene glycol monoacrylate.
As a preferable technical scheme of the invention, the hydroxyl-containing acrylic resin also comprises 100 parts of solvent B.
Preferably, the solvent B is selected from any one of ethyl acetate, toluene, butyl acetate or heptane or a combination of at least two thereof.
Preferably, the hydroxyl-containing acrylic resin raw material also comprises 0.01-0.05 part of initiator, such as 0.01 part, 0.02 part, 0.03 part, 0.04 part or 0.05 part.
Preferably, the initiator is selected from any one of or a combination of at least two of Benzoyl Peroxide (BPO), azobisisobutyronitrile (AIBN), methyl Ethyl Ketone Peroxide (MEKP), cyclohexanone peroxide (cyclohexone peroxide).
As a preferred technical scheme of the invention, the hydroxyl-containing acrylic resin is prepared by adopting the following method, and the method comprises the following steps:
(1) Adding a soft monomer, a hard monomer, a functional monomer containing active hydroxyl and a solvent into a reaction kettle in an inert gas atmosphere, and heating to reflux temperature under the stirring condition;
(2) And then adding a part of initiator into the reaction kettle, keeping the temperature for 1 to 3 hours (for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours and the like), then adding the rest initiator, keeping the temperature for 1 to 5 hours (for example, 1 hour, 2 hours, 3 hours, 4 hours or 5 hours and the like), and cooling to room temperature to obtain the hydroxyl-containing acrylic resin.
Preferably, the inert gas comprises nitrogen or argon.
In a preferred embodiment of the present invention, the monomer containing carbon-carbon double bonds is selected from isocyanate ethyl acrylate and/or isocyanate ethyl methacrylate.
Preferably, the molar ratio of the carbon-carbon double bond-containing monomer to the active hydroxyl group-containing functional monomer is (0.1 to 1.2) and can be, for example, 0.1.
According to the invention, the functional monomer containing active hydroxyl is used for preparing the acrylic resin containing hydroxyl, so that the acrylic resin has hydroxyl, and further, the carbon-carbon double bond is introduced into the viscosity-reducing adhesive tape through the reaction between the hydroxyl in the acrylic resin and the isocyanate group in the monomer containing carbon-carbon double bond, so that the viscosity-reducing adhesive tape has better initial viscosity and proper peel strength.
Meanwhile, according to the specific selection of the functional monomer containing active hydroxyl and the monomer containing carbon-carbon double bond in the invention, the molar ratio of the monomer containing carbon-carbon double bond to the functional monomer containing active hydroxyl is the molar ratio of isocyanate group to hydroxyl.
According to the invention, the content of the carbon-carbon double bond in the anti-adhesive tape can be controlled within a specific range by controlling the molar ratio of the monomer containing the carbon-carbon double bond to the functional monomer containing the active hydroxyl group within a specific range, so that the anti-adhesive tape with excellent performance is prepared. If the molar ratio of the monomer containing the carbon-carbon double bond to the functional monomer containing the active hydroxyl is too small, the hydroxyl content in the prepared viscosity-reducing adhesive is too much, and the prepared viscosity-reducing adhesive tape still has higher peel strength after being irradiated by UV; if the molar ratio of the monomer containing the carbon-carbon double bond to the functional monomer containing the active hydroxyl is too large, part of the monomer containing the carbon-carbon double bond cannot react with the hydroxyl of the hydroxyl-containing acrylic resin and exists in a micromolecule form, and the prepared anti-adhesive tape can generate residual adhesive.
In a preferred embodiment of the present invention, the crosslinking agent is selected from any one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, or hexamethylene diisocyanate, or a combination of at least two of them.
Preferably, the viscosity reducing adhesive composition further comprises 0.01-1 part of catalyst, such as 0.01 part, 0.02 part, 0.05 part, 0.1 part, 0.2 part, 0.5 part, 0.8 part or 1 part.
Preferably, the catalyst is selected from any one of N-ethyl morpholine, triethylene diamine, stannous octoate, dibutyltin dilaurate, bismuth isooctanoate and zirconium acetylacetonate or a combination of at least two of the above.
Preferably, the viscosity-reducing adhesive composition further comprises 0.1-2 parts of photoinitiator, such as 0.1 part, 0.2 part, 0.5 part, 0.8 part, 1 part, 1.3 part, 1.5 part, 1.7 part or 2 parts.
