CN110819273B - Thin-coating high-viscosity pressure-sensitive adhesive and pressure-sensitive adhesive tape - Google Patents

Thin-coating high-viscosity pressure-sensitive adhesive and pressure-sensitive adhesive tape Download PDF

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CN110819273B
CN110819273B CN201911221552.4A CN201911221552A CN110819273B CN 110819273 B CN110819273 B CN 110819273B CN 201911221552 A CN201911221552 A CN 201911221552A CN 110819273 B CN110819273 B CN 110819273B
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sensitive adhesive
resin
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CN110819273A (en
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陆星辰
马超
刘齐文
安明星
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Suzhou Fineset Material 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/005—Presence of polyester in the release coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a thin-coating high-viscosity pressure-sensitive adhesive which comprises the following components in parts by weight: 100 parts of acrylate resin syrup, 0.1-3 parts of curing agent and 15-50 parts of tackifying resin, wherein the weight average molecular weight of the acrylate resin syrup is 30-200 multiplied by 104g/mol, the molecular weight distribution index PDI is 2.0-8.0, the softening point range of the tackifying resin is 10-140 ℃, the relative molecular mass range is 300-2000g/mol, and the tackifying resin comprises 10-25 parts of rosin resin and 5-25 parts of terpene resin according to 100 parts of acrylate resin slurry. The pressure-sensitive adhesive has excellent initial adhesion and peeling force, the flowability of the adhesive is good, and the prepared pressure-sensitive adhesive tape is thin and has high bonding strength to the nanocrystalline.

Description

Thin-coating high-viscosity pressure-sensitive adhesive and pressure-sensitive adhesive tape
Technical Field
The invention relates to the technical field of pressure-sensitive adhesives, in particular to a thin-coating high-viscosity pressure-sensitive adhesive and a pressure-sensitive adhesive tape.
Background
In recent years, with the development demands of portability and lightness and thinness of electronic products such as mobile phones and flat panels, the thickness requirement of the double-sided tape for bonding and fixing the internal components of the electronic products tends to be thinner and thinner, and the total thickness of the ultrathin double-sided tape is reduced from 20um to 10um or even 5 um. Therefore, the double-sided adhesive tape for bonding and fixing the internal components of the mobile phone puts higher performance requirements: the adhesive tape can still maintain higher bonding strength at a very thin thickness, namely the double-sided adhesive tape has the characteristics of thin coating and high viscosity. Compared with the traditional double-sided pressure-sensitive adhesive tape, the peeling force and initial adhesion force are obviously reduced along with the reduction of the thickness, and the ultrathin adhesive tape with the thin-coating high-viscosity characteristic can still have the bonding effect of higher peeling force (more than or equal to 800g/25mm) under the condition of very thin coating thickness (1-2um) because the parameters such as the main polymer monomer, the molecular weight and the like of an adhesive layer of the ultrathin adhesive tape are specially designed and the adhesive tape is modified by adding tackifying resin.
On the other hand, in recent years, with the rapid development of wireless charging technology, the mainstream mobile phones in the market have a wireless charging function. The core technology component of wireless charging is ferrite or nanocrystalline, the ferrite or nanocrystalline is very fragile in structure and very easy to break in the die cutting and laminating processes, so that double-sided adhesive tapes are required to be pasted to protect the ferrite or nanocrystalline, and the edge of the ferrite or nanocrystalline is prevented from being warped and broken in the die cutting application process. In such application background, when the ultrathin adhesive tape is required to be bonded with ferrite or nanocrystal, the ultrathin adhesive tape needs to ensure higher bonding strength to the ferrite and the nanocrystal on the premise of very thin adhesive coating thickness. However, the existing ferrite or nanocrystal has the problem of uneven surface, the flow of glue is limited due to the uneven adhered surface, the glue with poor initial adhesion is difficult to effectively wet the surface of the ferrite or nanocrystal, and the adhesive property of the glue to the adhered surface is not ideal, so that the problems of delamination or warping and the like of the ferrite or nanocrystal magnetic material can occur. Therefore, when the ultrathin adhesive tape is applied to nanocrystalline bonding, the glue is required to have not only higher peeling force but also better initial adhesion force at a very thin coating thickness, and the glue is required to have good fluidity, so that the irregular nanocrystalline surface can be effectively filled. In short, the technical requirements of the ultrathin adhesive tape can be summarized from the increase of high viscosity in the early stage of simple thin coating to the increase of both peeling force and initial adhesion force under the condition of very thin coating thickness, and particularly, the ultrathin adhesive tape has higher adhesive strength for the difficult-to-adhere surface such as a nanocrystalline magnetic material. The adhesive tape has the advantages that the adhesive tape still has high peeling force (more than or equal to 800g/25mm) and high initial adhesion force (more than or equal to 10#) under the condition of very thin coating thickness (1-2um), and does not have the phenomena of delamination, warping and the like when being adhered with the nanocrystal.