Preferably, the photoinitiator is selected from any one of or a combination of at least two of benzil dimethyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 4-p-phenyl mercapto benzophenone, 4-methyl benzophenone, isopropyl thia-anthracene, 2-ethyl anthraquinone;
preferably, the solvent A is selected from any one of ethyl acetate, toluene, butyl acetate or heptane or a combination of at least two of the above.
In the invention, the preparation method of the viscose reducing composition comprises the following steps:
and uniformly mixing all the components of the viscosity-reducing adhesive composition, and defoaming to obtain the viscosity-reducing adhesive composition.
In a second aspect, the present invention provides a method for preparing an anti-adhesive tape, comprising the steps of:
coating the viscosity-reducing adhesive composition as described in the first aspect on either side of the substrate, and drying to obtain the viscosity-reducing adhesive tape.
In the invention, the hydroxyl-containing acrylic resin and the monomer containing the carbon-carbon double bond react in the drying process, and the carbon-carbon double bond is introduced into the viscosity-reducing adhesive tape to prepare the viscosity-reducing adhesive tape with excellent performance, and the reaction process is simplified.
Preferably, the substrate is selected from any one of a PET film (polyethylene terephthalate film), a PVC film (polyvinyl chloride film), a PO film (polyolefin film);
preferably, the temperature of the drying is 80 to 130 ℃, for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃ or 130 ℃ and the like.
Preferably, the drying time is 4min to 30min, for example, 4min, 7min, 10min, 12min, 15min, 18min, 20min, 23min, 25min, 27min or 30min.
Preferably, the drying step further comprises a post-treatment step.
Preferably, the method of post-processing comprises: covering a release film on the side of the anti-adhesive tape far from the substrate, curing at 40-50 deg.C (such as 40 deg.C, 42 deg.C, 44 deg.C, 46 deg.C, 48 deg.C or 50 deg.C) for 2-4 days (such as 2 days, 2.5 days, 3 days, 3.5 days or 4 days) in dark condition, and rolling.
In a third aspect, the present invention provides an anti-adhesive tape prepared by the preparation method of the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention can prepare the viscosity reducing adhesive composition with excellent performance by designing the components of the viscosity reducing adhesive composition, further using the monomer containing the carbon-carbon double bond and controlling the content of the monomer containing the carbon-carbon double bond within a specific range, and further prepare the viscosity reducing adhesive tape with stronger initial viscosity of 8# to 20#, no displacement after a viscosity holding test and 180 DEG peel strength of 1798 to 2367g/cm 2 After UV irradiation, the 180 DEG peel strength is 7-78 g/cm 2 And no adhesive residue.
(2) According to the invention, by using the carbon-carbon double bond-containing monomer molecules, the prepared viscosity-reducing adhesive composition has lower viscosity and better leveling property, the use of additional diluent and leveling agent is avoided, and the problem that adhesive tape generates adhesive residue due to the use of micromolecular diluent and leveling agent is further avoided.
(3) In the invention, the hydroxyl-containing acrylic resin and the monomer containing the carbon-carbon double bond react in the drying process, and the carbon-carbon double bond is introduced into the viscosity-reducing adhesive tape to prepare the viscosity-reducing adhesive tape with excellent performance, and the reaction process is simplified.
Drawings
FIG. 1 is an infrared spectrum of the hydroxyl group-containing acrylic resin 4 provided in Synthesis example 4 and the pressure-sensitive adhesive tape provided in application example 7.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Synthesis example 1
The present synthesis example provides a hydroxyl-containing acrylic resin 1 and a preparation method thereof, wherein the preparation method comprises the following steps:
uniformly mixing 20 parts of isooctyl acrylate, 50 parts of butyl acrylate, 10 parts of methyl methacrylate, 5 parts of hydroxyethyl acrylate, 2 parts of acrylic acid, 13 parts of glycidyl methacrylate and 100 parts of ethyl acetate, stirring and heating to 66 ℃ in a nitrogen atmosphere, adding 0.02 part of azobisisobutyronitrile, preserving heat for 2 hours, adding 0.01 part of azobisisobutyronitrile, heating to 76 ℃, preserving heat for 3 hours, and cooling to room temperature to obtain the hydroxyl functional group-containing resin 1.