The Chinese patent 106459685A, high thermal conductivity ultrathin adhesive tape modified based on synthetic graphite, effectively improves the thermal conductivity coefficient of the ultrathin adhesive tape by adding synthetic graphite and high thermal conductivity powder into the pressure sensitive adhesive, but the thickness of the prepared ultrathin adhesive tape can still be controlled below 20um, and the advantages of the adhesive property (stripping force and initial adhesion) and the applicability to ferrite or nanocrystalline are not shown.
The thickness range of the main stream products of the ultrathin double-sided adhesive tape on the market at present is below 10um and above 5 um. The ultrathin adhesive tape products with the thickness of 5um and below 5um still have the problems of poor bonding performance, especially poor initial adhesion, and poor actual bonding effect on the nanocrystalline, so that the yield of wireless charging module assembly of electronic products such as mobile phones is influenced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a thin-coating high-viscosity pressure-sensitive adhesive and a pressure-sensitive adhesive tape, wherein the pressure-sensitive adhesive has excellent initial adhesion and stripping force, the glue flowability is good, the prepared pressure-sensitive adhesive tape is thin, and the pressure-sensitive adhesive tape still has good bonding strength to nanocrystals under the thickness of 5 microns.
In order to achieve the purpose, the invention adopts the technical scheme that: the thin-coating high-viscosity pressure-sensitive adhesive comprises the following components in parts by weight: 100 parts of acrylate resin syrup, 0.1-3 parts of curing agent and 15-50 parts of tackifying resin, wherein the weight average molecular weight of the acrylate resin syrup is 30-200 multiplied by 104g/mol, the molecular weight distribution index PDI is 2.0-8.0, the softening point range of the tackifying resin is 10-140 ℃, the relative molecular mass range is 300-2000g/mol, and the tackifying resin comprises 10-25 parts of rosin resin and 5-25 parts of terpene resin according to 100 parts of acrylate resin slurry.
In a specific embodiment, the rosin-based resin is at least one resin selected from the group consisting of glycerol ester of rosin, pentaerythritol ester of rosin, glycerol ester of hydrogenated rosin, pentaerythritol ester of hydrogenated rosin, glycerol ester of perhydrogenated rosin, pentaerythritol ester of perhydrogenated rosin, glycerol ester of disproportionated rosin, and pentaerythritol ester of disproportionated rosin.
In a specific embodiment, the terpene-based tackifying resin is at least one selected from the group consisting of α -pinene resin, d-limonene resin, β -pinene resin, α -pinene phenol resin, terpene diene-phenol resin, and terpene-bisphenol resin.
Preferably, the acrylate resin syrup comprises the following raw materials in parts by weight: 85-95 parts of acrylate soft and hard monomer, 5-15 parts of hydroxyl functional monomer, 0.1-3 parts of thermal initiator, 80-140 parts of organic solvent and 0.02-0.2 part of molecular weight regulator. Here, the acrylic estersThe glass transition temperature of the resin slurry is-35 to-15 ℃, and the storage modulus (G') under the condition of 25 ℃ is 7.0 multiplied by 104-1.8×105Pa, loss factor tan delta at 25 ℃ is 0.8-1.5.
In a specific embodiment, the acrylate soft and hard monomer is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, isooctyl acrylate, isodecyl acrylate, butyl acrylate, isobutyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, isobornyl methacrylate, vinyl acetate, and styrene.
As a specific embodiment, the hydroxyl-containing functional monomer is at least one selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate and N-methylol acrylamide.