Synthesis example 2
The synthesis example provides a hydroxyl-containing acrylic resin 2 and a preparation method thereof, wherein the preparation method comprises the following steps:
uniformly mixing 20 parts of isooctyl acrylate, 50 parts of butyl acrylate, 10 parts of methyl methacrylate, 10 parts of hydroxyethyl acrylate, 2 parts of acrylic acid, 8 parts of glycidyl methacrylate and 100 parts of ethyl acetate, stirring and heating to 66 ℃ in the nitrogen atmosphere, adding 0.02 part of azobisisobutyronitrile, keeping the temperature for 2 hours, adding 0.01 part of azobisisobutyronitrile, heating to 76 ℃, keeping the temperature for 3 hours, and cooling to room temperature to obtain the resin 2 containing hydroxyl functional groups.
Synthesis example 3
The synthesis example provides a hydroxyl-containing acrylic resin 3 and a preparation method thereof, wherein the preparation method comprises the following steps:
uniformly mixing 20 parts of isooctyl acrylate, 50 parts of butyl acrylate, 5 parts of methyl methacrylate, 15 parts of hydroxyethyl acrylate, 2 parts of acrylic acid, 8 parts of glycidyl methacrylate and 100 parts of ethyl acetate, stirring and heating to 66 ℃ in a nitrogen atmosphere, adding 0.03 part of azobisisobutyronitrile, preserving heat for 2 hours, adding 0.01 part of azobisisobutyronitrile, heating to 76 ℃, preserving heat for 3 hours, and cooling to room temperature to obtain the hydroxyl functional group-containing resin 3.
Synthesis example 4
The present synthesis example provides a hydroxyl-containing acrylic resin 4 and a preparation method thereof, wherein the preparation method comprises the following steps:
uniformly mixing 20 parts of isooctyl acrylate, 50 parts of butyl acrylate, 10 parts of methyl methacrylate, 10 parts of hydroxyethyl acrylate, 10 parts of N, N-dimethylacrylamide and 100 parts of ethyl acetate, stirring and heating to 66 ℃ in a nitrogen atmosphere, adding 0.02 part of azobisisobutyronitrile, preserving heat for 2 hours, adding 0.01 part of azobisisobutyronitrile, heating to 76 ℃, preserving heat for 3 hours, and cooling to room temperature to obtain the hydroxyl functional group-containing resin 4.
Synthesis example 5
The synthesis example provides a hydroxyl-containing acrylic resin 5 and a preparation method thereof, wherein the preparation method comprises the following steps:
uniformly mixing 64 parts of isooctyl acrylate, 5 parts of methyl methacrylate, 30 parts of hydroxyethyl acrylate, 1 part of acrylic acid and 50 parts of ethyl acetate, stirring in a nitrogen atmosphere, heating to 66 ℃, adding 0.03 part of azobisisobutyronitrile, preserving heat for 2 hours, adding 0.02 part of azobisisobutyronitrile, heating to 76 ℃, preserving heat for 3 hours, and cooling to room temperature to obtain the resin 5 containing hydroxyl functional groups.
Synthesis example 6
The synthesis example provides a hydroxyl-containing acrylic resin 6 and a preparation method thereof, wherein the preparation method comprises the following steps:
uniformly mixing 30 parts of lauryl acrylate, 10 parts of isooctyl acrylate, 10 parts of cyclohexyl methacrylate, 20 parts of N, N-dimethylacrylamide, 30 parts of diethylene glycol monoacrylate and 100 parts of ethyl acetate, stirring and heating to 66 ℃ in a nitrogen atmosphere, adding 0.02 part of azobisisobutyronitrile, keeping the temperature for 2 hours, adding 0.01 part of azobisisobutyronitrile, heating to 76 ℃, keeping the temperature for 3 hours, and cooling to room temperature to obtain the hydroxyl functional group-containing resin 6.
The performance of the hydroxyl-containing acrylic resin provided by the synthesis example is tested, and the specific test method is as follows:
solid content: tests were performed with reference to GB/T2793-1995;
viscosity: the test is carried out with reference to GB/T21059-2007;
molecular weight: the test was carried out with reference to GB/T27843-2011.
The performance test results of the hydroxyl-containing acrylic resin provided by the above synthesis example are shown in the following table 1:
TABLE 1
Example 1
The embodiment provides a viscosity reducing adhesive composition and a preparation method thereof, wherein the viscosity reducing adhesive composition comprises the following components in parts by weight:
90 parts of a hydroxyl-functional resin 1, 2.19 parts of ethyl isocyanate acrylate, 0.02 part of dibutyltin dilaurate, 0.45 part of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 0.4 part of dicyclohexylmethane diisocyanate and 100 parts of ethyl acetate.
The molar ratio of isocyanate groups to hydroxyl groups in the visbreaking composition is 0.8.
The preparation method of the viscose reducing composition comprises the following steps:
uniformly mixing all the components in the viscosity-reducing adhesive composition, standing for 20min for defoaming, and thus obtaining the viscosity-reducing adhesive composition.
Example 2
The present example provides a viscosity reducing adhesive composition and a preparation method thereof, which is different from example 1 only in that the weight part of isocyanate ethyl acrylate is 2.73 parts, and the molar ratio of isocyanate groups to hydroxyl groups in the viscosity reducing adhesive composition is 1; other conditions were the same as in example 1.
Example 3
The embodiment provides a viscosity reducing adhesive composition and a preparation method thereof, wherein the viscosity reducing adhesive composition comprises the following components in parts by weight:
90 parts of hydroxyl functional group-containing resin 2, 5.46 parts of isocyanate ethyl acrylate, 0.04 part of dibutyltin dilaurate, 0.5 part of benzil dimethyl ether, 0.5 part of dicyclohexylmethane diisocyanate and 100 parts of ethyl acetate;
the molar ratio of isocyanate groups to hydroxyl groups in the visbreaking composition is 1.
The preparation method of the viscose reducing composition comprises the following steps:
uniformly mixing all the components in the viscosity-reducing adhesive composition, standing for 20min for defoaming, and thus obtaining the viscosity-reducing adhesive composition.
Example 4
The embodiment provides a viscosity reducing adhesive composition and a preparation method thereof, wherein the viscosity reducing adhesive composition comprises the following components in parts by weight:
90 parts of hydroxyl functional group-containing resin 3, 4.91 parts of isocyanate ethyl acrylate, 0.06 part of dibutyltin dilaurate, 0.5 part of benzil dimethyl ether, 1 part of crosslinking agent dicyclohexylmethane diisocyanate and 100 parts of ethyl acetate;
the mole ratio of isocyanate groups to hydroxyl groups in the visbreaking composition is 0.6.
The preparation method of the viscose reducing composition comprises the following steps:
uniformly mixing all components in the viscosity-reducing adhesive composition, standing for 20min, and defoaming to obtain the viscosity-reducing adhesive composition.
Example 5
The embodiment provides a viscosity reducing adhesive composition and a preparation method thereof, wherein the viscosity reducing adhesive composition comprises the following components in parts by weight:
90 parts of resin containing hydroxyl functional groups, 6.55 parts of isocyanate ethyl acrylate, 0.06 part of dibutyltin dilaurate, 0.5 part of benzil dimethyl ether, 0.7 part of crosslinking agent dicyclohexylmethane diisocyanate and 100 parts of ethyl acetate;
the molar ratio of isocyanate groups to hydroxyl groups in the visbreaking composition is 0.8.
The preparation method of the viscose reducing composition comprises the following steps:
uniformly mixing all the components in the viscosity-reducing adhesive composition, standing for 20min for defoaming, and thus obtaining the viscosity-reducing adhesive composition.
Example 6
The embodiment provides a viscosity reducing adhesive composition and a preparation method thereof, wherein the viscosity reducing adhesive composition comprises the following components in parts by weight:
90 parts of hydroxyl functional group-containing resin 3, 8.19 parts of isocyanate ethyl acrylate, 0.06 part of dibutyltin dilaurate, 0.5 part of benzil dimethyl ether, 0.4 part of dicyclohexylmethane diisocyanate and 100 parts of ethyl acetate;
the molar ratio of isocyanate groups to hydroxyl groups in the visbreaking composition is 1.
The preparation method of the viscose reducing composition comprises the following steps:
uniformly mixing all components in the viscosity-reducing adhesive composition, standing for 20min, and defoaming to obtain the viscosity-reducing adhesive composition.
Example 7
This example provides a viscosity reducing adhesive composition and a method for preparing the same, which differs from example 3 only in that a hydroxyl functional group-containing resin 2 is replaced with a hydroxyl functional group-containing resin 4, and the molar ratio of isocyanate groups to hydroxyl groups in the viscosity reducing adhesive composition is 1; other conditions were the same as in example 1.