As a specific embodiment, the thermal initiator is selected from at least one of dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, azobisisobutyronitrile, azobisisovaleronitrile, and azobisisoheptonitrile.
As a specific embodiment, the molecular weight regulator is at least one selected from dodecyl mercaptan, acetic acid and phenol.
Preferably, the acrylate resin syrup is prepared by the following steps:
weighing the raw materials according to the parts by weight, adding 1/2 of the total mass of the soft and hard acrylate monomers, 1/2 of the total mass of the hydroxyl-containing monomers, 1/3 of the total mass of the organic solvent and 3/5 of the total mass of the thermal initiator into a four-neck flask with a reflux condenser, stirring and mixing for 30-60min under nitrogen flow, then slowly dropwise adding 1/5 of the total mass of the thermal initiator and 1/3 of the total mass of the remaining soft and hard acrylate monomers, the hydroxyl-containing monomers and the organic solvent, reacting for 8-15 hours at the temperature of 60-85 ℃, finally dropwise adding the remaining thermal initiator, the remaining organic solvent and the molecular weight regulator, regulating the molecular weight of the acrylate pressure-sensitive adhesive, and preserving the temperature for 1-2 hours to ensure that the polymerization reaction is complete, thereby obtaining the acrylate resin slurry.
Another object of the present invention is to provide a pressure-sensitive adhesive tape prepared from the above thin-coated high-viscosity pressure-sensitive adhesive.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the invention relates to a thin-coating high-viscosity pressure-sensitive adhesive, which comprises raw materials of acrylate resin syrup, a curing agent and tackifying resin, wherein the weight-average molecular weight of the acrylate resin syrup is 30-200 multiplied by 104g/mol, the molecular weight distribution index PDI is 2.0-8.0, and the adopted tackifying resin is formed by mixing rosin resin and terpene resin, so that the prepared pressure-sensitive adhesive has excellent initial adhesion and stripping force, the glue has good fluidity, and the prepared pressure-sensitive adhesive tape has thin thickness and high bonding strength to nanocrystalline; the ultrathin double-sided tape prepared from the pressure-sensitive adhesive still has higher initial adhesion (not less than 10#) and peeling force (not less than 800g/25mm) on the premise of very thin coating thickness (1-2um), and especially has excellent bonding effect on nanocrystalline.
Detailed Description
The technical solution of the present invention is further illustrated below with reference to specific examples.
Preparation of acrylate resin syrup
The embodiment provides a preparation method of acrylate resin syrup, which comprises the following specific steps: weighing raw materials according to the parts by weight, adding 1/2 of the total mass of the soft and hard acrylate monomers, 1/2 of the total mass of the hydroxyl-containing monomers, 1/3 of the total mass of the organic solvent and 3/5 of the total mass of the thermal initiator into a four-neck flask with a reflux condenser, stirring and mixing for 30-60min under nitrogen flow, then slowly dropwise adding 1/5 of the total mass of the thermal initiator and 1/3 of the total mass of the remaining soft and hard acrylate monomers, the hydroxyl-containing monomers and the organic solvent, reacting for 8-15 hours at the temperature of 60-85 ℃, finally dropwise adding the remaining thermal initiator, the remaining organic solvent and the molecular weight regulator, and preserving heat for 1-2 hours to ensure that the polymerization reaction is complete to obtain the acrylate resin slurry.
Specifically, the acrylate soft and hard monomers in the present example are a mixture of Methyl Methacrylate (MMA), Ethyl Acrylate (EA) and Butyl Acrylate (BA); hydroxyl monomer is hydroxyethyl methacrylate (HEMA); the thermal initiator is Azodiisobutyronitrile (AIBN); the molecular weight regulator is dodecyl mercaptan (NDM); the organic solvent is a mixed solvent of ethyl acetate (EtAc) and toluene (Tol).
The proportion of the concrete examples is shown in table 1.
TABLE 1
Figure GDA0002355974700000041
The following tests were carried out on the acrylate resin syrup prepared in each example in table 1, and the test results are shown in table 1:
1) the glass transition temperature of the acrylate resin syrup was measured by DSC measurement. A measuring device: pyris DSC-8000 (manufactured by Perkin Elmer). The testing temperature range is-60-100 ℃, and the heating rate is 5 ℃/min.
2) The average molecular weight and molecular weight distribution of the acrylic polymer contained in the obtained acrylic resin syrup were measured by GPC measurement method, and the measuring apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
GPC column composition: the following 5 columns (all manufactured by Tosoh Corp.)
(1) TSK-GEL HXL-H (guard column)
(2)TSK-GEL G 7000H X L.
(3)TSK-GEL GMHXL
(4)TSK-GEL GMHXL
(5)TSK-GEL G 2500H X L.
Sample concentration: diluting with tetrahydrofuran to 1.0mg/cm3And a mobile phase solvent: tetrahydrofuran, flow rate: 1.0cm3Min, column temperature: at 40 ℃.
3) The prepared acrylate resin syrup is subjected to rheological test for storage modulus. A measuring device: rotating the rheometer: DHR-2 (manufactured by TA corporation), jig selection: parallel plate clamp, measurement temperature range: -60-150 ℃ and measuring frequency 10 rad/s. The temperature rise speed is 3 ℃/min.
4) The content ratio of the acrylic polymer contained in the acrylic syrup was measured by a method of measuring the amount of non-volatile components (solid content). 1g of the acrylate resin syrup was put into a precisely weighed tin plate (n1), the total weight was precisely weighed (n2), and then heated at 105 ℃ for 3 hours, and then the tin plate was left in a desiccator at room temperature for 1 hour, and then precisely weighed again, and the total weight after heating was measured (n 3). By using the obtained weight measurement values (n1 to n3), the amount of the nonvolatile component was calculated from the following formula (1).
The amount of the nonvolatile component of the formula (1), nV (wt%) < 100 × [ weight after heating (n3-n 1)/weight before heating (n2-n1)
Preparation of two-layer, thin-coating high-viscosity acrylic pressure-sensitive adhesive
Taking the mass parts of the acrylate resin syrup obtained in the table 1 as 100 parts, adding tackifying resin into the obtained acrylate resin syrup, fully stirring for 30min, then adding isocyanate curing agent, finally adding organic solvent for dilution so as to facilitate coating, and fully stirring for 30 min. The organic solvent here has the same composition as the organic solvent used for preparing the acrylate resin syrup. The pressure-sensitive adhesive liquid is obtained and is kept stand for defoaming for coating. The proportions of the tackifier resin and the curing agent in the specific examples and the comparative examples are shown in Table 2.
TABLE 2
Figure GDA0002355974700000061
Figure GDA0002355974700000071
In Table 2, L-45 (Soken chemical Co., Ltd.) was used as a curing agent, GA-AT (softening point 10 ℃ C., molecular weight 300 g/mol.) was used as a rosin tackifier resin A, Foral 85(Eastman Co., Ltd., softening point 85 ℃ C., molecular weight 1000g/mol) was used as a rosin tackifier resin B, KL2000W (Kyodo Ke Lin chemical Co., Ltd., softening point 5 ℃ C., molecular weight 250g/mol) was used as a rosin tackifier resin C, Dertoprene T135 (DRT Co., softening point 140 ℃ C., molecular weight 2000 g/mol) was used as a phenol-formaldehyde-modified terpene resin A, Dertoprene T160 (DRT Co., softening point 160 ℃ C., molecular weight 3000g/mol) was used as a phenol-formaldehyde-modified terpene resin B
Preparation of ultrathin double-sided adhesive tape
Coating the acrylate pressure-sensitive adhesive on the release surface of a 75-um PET release film by using a coating wire rod, placing the release surface in a 90-DEG C oven for 5min, volatilizing and drying a solvent, controlling the thickness of the dry adhesive to be 1.5um, and then attaching the release surface to a 2-um PET substrate to obtain the single-sided adhesive tape.
Coating the acrylate pressure-sensitive adhesive on the release surface of a 25um PET release film by using a coating wire rod, placing the release surface in a 90 ℃ oven for 5min, volatilizing and drying a solvent, controlling the thickness of the dry adhesive to be 1.5um, and then attaching the dry adhesive to the other surface of the 2um PET substrate of the single-sided adhesive tape to obtain the 5um double-sided adhesive tape.