Example 8
The present embodiment provides a viscosity reducing adhesive composition and a preparation method thereof, which is different from embodiment 1 in that the viscosity reducing adhesive composition includes the following components in parts by weight:
95 parts of hydroxyl functional group-containing resin 5, 30 parts of isocyanate ethyl methacrylate, 0.06 part of dibutyltin dilaurate, 0.5 part of benzil dimethyl ether, 2 parts of dicyclohexylmethane diisocyanate and 150 parts of ethyl acetate;
the molar ratio of isocyanate groups to hydroxyl groups in the visbreaking composition is 1.2.
Other conditions were the same as in example 1.
Example 9
The embodiment provides a viscosity reducing adhesive composition and a preparation method thereof, and the difference from the embodiment 1 is that the viscosity reducing adhesive composition comprises the following components in parts by weight:
65 parts of hydroxyl functional group-containing resin 1, 1 part of isocyanate ethyl acrylate, 0.04 part of dibutyltin dilaurate, 0.3 part of benzil dimethyl ether, 1 part of dicyclohexyl methane diisocyanate and 100 parts of ethyl acetate;
the molar ratio of isocyanate groups to hydroxyl groups in the visbreaking composition is 0.5.
Other conditions were the same as in example 1.
Example 10
The embodiment provides a viscosity reducing adhesive composition and a preparation method thereof, and the difference from the embodiment 1 is that the viscosity reducing adhesive composition comprises the following components in parts by weight:
90 parts of hydroxyl functional group-containing resin 6, 1.31 parts of isocyanate ethyl methacrylate, 0.04 part of dibutyltin dilaurate, 0.3 part of benzil dimethyl ether, 1 part of dicyclohexylmethane diisocyanate and 100 parts of ethyl acetate;
the molar ratio of isocyanate groups to hydroxyl groups in the visbreaking composition is 0.1.
Example 11
The present embodiment provides a viscosity reducing adhesive composition and a preparation method thereof, and is different from example 10 in that, in the viscosity reducing adhesive composition, the weight part of the hydroxyl functional group-containing resin 1 is 90, the weight part of the isocyanate ethyl acrylate is 13.1, and the molar ratio of the isocyanate group to the hydroxyl group in the viscosity reducing adhesive composition is 1.
Example 12
The present embodiment provides a viscosity reducing adhesive composition and a preparation method thereof, and is different from example 1 in that, in the viscosity reducing adhesive composition, the weight part of the resin 1 containing a hydroxyl functional group is 90, the weight part of the isocyanate ethyl acrylate is 0.137, and the molar ratio of the isocyanate group to the hydroxyl group in the viscosity reducing adhesive composition is 0.05; other conditions were the same as in example 1.
Example 13
The present embodiment provides a viscosity reducing adhesive composition and a preparation method thereof, and is different from example 1 in that, in the viscosity reducing adhesive composition, the weight part of the resin 1 containing a hydroxyl functional group is 90, the weight part of the isocyanate ethyl acrylate is 4.12, and the molar ratio of the isocyanate group to the hydroxyl group in the viscosity reducing adhesive composition is 1.5; other conditions were the same as in example 1.
Comparative example 1
This comparative example provides a viscosity reducing adhesive composition and a method for preparing the same, which are different from example 1 in that the viscosity reducing adhesive composition does not include isocyanate ethyl acrylate; other conditions were the same as in example 1.
Comparative example 2
The present comparative example provides a viscosity reducing adhesive composition and a preparation method thereof, and is different from example 1 in that the weight part of isocyanate ethyl acrylate in the viscosity reducing adhesive composition is 20 parts, and the molar ratio of isocyanate groups to hydroxyl groups in the viscosity reducing adhesive composition is 7.3; other conditions were the same as in example 1.
Application examples 1 to 13
Application examples 1 to 13 respectively provide a viscosity reducing adhesive tape and a preparation method thereof, and the preparation method of the adhesive tape comprises the following steps:
(1) Respectively coating the surface of the PO base material with the thickness of 150 mu m with the viscosity reducing glue compositions obtained in the embodiments 1-13, and respectively drying the PO base material by using an oven at 100 ℃ to respectively obtain the viscosity reducing glue layers;
(2) Covering a PET release film on the surface of the side of the anti-adhesive layer far away from the PO substrate, and curing for 3 days at 45 ℃ in a dark condition to obtain the anti-adhesive tape.