The coated double-sided tape was aged at room temperature (25 ℃) for 7 days or at 40 ℃ for 2 days, and after the aging was completed, the tape was left at room temperature for 24hrs and then subjected to physical property testing.
Peel force test of double-sided tape according to the test method of JIS Z0237 pressure-sensitive tape, after removing a release film from one side of the pressure-sensitive tape, a PET film of 25 μm was backed, the other side was pasted on a stainless steel plate, and placed in an environment of 23 ℃, the soaking time allowed for the tape to adhere to the stainless steel plate SUS304 was 30min, and the peel force was measured by measuring the peel adhesion force to the adherend SUS in the direction of 180 °. The unit is N/25 mm.
Initial adhesion test of the double-sided adhesive tape the maximum steel ball number of the pressure-sensitive adhesive on which the retardation can be completely stopped on the adhesive surface was recorded by a rolling ball slope stopping method in accordance with the test method of JIS 20237 pressure-sensitive adhesive tapes.
Simulation of nano-crystal adhesion effect test
Cutting the ultrathin double-sided tape into small strips of 3mm × 20cm, tearing off the release film of 25um, sticking the tape surface to the surface of the nanocrystalline magnetic material, tearing off the release film of 75um, sticking the tape surface to the 25um PET film, and rolling back and forth for 3 times by using a 2kg compression roller. And then fixing the nanocrystalline material on a PC plate, wherein the thickness of the PC plate is 3mm, the pasting position is close to the edge of the PC plate, the PC plate is completely coated by the double-sided adhesive tape from the side surface, the double-sided adhesive tape is placed at the normal temperature for 72hrs, and whether delamination or warping occurs between the nanocrystalline material on the PC plate and the ultrathin adhesive tape is observed.
The peeling force, initial adhesion data and the adhesion effect with the nanocrystals of the ultrathin double-sided tapes prepared by coating the examples and comparative examples in table 2 are summarized in table 3 (the total thickness of the ultrathin tapes is 5 um).
TABLE 3
Figure GDA0002355974700000081
Figure GDA0002355974700000091
In table 3:
description of peel force determination grade:
o: high peeling force, the reference peeling force specification range is more than or equal to 800g/25mm
Low peel force, reference peel force specification range < 800g/25mm
Description of initial adhesion determination grade:
o: high initial adhesion, reference adhesion specification range of ≥ 10#
The low initial adhesion is less than 10 #according to the specification range of the initial adhesion
Description of nanocrystal adhesion determination grade:
o: the adhesive property is excellent, and delamination and warping phenomena do not occur between the adhesive layer and the nanocrystalline.
And (x) the adhesive property is general, delamination occurs between the adhesive layer and the nanocrystalline, and the phenomenon of warping occurs.
From table 3, the following can be concluded:
as can be seen from the examples, due to the addition of the rosin resin and the phenolic aldehyde modified terpene resin, and the reasonable control of the proportion of the rosin resin and the phenolic aldehyde modified terpene resin, the appropriate proportion of the rosin tackifying resin is 10-25 parts, and the appropriate proportion of the terpene tackifying resin is 5-25 parts, under the condition, the acrylate pressure-sensitive adhesive can still have good adhesive property even under the condition of very thin coating thickness, which is reflected in that the stripping force reaches more than 800g/25mm, the initial adhesion force reaches more than 10 balls, the acrylate pressure-sensitive adhesive is not delaminated and is not warped with the nanocrystalline. Rosin resins and terpene resins have different functions in improving adhesive properties. The rosin resin has a relatively low softening point, and can obviously improve the fluidity of the glue after being added, so that the initial adhesion of the pressure-sensitive adhesive is improved, the phenolic modified terpene resin has a relatively high softening point, so that the peeling force of the pressure-sensitive adhesive is improved after being added, the rosin resin and the modified terpene resin are very important in improving the performance of the pressure-sensitive adhesive, and if no tackifying resin is added, an ideal using effect cannot be achieved. In comparative examples 1 to 3, since no tackifier resin was added, the desired adhesion effect could not be achieved only by the starting polymer.