Infrared spectroscopic measurements were carried out on the hydroxyl-containing acrylic resin 4 as provided in Synthesis example 4 and the pressure-sensitive adhesive tape as provided in application example 7. As shown in FIG. 1, it can be seen from FIG. 1 that the measurement results of example 7 were measured at 1530cm -1 An obvious absorption peak is shown, which is an N-H absorption peak of-NHCO-functional group obtained by the reaction of hydroxyl (-OH) in the hydroxyl-containing acrylic resin 4 and isocyanate (-NCO) in the carbon-carbon double bond-containing monomer provided in the synthesis example 4, and indicates that the hydroxyl in the hydroxyl-containing acrylic resin 4 and the isocyanate in the carbon-carbon double bond-containing monomer are reacted, so that the carbon-carbon double bond is introduced into the viscosity-reducing adhesive tape, and meanwhile, in the red light spectrum of the application example 7, the absorption peak is 809cm -1 The obvious peak is shown, which is the absorption peak of the C = C double bond, and the method for preparing the viscosity reducing adhesive tape provided by the invention is also demonstrated that the carbon-carbon double bond is successfully introduced into the viscosity reducing adhesive tape.
Comparative examples 1 to 2 of application
Application comparative examples 1-2 respectively provide an anti-adhesive tape and a preparation method thereof, and the preparation method of the adhesive tape comprises the following steps:
(1) Respectively coating the anti-adhesion glue compositions obtained in the comparative examples 1-2 on the surface of the PO base material with the thickness of 150 mu m, and respectively drying by using a drying oven at 100 ℃ to respectively obtain the anti-adhesion glue layers;
(2) Covering a PET release film on the surface of the side of the anti-adhesive layer far away from the PO substrate, and curing for 3 days at 45 ℃ in a dark condition to obtain the anti-adhesive tape.
The PET release films of the adhesive tapes provided in application examples 1 to 13 and application comparative examples 1 to 2 were removed, and the PET release films were attached to SUS304 steel plates, respectively, and the properties thereof were tested as follows:
initial viscosity: the test is carried out according to GB/T4852 2002 by a rolling ball slope stopping experiment method, wherein the inclination angle of the slope is 30 degrees;
viscosity retention: according to the method of GB/T4851 1998, a cohesive force tester is used for testing, the testing temperature is 80 ℃, and the weight is 1kg;
180 ° peel strength: according to the method of GB/T2792-1998, an electronic tensile testing machine is used for testing, wherein the bandwidth of the anti-adhesive tape is 25mm, and the stripping rate is 300mm/min;
stripping residual adhesive property: after the anti-adhesive tape attached to the SUS304 steel plate was peeled off by an electronic tensile testing machine, whether or not there was any adhesive residue on the SUS304 steel plate was observed
The adhesive tapes provided in application examples 1 to 13 and application comparative examples 1 to 2 were attached to an SUS304 steel plate, and the 180-degree peel strength and peel residue property of the adhesive tape after ultraviolet irradiation were measured after irradiation with an ultraviolet lamp having an intensity of 300mJ/cm2, according to the above-described measurement method.
The results of the performance tests of the adhesive tapes provided in application examples 1 to 13 and application comparative examples 1 to 2 are shown in table 2 below:
TABLE 2
In summary, the components of the anti-tack adhesive composition are designed, the content of the monomer containing the carbon-carbon double bond is further controlled, and the molar ratio of the monomer containing the carbon-carbon double bond to the functional monomer containing the active hydroxyl group is controlled within a specific range, so that the anti-tack adhesive composition with excellent performance can be prepared, and the anti-tack adhesive composition with strong initial tack, high holding tack and high peeling strength can be further preparedThe initial viscosity of the viscosity-reducing adhesive tape is adjustable within the range of 8-20 #, no displacement exists after the viscosity-holding test, the 180-degree peel strength before and after UV irradiation is adjustable according to the difference of the type of the hydroxyl-containing resin and the adding amount of the carbon-carbon double bond-containing monomer, and the 180-degree peel strength is 1798-2367 g/cm 2 After UV irradiation, the 180 DEG peel strength is 7-78 g/cm 2 And no adhesive residue exists; meanwhile, the viscosity-reducing adhesive composition provided by the invention has lower viscosity and better leveling property, avoids the use of additional diluent and leveling agent, has a simple and convenient preparation method, is suitable for industrial production, and can meet the use requirements of the market.
Compared with application example 1, if the molar ratio of the monomer containing the carbon-carbon double bond to the monomer containing the active hydroxyl group is too small (application example 12), the adhesive residue phenomenon is caused, the 180-degree stripping force after UV irradiation is large, and the molar ratio of the monomer containing the carbon-carbon double bond to the monomer containing the active hydroxyl group is too large (application example 13), the 180-degree stripping force before UV is reduced due to the introduction of small molecules, and the performances are poor.
Compared with example 1, if the viscosity-reducing adhesive composition does not contain the monomer containing the carbon-carbon double bond (application comparative example 1), the prepared adhesive tape does not have the viscosity-reducing effect, or if the content of the monomer containing the carbon-carbon double bond in the viscosity-reducing adhesive composition is too large (application comparative example 2), residual adhesive and 180-degree peeling force before UV are reduced, and the comprehensive performance of the prepared viscosity-reducing adhesive tape is poor.
In summary, the components of the viscosity reducing adhesive composition are designed, so that the viscosity reducing adhesive composition with excellent performance can be prepared, the viscosity reducing adhesive tape with adjustable initial viscosity, constant viscosity and high peel strength can be further prepared, and after the viscosity reducing adhesive tape is irradiated by UV, the peel strength is obviously reduced, and no residual adhesive is left.
The applicant states that the present invention is illustrated by the above examples to show the detailed process flow of the present invention, but the present invention is not limited to the above detailed process flow, which means that the present invention does not depend on the above detailed process flow to be implemented. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The viscosity reducing adhesive composition is characterized by comprising the following components in parts by weight:
65-95 parts of hydroxyl-containing acrylic resin, 1-30 parts of carbon-carbon double bond-containing monomer, 0.2-2 parts of cross-linking agent and 50-200 parts of solvent A.
2. The viscosity-reducing adhesive composition according to claim 1, wherein the hydroxyl-containing acrylic resin has a glass transition temperature of-60 to 20 ℃;
preferably, the weight average molecular weight of the hydroxyl-containing acrylic resin is 20 to 80 ten thousand;
preferably, the hydroxyl group content of the hydroxyl group-containing acrylic resin is 0.1 to 2mmol/g.
3. The viscosity-reducing adhesive composition according to claim 1 or 2, wherein the hydroxyl-containing acrylic resin is prepared from the following raw materials in parts by weight:
40-80 parts of soft monomer, 5-10 parts of hard monomer, 1-20 parts of functional monomer and 1-30 parts of functional monomer containing active hydroxyl.
4. A viscosity reducing adhesive composition according to claim 3, wherein the soft monomer is an alkyl acrylate, and the number of carbon atoms of the alkyl group is an integer of 1 to 12;
preferably, the soft monomer is selected from any one of methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate or lauryl acrylate or the combination of at least two of the methyl acrylate, the ethyl acrylate, the butyl acrylate, the isooctyl acrylate and the lauryl acrylate;
preferably, the hard monomer is alkyl methacrylate, and the number of carbon atoms of the alkyl group is an integer of 1 to 6;
preferably, the hard monomer is selected from any one or a combination of at least two of methyl methacrylate, ethyl methacrylate, butyl methacrylate or cyclohexyl methacrylate;
the functional monomer is selected from any one or the combination of at least two of acrylic acid, methacrylic acid, N-hydroxymethyl acrylamide, glycidyl methacrylate or N, N-dimethylacrylamide;
the functional monomer containing active hydroxyl is selected from any one or the combination of at least two of hydroxyethyl acrylate, hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate or diethylene glycol monoacrylate.
5. The viscosity-reducing adhesive composition according to claim 3, wherein the hydroxyl-containing acrylic resin is prepared from 100 parts of solvent B;
preferably, the raw materials for preparing the hydroxyl-containing acrylic resin also comprise 0.01-0.05 part of initiator;
preferably, the initiator is selected from any one of or a combination of at least two of benzoyl peroxide, azobisisobutyronitrile, methyl ethyl ketone peroxide and cyclohexanone peroxide.
6. A viscosity reducing adhesive composition according to any one of claims 3 to 5, wherein the hydroxyl-containing acrylic resin is prepared by a method comprising the steps of:
(1) Adding a soft monomer, a hard monomer, a functional monomer containing active hydroxyl and a solvent into a reaction kettle in an inert gas atmosphere, and heating to reflux temperature under the stirring condition;
(2) And then adding part of initiator into the reaction kettle, keeping the temperature for 1-3 h, then adding the rest initiator, keeping the temperature for 1-5 h, and cooling to room temperature to obtain the hydroxyl-containing acrylic resin.