In comparative example 4, the addition amount of the rosin resin is too much (> 25 parts), although the initial adhesion of the pressure-sensitive adhesive can be obviously increased, the softening point is lower, and the excessive addition amount causes the whole glue to be softer, the storage modulus is reduced, and the stripping force performance is reduced. The addition amount of the phenolic modified terpene resin in the comparative example 6 is more than 25 parts, although the stripping force of the pressure-sensitive adhesive can be obviously increased, the softening point is higher, and the whole glue is harder due to excessive addition amount, so that the flowability of the glue is influenced, and the initial adhesion is obviously reduced. The rosin resin in the comparative example 5 is added in an amount less than 10 parts, and the phenolic modified terpene resin in the comparative example 7 is added in an amount less than 5 parts, so that enough bonding strength cannot be achieved, and the addition amount of the tackifying resin must be controlled to be a proper ratio if balanced stripping force and initial adhesion performance of the pressure sensitive adhesive is achieved, in the case of the invention, the optimal addition amount of the rosin resin is 10-25 parts, and the optimal addition amount of the terpene resin is 5-25 parts.
Examples 7-12 correspond to the acrylate masterpolymer formulation A4 used, examples 13-14 correspond to the acrylate masterpolymer formulation A7 used, and examples 15-20 correspond to the acrylate masterpolymer formulation A8 used. The molecular weight of a main polymer is improved through the formula design, so that the stripping force of the pressure-sensitive adhesive is relatively high, and particularly, the thin-coating high-viscosity pressure-sensitive adhesive prepared on the basis of the acrylate formula A7& A8 has the advantages that the molecular weight distribution is changed on the premise of high overall molecular weight, a small part of low-molecular weight polymer is properly introduced, so that the molecular weight distribution is widened, the overall fluidity of the pressure-sensitive adhesive is improved, the initial adhesion is further improved, and the performance that the initial adhesion and the stripping force are more balanced and excellent is obtained. In the present invention, the molecular weight distribution PDI is controlled to be in the range of 2.0 to 8.0.
Comparative examples 8-12, comparative examples 17-20 selected tackifying resins having softening points < 10 ℃ or > 140 ℃ and selected tackifying resins having molecular weights < 300g/mol or > 2000 g/mol. If the tackifying resin has too low a softening point and too low a molecular weight, the cohesive strength of the pressure-sensitive adhesive is significantly reduced after the tackifying resin is added, and the adhesive strength is not improved but is obviously reduced. If the tackifying resin has an excessively high softening point and an excessively high molecular weight, the fluidity of the pressure-sensitive adhesive is significantly reduced after the tackifying resin is added, the adhesive becomes brittle, and the initial adhesion is significantly reduced. Therefore, the tackifying resin with a proper softening point/molecular weight is selected in practical application. In the present invention, the softening point of the tackifying resin is selected from the range of 10-140 ℃, and the molecular weight of the tackifying resin is controlled to be 300-2000 g/mol.
In comparative example 13, the amount of the curing agent used was too low (<0.1 part), the pressure-sensitive adhesive polymer failed to form a three-dimensional network structure, and the strength and modulus of the whole colloid were too low, resulting in too low peel strength, in which case, even if a tackifying resin was added externally, the adhesive strength could not be effectively improved, and the practical application performance was not good. In comparative example 14, the amount of the curing agent is too high (>3 parts), the crosslinking degree of the pressure-sensitive adhesive polymer is too high, the colloid loses fluidity, effective wetting and adhesion to the adhered surface cannot be formed, and the peeling force and the initial adhesion are too low. In the present case, the optimum amount of the curing agent is 0.1 to 3 parts.
Comparative example 15 corresponds toThe acrylate resin syrup A-9 has too much thermal initiator AIBN (more than 3 parts) added in the polymer synthesis process, so that the molecular weight of the polymerized resin syrup is too small, the strength and the storage modulus of colloid are too low, even if tackifying resin is added externally, the bonding strength cannot be effectively improved, and the actual application performance is poor. Comparative example 16, corresponding acrylate syrup A-10, in which AIBN, a thermal initiator added during the polymer synthesis, was too small (<0.1 part), which results in too large molecular weight of the polymerized resin slurry, poor fluidity of colloid, and poor initial viscosity, and even if tackifying resin is added externally, the bonding strength cannot be effectively improved, and the practical application performance is not good. In the case of the present invention, the optimum amount of the thermal initiator is 0.1 to 3 parts, and the molecular weight range is controlled to 30 to 200X 104g/mol。
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (9)

1. The thin-coating high-viscosity pressure-sensitive adhesive is characterized by comprising the following components in parts by weight: 100 parts of acrylate resin syrup, 0.1-3 parts of curing agent and 15-50 parts of tackifying resin, wherein the weight average molecular weight of the acrylate resin syrup is 30-200 multiplied by 104The adhesive comprises, by weight, g/mol, a molecular weight distribution index PDI of 2.0-8.0, a softening point of 10-140 ℃ and a relative molecular mass of 300-2000g/mol, wherein the tackifying resin comprises 10-25 parts of rosin resin and 5-25 parts of terpene resin according to 100 parts of acrylate resin slurry, the terpene resin adopts phenolic modified terpene resin A, the phenolic modified terpene resin A adopts Dertoprene T135 and is produced by DRT company, the softening point is 140 ℃ and the molecular weight is 2000 g/mol.
2. The thin coated high viscosity pressure sensitive adhesive of claim 1, wherein the rosin-based resin is at least one selected from the group consisting of glycerol ester of rosin, pentaerythritol ester of rosin, glycerol ester of hydrogenated rosin, pentaerythritol ester of hydrogenated rosin, glycerol ester of perhydrogenated rosin, pentaerythritol ester of perhydrogenated rosin, glycerol ester of disproportionated rosin, and pentaerythritol ester of disproportionated rosin.
3. The thin-coating high-viscosity pressure-sensitive adhesive as claimed in claim 1, wherein the acrylate resin syrup comprises the following raw materials in parts by mass: 85-95 parts of acrylate soft and hard monomer, 5-15 parts of hydroxyl functional monomer, 0.02-0.2 part of molecular weight regulator, 0.1-3 parts of thermal initiator and 80-140 parts of organic solvent.
4. The thin-coated high viscosity pressure sensitive adhesive according to claim 3, wherein the acrylate soft and hard monomer is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, isooctyl acrylate, isodecyl acrylate, butyl acrylate, isobutyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, isobornyl methacrylate, vinyl acetate, and styrene.
5. The thin-coating high-viscosity pressure-sensitive adhesive according to claim 3, wherein the hydroxyl functional monomer is at least one selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, and N-methylol acrylamide.
6. The thin-coated high viscosity pressure sensitive adhesive of claim 3, wherein the thermal initiator is at least one selected from the group consisting of dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, azobisisobutyronitrile, azobisisovaleronitrile, and azobisisoheptonitrile.
7. The thin-coating high-viscosity pressure-sensitive adhesive as claimed in claim 3, wherein the molecular weight regulator is at least one selected from the group consisting of dodecyl mercaptan, acetic acid, and phenol.
8. The thin-coated high viscosity pressure sensitive adhesive according to any one of claims 3 to 7, wherein the acrylate resin syrup is prepared by the steps of:
weighing raw materials according to the parts by weight, adding 1/2 of the total mass of the acrylate soft and hard monomers, 1/2 of the total mass of the hydroxyl-containing monomers, 1/3 of the total mass of the organic solvent and 3/5 of the total mass of the thermal initiator into a four-neck flask with a reflux condenser, stirring and mixing for 30-60min under nitrogen flow, then slowly dropwise adding 1/5 of the total mass of the thermal initiator, the rest of the acrylate soft and hard monomers, the rest of the hydroxyl-containing monomers and 1/3 of the total mass of the organic solvent, reacting for 8-15 hours at the temperature of 60-85 ℃, finally dropwise adding the rest of the thermal initiator, the rest of the organic solvent and a molecular weight regulator, regulating the molecular weight of the acrylate pressure-sensitive adhesive, and preserving heat for 1-2 hours to ensure that the polymerization reaction is complete, thereby obtaining the acrylate resin slurry.
9. A pressure-sensitive adhesive tape, which is prepared from the thin-coating high-viscosity pressure-sensitive adhesive according to any one of claims 1 to 8.
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