7. A viscosity reducing adhesive composition according to any one of claims 1 to 6, wherein the monomer containing a carbon-carbon double bond is selected from isocyanate ethyl acrylate and/or isocyanate ethyl methacrylate;
preferably, the molar ratio of the monomer containing the carbon-carbon double bond to the functional monomer containing the active hydroxyl is (0.1-1.2): 1.
8. A vis-breaking adhesive composition according to any one of claims 1 to 5, characterized in that the crosslinker is selected from any one of or a combination of at least two of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate or hexamethylene diisocyanate;
preferably, the visbreaking adhesive composition also comprises 0.01-1 part of catalyst;
preferably, the visbreaking adhesive composition also comprises 0.1-2 parts of a photoinitiator;
preferably, the solvent A is selected from any one of ethyl acetate, toluene, butyl acetate or heptane or a combination of at least two of the above.
9. The preparation method of the anti-sticking adhesive tape is characterized by comprising the following steps:
coating the viscosity-reducing adhesive composition according to any one of claims 1 to 8 on either side of a substrate, and drying to obtain the viscosity-reducing adhesive tape;
preferably, the drying temperature is 80-130 ℃;
preferably, the drying time is 4 min-30 min.
10. An anti-adhesive tape produced by the production method according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211518410.6A CN115926690A (en) | 2022-11-29 | 2022-11-29 | Viscosity-reducing adhesive composition, viscosity-reducing adhesive tape and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211518410.6A CN115926690A (en) | 2022-11-29 | 2022-11-29 | Viscosity-reducing adhesive composition, viscosity-reducing adhesive tape and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115926690A true CN115926690A (en) | 2023-04-07 |
Family
ID=86697189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211518410.6A Pending CN115926690A (en) | 2022-11-29 | 2022-11-29 | Viscosity-reducing adhesive composition, viscosity-reducing adhesive tape and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115926690A (en) |
-
2022
- 2022-11-29 CN CN202211518410.6A patent/CN115926690A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3388674B2 (en) | Energy ray-curable pressure-sensitive adhesive composition and method of using the same | |
| KR101278454B1 (en) | Adhesive sheet | |
| JP5513866B2 (en) | Adhesive sheet for processing electronic parts | |
| JP4066394B2 (en) | Removable adhesive | |
| KR20100138979A (en) | Energy ray-curable polymer, energy ray-curable pressure sensitive adhesive composition, pressure-sensitive adhesive sheet and method of processing semiconductor wafer | |
| CN110093111B (en) | Adhesive sheet, method for producing same, and image display device | |
| EP0902071B1 (en) | Thermosetting pressure-sensitive adhesive and adhesive sheets made by using the same | |
| CN115232578B (en) | UV (ultraviolet) adhesive and preparation method thereof | |
| JPH0156112B2 (en) | ||
| EP2439246A1 (en) | Photocurable adhesive composition, photocurable adhesive layer, and photocurable adhesive sheet | |
| KR100945638B1 (en) | Photocuring Composition for Pressure Sensitive Adhesive Layer and Dicing Die Bonding Film Comprising the Same | |
| JP5572487B2 (en) | Viscoelastic body and method for producing the same | |
| CN115926690A (en) | Viscosity-reducing adhesive composition, viscosity-reducing adhesive tape and preparation method thereof | |
| CN114605929B (en) | Removable adhesive comprising photo-curable adhesive and thermal foaming agent and removable tape comprising the same | |
| TWI721364B (en) | Back grinding tape | |
| JPH08143847A (en) | Acrylic adhesive composition | |
| JP3384980B2 (en) | Baseless pressure-sensitive double-sided adhesive tape / sheet and method for producing the same | |
| TWI791842B (en) | Back grinding tape | |
| US20230104276A1 (en) | Double-sided adhesive tape | |
| KR102248556B1 (en) | Protective film for semiconductor wafer | |
| JP6427251B2 (en) | Adhesive tape | |
| JPH073212A (en) | Photopolymerizable composition and adhesive tape or sheet | |
| CN117801730A (en) | Reversible thermal viscosity-reducing pressure-sensitive adhesive, double-sided adhesive tape and preparation method thereof | |
| JPS6254779A (en) | Pressure-sensitive adhesion composition and pressure-sensitive adhesive sheet | |
| WO2019143076A1 (en) | Back grinding tape |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |