WO2017100995A1 - 可固化组合物、压敏粘合剂、胶带、粘合制品 - Google Patents

可固化组合物、压敏粘合剂、胶带、粘合制品 Download PDF

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WO2017100995A1
WO2017100995A1 PCT/CN2015/097364 CN2015097364W WO2017100995A1 WO 2017100995 A1 WO2017100995 A1 WO 2017100995A1 CN 2015097364 W CN2015097364 W CN 2015097364W WO 2017100995 A1 WO2017100995 A1 WO 2017100995A1
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monomer
block
weight
curable composition
acrylate
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English (en)
French (fr)
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张文杰
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3M Innovative Properties Co
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3M Innovative Properties Co
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Priority to CN201580085388.2A priority Critical patent/CN108473839A/zh
Priority to PCT/CN2015/097364 priority patent/WO2017100995A1/zh
Priority to KR1020187019899A priority patent/KR20180093047A/ko
Priority to JP2018531124A priority patent/JP2019505617A/ja
Priority to US16/061,739 priority patent/US20190390086A1/en
Publication of WO2017100995A1 publication Critical patent/WO2017100995A1/zh
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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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such 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
    • C09J7/30—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
    • C09J7/387—Block-copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block 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
    • C09J7/30—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/006—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such 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
    • 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
    • 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
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/006—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • C09J2453/00—Presence of block copolymer

Definitions

  • the invention belongs to the technical field of acrylate pressure sensitive adhesives, and in particular relates to a curable composition, a pressure sensitive adhesive, a tape, and an adhesive article.
  • PSA Pressure Sensitive Adhesive
  • Acrylate pressure sensitive adhesive is an important type of pressure sensitive adhesive, which has the characteristics of good weather resistance, high cost performance, good transparency, high cohesive strength, high adhesion and wide application surface.
  • Acrylate pressure sensitive adhesives are often used in consumer electronics.
  • a mobile terminal mobile phone
  • a tablet a notebook computer or the like
  • an acrylate pressure sensitive adhesive such as acrylate foam double-sided tape can be used to bond the display panel to the casing.
  • the width of the acrylate foam double-sided tape in the above equipment is getting smaller and smaller, and the size and weight of the display panel are getting larger and larger, which is pressure-sensitive adhesive bonding to acrylate.
  • the anti-drop properties of the agent put forward higher requirements. That is to say, when the mobile phone or the like accidentally falls, the display panel and the casing cannot be separated due to the impact of the drop.
  • the curable composition of the present invention comprises:
  • a monomer component comprising at least two polymerizable monomers, the polymerizable monomer comprising a (meth) acrylate monomer other than a tertiary alcohol, an acid functional non-ester unsaturated monomer having at least one olefinic bond;
  • At least one block copolymer belonging to an elastomer comprising at least two A blocks at both ends and at least one B block located in the middle; wherein the A is embedded
  • the segment is formed by polymerization of a methacrylate monomer formed by polymerization of an acrylate monomer.
  • the above block copolymer is a triblock copolymer of the A block-B block-A block structure.
  • the A block is formed by polymerization of a methyl methacrylate monomer; the B block is formed by polymerization of a n-butyl acrylate monomer.
  • the curable composition further comprises: a (meth) acrylate copolymer formed by copolymerization of a raw material comprising at least two polymerizable monomers, including: a non-tertiary alcohol (A) a acrylate monomer, an acid functional non-ester unsaturated monomer having at least one olefinic bond; the (meth) acrylate copolymer having a weight average molecular weight of between 500,000 Daltons and 10,000,000 Daltons.
  • a (meth) acrylate copolymer formed by copolymerization of a raw material comprising at least two polymerizable monomers, including: a non-tertiary alcohol (A) a acrylate monomer, an acid functional non-ester unsaturated monomer having at least one olefinic bond; the (meth) acrylate copolymer having a weight average molecular weight of between 500,000 Daltons and 10,000,000 Daltons.
  • the monomer component and the (meth) acrylate copolymer constitute a slurry polymer; the slurry polymer is formed by partially copolymerizing a raw material comprising at least two polymerizable monomers, the polymerizable
  • the monomer includes a (meth) acrylate monomer other than a tertiary alcohol, and an acid functional non-ester unsaturated monomer having at least one olefinic bond.
  • Another object of the present invention is to provide a pressure sensitive adhesive which is formed by curing the above curable composition to have good drop resistance.
  • Another object of the present invention is to provide an adhesive tape comprising the above pressure sensitive adhesive to have good drop resistance.
  • Another object of the present invention is to provide an adhesive article comprising the above pressure sensitive adhesive to have good drop resistance.
  • the adhesive article is any one of a mobile terminal, a tablet computer, and a notebook computer; and wherein the casing and the display panel are bonded together by the pressure sensitive adhesive described above.
  • FIG. 1 is a schematic diagram of a method for testing a drop resistance performance according to an embodiment of the present invention.
  • a to B or “between A and B” includes the value of A, the value of B, and any value greater than A and less than B; for example, 1 to 10 includes 1, 10, and any greater than 1 and less than A value of 10, such as 2, 3, 4, 5, 6, 7, 8, 9, 2.3, 3.5, 5.26, 7.18, 9.999, and the like.
  • A is basically B and "A is about B” means that A is in general B condition, but there may be some difference from B, and the difference is small on the scale of B. of.
  • Viscosity unless otherwise specified, the viscosity referred to in the present invention is measured by an Ubbelohde viscometer.
  • Molecular weight unless otherwise specified, the molecular weights referred to in the present invention are all weight average molecular weights, and are all obtained by a gel gas chromatography method (GPC).
  • Glass transition temperature (Tg) refers to the temperature at which a polymer transitions between a high elastic state and a glass state, that is, a temperature at which an amorphous portion of the polymer is from a frozen state to a thawed state. Unless otherwise stated, the glass transition temperatures referred to in the present invention are all measured by differential scanning calorimetry (DSC).
  • Glass transition temperature of a monomer means the glass transition temperature of a homopolymer of the corresponding monomer.
  • Substance amount unless otherwise specified, the amount or ratio of the substances in the present invention means weight or weight ratio.
  • % by weight of B in A means that B is a part of A, and the percentage of the weight of B when the weight of A (including B) is 100%.
  • % by weight relative to the weight of A means that B does not belong to A, and when the weight of A (excluding B) is 100%, the weight of B is a percentage of the weight of A.
  • “Elastomer” means a polymer material that can be substantially restored to its original shape after a large deformation, or a material having a large elastic deformation range; for example, it can be released after being stretched to twice the original length. Restore the original length of polymer material.
  • (meth)acrylic acid represents both acrylic acid and methacrylic acid.
  • (meth) acrylate stands for both (meth) acrylate and methacrylate.
  • esters of (meth)acrylic acid and its homologues specific optional examples include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and the like.
  • tertiary alcohol means an alcohol in which the other three groups to which the hydroxyl group is attached is a substituent other than a hydrogen atom; "non-tertiary alcohol” means an alcohol which does not belong to a tertiary alcohol.
  • Polymer means a material formed by the polymerization of one or more polymerizable monomers, including homopolymers, copolymers, terpolymers, and the like.
  • Copolymer means a polymer formed by the polymerization of at least two different polymerizable monomers, that is, all polymers except homopolymers, including random copolymers, block copolymers, graft copolymers , alternating copolymers, mixtures thereof, and the like.
  • Block copolymer also known as a mosaic copolymer, is a polymer formed by joining two or more different polymer segments together, wherein each polymer segment is formed by polymerization of the same polymerizable monomer.
  • a continuous chain referred to as a "block”; due to its specific structure, most block copolymers are elastomers.
  • Triblock copolymer means a block copolymer composed of three blocks, and further refers to a block copolymer composed of two A blocks and one B block.
  • Partial copolymerization means that a part of the polymerizable monomer as a raw material has been copolymerized to form a copolymer, and at the same time, a part of the polymerizable monomer has not yet polymerized, maintaining the form of the monomer.
  • “Curing” refers to the process by which a liquid substance is converted from a liquid state to a solid state having viscoelastic properties by polymerization and/or crosslinking of components therein.
  • Pressure-sensitive adhesive means a substance that can be bonded to a substrate, and which satisfies the following conditions at least at ambient temperature (5 ° C to 40 ° C): (1) has a long-lasting viscosity; (2) with a finger The bonding can be achieved under pressure of the pressing; (3) the shape can be changed to adhere to the substrate; and (4) the cohesive strength is sufficient to cause it to be substantially cleanly removed from the adherend.
  • Tape means a product having a substantially strip shape that can be bonded to a substrate or that can bond the two substrates together.
  • the present invention provides a curable composition which is curable to form a pressure sensitive adhesive having excellent drop resistance, especially by ultraviolet light curing.
  • the curable composition of the present invention comprises:
  • a monomer component comprising at least two polymerizable monomers, the polymerizable monomer comprising a (meth) acrylate monomer of a non-tertiary alcohol, an acid functional non-ester unsaturated monomer having at least one olefinic bond;
  • At least one block copolymer the block copolymer being an elastomer comprising at least two A blocks at each end and at least one B block in the middle; wherein the A block is composed of a methacrylate monomer Polymerization is formed and the B block is formed by polymerization of an acrylate monomer.
  • the curable composition of the present invention comprises a (meth) acrylate monomer which is a main component for forming an acrylate pressure-sensitive adhesive, whereby the pressure-sensitive adhesive formed by the curable composition of the present invention belongs to Acrylate pressure sensitive adhesive.
  • the curable composition further includes a polyacrylate elastomer, the elastomer is a block copolymer, and both ends of the block copolymer have an A block formed by polymerization of a methacrylate monomer, and the middle There is then at least one B block formed by the polymerization of an acrylate monomer.
  • the inventors have found that the addition of the above acrylate-based elastomer (block copolymer) to a (meth) acrylate monomer allows a pressure-sensitive adhesive formed by curing the curable composition to have good properties. Performance, especially excellent drop resistance.
  • the curable composition may further comprise a (meth) acrylate copolymer formed by copolymerization of a raw material comprising at least two polymerizable monomers, including: a non-tertiary alcohol (methyl group) An acrylate monomer, an acid functional non-ester unsaturated monomer having at least one olefinic bond; the (meth) acrylate copolymer having a weight average molecular weight of between 500,000 Daltons and 10,000,000 Daltons.
  • a (meth) acrylate copolymer formed by copolymerization of a raw material comprising at least two polymerizable monomers, including: a non-tertiary alcohol (methyl group) An acrylate monomer, an acid functional non-ester unsaturated monomer having at least one olefinic bond; the (meth) acrylate copolymer having a weight average molecular weight of between 500,000 Daltons and 10,000,000 Daltons.
  • a (meth) acrylate copolymer may be further included in the curable composition, which may be formed by polymerizing the same kind of raw materials as the above monomer components; when the above copolymer is present, it is advantageous to improve the curable combination.
  • the quality of the pressure sensitive adhesive formed by the material, especially the viscosity of the curable composition because if the content of the monomer component in the curable composition is too large, the viscosity is too low to form a pressure sensitive adhesive.
  • the agent is technically difficult.
  • the above monomer component and (meth) acrylate copolymer may constitute a slurry polymer
  • the slurry polymer is formed by partial copolymerization of a raw material comprising at least two polymerizable monomers, including a (meth) acrylate monomer other than a tertiary alcohol, and an acid functional non-ester unsaturated single having at least one olefinic bond. body.
  • partial copolymerization may be carried out using a raw material including the above polymerizable monomer to form a mixture composed of a monomer and a copolymer, that is, a slurry polymer.
  • a slurry polymer a part of the polymerizable monomer has been copolymerized to form a copolymer, which is the above (meth) acrylate copolymer; at the same time, some of the polymerizable monomers have not yet polymerized to maintain the monomer. In the form, it is the above monomer component.
  • a polymerizable monomer which does not undergo polymerization is used as a solvent, and a copolymer as a solute is dissolved therein to form a homogeneous phase system.
  • the advantage of using a slurry polymer is that the same monomer component and (meth) acrylate copolymer can be directly obtained from the same starting materials without separately preparing different monomer components and (meth) acrylate copolymers.
  • the monomer component and the (meth) acrylate copolymer are in the form of a slurry polymer, they are necessarily formed from the same raw material; however, it does not mean the monomer component and (meth)acrylic acid.
  • the actual composition of the ester copolymer is the same, because the rate and order of copolymerization of different polymerizable monomers may be different during the copolymerization process; further, if the monomer component and (meth) acrylate separately prepared separately are used
  • the copolymer is formulated with a slurry polymer and does not require the same raw materials.
  • the slurry polymer is a mixture formed by partially copolymerizing a raw material comprising at least two polymerizable monomers, the mixture including a polymerizable monomer which is not polymerized (i.e., a monomer component) and a copolymer formed by copolymerization of a polymerizable monomer. (ie (meth) acrylate copolymer).
  • the slurry polymer is a liquid homogeneous system as a whole, which has fluidity and is convenient for coating and the like.
  • the weight average molecular weight of the (meth) acrylate copolymer in the slurry polymer is preferably 500000 Daltons (grams per mole) to 10,000,000 Daltons, more preferably between 750,000 Daltons and 6,000,000 Daltons.
  • the copolymer already formed in the slurry polymer may have a weight average molecular weight of at least 500,000 Dalton centipoise, or at least 750,000 Daltons, or at least 1,000,000 Daltons; and the weight average molecular weight is at most It is 10,000,000 Daltons, or at most 6,000,000 Daltons, or at most 5,000,000 Daltons.
  • the viscosity of the slurry polymer at 22 ° C is preferably between 500 centipoise (cps) and 10,000 centipoise, more preferably between 500 centipoise and 7000 centipoise.
  • the slurry polymer may have a viscosity of at least 500 centipoise, or at least 1500 centipoise, or at least 2500 centipoise; and the viscosity may be at most 10,000 centipoise, or at most 7000 centipoise, or at most 5,500 cps.
  • the proportion of the weight of the polymerizable monomer that has undergone polymerization is between 1% and 30%. That is, if the raw material of all the polymerizable monomers for forming the slurry polymer is 100 parts by weight, the amount of the polymerizable monomer in which polymerization has occurred to become a copolymer is from 1 part by weight to 30 parts by weight.
  • the polymerizable monomer which does not undergo polymerization is in the range of 70 parts by weight to 99 parts by weight, or the monomer conversion rate is 1% to 30%.
  • the above monomer conversion rate may be at least 1%, or at least 2%, or at least 5%, or at least 7%; and the monomer conversion rate may be at most 30%, or at most 20%. Or at most 15%, or at most 12%.
  • a slurry polymer having the above viscosity, weight average molecular weight, and monomer conversion ratio is more suitable for use in a curable composition.
  • the above polymerizable monomers for forming a slurry polymer include a (meth) acrylate monomer of a non-tertiary alcohol, an acid-functional non-ester unsaturated monomer having at least one olefinic bond: and preferably may also include a non-acid functional group Ethylenically unsaturated polar monomers and/or vinyl monomers.
  • the slurry polymer is preferably formed by partially copolymerizing a raw material including the above polymerizable monomer; thus, the monomer component of the curable composition naturally also includes these polymerizable monomers, and the curable composition
  • the (meth) acrylate copolymer is also formed by copolymerization of these polymerizable monomers.
  • the number of carbon atoms in the non-tertiary alcohol used to form the (meth) acrylate monomer of the non-tertiary alcohol is between 1 and 20, more preferably between 2 and 18, further preferably at 4 From 12 to 12.
  • the segment of the non-tertiary alcohol used to form the (meth) acrylate monomer of the above non-tertiary alcohol may be linear, branched, or a combination of the two.
  • the above non-tertiary alcohols include, but are not limited to, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol , 2-methyl-1-butanol, 3-methyl-1-butanol, 1-hexanol, 2-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol , 2-ethyl-1-butanol, 3,5,5-trimethyl-1-hexanol, 3-heptanol, 1-octanol, 2-octanol, isooctanol, 2-ethyl- Any one or more of 1-hexanol, 1-n
  • the non-tertiary alcohol is preferably any one or more of butanol, isooctanol, 2-ethylhexanol (corresponding esters) That is, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, butyl (meth)acrylate); and in other preferred embodiments, the non-tertiary alcohol is derived from An alcohol of a renewable origin, such as any one or more of 2-octanol, citronellol, and dihydrocitronellol.
  • the (meth) acrylate monomer of the non-tertiary alcohol is between 50% and 99.5%.
  • the (meth) acrylate monomer of the above non-tertiary alcohol preferably accounts for 50 parts by weight to 99.5 parts by weight, more preferably 95%, per 100 parts by weight of the polymerizable monomer for forming a slurry polymer. Parts by weight to 99.5 parts by weight.
  • the (meth) acrylate monomer of the above non-tertiary alcohol may be at least 50 parts by weight, or at least 70 parts by weight, or at least 90 parts by weight, or at least 95 parts by weight; and the above non-tertiary alcohol
  • the (meth) acrylate monomer may be up to 99.5 parts by weight, or up to 98 parts by weight, or up to 96 parts by weight, or up to 90 parts by weight.
  • a part thereof has a high Tg (glass transition temperature), that is, a homopolymer thereof has a Tg of at least 25 ° C, and preferably at least 50 ° C. .
  • the (meth) acrylate monomer having a higher Tg non-tertiary alcohol includes, but is not limited to, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, Isobutyl acrylate, sec-butyl methacrylate, stearyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, methacrylic acid Benzyl ester, 3,3,5-trimethylcyclohexyl acrylate, cyclohexyl acrylate, N-octyl propyl Any one or more of an enamide or a propyl methacrylate.
  • the (meth) acrylate monomer having a higher Tg of a non-tertiary alcohol preferably accounts for from 0 part by weight to 25 parts by weight per 100 parts by weight of the polymerizable monomer for forming a slurry polymer (0 means no Inclusive, more preferably from 0 part by weight to 20 parts by weight.
  • the above higher Tg non-tertiary alcohol (meth) acrylate monomer may be free, or at least 2 parts by weight, or at least 5 parts by weight; and the higher Tg non-tertiary alcohol (methyl)
  • the acrylate monomer may be up to 25 parts by weight, or up to 20 parts by weight, or up to 15 parts by weight.
  • the amount of the (meth) acrylate monomer having a higher Tg of a non-tertiary alcohol is included in the amount of the (meth) acrylate monomer of all non-tertiary alcohols; for example, if it is not a tertiary alcohol (methyl)
  • the total amount of the acrylate monomer is 90 parts by weight, and the amount of the (meth) acrylate monomer having a higher Tg of the non-tertiary alcohol is 10 parts by weight, which means that a total of 90 parts by weight of the non-tertiary alcohol Of the (meth) acrylate monomers, 10 parts by weight are higher in Tg, and the remaining 80 parts by weight are other non-tertiary alcohol (meth) acrylate monomers having a lower Tg.
  • the acid-functional non-ester unsaturated monomer having at least one ethylenic bond includes both an olefinic bond and an acid functional group, and the acid functional group may be an acid such as a carboxylic acid or an acid salt such as an alkali metal salt of a carboxylic acid. But not an ester.
  • the acid-functional non-ester unsaturated monomer having at least one ethylenic bond may be an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated sulfonic acid, an ethylenically unsaturated phosphonic acid, etc.; specifically, Limited to: acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, citraconic acid, maleic acid, oleic acid, styrenesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, vinyl Any one or more of phosphonic acids.
  • the acid-functional non-ester unsaturated monomer having at least one ethylenic bond is more preferably an ethylenically unsaturated carboxylic acid such as (meth)acrylic acid in view of feasibility.
  • the above acid functional group having at least one olefinic bond is between 0.5% and 15%, more preferably between 0.5% and 5%.
  • the above-mentioned acid-functional non-ester unsaturated monomer having at least one ethylenic bond preferably accounts for 0.5 part by weight to 15 parts by weight, more preferably It is preferably from 0.5 to 5 parts by weight.
  • the above acid-functional non-ester unsaturated monomer having at least one ethylenic bond may be at least 0.5 part by weight, or at least 1 part by weight, or at least 2 parts by weight; and the acid function has at least one ethylenic bond.
  • the non-ester unsaturated monomer may be up to 15 parts by weight, or up to 10 parts by weight, or up to 5 parts by weight.
  • the polymerizable monomer used to form the slurry polymer may further comprise a non-acid functional ethylenically unsaturated polar monomer (which may include an ester but differs from the previous non-tertiary alcohol (meth) acrylate) monomer).
  • a non-acid functional ethylenically unsaturated polar monomer which may include an ester but differs from the previous non-tertiary alcohol (meth) acrylate) monomer.
  • non-acid functional ethylenically unsaturated polar monomers include, but are not limited to, 2-hydroxyethyl (meth)acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, acrylamide, mono- N-alkyl substituted acrylamide, di-N-alkyl substituted acrylamide, t-butyl acrylamide, dimethylaminoethyl acrylamide, N-octyl acrylamide, poly(alkoxyalkyl) Any one or more of (meth) acrylate; wherein the poly(alkoxyalkyl) (meth) acrylate comprises 2-(2-ethoxyethoxy) (meth) acrylate Ester, 2-ethoxyethyl (meth)acrylate, 2-methoxyethoxyethyl (meth)acrylate, 2-methoxyethyl methacrylate, polyethylene glycol mono (methyl) Any one or more of acrylates.
  • non-acid functional ethylenically unsaturated polar monomers described herein do not include the other monomers described above, i.e., they differ from the above non-tertiary alcohol (meth) acrylate monomers.
  • the non-acid functional ethylenically unsaturated polar single is less than or equal to 45%.
  • the non-acid functional ethylenically unsaturated polar monomer preferably accounts for from 0 part by weight to 45 parts by weight per 100 parts by weight of the polymerizable monomer for forming the slurry polymer (0 means not included ).
  • the non-acid functional ethylenically unsaturated polar monomer may be free, or at least 1 part by weight, or at least 2 parts by weight, or at least 5 parts by weight; and the non-acid functional ethylenic group
  • the unsaturated polar monomer may be up to 45 parts by weight, or up to 40 parts by weight, or up to 35 parts by weight.
  • the polymerizable monomer used to form the slurry polymer may further include a vinyl monomer, which refers to a monomer having a vinyl group as an important part, including but not limited to: a vinyl ester ( For example, any one or more of vinyl acetate, vinyl propionate, styrene, substituted styrene (such as ⁇ -methylstyrene), and vinyl halide.
  • a vinyl ester For example, any one or more of vinyl acetate, vinyl propionate, styrene, substituted styrene (such as ⁇ -methylstyrene), and vinyl halide.
  • the vinyl monomers described herein do not include the other monomers described above, ie, the (meth) acrylate monomers other than the above non-tertiary alcohols, the acid-functional non-ester unsaturated monomers having at least one olefinic bond.
  • the weight percentage of the vinyl monomer is less than or equal to 5%.
  • the vinyl monomer is preferably from 0 part by weight to 5 parts by weight per 100 parts by weight of the polymerizable monomer for forming a slurry polymer (0 means that it may not be contained).
  • the vinyl monomer may be free, or at least 0.1 part by weight, or at least 0.5 part by weight; and the vinyl monomer may be at most 5 parts by weight, or at most 4 parts by weight, or at most 3 parts by weight. Share.
  • non-acid functional ethylenically unsaturated polar monomer and vinyl monomer are optional components, ie, the polymerizable monomers used to form the slurry polymer may not include them, but as an improved slurry Alternative components of polymer properties are known for use in slurry polymers.
  • Also included in the curable composition of the present invention is one or more block copolymers which are elastomers.
  • the block copolymer of the present invention comprises at least two A blocks respectively located at both ends and at least one B block located in the middle; wherein the A block is formed by polymerization of a methacrylate monomer, and the B block is composed of an acrylate single Bulk polymerization is formed.
  • both ends of the block copolymer of the present invention are necessarily A blocks formed by polymerization of a methacrylate monomer, and in the middle there is a B block formed by polymerization of an acrylate monomer.
  • the above A block has a higher hardness than the B block, which is advantageous for improving the elasticity of the elastomer.
  • the above A block is formed by polymerization of an alkyl methacrylate monomer, and wherein the alkyl group has from 1 to 6 carbon atoms, or between 1 and 4, or in 1 Between 3 and 3
  • the above B block is formed by polymerization of an alkyl acrylate monomer, and wherein the alkyl group has between 3 and 20 carbon atoms, or between 4 and 20, or between 4 and 10 Between, or between 4 and 6; obviously, when the above number of carbon atoms is in a certain range, each block can be formed from a plurality of different specific monomers.
  • the alkyl group of the alkyl methacrylate monomer used to form the A block has a carbon number smaller than that of the alkyl group of the alkyl acrylate monomer used to form the B block.
  • the A block is formed by polymerization of a methyl methacrylate monomer
  • the B block is formed by polymerization of a n-butyl acrylate monomer; that is, the A block is poly(methyl methacrylate).
  • B block is poly (C N-butyl acrylate).
  • the above block copolymer is a triblock copolymer of the A block-B block-A block structure. That is to say, the block copolymer preferably consists of only two A blocks located at both ends and one B block located at the both ends, and does not include other structures, thereby being a simple ABA structure.
  • the block copolymer is a poly(methyl methacrylate)-poly(n-butyl acrylate)-poly(methyl methacrylate) triblock copolymer.
  • the block copolymer comprises other blocks or comprises alternating (AB) blocks in between.
  • the above block copolymer (elastomer) may be an elastomer product such as LA1114, LA2140, LA2250, LA2330 produced by Kuraray Co., Ltd. of Tokyo, Japan.
  • the above block copolymer has a weight average molecular weight between 2000 Daltons and 500,000 Daltons.
  • the above block copolymer has a weight average molecular weight of at least 2000 Daltons, or at least 3000 Daltons, or at least 5000 Daltons, or at least 10,000 Daltons, or at least 40,000 Daltons. , or at least 60,000 Daltons; and having a weight average molecular weight of no more than 500,000 Daltons, or no more than 300,000 Daltons, or no more than 200,000 Daltons, or no more than 120,000 Daltons, or no more than 80,000 Dalton.
  • the weight percentage of the A block is between 5% and 50%, preferably between 20% and 30%; and the weight percentage of the B block is between 50% and 95%. Preferably, it is between 70% and 80%.
  • the proportion of the A block should be small, and the weight percentage should be at least 5%, or at least 7%, or at least 10%, or at least 20%, or at least It is 23%, and the weight percentage of the A block should be at most not more than 50%, or not more than 40%, or not more than 35%, or not more than 30%.
  • the proportion of the B block should be large, and the weight percentage should be at least 50%, or at least 55%, or at least 60%, or at least 65%, or at least 70%, and the weight percentage of the B block should be at most no more than 95%, or no more than 90%, or no more than 85%, or no more than 80%, or no more than 75%.
  • the curable composition of the present invention is photoinitiated and may contain a photoinitiator therein.
  • a photoinitiator is used to generate a radical under irradiation of ultraviolet light to initiate a polymerization reaction.
  • No additional organic solvent ie, solvent other than polymerizable monomer
  • Photoinitiated polymerization so it is not heated on the one hand, simple and easy to operate, low energy consumption, high efficiency; on the other hand, when the ultraviolet light source is turned off and air is introduced, the reaction can be terminated immediately, so the viscosity of the product, single The body conversion rate, weight average molecular weight, and the like can be accurately controlled.
  • photoinitiators include, but are not limited to, benzoin ethers, such as benzoin methyl ether, benzoin isopropyl ether; substituted acetophenones, such as 2,2-dimethoxyacetophenone Dimethoxy hydroxyacetophenone; substituted ⁇ -keto alcohols such as 2-methyl-2-hydroxypropiophenone; aromatic sulfonyl chlorides such as 2-naphthalene-sulfonyl chloride; photosensitive oximes such as 1-phenyl -1,2-propanedione-2-(O-ethoxy-carbonyl)purine; 1-hydroxycyclohexyl phenyl ketone; 1-[4-(2-hydroxyethoxy)phenyl]-2- Hydroxy-2-methyl-1-propan-1-one; (4-methylthiobenzoyl)-1-methyl-1-morpholinylethane; (4-morpholinylbenzoyl)- 1-benzyl-1-dimethyla
  • the photoinitiator is used in an amount of from 0.001 part by weight to 3 parts by weight per 100 parts by weight of the polymerizable monomer used to form the slurry polymer.
  • the photoinitiator can be used in an amount of at least 0.001 parts by weight, or at least 0.005 parts by weight, or at least 0.01 parts by weight; and the photoinitiator can be used in an amount of up to 3 parts by weight, or at most 1 part by weight. Or at most 0.5 parts by weight.
  • the amount of photoinitiator herein refers to the total amount of photoinitiator added to the curable composition, and these photoinitiators may have a part (usually the weight percentage in the total amount is 10% to 20%) is first added to the raw material of the slurry polymer for causing partial polymerization to obtain a slurry polymer, after which the remainder is added to the slurry polymer obtained by the reaction for finalizing the curable composition.
  • the polymerization is a pressure sensitive adhesive.
  • the curable composition of the present invention may further contain a crosslinking agent, and the addition of the crosslinking agent may increase the cohesive strength of the pressure-sensitive adhesive formed.
  • Crosslinking agents useful in the present invention may include photosensitive crosslinking agents which are activated by ultraviolet light irradiation, and common photosensitive crosslinking agents include, but are not limited to: Benzophenone; a copolymerizable aromatic ketone; a triazine such as 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-triazine.
  • Another useful crosslinking agent is a polyfunctional (meth) acrylate such as di(meth) acrylate, tri(meth) acrylate, tetra (meth) acrylate, etc., specific examples of which include but not Limited to: 1,6-hexanediol di(meth)acrylate, poly(ethylene glycol) di(meth)acrylate, polybutadiene di(meth)acrylate, polyurethane di(meth)acrylic acid Any one or more of ester, propoxylated tris(meth)acrylate; the polyfunctional (meth)acrylate crosslinker is a non-photosensitive crosslinker, but it can improve the acrylate The cohesive strength of the pressure sensitive adhesive (see U.S.
  • Another useful crosslinking agent is a heat activated crosslinking agent such as a polyfunctional aziridine, isocyanate, epoxy resin or the like, specifically 1,1'-(1,3-phthaloyl)- Bis-(2-methylaziridine).
  • the most preferred crosslinking agent of the present invention is a polyfunctional (meth) acrylate.
  • the crosslinking agent is preferably used in an amount of less than or equal to 5 parts by weight per 100 parts by weight of the polymerizable monomer used to form the slurry polymer; that is, the crosslinking agent It may be free of, or at least 0.01 parts by weight, or at least 0.03 parts by weight; and the crosslinking agent may be used in an amount of up to 5 parts by weight, or up to 2 parts by weight, or up to 1 part by weight.
  • the pressure-sensitive adhesive of the present invention is mainly used for bonding a display panel of a mobile phone, a tablet computer or the like to a casing, it is desirable to have a black appearance to achieve shading and to be clearly seen from the outside.
  • a black pigment may be added to the curable composition, and available black pigments include 9B117 (Penn Color, Inc., Pennsylvania, USA) and the like.
  • the amount of the black pigment is preferably less than or equal to 10 parts by weight per 100 parts by weight of the polymerizable monomer for forming the slurry polymer; that is, the black pigment may be free, or at least It is 0.5 parts by weight, or at least 1 part by weight; and the black pigment may be used in an amount of up to 10 parts by weight, or up to 8 parts by weight, or up to 7 parts by weight.
  • the expanded polymeric microspheres may be added to the curable composition.
  • the expanded polymeric microspheres are substantially spherical known materials consisting of a polymeric shell and a cavity located within the housing, which are obtained by heating polymer particles coated with a gasifiable material, ie by Gasification of the gasifiable material swells the polymer shell.
  • the particle size of the expanded polymeric microspheres is preferably between 10 microns and 100 microns, more preferably between 20 microns and 90 microns.
  • the specifically usable expanded polymer microspheres can be seen in Chinese patent CN103320037B and the like, and will not be described in detail herein.
  • the amount of the expanded polymeric microspheres is preferably less than or equal to 10 parts by weight per 100 parts by weight of the polymerizable monomer used to form the slurry polymer; that is, the expanded
  • the polymeric microspheres may be free of, or at least 0.1 parts by weight, or at least 0.5 parts by weight; and the expanded polymeric microspheres may be used in an amount of up to 10 parts by weight, or up to 9 parts by weight, or at most 8 parts by weight.
  • a tackifying resin may also be added to the curable composition.
  • the tackifying resin may be used in combination of one or more kinds.
  • Useful tackifying resins include, but are not limited to, hydrogenated rosin resin FORAL 85LB (Pinova, Georgia, USA), hydrogenated terpene phenolic resin UH115 (Yasuhara Chemical Co., Ltd. , Hiroshima City, Japan), hydrocarbon resin tackifying resin REGRELTZ 6108 (Eastman Chemical Company, Tennessee, USA), US Patent US20150044457, and acrylate polymer tackifying resin in Chinese patent CN2014074139.
  • the use of the tackifying resin is not affected by other properties.
  • the tackifying resin is preferably not more than 35 parts by weight, or not more than 25 parts by weight, or not more than 10 parts by weight, or not more than 2 parts per 100 parts by weight of the polymerizable monomer for forming the slurry polymer.
  • the content of the tackifying resin is preferably not less than 0.1 part by weight, or not less than 1 part by weight, or not less than 2 parts by weight.
  • various other known additives may be added to the curable composition, including, but not limited to, plasticizers, antioxidants, dispersants, anti-settling agents. Any one or more of them.
  • functional components may also be added to the curable composition, such as having a die-cutting property for improving the product, which may be added thereto. Short fibers, etc.
  • the above curable composition can be obtained by uniformly mixing the respective raw materials.
  • a slurry polymer When a slurry polymer is used as a raw material of the curable composition, there are mainly two methods for preparing the slurry polymer, one is ultraviolet light-induced bulk polymerization, which is referred to as ultraviolet light initiation method; the other is thermally induced solution.
  • the polymerization method abbreviated as the solution method, is introduced one by one below.
  • the raw material of the polymerizable monomer is directly mixed and partially copolymerized (bulk polymerization), and the polymerizable monomer in which the polymerization is not generated is used as a solvent to dissolve the polymerized copolymer.
  • a slurry polymer is obtained.
  • the process of the ultraviolet light initiation method specifically includes:
  • each of the polymerizable monomers used to form the slurry polymer is mixed.
  • the above-mentioned (meth) acrylate monomer having a higher Tg of a non-tertiary alcohol is present in the polymerizable monomer, it may be added all in this step (this method is adopted in each embodiment of the present invention), Alternatively, only a portion may be added, or may not be added, and the unadded portion should be directly added to the finished partially copolymerized slurry polymer (that is, directly added to the curable composition); this is because of the higher Tg.
  • the polymerization of the (meth) acrylate monomer of the tertiary alcohol tends to be slow, and at this time, it is not possible to polymerize in a large amount.
  • the content of the (meth) acrylate monomer having a higher Tg of the non-tertiary alcohol is different for the finally obtained slurry polymer product in the portion where polymerization has occurred and polymerization has not occurred.
  • the specific components (including the content) of the monomer component and the (meth) acrylate copolymer corresponding to the polymerizable monomer raw material may be different.
  • the photoinitiator added in this step is part of the photoinitiator of the curable composition, typically from 10% to 20% by weight of the total.
  • ultraviolet light is irradiated to the above raw materials to partially copolymerize the polymerizable monomers to obtain a slurry polymer.
  • UV light sources are generally divided into two types: one is a low-intensity ultraviolet light source, such as black light, and its wavelength is from 280 nm to 400 nm, and the intensity is usually below 10 mW/cm 2 ;
  • High intensity ultraviolet light sources such as medium pressure mercury lamps, typically have a strength greater than 10 milliwatts per square centimeter, more preferably between 15 milliwatts per square centimeter and 450 milliwatts per square centimeter.
  • the UV intensity is measured by the UVIMAPTM UM 365L-S radiometer (General Electronic Instrument Technology Co., Ltd., Virginia, USA) according to the regulations of the National Institute of Standards and Technology (NIST). .
  • a low-intensity ultraviolet light source having an ultraviolet light intensity of from 0.1 mW/cm 2 to 150 mW/cm 2 ; specifically, the above ultraviolet light intensity is at least 0.1 mW/cm 2 , or at least 0.5 mW/cm 2 , or at least 1.5 mW/cm 2 ; and the UV light intensity is at most 150 mW/cm 2 , or at most 100 mW/cm 2 , or at most 50 mW/cm 2 .
  • the time of ultraviolet light irradiation can be adjusted according to the intensity of light and the polymerization, usually about several minutes. Alternatively, it is also possible to use ultraviolet light of high intensity and short irradiation time, for example, irradiation with 600 mW/cm 2 for 1 second.
  • the Ukrainian viscometer is used to continuously measure the viscosity of the slurry polymer, and the refractive index of the slurry polymer is continuously measured to determine the monomer conversion rate. After it reaches a predetermined standard, the ultraviolet light is removed and the slurry is polymerized. Air or oxygen is introduced into the material to quench the free radicals and the polymerization is terminated.
  • the ultraviolet light-initiating method does not use an additional organic solvent (ie, a solvent other than the polymerizable monomer) in the preparation process, so that the entire production process is substantially free of waste water and exhaust gas pollution, and is more environmentally friendly and highly efficient.
  • ultraviolet light is used to initiate polymerization in the ultraviolet light-initiating method, so that it is not heated on the one hand, simple and easy to operate, low in energy consumption and high in efficiency; on the other hand, when the ultraviolet light source is turned off and gas is introduced, it can be terminated immediately.
  • the reaction so the viscosity of the product, monomer conversion rate, weight average molecular weight, etc. can be accurately controlled.
  • the ultraviolet light initiating method is a preferred method of preparing a slurry polymer in the present invention, and in each of the embodiments of the present invention, the slurry polymer is prepared by the present method.
  • the above slurry polymer can also be prepared by a solution method, that is, the polymerizable monomer can be dissolved in an organic solvent to be polymerized, and the added organic solvent is removed after the polymerization is completed, and the remaining material is a slurry polymer.
  • Specific steps of the solution method can include:
  • Each of the polymerizable monomers, thermal initiators, and the like used to form the slurry polymer is dissolved in a solvent and sufficiently purified by nitrogen.
  • useful solvents include, but are not limited to: methanol, tetrahydrofuran, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, toluene, xylene, ethylene glycol alkyl ether, any one or more Kind.
  • the thermal initiator is an organic peroxide capable of generating a radical, an organic hydroperoxide, an azo compound or the like.
  • Useful organic peroxides include, but are not limited to, benzoyl peroxide, lauroyl peroxide, di-tert-amyl peroxide, t-butyl peroxybenzoate, 2,5-dimethyl-2,5- Any one of bis-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3, dicumyl peroxidekind or more.
  • Useful organic hydroperoxides include, but are not limited to, tert-carbonyl hydroperoxide and/or t-butyl hydroperoxide.
  • Useful azo compounds include, but are not limited to, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis Any one or more of (2,4-dimethylvaleronitrile).
  • the thermal initiator is preferably added in an amount of from 0.05 to about 1 part by weight, preferably from about 0.1 to about 0.5 part by weight, per 100 parts by weight of the polymerizable monomer for forming a slurry polymer.
  • the heating temperature is usually in the range of 40 ° C to 100 ° C
  • the heating time is usually in the range of 1 hour to 20 hours, and the specific selection depends on the total amount of the substance, the required monomer conversion rate, and the like.
  • the specific vacuum distillation temperature can be determined according to the type of the external solvent, and the time is such that the external solvent can be substantially removed.
  • the product curable composition can be obtained.
  • a black pigment, a photoinitiator, a crosslinking agent, a tackifying resin, and the like are generally added, and after they are completely dissolved, a block copolymer (elastomer) is added, if there is an expanded polymerization.
  • the microspheres are added last; such an order of addition is advantageous to ensure that the components are evenly distributed.
  • mixing is performed in the above order.
  • the present invention also provides a pressure sensitive adhesive which is obtained by curing the above curable composition.
  • the above curable composition can be substantially completely cured by ultraviolet light irradiation to form a pressure-sensitive adhesive having excellent drop resistance.
  • the ultraviolet light is irradiated for a period of time such that the curable composition is substantially completely cured, usually in the order of several minutes.
  • the present invention also provides an adhesive tape comprising the above pressure sensitive adhesive.
  • the above pressure sensitive adhesive can be formed into a tape form for application.
  • the tape of the present invention may include a backing and the above pressure sensitive adhesive formed on the backing.
  • the above curable composition can be applied to a backing and then cured by irradiation with ultraviolet light to obtain an adhesive tape comprising a backing and the above pressure sensitive adhesive.
  • the curable composition may be coated on a separable temporary substrate (such as a release film) and cured by ultraviolet light to form a film, after which the pressure-sensitive adhesive film is transferred to other backings. on.
  • the above method for coating the curable composition includes, but is not limited to, roll coating, flow coating, dip coating, spin coating, spray coating, blade coating, die coating, etc., which will not be described in detail herein;
  • the thickness of the dry glue i.e., pressure sensitive adhesive
  • the thickness of the dry glue is typically from 50 microns to 500 microns, more preferably at least 100 microns, or at least 200 microns, and preferably has a thickness of up to 400 microns, or up to 300 microns.
  • the backing is preferably flexible, which may comprise plastics such as polyolefins such as polyethylene, polypropylene (including isotactic polypropylene), polystyrene, polyester, polyvinyl alcohol, poly(terephthalic acid). Ethylene glycol), poly(butylene terephthalate), poly(caprolactam), poly(vinylidene fluoride), polylactide, cellulose acetate, ethyl cellulose, etc.;
  • the surface may also be provided with a specific microreplicated structure to improve the performance of the tape.
  • the microreplicated structure can be as described in U.S. Patent No. 5,141,790, U.S. Patent 5,296,277, U.S. Pat.
  • the backing may also be a fabric such as cotton, nylon, rayon, glass thread, ceramic wire or the like.
  • the backing may also be a nonwoven fabric, such as a nonwoven fabric obtained by air laying a natural fiber and/or a synthetic fiber.
  • the backing may be provided with the above-mentioned pressure-sensitive adhesive on one side and no adhesive or other adhesive on the other side; or, both sides of the backing may have the above The pressure sensitive adhesive, so that the tape becomes a double sided tape.
  • the backing it may be a pressure-sensitive adhesive having only the present invention, or may have other known adhesives at the same time.
  • the pressure sensitive adhesive of the present invention is directly in contact with the backing, and the other side is provided with other known adhesives (ie, the pressure sensitive adhesive of the present invention functions as an intermediary); or It is also possible that other known pressure sensitive adhesives are in direct contact with the backing, and the outer side of the adhesive is provided with the adhesive of the present invention (i.e., the pressure sensitive adhesive of the present invention directly acts as a bonding agent).
  • the backing may also be composed of the pressure sensitive adhesive of the present invention; preferably, other known adhesives may be provided on one or both sides of the backing.
  • the pressure-sensitive adhesive of the present invention (especially a pressure-sensitive adhesive having a foaming property) can also be used as a backing, which can be present alone, thereby forming a "adhesive film" having a viscosity on both sides.
  • the backing may be used with other adhesives, i.e., other known adhesives may be provided on one or both sides thereof.
  • the pressure sensitive adhesive of the present invention can be used as a separate film (backing or foam), or as a backing with tape with other adhesives, or as an adhesive. On the backing.
  • a release film or release paper may also be provided for avoiding accidental bonding when not in use.
  • the form of release film or release paper is well known and diverse, such as silicone coated kraft paper, glassine paper, lathered kraft paper, poly(ethylene terephthalate), and the like.
  • the pressure sensitive adhesive when the film composed of the pressure sensitive adhesive is directly in contact with the release film or the release paper, the pressure sensitive adhesive may be directly formed on the release film or the release paper.
  • the present invention also provides an adhesive article comprising a first component to which at least a portion of the surface of the first component is bonded with the pressure sensitive adhesive described above.
  • the present invention provides an adhesive article comprising the above pressure-sensitive adhesive such that the adhesive article can be bonded to other products by the above pressure-sensitive adhesive, or a plurality of adhesive articles
  • the components can be bonded together by the pressure sensitive adhesive described above.
  • the above bonded article further comprises a second member, the first member and the second member being bonded together by the pressure sensitive adhesive described above.
  • the plurality of components in the bonded article can be bonded together by the pressure sensitive adhesive described above.
  • the pressure sensitive adhesive can be used as a separate film (backing or foam), or as a backing with tape with other adhesives, or as an adhesive. On other backings.
  • the above adhesive article is any one of a mobile terminal, a tablet computer, and a notebook computer; the first component is a casing; and the second component is a display panel.
  • the pressure-sensitive adhesive of the present invention is preferably used for bonding a display panel of a mobile terminal (mobile phone), a tablet computer, a notebook computer or the like to a casing. This is because these products tend to fall off accidentally, so the drop resistance of the pressure sensitive adhesive is important.
  • a monomer component comprising at least two polymerizable monomers, the polymerizable monomer comprising a (meth) acrylate monomer other than a tertiary alcohol, an acid functional non-ester unsaturated monomer having at least one olefinic bond;
  • At least one block copolymer the block copolymer being an elastomer comprising at least two A blocks at each end and at least one B block in the middle; wherein the A block is methyl
  • the acrylate monomer is formed by polymerization, and the B block is formed by polymerization of an acrylate monomer.
  • the block copolymer is a triblock copolymer of an A block-B block-A block structure.
  • the A block is formed by polymerization of an alkyl methacrylate monomer; the B block is formed by polymerization of an alkyl acrylate monomer.
  • the alkyl methacrylate monomer has an alkyl group having from 1 to 6 carbon atoms; and the alkyl acrylate monomer has an alkyl group having from 3 to 20 carbon atoms. And the alkyl group of the alkyl methacrylate monomer has a carbon number smaller than that of the alkyl group of the alkyl acrylate monomer.
  • the alkyl methacrylate monomer is a methyl methacrylate monomer; and the alkyl acrylate monomer is a n-butyl acrylate monomer.
  • the block copolymer has a weight average molecular weight between 2000 Daltons and 500,000 Daltons.
  • the block copolymer has a weight average molecular weight of between 40,000 Daltons and 120,000 Daltons.
  • the weight percentage of the A block is between 5% and 50%; and the weight percentage of the B block is between 50% and 95%.
  • the weight percentage of the A block is between 20% and 30%; and the weight percentage of the B block is between 70% and 80%. .
  • the curable composition further comprises: a (meth) acrylate copolymer formed by copolymerization of a raw material comprising at least two polymerizable monomers, including: a non-tertiary alcohol (A) a acrylate monomer, an acid functional non-ester unsaturated monomer having at least one olefinic bond; the (meth) acrylate copolymer having a weight average molecular weight of between 500,000 Daltons and 10,000,000 Daltons.
  • a (meth) acrylate copolymer formed by copolymerization of a raw material comprising at least two polymerizable monomers, including: a non-tertiary alcohol (A) a acrylate monomer, an acid functional non-ester unsaturated monomer having at least one olefinic bond; the (meth) acrylate copolymer having a weight average molecular weight of between 500,000 Daltons and 10,000,000 Daltons.
  • the monomer component and the (meth) acrylate copolymer constitute a slurry polymer; the slurry polymer is formed by partially copolymerizing a raw material comprising at least two polymerizable monomers, the polymerizable
  • the monomer includes a (meth) acrylate monomer other than a tertiary alcohol, and an acid functional non-ester unsaturated monomer having at least one olefinic bond.
  • the non-tertiary alcohol (meth) acrylate monomer is contained in an amount of 50% to 99.5% by weight; the acid The functional non-esterically unsaturated monomer having at least one ethylenic bond is present in an amount between 0.5% and 15% by weight.
  • the non-uncle The weight percentage of the (meth) acrylate monomer of the alcohol is between 95% and 99.5%; the weight percentage of the acid functional non-ester unsaturated monomer having at least one olefinic bond is 0.5% to Between 5%.
  • the polymerizable monomer for forming the slurry polymer further comprises: a non-acid functional ethylenically unsaturated polar monomer having a weight percentage of less than or equal to 45%; and the non-acid a functional ethylenically unsaturated polar monomer different from the non-tertiary alcohol (meth) acrylate monomer; and/or a vinyl monomer, the weight percentage being less than or equal to 5%;
  • the vinyl monomer is different from the (meth) acrylate monomer of the non-tertiary alcohol, the acid-functional non-ester unsaturated monomer having at least one olefinic bond, and the non-acid functional ethylenically unsaturated polar monomer .
  • the copolymerizable monomer which has undergone copolymerization to form the (meth) acrylate copolymer has a weight percentage of from 1% to 30% Between %; the viscosity of the slurry polymer at 22 ° C is between 500 centipoise to 10,000 centipoise.
  • the weight ratio of the elastomer is between 0.1% and 55% with respect to the total weight of the monomer component and the polymerizable monomer used to form the (meth) acrylate copolymer.
  • the weight ratio of the elastomer is between 0.5% and 30% with respect to the total weight of the monomer component and the polymerizable monomer used to form the (meth) acrylate copolymer.
  • the weight ratio of the elastomer is between 0.5% and 20% with respect to the total weight of the monomer component and the polymerizable monomer used to form the (meth) acrylate copolymer.
  • the monomer component further comprises: a non-acid functional ethylenically unsaturated polar monomer; and the non-acid functional ethylenically unsaturated polar monomer is different from the non-tertiary alcohol a (meth) acrylate monomer; and/or a vinyl monomer; and the vinyl monomer is different from the (meth) acrylate monomer of the non-tertiary alcohol, and has at least one olefinic bond of an acid function Non-ester unsaturated monomer, non-acid functional ethylenically unsaturated polar monomer.
  • the curable composition further comprises: a photoinitiator; and/or a crosslinking agent.
  • the curable composition further comprises any one or more of the following components: a tackifying resin; a black pigment; an expanded polymeric microsphere.
  • Embodiments of the present invention also provide a pressure sensitive adhesive formed by curing of a curable composition, wherein the curable composition comprises:
  • a monomer component comprising at least two polymerizable monomers, the polymerizable monomer comprising a (meth) acrylate monomer other than a tertiary alcohol, an acid functional non-ester unsaturated monomer having at least one olefinic bond;
  • At least one block copolymer the block copolymer being an elastomer comprising at least two A blocks at each end and at least one B block in the middle; wherein the A block is methyl
  • the acrylate monomer is formed by polymerization, and the B block is formed by polymerization of an acrylate monomer.
  • Embodiments of the present invention also provide an adhesive tape comprising a pressure sensitive adhesive formed by curing of a curable composition, wherein the curable composition comprises:
  • a monomer component comprising at least two polymerizable monomers, the polymerizable monomer comprising a (meth) acrylate monomer other than a tertiary alcohol, an acid functional non-ester unsaturated monomer having at least one olefinic bond;
  • At least one block copolymer the block copolymer being an elastomer comprising at least two A blocks at each end and at least one B block in the middle; wherein the A block is methyl
  • the acrylate monomer is formed by polymerization, and the B block is formed by polymerization of an acrylate monomer.
  • the tape comprises a backing and the pressure sensitive adhesive disposed on at least one side of the backing; or the tape comprises a backing comprised of the pressure sensitive adhesive.
  • Embodiments of the present invention also provide an adhesive article comprising a first component having at least a portion of its surface adhered with a pressure sensitive adhesive cured by a curable composition Forming, wherein the curable composition comprises:
  • a monomer component comprising at least two polymerizable monomers, the polymerizable monomer comprising a (meth) acrylate monomer other than a tertiary alcohol, an acid functional non-ester unsaturated monomer having at least one olefinic bond;
  • At least one block copolymer the block copolymer being an elastomer comprising at least two A blocks at each end and at least one B block in the middle; wherein the A block is methyl
  • the acrylate monomer is formed by polymerization, and the B block is formed by polymerization of an acrylate monomer.
  • the adhesive article further comprises: a second component, the second component and the first component being bonded together by the pressure sensitive adhesive.
  • the adhesive article is any one of a mobile terminal, a tablet computer, and a notebook computer; the first component is a casing; and the second component is a display panel.
  • the present invention is exemplarily illustrated by using different formulations and parameters to prepare different curable compositions, pressure sensitive adhesives, tapes as examples and comparative examples.
  • the monomer conversion rate of the slurry polymer is tested by a weight loss method, which specifically includes: weighing a certain weight of the test object into an aluminum pan, and baking 60 ⁇ 30 at a temperature of 105 ⁇ 3° C. in a forced convection oven. In minutes, the unpolymerized polymerizable monomer was evaporated, the residue was taken out and cooled for 5 minutes, and then weighed, and the monomer conversion rate was calculated according to the following formula:
  • M1 is the total weight of the test object before baking
  • M2 is the total weight of the test object (residue) after baking
  • neither M1 nor M2 includes the weight of the aluminum pan.
  • Specific test methods for weight average molecular weight include: weigh 0.1 gram of the sample into a 5 ml sample vial, add 3 ml of tetrahydrofuran (TEDIA Co., Ltd., Ohio, USA) for dissolution; and use the solution with a 0.45 ⁇ m pore size filter membrane. After filtration, it was added to the sample vial; it was tested with a chromatograph (Waters, Maryland, USA). The resulting column was calibrated using standard known weight average molecular weight polystyrene and the calibration curve was established by linear least squares analysis. A weight average molecular weight is obtained.
  • TEDIA Co., Ltd., Ohio, USA tetrahydrofuran
  • the test for drop resistance includes the following steps:
  • PMMA sheet Two sheets of polymethyl methacrylate (PMMA) sheet (hereinafter referred to as PMMA sheet) having a size of 108 mm ⁇ 57 mm ⁇ 6 mm and weighing 38 g; Purchased from Sinopharm Chemical Reagent Co., Ltd., Shanghai, China), wipe the PMMA plate three times and ensure that the solvent is completely evaporated; use a cutting knife to carefully cut two 1.5 mm ⁇ 150 mm tape from the tape to be tested.
  • PMMA sheet polymethyl methacrylate
  • the slurry polymer is one of the components in the curable composition, and in the present invention, a slurry polymer is prepared as a raw material of the curable composition in the following manner.
  • the specific preparation method of the slurry polymer comprises: feeding a 1-quart wide-mouth glass bottle according to the monomer type and weight listed in the table, and adding a photoinitiator IRGACURE 651, wherein 100 parts by weight is used for the slurry.
  • the polymerizable monomer of the polymer, at this time, IRGACURE 651 was added in an amount of 0.04 parts by weight (subsequent part of the photoinitiator was directly added to the curable composition); the raw material was purged with nitrogen for 15 minutes under magnetic stirring, and then exposed.
  • the total amount of the monomer raw materials of each of the slurry polymers is 100 parts by weight, and the slurry polymers selected in the subsequent examples and comparative examples are also 100 parts by weight of the polymerizable polymer.
  • the monomers are prepared, and the amounts of other substances are also based on them.
  • the curable compositions of the respective examples and comparative examples were prepared according to different formulations and used to form pressure sensitive adhesives, tapes to test properties.
  • An S1 slurry polymer composed of 100 parts by weight of a polymerizable monomer was added to a 1 quart wide-mouth glass bottle, and then other materials were added according to the following table, and stirred until uniform to dissolve to form a comparative example C1-C5 and Examples A curable composition of 1-14.
  • the photoinitiator IRGACURE 651 in the table refers to a photoinitiator directly added to the curable composition, which together with the above photoinitiator (0.04 parts by weight) added to the slurry polymer raw material constitutes the above photoinitiator component.
  • the photoinitiators of the other examples below are the same as herein.
  • the curable composition of each of the above examples was applied between two release films of 0.05 mm film of CP Film T10 PET (available from Solutia, Tennessee, USA), and the thickness of the film was controlled to be 0.15 mm, irradiated with the aforementioned low-intensity ultraviolet light (365 nm, 1.5 mW/cm 2 ) for 5 minutes to 10 minutes to obtain a film.
  • the coating compositions C1-C4 and the curable compositions of Examples 1-9 were coated with a layer of Cerex 23030 nylon fabric (Cerex Performance Fiber Co., Ltd., Florida, US) as a backing.
  • a primer is applied on both sides of the above film, and the primer is a solution having a solute weight percentage of 10%, wherein the solute is Macromelt 6240 (Henkel, Düsseldorf, Germany), solvent Including: 47.5 parts by weight of isopropanol (National Pharmaceutical Group Chemical Reagent Co., Ltd., Shanghai, China), 47.5 parts by weight of n-propanol (National Pharmaceutical Group Chemical Reagent Co., Ltd., Shanghai, China), 5 parts by weight of water. After drying at 80 ° C for 10 minutes, an undercoat layer having a thickness of 5 ⁇ m to 10 ⁇ m was obtained. Conventional pressure-sensitive adhesive tape 9482PC (0.05M, thickness) of 0.05 mm is laminated on the undercoat layers on both sides. Minnesota, USA), hand-pressed using a 2 kg rubber roller to prepare a double-sided tape with a total thickness of 0.25 mm.
  • solute is Macromelt 6240 (Henkel, Düsseldorf, Germany)
  • solvent Including: 47.5 parts by weight of is
  • the tape prepared above mainly comprises two different structures: the first one (Comparative Examples C1-C4, Examples 1-9) is provided with the pressure sensitive of the present invention sequentially on a nylon backing (Cerex 23030). Adhesive and existing adhesive (pressure sensitive tape 9482PC); second (Comparative Example C5, Examples 10-14) is provided with existing bonding on the backing of the pressure sensitive adhesive of the present invention Agent (pressure sensitive tape 9482PC).
  • Example 2 a sample in which the pressure-sensitive adhesive tape 9482PC and the nylon backing were not provided (of course, no primer) was prepared, that is, it was a simple pressure-sensitive adhesive of the present invention.
  • the film of the agent (referred to as "film").
  • Example 7 a sample in which only one side of the pressure-sensitive adhesive tape 9482PC (of course, one side only had a primer) was prepared (indicated as "single-sided adhesive"), That is, the surface on the other side is the pressure sensitive adhesive of the present invention.
  • Example 7 a sample in which the pressure-sensitive adhesive tape 9482PC and the nylon backing were not provided (of course, no primer) was prepared, that is, it was a simple pressure-sensitive adhesive of the present invention.
  • the film of the agent (referred to as "film").
  • a comparative example C6 which comprises: overlaying pressure sensitive on both sides of black polyethylene (PE) foam (Hubei Xiangyuan New Material Technology Co., Ltd., Xiaogan City, Hubei province, China) with a thickness of 0.15 mm.
  • PE polyethylene
  • Tape 9482PC double-sided corona treatment (Softal corona machine, Hamburg, Germany) before bonding, so that the surface energy is greater than 52 dynes/cm, and hand-pressed with a rubber roller weighing 2 kg to ensure the glue
  • the film and polyethylene foam are completely conformable.
  • the curable composition was applied between the release faces of two CP Film T10 PET transparent release films having a thickness of 0.05 mm, and the thickness of the control film was 0.1 mm, and the low-intensity ultraviolet light was irradiated for 5 minutes to 10 minutes. Minutes, get the film.
  • a primer layer is formed on each side of the film in accordance with the above method.
  • a pressure-sensitive adhesive tape 9458 (3M Company, Minnesota, USA) having a thickness of 0.025 mm was laminated on the undercoat layers on both sides, and a total thickness of 0.15 mm was prepared by hand-pressing using a 2 kg weight rubber roller. double-sided tape.
  • a comparative example C8 is further added, which comprises: corona treatment of black polyethylene foam (Hubei Xiangyuan New Material Technology Co., Ltd., Xiaogan City, Hubei province, China) having a thickness of 0.1 mm according to the above method, and then The pressure sensitive adhesive tape 9458 is respectively covered on both sides thereof.
  • black polyethylene foam Hubei Xiangyuan New Material Technology Co., Ltd., Xiaogan City, Hubei province, China
  • the block copolymer (elastomer) was not completely dissolved at all, and thus a uniform product could not be formed, and thus the properties were not tested.
  • the drop resistance of the pressure-sensitive adhesive can be greatly improved after the addition of the specific block copolymer (elastomer) of the present invention.
  • the curable composition was applied between the release faces of two CP Film T10 PET transparent release films having a thickness of 0.05 mm, and the thickness of the control film was 0.2 mm, and the low-intensity ultraviolet light was irradiated for 5 minutes to 10 minutes. Minutes, get the film.
  • a primer layer is formed on each side of the film in accordance with the above method.
  • a pressure-sensitive adhesive tape 467MP (3M Company, Minnesota, USA) having a thickness of 0.05 mm was laminated on both sides of the undercoat layer, and a total thickness of 0.3 mm was prepared by hand-pressing using a 2 kg weight rubber roller. double-sided tape.
  • the drop resistance of the pressure-sensitive adhesive can be greatly improved after the addition of the specific block copolymer (elastomer) of the present invention.
  • composition of the curable composition of Table 9 Comparative Example C10 and Examples 21-24 (in parts by weight)
  • the curable composition to two CP Film T10 PET transparent with a thickness of 0.05 mm Between the release faces of the release film, the thickness of the control film is 0.25 mm, and the film is obtained by irradiating with the aforementioned low-intensity ultraviolet light for 5 minutes to 10 minutes.
  • a primer layer is formed on each side of the film in accordance with the above method.
  • a pressure-sensitive adhesive tape 467MP (3M Company, Minnesota, USA) having a thickness of 0.05 mm was laminated on both sides of the undercoat layer, and a total thickness of 0.35 mm was prepared by hand-pressing using a 2 kg weight rubber roller. double-sided tape.
  • the block copolymer (elastomer) was not completely dissolved at all, and thus a uniform product could not be formed, and thus the properties were not tested.
  • the drop resistance of the pressure-sensitive adhesive can be greatly improved after the addition of the specific block copolymer (elastomer) of the present invention.
  • the curable composition was applied between the release faces of two CP Film T10 PET transparent release films having a thickness of 0.05 mm, and the thickness of the control film was 0.3 mm, and the low-intensity ultraviolet light was irradiated for 5 minutes to 10 minutes. Minutes, get the film.
  • a primer layer is formed on each side of the film in accordance with the above method.
  • Pressure-sensitive adhesive tapes 467MP and 9482PC (3M Company, Minnesota, USA) having a thickness of 0.05 mm were laminated and hand-pressed using a 2 kg weight rubber roller to prepare a double-sided tape having a total thickness of 0.4 mm.
  • the drop resistance of the pressure-sensitive adhesive can be greatly improved after the addition of the specific block copolymer (elastomer) of the present invention.
  • the components are fused to each other, so when they are added, the impact force can be absorbed in a large amount at the time of dropping, thereby reducing the impact on other positions and improving the drop performance of the pressure-sensitive adhesive.
  • the above analysis does not constitute a limitation on the principle of action of the present invention.
  • the acrylate pressure sensitive adhesive such as tackifying resins, black pigments, expanded polymeric microspheres, vinyl monomers, non-acid functional ethylenically unsaturated polarities
  • the use of the specific block copolymer (elastomer) of the present invention all has an effect of improving the drop resistance of the pressure-sensitive adhesive.
  • the pressure sensitive adhesive eg, as a separate film or foam, as a backing for tape, as an adhesive on a tape backing, as a single-sided or double-sided adhesive, Use alone Or with other known adhesives, etc.
  • the block copolymer (elastomer) in the curable composition is particularly high and cannot be too high, and the upper limit of the content is also related to other components.
  • each of the examples using the slurry polymer S1 as a whole has better drop resistance.
  • the raw material of the slurry polymer has a higher (meth) acrylate monomer content of the non-tertiary alcohol (eg, from 95% to 99.5%) and a lower acid-functional non-ester having at least one olefinic bond.
  • Saturated monomer content e.g., from 0.5% to 5%

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Abstract

可固化组合物、压敏粘合剂、胶带、粘合制品，属于压敏粘合剂技术领域，其可解决现有的压敏粘合剂的抗跌落性能不足的问题。可固化组合物包括：单体组分，包括至少两种可聚合单体，所述可聚合单体包括非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体；至少一种嵌段共聚物，所述嵌段共聚物属于弹性体，其包括至少两个分别位于两端的A嵌段和至少一个位于中间的B嵌段；其中，所述A嵌段由甲基丙烯酸酯单体聚合形成，所述B嵌段由丙烯酸酯单体聚合形成。

Description

可固化组合物、压敏粘合剂、胶带、粘合制品 技术领域
本发明属于丙烯酸酯压敏粘合剂技术领域，具体涉及一种可固化组合物、压敏粘合剂、胶带、粘合制品。
背景技术
压敏粘合剂(PSA，Pressure Sensitive Adhesive)是一种压力敏感型的胶粘剂，其无需借助于溶剂、加热等其它手段，而只需依靠施加指压的轻度压力即可与被粘物产生牢固的粘结。丙烯酸酯压敏粘合剂是压敏粘合剂的一种重要类型，其具有耐候性好、性价比高、透明性好、内聚强度高、粘结力高、适用表面广等特点。
丙烯酸酯压敏粘合剂常被用于消费电子产品中。例如，在移动终端(手机)、平板电脑、笔记本电脑等中，可用丙烯酸酯压敏粘合剂(如丙烯酸酯泡棉双面胶带)将显示面板粘结在壳体上。
随着窄边框、无边框设计的流行，以上设备中丙烯酸酯泡棉双面胶带的宽度越来越小，而显示面板的尺寸和重量却越来越大，这就对丙烯酸酯压敏粘合剂的抗跌落性能提出了更高的要求。也就是说，当手机等意外跌落时，显示面板与壳体间不能因为跌落的冲击而分离。
但是，现有丙烯酸酯压敏粘合剂的抗跌落性能往往不能满足要求。
发明内容
本发明的一个目的是提供一种可固化组合物，由该可固化组合物固化形成的压敏粘合剂具有优异的抗跌落性能。
本发明的可固化组合物包括：
单体组分，包括至少两种可聚合单体，所述可聚合单体包括非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体；
至少一种嵌段共聚物，所述嵌段共聚物属于弹性体，其包括至少两个分别位于两端的A嵌段和至少一个位于中间的B嵌段；其中，所述A嵌 段由甲基丙烯酸酯单体聚合形成，所述B嵌段由丙烯酸酯单体聚合形成。
优选的，以上嵌段共聚物为A嵌段-B嵌段-A嵌段结构的三嵌段共聚物。
优选的，所述A嵌段由甲基丙烯酸甲酯单体聚合形成；所述B嵌段由丙烯酸正丁酯单体聚合形成。
优选的，所述可固化组合物还包括：(甲基)丙烯酸酯共聚物，其由包括至少两种可聚合单体的原料共聚形成，所述可聚合单体包括：非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体；所述(甲基)丙烯酸酯共聚物的重均分子量在500000道尔顿至10000000道尔顿之间。
更优选的，所述单体组分和所述(甲基)丙烯酸酯共聚物构成浆液聚合物；所述浆液聚合物由包括至少两种可聚合单体的原料部分共聚形成，所述可聚合单体包括非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体。
本发明的另一个目的是提供一种压敏粘合剂，其由上述可固化组合物固化形成，从而具有良好的抗跌落性能。
本发明的另一个目的是提供一种胶带，其包括上述的压敏粘合剂，从而具有良好的抗跌落性能。
本发明的另一个目的是提供一种粘合制品，其包括上述的压敏粘合剂，从而具有良好的抗跌落性能。
优选的，所述粘合制品为移动终端、平板电脑、笔记本电脑中的任意一种；且其中的壳体和显示面板通过上述的压敏粘合剂粘结在一起。
附图说明
图1为本发明实施例的抗跌落性能测试方法的示意图。
具体实施方式
为使本领域技术人员更好地理解本发明的技术方案，下面结合附图和具体实施方式对本发明作进一步详细描述。
用语解释
在本发明中，下列术语或描述方式的意义如下：
“A和/或B”的描述表示其中任意一种或两种同时的情况都可能发生，即包括“A和B”、“A”、“B”三种情况。
“A至B”或“A至B之间”的描述包括A的值、B的值，以及任何大于A并小于B的值；例如，1至10包括1、10，以及任何大于1并小于10的值，如2、3、4、5、6、7、8、9、2.3、3.5、5.26、7.18、9.999等。
“A基本为B”、“A约为B”的描述表示A从整体上看是符合B条件的，但与B间又可能存在一定的差别，且该差别在B的尺度上看是很小的。
“粘度”，如无特别说明，本发明中所称的粘度均是用乌氏粘度计测量得到的。
“分子量”，如无特别说明，则本发明中所称的分子量均为重均分子量，且均是通过凝胶气相色谱方法(GPC)得到的。
“玻璃化转变温度(Tg)”，是指聚合物在高弹态与玻璃态之间转变时的温度，也即聚合物的无定形部分从冻结状态到解冻状态时的温度。如无特别说明，本发明中所称的玻璃化转变温度均是通过差示扫描量热法(DSC)测定的。
“单体的玻璃化转变温度”是指相应单体的均聚物的玻璃化转变温度。
“物质用量”，如无特别说明，则本发明中物质的用量或用量比均指重量或重量比。
“在A中B的重量百分含量”是指B是属于A的一部分，当以A(包括B)的重量为100％时，其中B的重量所占的百分比。
“相对于A的重量，B的重量比例”是指B不属于A，当以A(不包括B)的重量为100％时，B的重量相对于A的重量的百分比。
“弹性体”是指在发生较大变形后仍可基本恢复为原始形状的聚合物材料，或者说弹性变形范围较大的材料；例如，在被拉伸为原始长度两倍后释放仍可基本恢复原始长度的聚合物材料。
“(甲基)丙烯酸”的描述代表丙烯酸和甲基丙烯酸两种情况。
“(甲基)丙烯酸酯”的描述代表(甲基)丙烯酸酯和甲基丙烯酸酯两种 情况，即(甲基)丙烯酸及其同系物的酯类的总称，具体可选的例子包括丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯等。
“叔醇”是指羟基所在的碳原子上所连接的其它三个基团均为非氢原子的取代基的醇；“非叔醇”则指不属于叔醇的醇。
“聚合物”是指由一种或多种可聚合单体发生聚合反应而形成的物质，其包括均聚物、共聚物、三聚物等。
“共聚物”是指由至少两种不同的可聚合单体聚合形成的聚合物，即其是除均聚物以外所有的聚合物，包括无规共聚物、嵌段共聚物、接枝共聚物、交替共聚物以及它们的混合等。
“嵌段共聚物”又称镶嵌共聚物，是由两种或两种以上不同聚合物链段连在一起形成的聚合物，其中每个聚合物链段为由相同可聚合单体聚合形成的连续的链，其称为“嵌段”；由于其特定的结构，故多数嵌段共聚物都属于弹性体。
“三嵌段共聚物”是指由三个嵌段组成的嵌段共聚物，更进一步是指由两个A嵌段和一个B嵌段构成的嵌段共聚物。
“部分共聚”是指作为原料的可聚合单体中有一部分已经发生共聚而形成了共聚物，同时，还有一部分可聚合单体仍未发生聚合，保持单体的形式。
“固化”是指液态物质通过其中组分的聚合和/或交联而由液态转变为具有粘弹特性的固态的过程。
“压敏粘合剂”是指可粘结在基体上的物质，且其至少在环境温度(5℃至40℃)下满足以下条件：(1)具有持久的粘性；(2)在用手指按压的压力下就能实现粘结；(3)能改变形状以附着在基体上；(4)其内聚强度足以使其从粘附体上基本干净的移除。
“胶带”是指可粘结在基体上或可将两个基体粘结在一起的形状基本为带状的产品。
可固化组合物
本发明提供一种可固化组合物，该可固化组合物可固化形成具有优异抗跌落性能的压敏粘合剂，尤其是通过紫外光固化。
本发明的可固化组合物包括：
单体组分，包括至少两种可聚合单体，可聚合单体包括非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体；
至少一种嵌段共聚物，嵌段共聚物属于弹性体，其包括至少两个分别位于两端的A嵌段和至少一个位于中间的B嵌段；其中，A嵌段由甲基丙烯酸酯单体聚合形成，B嵌段由丙烯酸酯单体聚合形成。
本发明的可固化组合物包括(甲基)丙烯酸酯单体，其是用于形成丙烯酸酯压敏粘合剂的主要组分，从而本发明的可固化组合物形成的压敏粘合剂属于丙烯酸酯压敏粘合剂。
同时，可固化组合物中还包括聚丙烯酸酯类弹性体，该弹性体为嵌段共聚物，且嵌段共聚物的两端具有由甲基丙烯酸酯单体聚合形成的A嵌段，而中间则至少有一个由丙烯酸酯单体聚合形成的B嵌段。
发明人创造性的发现，在(甲基)丙烯酸酯单体中添加以上的丙烯酸酯类弹性体(嵌段共聚物)，可使由该可固化组合物固化形成的压敏粘合剂具有良好的性能，尤其是优异的抗跌落性能。
其中，优选的，可固化组合物中还可包括(甲基)丙烯酸酯共聚物，其由包括至少两种可聚合单体的原料共聚形成，可聚合单体包括：非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体；(甲基)丙烯酸酯共聚物的重均分子量在500000道尔顿至10000000道尔顿之间。
也就是说，可固化组合物中还可包括(甲基)丙烯酸酯共聚物，其可由与以上单体组分相同种类的原料聚合形成；当存在以上的共聚物时，有利于改善可固化组合物所形成的压敏粘合剂的质量，尤其是可调节可固化组合物的粘度，因为如果可固化组合物中单体组分的含量过大，则粘度太低，在形成压敏粘合剂时工艺上较困难。当然，由于以上单体组分共聚后形成的实际也是(甲基)丙烯酸酯共聚物，故若可固化组合物中没有(甲基)丙烯酸酯共聚物，而直接由单体组分在固化时聚合形成压敏粘合剂，理论上也是可行的。
更优选的，以上单体组分和(甲基)丙烯酸酯共聚物可组成浆液聚合物， 浆液聚合物由包括至少两种可聚合单体的原料部分共聚形成，可聚合单体包括非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体。
也就是说，可用包括上述可聚合单体的原料进行部分共聚，从而形成由单体和共聚物构成的混合物，也就是浆液聚合物。浆液聚合物中，部分可聚合单体已经发生了共聚而形成共聚物，其即为以上的(甲基)丙烯酸酯共聚物；同时，还有部分可聚合单体仍未发生聚合而保持单体的形式，其即为以上的单体组分。在浆液聚合物中，未发生聚合的可聚合单体作为溶剂，将作为溶质的共聚物溶解在其中，从而形成匀相体系。
使用浆液聚合物的优点在于，可用同样的原料直接得到合适的单体组分和(甲基)丙烯酸酯共聚物，而不用单独制备不同的单体组分和(甲基)丙烯酸酯共聚物。
显然，当单体组分和(甲基)丙烯酸酯共聚物采用浆液聚合物的形式时，二者必然是由相同的原料形成的；但其并不表示单体组分和(甲基)丙烯酸酯共聚物的实际成分相同，因为在共聚过程中，不同可聚合单体发生共聚的速度和顺序有可能不同；进一步的，如果是用分别单独制备的单体组分和(甲基)丙烯酸酯共聚物配置浆液聚合物，也不要求二者的原料完全相同。
下面对各组分的作用、可选物质、含量等进行介绍。
为简便，以下单体组分和(甲基)丙烯酸酯共聚物采用浆液聚合物的形式描述，但应当理解，其并非对本发明的限定。
1、浆液聚合物
1)浆液聚合物的性质
浆液聚合物为由包括至少两种可聚合单体的原料部分共聚形成的混合物，该混合物包括未发生聚合的可聚合单体(即单体组分)以及由可聚合单体共聚形成的共聚物(即(甲基)丙烯酸酯共聚物)。由于浆液聚合物中的可聚合单体只是部分共聚，故其没有发生交联或仅有极少部分的交联，由此其中的共聚物仍可溶解在未聚合的可聚合单体中；所以，浆液聚合物整体上是液态的均相体系，具有流动性，便于进行涂布等操作。
优选的，浆液聚合物中的(甲基)丙烯酸酯共聚物的重均分子量优选在 500000道尔顿(Daltons，克/摩尔)至10000000道尔顿之间，更优选在750000道尔顿至6000000道尔顿之间。具体的，该浆液聚合物中已经形成的共聚物的重均分子量至少可为500000道尔顿厘泊，或至少为750000道尔顿，或至少为1000000道尔顿；而该重均分子量至多可为10000000道尔顿，或至多为6000000道尔顿，或至多为5000000道尔顿。
优选的，浆液聚合物在22℃时的粘度优选在500厘泊(cps)至10000厘泊之间，更优选在500厘泊至7000厘泊之间。具体的，该浆液聚合物的粘度至少可为500厘泊，或至少为1500厘泊，或至少为2500厘泊；而该粘度至多可为10000厘泊，或至多为7000厘泊，或至多为5500厘泊。
优选的，在用于形成浆液聚合物的可聚合单体中，已发生聚合的可聚合单体的重量的比例在1％至30％之间。也就是说，若以用于形成浆液聚合物的全部可聚合单体的原料为100重量份，则其中已经发生聚合而变成共聚物的可聚合单体的量在1重量份至30重量份，而未发生聚合的可聚合单体在70重量份至99重量份，或者说单体转化率在1％至30％。具体的，以上单体转化率至少可为1％，或至少为2％，或至少为5％，或至少为7％；而该单体转化率至多可为30％，或至多为20％，或至多为15％，或至多为12％。
具有以上粘度、重均分子量、单体转化率的浆液聚合物比较适用于可固化组合物。
2)用于形成浆液聚合物的可聚合单体
以上用于形成浆液聚合物的可聚合单体包括非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体：且优选还可包括非酸官能的烯键式不饱和极性单体和/或乙烯基单体。
也就是说，浆液聚合物优选是由包括以上可聚合单体的原料部分共聚形成的；由此，可固化组合物的单体组分中自然也包括这些可聚合单体，而可固化组合物中的(甲基)丙烯酸酯共聚物也是由这些可聚合单体共聚形成的。
下面，对各可聚合单体进行进一步的介绍。
(1)非叔醇的(甲基)丙烯酸酯单体
优选的，用于形成该非叔醇的(甲基)丙烯酸酯单体的非叔醇中的碳原子数在1个至20个之间，更优选在2个至18个，进一步优选在4个至12个。
用于形成以上非叔醇的(甲基)丙烯酸酯单体的非叔醇的链段可以是直链，也可带有支链或是两者的组合。具体的，以上非叔醇包括但不限于：甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、1-戊醇、2-戊醇、3-戊醇、2-甲基-1-丁醇、3-甲基-1-丁醇、1-己醇、2-己醇、2-甲基-1-戊醇、3-甲基-1-戊醇、2-乙基-1-丁醇、3，5，5-三甲基-1-己醇、3-庚醇、1-辛醇、2-辛醇、异辛醇、2-乙基-1-己醇、1-癸醇、2-丙基庚醇、1-十二烷醇、1-十三烷醇、1-十四烷醇中的任意一种或多种。虽然以上的非叔醇都是适用的，但在一些优选的实施方式中，非叔醇优选为丁醇、异辛醇、2-乙基己醇中的任意一种或多种(相应的酯即为(甲基)丙烯酸异辛酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸丁酯)；而在另一些优选的实施方式中，非叔醇是衍生自可再生来源的醇，如2-辛醇、香茅醇、二氢香茅醇中的任意-种或多种。
在用于形成浆液聚合物的可聚合单体(即单体组分和用于形成(甲基)丙烯酸酯共聚物的可聚合单体)中，非叔醇的(甲基)丙烯酸酯单体的重量百分含量在50％至99.5％之间。
也就是说，在每100重量份的用于形成浆液聚合物的可聚合单体中，以上非叔醇的(甲基)丙烯酸酯单体优选占50重量份至99.5重量份，更优选占95重量份至99.5重量份。具体的，以上非叔醇的(甲基)丙烯酸酯单体至少可占50重量份，或至少占70重量份，或至少占90重量份，或至少占95重量份；而以上非叔醇的(甲基)丙烯酸酯单体至多可占99.5重量份，或至多占98重量份，或至多占96重量份，或至多占90重量份。
在以上非叔醇的(甲基)丙烯酸酯单体中，优选有一部分是具有较高Tg(玻璃化转变温度)的，即其均聚物的Tg至少为25℃，并优选至少为50℃。该具有较高Tg的非叔醇的(甲基)丙烯酸酯单体包括但不限于：甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸仲丁酯、甲基丙烯酸十八烷醇酯、甲基丙烯酸苯酯、甲基丙烯酸环己酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、甲基丙烯酸苯甲酯、丙烯酸3，3，5-三甲基环己酯、丙烯酸环己酯、N-辛基丙 烯酰胺、甲基丙烯酸丙酯中的任意一种或多种。
在每100重量份的用于形成浆液聚合物的可聚合单体中，该具有较高Tg的非叔醇的(甲基)丙烯酸酯单体优选占0重量份至25重量份(0表示可不含)，更优选占0重量份至20重量份。具体的，以上较高Tg的非叔醇的(甲基)丙烯酸酯单体可不含，或至少占2重量份，或至少占5重量份；而该较高Tg的非叔醇的(甲基)丙烯酸酯单体至多可占25重量份，或至多占20重量份，或至多占15重量份。其中，该具有较高Tg的非叔醇的(甲基)丙烯酸酯单体的量包括在全部非叔醇的(甲基)丙烯酸酯单体的量中；例如，若非叔醇的(甲基)丙烯酸酯单体的总量为90重量份，而具有较高Tg的非叔醇的(甲基)丙烯酸酯单体的量为10重量份，则表示在总共90重量份的非叔醇的(甲基)丙烯酸酯单体中，有10重量份是具有较高Tg的，其余80重量份则是具有较低Tg的其它的非叔醇的(甲基)丙烯酸酯单体。
(2)酸官能的具有至少一个烯键的非酯不饱和单体
该酸官能的具有至少一个烯键的非酯不饱和单体中同时包括烯键和酸官能团，该酸官能团可以是酸，如羧酸，也可是酸的盐，如羧酸的碱金属盐，但不能是酯。该酸官能的具有至少一个烯键的非酯不饱和单体可为烯键式不饱和羧酸、烯键式不饱和磺酸、烯键式不饱和膦酸等；具体的，其包括但不限于：丙烯酸、甲基丙烯酸、衣康酸、富马酸、巴豆酸、柠康酸、马来酸、油酸、苯乙烯磺酸、2-丙烯酰胺-2-甲基丙磺酸、乙烯基膦酸中的任意一种或多种。考虑到可实施性，该酸官能的具有至少一个烯键的非酯不饱和单体更优选为烯键式不饱和羧酸，如(甲基)丙烯酸。
在用于形成浆液聚合物的可聚合单体中(即单体组分和用于形成(甲基)丙烯酸酯共聚物的可聚合单体)中，以上酸官能的具有至少一个烯键的非酯不饱和单体的重量百分含量在0.5％至15％之间，更优选在0.5％至5％之间。
也就是说，在每100重量份的用于形成浆液聚合物的可聚合单体中，上述酸官能的具有至少一个烯键的非酯不饱和单体优选占0.5重量份至15重量份，更优选在0.5至5重量份。具体的，以上酸官能的具有至少一个烯键的非酯不饱和单体至少可占0.5重量份，或至少占1重量份，或至少占2重量份；而该酸官能的具有至少一个烯键的非酯不饱和单体至多可占15重量份，或至多占10重量份，或至多占5重量份。
(3)非酸官能的烯键式不饱和极性单体
优选的，用于形成浆液聚合物的可聚合单体还可包括非酸官能的烯键式不饱和极性单体(可包括酯，但不同于之前的非叔醇的(甲基)丙烯酸酯单体)。其中，可用的非酸官能的烯键式不饱和极性单体包括但不限于：(甲基)丙烯酸2-羟乙酯、N-乙烯基吡咯烷酮、N-乙烯基己内酰胺、丙烯酰胺、单-N-烷基取代的丙烯酰胺、二-N-烷基取代的丙烯酰胺、叔丁基丙烯酰胺、二甲基氨基乙基丙烯酰胺、N-辛基丙烯酰胺、聚(烷氧基烷基)(甲基)丙烯酸酯中的任意一种或多种；其中，聚(烷氧基烷基)(甲基)丙烯酸酯包括(甲基)丙烯酸2-(2-乙氧基乙氧基)乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-甲氧基乙氧基乙酯、甲基丙烯酸2-甲氧基乙酯、聚乙二醇单(甲基)丙烯酸酯中的任意一种或多种。显然，这里描述的非酸官能的烯键式不饱和极性单体不包括上述的其它单体，即其不同于以上的非叔醇的(甲基)丙烯酸酯单体。
在用于形成浆液聚合物的可聚合单体(即单体组分和用于形成(甲基)丙烯酸酯共聚物的可聚合单体)中，非酸官能的烯键式不饱和极性单体的重量百分含量小于或等于45％。
也就是说，在每100重量份的用于形成浆液聚合物的可聚合单体中，非酸官能的烯键式不饱和极性单体优选占0重量份至45重量份(0表示可不含)。具体的，该非酸官能的烯键式不饱和极性单体可不含，或至少占1重量份，或至少占2重量份，或至少占5重量份；而该非酸官能的烯键式不饱和极性单体至多可占45重量份，或至多占40重量份，或至多占35重量份。
(4)乙烯基单体
优选的，用于形成浆液聚合物的可聚合单体还可包括乙烯基单体，该乙烯基单体是指以乙烯基团为重要部分的单体，其包括但不限于：乙烯基酯(如乙酸乙烯酯、丙酸乙烯酯)、苯乙烯、取代的苯乙烯(如α-甲基苯乙烯)、乙烯基卤化物中的任意一种或多种。显然，这里描述的乙烯基单体不包括上述的其它单体，即其不同于以上的非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体、非酸官能的烯键式不饱和极性单体。
在用于形成浆液聚合物的可聚合单体(即单体组分和用于形成(甲基)丙烯酸酯共聚物的可聚合单体)中，乙烯基单体的重量百分含量小于或等于5％。
也就是说，在每100重量份的用于形成浆液聚合物的可聚合单体中，该乙烯基单体优选占0重量份至5重量份(0表示可不含)。具体的，该乙烯基单体可不含，或至少占0.1重量份，或至少占0.5重量份；而该乙烯基单体至多可占5重量份，或至多占4重量份，或至多占3重量份。
其中，以上的非酸官能的烯键式不饱和极性单体和乙烯基单体是可选的组分，即用于形成浆液聚合物的可聚合单体中可不包括它们，但作为改善浆液聚合物性能的备选组分，将它们用于浆液聚合物中是已知的。
2、嵌段共聚物
本发明的可固化组合物中还包括一种或多种嵌段共聚物，该嵌段共聚物属于弹性体。
本发明的嵌段共聚物包括至少两个分别位于两端的A嵌段和至少一个位于中间的B嵌段；其中，A嵌段由甲基丙烯酸酯单体聚合形成，B嵌段由丙烯酸酯单体聚合形成。
也就是说，本发明的嵌段共聚物的两端必然是由甲基丙烯酸酯单体聚合形成的A嵌段，而中间则有由丙烯酸酯单体聚合形成的B嵌段。通常而言，以上A嵌段具有比B嵌段更高的硬度，这样有利于改善弹性体的弹性。
优选的，以上A嵌段由甲基丙烯酸烷基酯单体聚合形成，且其中烷基的碳原子数在1个至6个之间，或在1个至4个之间，或在1个至3个之间。而以上B嵌段由丙烯酸烷基酯单体聚合形成，且其中烷基的碳原子数在3个至20个之间，或在4个至20个之间，或在4个至10个之间，或在4个至6个之间；显然，当以上碳原子数为一定范围时，每个嵌段均可由多种不同的具体单体形成。
优选的，用于形成A嵌段的甲基丙烯酸烷基酯单体的烷基的碳原子数小于用于形成B嵌段的丙烯酸烷基酯单体的烷基的碳原子。例如，作为一种最优选的方案，A嵌段由甲基丙烯酸甲酯单体聚合形成，而B嵌段由丙烯酸正丁酯单体聚合形成；即A嵌段为聚(甲基丙烯酸甲酯)，B嵌段为聚(丙 烯酸正丁酯)。
更优选的，以上嵌段共聚物为A嵌段-B嵌段-A嵌段结构的三嵌段共聚物。也就是说，该嵌段共聚物优选仅由两个分别位于两端的A嵌段和一个位于中间的B嵌段构成，而不包括其它的结构，从而为单纯的ABA结构。例如，作为最优方案，该嵌段共聚物为聚(甲基丙烯酸甲酯)-聚(丙烯酸正丁酯)-聚(甲基丙烯酸甲酯)的三嵌段共聚物。
当然，如果该嵌段共聚物中包括其它的嵌段，或在中间包括交替设置的(AB)嵌段，也是可行的。具体的，以上嵌段共聚物(弹性体)可为日本东京的可乐丽株式会社生产的LA1114、LA2140、LA2250、LA2330等弹性体产品。
优选的，以上嵌段共聚物的重均分子量在2000道尔顿至500000道尔顿之间。
也就是说，以上嵌段共聚物的重均分子量至少为2000道尔顿，或至少为3000道尔顿，或至少为5000道尔顿，或至少为10000道尔顿，或至少为40000道尔顿，或至少为60000道尔顿；且其重均分子量不超过500000道尔顿，或不超过300000道尔顿，或不超过200000道尔顿，或不超过120000道尔顿，或不超过80000道尔顿。
优选的，以上嵌段共聚物中，A嵌段的重量百分含量在5％至50％之间，优选在20％至30％；B嵌段的重量百分含量在50％至95％之间，优选在70％至80％之间。
也就是说，在嵌段共聚物中，A嵌段所占比例应较小，其重量百分比应至少为5％，或至少为7％，或至少为10％，或至少为20％，或至少为23％，而A嵌段的重量百分比应至多不超过50％，或不超过40％，或不超过35％，或不超过30％。相应的，在嵌段共聚物中，B嵌段所占比例应较大，其重量百分比应至少为50％，或至少为55％，或至少为60％，或至少为65％，或至少为70％，而B嵌段的重量百分比应至多不超过95％，或不超过90％，或不超过85％，或不超过80％，或不超过75％。
3、光引发剂
优选的，本发明的可固化组合物是光引发的，故其中可含有光引发剂。 光引发剂用于在紫外光照射下产生自由基，从而引发聚合反应。光引发过程中不使用额外的有机溶剂(即除可聚合单体之外的溶剂)，从而使得整个生产过程中基本上无废水、废气污染，更环保、效率高；而且，光引发中使用紫外光引发聚合，故其一方面不要加热，简便易行、能耗低、效率高；另一方面，当关掉紫外光光源并通入空气时，可立即终止反应，故其产品的粘度、单体转化率、重均分子量等可准确控制。
其中，具体可用的光引发剂包括但不限于：苯偶姻醚，如苯偶姻甲醚、苯偶姻异丙醚；取代的苯乙酮，如2，2-二甲氧基苯乙酮；二甲氧基羟基苯乙酮；取代的α-酮醇，如2-甲基-2-羟基苯丙酮；芳族磺酰氯，如2-萘-磺酰氯；光敏肟，如1-苯基-1，2-丙二酮-2-(O-乙氧基-羰基)肟；1-羟基环己基苯基酮；1-[4-(2-羟基乙氧基)苯基]-2-羟基-2-甲基-1-丙-1-酮；(4-甲硫基苯甲酰基)-1-甲基-1-吗啉基乙烷；(4-吗啉基苯甲酰基)-1-苄基-1-二甲基氨基丙烷；(4-吗啉基苯甲酰基)-1-(4-甲基苄基)-1-二甲基氨基丙烷；二(2，4，6-三甲基苯甲酰基)苯基氧化膦；1-羟基环己基苯甲酮中的任意一种或多种。其中，特别优选的光引发剂是取代的苯乙酮。
优选的，在可固化组合物中，相对于每100重量份的用于形成浆液聚合物的可聚合单体，光引发剂的用量在0.001重量份至3重量份之间。具体的，光引发剂的用量至少可为0.001重量份，或至少为0.005重量份，或至少为0.01重量份；而该光引发剂的用量至多可为3重量份，或至多为1重量份，或至多为0.5重量份。
需要注意的是，此处的光引发剂用量是指加入到可固化组合物中的光引发剂的总量，而这些光引发剂可有一部分(通常其在总量中的重量百分含量为10％至20％)先加入到浆液聚合物的原料中，用于引起部分聚合反应以得到浆液聚合物，之后剩余部分再加入到反应得到的浆液聚合物中，用于使可固化组合物最终聚合为压敏粘合剂。
4、交联剂
优选的，本发明的可固化组合物中还可含有交联剂，交联剂的加入可提高所形成的压敏粘合剂的内聚强度。本发明可用的交联剂可包括光敏型交联剂，其可通过紫外光照射激活，常见的光敏型交联剂包括但不限于： 苯甲酮；可共聚的芳香酮；三嗪类物质(Triazine)，如2，4-双(三氯甲基)-6-(4-甲氧基苯)-三嗪等。另一种可用的交联剂是多官能(甲基)丙烯酸酯，如二(甲基)丙烯酸酯、三(甲基)丙烯酸酯、四(甲基)丙烯酸酯等，其具体例子包括但不限于：1，6-己二醇二(甲基)丙烯酸酯、聚(乙二醇)二(甲基)丙烯酸酯、聚丁二烯二(甲基)丙烯酸酯、聚氨酯二(甲基)丙烯酸酯、丙氧基化的甘油三(甲基)丙烯酸酯中的任意一种或多种；该多官能(甲基)丙烯酸酯交联剂是非光敏型的交联剂，但其可以提高丙烯酸酯压敏粘合剂的内聚强度(见美国专利US4379201)。另一种可用的交联剂是热活化型交联剂，如多官能的氮丙啶、异氰酸酯、环氧树脂等，具体可为1，1′-(1，3-苯二甲酰)-双-(2-甲基氮丙啶)。其中，本发明最优选的交联剂为多官能(甲基)丙烯酸酯。
优选的，在可固化组合物中，相对于每100重量份的用于形成浆液聚合物的可聚合单体，交联剂的用量优选小于或等于5重量份；也就是说，该交联剂可不含，或至少为0.01重量份，或至少为0.03重量份；而该交联剂的用量至多可为5重量份，或至多为2重量份，或至多为1重量份。
5、黑色颜料
由于本发明的压敏粘合剂主要用于手机、平板电脑等的显示面板与壳体的粘接，故希望其优选具有黑色外观，以实现遮光并避免被外界明显的看到。为此，可在可固化组合物中添加黑色颜料，可用的黑色颜料包括9B117(Penn Color公司，宾夕法尼亚州，美国)等。
在可固化组合物中，相对于每100重量份的用于形成浆液聚合物的可聚合单体，黑色颜料的用量优选小于或等于10重量份；也就是说，该黑色颜料可不含，或至少为0.5重量份，或至少为1重量份；而该黑色颜料的用量至多可为10重量份，或至多为8重量份，或至多为7重量份。
6、已膨胀的聚合物微球
为了进一步提高压敏粘合剂的抗跌落性能，优选其应具有类似“泡棉”的特性；为此，可在可固化组合物中添加已膨胀的聚合物微球。已膨胀的聚合物微球是由聚合物壳体和位于壳体内的空腔构成的基本为球形的已知材料，其通过对包裹有可气化材料的聚合物颗粒进行加热而得，即通过 可气化材料的气化将聚合物壳体胀大。已膨胀的聚合物微球的粒径优选在10微米至100微米之间，更优选在20微米至90微米之间。具体可用的已膨胀的聚合物微球可见中国专利CN103320037B等，在此不再详细描述。
在可固化组合物中，相对于每100重量份的用于形成浆液聚合物的可聚合单体，已膨胀的聚合物微球的用量优选小于或等于10重量份；也就是说，该已膨胀的聚合物微球可不含，或至少为0.1重量份，或至少为0.5重量份；而该已膨胀的聚合物微球的用量至多可为10重量份，或至多为9重量份，或至多为8重量份。
7、增粘树脂
为提高压敏粘合剂的粘结性性能，还可在可固化组合物中添加增粘树脂。其中，增粘树脂可为一种或者多种的混用，可用的增粘树脂包括但不限于：氢化松香树脂FORAL 85LB(Pinova公司，佐治亚州，美国)、氢化萜烯酚醛树脂UH115(Yasuhara化学公司，广岛市，日本)、碳氢树脂类增粘树脂REGRELTZ 6108(伊士曼化学公司，田纳西州，美国)、美国专利US20150044457和中国专利CN2014074139中的丙烯酸酯聚合物增粘树脂等。
在可固化组合物中，增粘树脂的使用以不影响其它性能为准。具体的，相对于每100重量份的用于形成浆液聚合物的可聚合单体，增粘树脂优选不超过35重量份，或不超过25重量份，或不超过10重量份，或不超过2重量份；而该增粘树脂的含量优选可不低于0.1重量份，或不低于1重量份，或不低于2重量份。
8、其它添加剂(如增塑剂、抗氧化剂、分散剂、防沉降剂等)和功能性组分
优选的，为改善产品胶带的不同性能，还可向可固化组合物中加入各种其它的已知添加剂，可选的添加剂包括但不限于：增塑剂、抗氧化剂、分散剂、防沉降剂中的任意一种或多种。
另外，优选的，为了使产品胶带具有所需的特定功能，还可向可固化组合物中添加功能性组分，如具有为提高产品的模切性能，可向其中加入 短纤维等。
当然，应当理解，以上各可选组分的加入均应以不影响压敏粘合剂本身的性能(尤其是抗跌落性能)为准。
同时，如果需要，本领域技术人员还可向可固化组合物添加其它的已知组分，在此不再详细描述。
可固化组合物的制备方法
以上可固化组合物通过将其各原料混合均匀即可得到。
下面对可固化组合物的部分主要原料的制备过程进行描述。
1、浆液聚合物的制备方法
当采用浆液聚合物作为可固化组合物的原料时，浆液聚合物的制备方法主要有两种，一种是紫外光引发的本体聚合法，简称紫外光引发法；另一种是热引发的溶液聚合法，简称溶液法，下面对其逐一进行介绍。
1)紫外光引发法
紫外光引发法中不使用外加溶剂，而是直接将可聚合单体的原料混合并进行部分共聚(本体聚合)，并以其中未发生聚合的可聚合单体作为溶剂溶解聚合生成的共聚物，得到浆液聚合物。紫外光引发法的过程具体包括：
(1)准备原料
也就是说，将用于形成浆液聚合物的各可聚合单体混合。
其中，若可聚合单体中存在上述具有较高Tg的非叔醇的(甲基)丙烯酸酯单体，则其可在本步骤中全部加入(本发明各实施例均采用这种方法)，或者也可只加入一部分，或者可不加入，而未加入的部分应直接加入到完成部分共聚后的浆液聚合物中(也就是直接加入可固化组合物中)；这是因为具有较高Tg的非叔醇的(甲基)丙烯酸酯单体的聚合往往较慢，在此时加入了也不能大量聚合。
由此，对最后制得的浆液聚合物产品而言，其已发生聚合和未发生聚合的部分中，该具有较高Tg的非叔醇的(甲基)丙烯酸酯单体的含量是不同的。也就是说，在可固化组合物中，单体组分和(甲基)丙烯酸酯共聚物所对应的可聚合单体原料的具体成分(包括含量)可能是不一样的。
本步骤中还需将可固化组合物中的全部或部分光引发剂也与上述可聚合单体混合，以便能用紫外光引发聚合反应。通常而言，本步骤中加入的光引发剂为可固化组合物的光引发剂的一部分，通常其在总量中的重量百分含量为10％至20％。
(2)紫外光照射以上原料，使可聚合单体部分共聚得到浆液聚合物
其中，可用的紫外光源通常分为两种：一是低强度紫外光源，如黑光，其波长在280纳米至400纳米，强度通常为10毫瓦/平方厘米(mw/cm2)以下；二是高强度紫外光源，如中压汞灯，其强度通常大于10毫瓦/平方厘米，更优选在15毫瓦/平方厘米至450毫瓦/平方厘米之间。其中，紫外光强度是用UVIMAPTM UM 365L-S辐射计(通用电子仪器技术有限公司，弗吉尼亚州，美国)按照美国国家标准和技术协会(NIST，United States National Institute of Standards and Technology)的规定测量的。在本发明中，优选使用低强度紫外光源，其紫外光强度在0.1毫瓦/平方厘米至150毫瓦/平方厘米；具体的，以上紫外光强度至少在0.1毫瓦/平方厘米，或至少在0.5毫瓦/平方厘米，或至少在1.5毫瓦/平方厘米；而该紫外光强度至多为150毫瓦/平方厘米，或至多为100毫瓦/平方厘米，或至多为50毫瓦/平方厘米。而紫外光照射的时间可根据光的强度和聚合情况调整，通常约在数分钟。或者，也可使用高强度而短照射时间的紫外光，如用600毫瓦/平方厘米照射1秒。
在聚合过程中，用乌氏粘度计不断测量浆液聚合物的粘度，并不断测量浆液聚合物的折射率以判断其中的单体转化率，待其达到预定标准后撤去紫外光，并向浆液聚合物中通入空气或氧气，使自由基淬灭，聚合终止。
紫外光引发法在制备过程中不使用额外的有机溶剂(即除可聚合单体之外的溶剂)，从而使得整个生产过程中基本上无废水、废气污染，更环保，效率高。同时，紫外光引发法中使用紫外光引发聚合，故其一方面不要加热，简便易行，能耗低，效率高；另一方面，当关掉紫外光光源并通入气体时，可立即终止反应，故其产品的粘度、单体转化率、重均分子量等可准确控制。
因此，紫外光引发法是本发明中优选的制备浆液聚合物的方法，本发明的各实施例中，浆液聚合物均是用本方法制备的。
2)溶液法
以上浆液聚合物也可使用溶液法制备，也就是可使可聚合单体溶解在外加有的机溶剂中聚合，聚合完成后再除去外加的有机溶剂，剩余物质即为浆液聚合物。溶液法的具体步骤可包括：
(1)准备原料
将用于形成浆液聚合物的各可聚合单体、热引发剂等溶解在溶剂中并通氮气充分净化。
其中，可用的溶剂包括但不限于：甲醇、四氢呋喃、乙醇、异丙醇、丙酮、甲乙酮、乙酸甲酯、乙酸乙酯、甲苯、二甲苯、乙二醇烷基醚中的任意一种或多种。
热引发剂为可产生自由基的有机过氧化物、有机氢过氧化物、偶氮类化合物等。可用的有机过氧化物包括但不限于：过氧化苯甲酰、过氧化月桂酰、二叔戊基过氧化物、过氧化苯甲酸叔丁酯、2，5-二甲基-2，5-二-(叔丁基过氧基)己烷、2，5-二甲基-2，5-二-(叔丁基过氧基)己炔-3、二枯基过氧化物中的任意一种或多种。可用的有机氢过氧化物包括但不限于：叔茂基过氧化氢和/或叔丁基过氧化氢。可用的偶氮类化合物包括但不限于：2，2′-偶氮双(异丁腈)、2，2′-偶氮双(2-甲基丁腈)、2，2′-偶氮双(2，4-二甲基戊腈)中的任意一种或多种。
其中，对于每100重量份的用于形成浆液聚合物的可聚合单体，热引发剂的加入量优选为0.05至约1重量份，优选约0.1至约0.5重量份。
(2)加热溶液，使可聚合单体发生部分共聚
其中，加热温度通常在40℃至100℃的范围内，加热时间通常在1小时至20小时内，其具体选择取决于总物质用量、所需的单体转化率等。
(3)真空蒸馏除去外加的溶剂，得到浆液聚合物
其中，具体的真空蒸馏温度可根据外加溶剂的类型确定，而其时间以能将外加溶剂基本除去为准。
应当注意，虽然通过溶液法制备浆液聚合物也是可行的，但其并不是最优方法，因为其中需要使用外加的溶剂并要增加除去溶剂的步骤，故其成本高且工艺复杂；同时其需要加热，能耗高；另外，单体在溶液中的聚 合往往更慢，故其所需的时间长(通常需要数小时，而紫外光引发法通常只要数分钟)、效率低。
在得到浆液聚合物后，只要将可固化组合物中的其它组分(嵌段共聚物、光引发剂、交联剂等)都加入其中并使之完全溶解，即可得到产品可固化组合物。其中，优选的，一般可先将黑色颜料、光引发剂、交联剂、增粘树脂等组分加入，待它们完全溶解而后再加入嵌段共聚物(弹性体)，如果有已膨胀的聚合物微球，则最后加入；这样的加入顺序有利于保证各组分都能分布均匀。本发明各实施例中均按以上顺序进行混合。
压敏粘合剂
本发明还提供一种压敏粘合剂，其是由上述可固化组合物固化而得的。
也就是说，可通过紫外光照射的方式使上述可固化组合物基本完全固化，形成压敏粘合剂，该压敏粘合剂具有优异的抗跌落性能。其中，紫外光照射的时间以能使可固化组合物基本完全固化为准，通常约在数分钟。
胶带
本发明还提供一种胶带，其包括上述的压敏粘合剂。
也就是说，以上压敏粘合剂可形成胶带形式，以便应用。
具体的，本发明的胶带可包括背衬和形成在背衬上的上述压敏粘合剂。当具有背衬时，可将上述可固化组合物涂布在背衬上，之后用紫外光照射进行固化，从而得到包括背衬和上述压敏粘合剂的胶带。或者，也可将可固化组合物涂布在可分离的临时基体(如离型膜)上，并用紫外光照射进行固化而形成胶膜，之后将压敏粘合剂胶膜转移至其它背衬上。
其中，以上涂布可固化组合物的方法包括但不限于辊涂、流涂、浸涂、旋涂、喷涂、刮涂、模涂等，在此不再详细描述；而其涂布后形成的干胶(即压敏粘合剂)的厚度通常在50微米至500微米，更优选在至少为100微米，或至少为200微米，而其厚度优选至多为400微米，或至多为300微米。
其中，背衬优选是柔性的，其可包括塑料，如聚烯烃如聚乙烯、聚丙烯(包括全同立构聚丙烯)、聚苯乙烯、聚酯、聚乙烯醇、聚(对苯二甲酸乙二酯)、聚(对苯二甲酸丁二酯)、聚(己内酰胺)、聚(偏二氟乙烯)、聚丙交酯、纤维素乙酸酯、乙基纤维素等；而且，背衬的表面还可带有特定的微复制结构以改善胶带的性能，微复制结构可如美国专利US5141790，US5296277、US5362516等中描述。或者，背衬也可为织物，例如棉、尼龙、人造丝、玻璃线、陶瓷线等的织物。或者，背衬也可为无纺布，例如天然纤维和/或合成纤维通过气流成网得到的无纺布。
在具有背衬的胶带中，可以是背衬只有一侧有上述的压敏粘合剂，另一侧无粘合剂或有其它粘合剂；或者，也可以是背衬两侧都有上述的压敏粘合剂，从而胶带成为双面胶带。
同时，在背衬上，可以是只具有本发明的压敏粘合剂，或也可同时具有其它已知的粘合剂。具体的，可以是本发明的压敏粘合剂直接与背衬接触，其外侧再设有其它已知的粘合剂(即本发明的压敏粘合剂起类似中介的作用)；或者，也可以是其它已知的压敏粘合剂直接与背衬接触，其外侧再设有本发明的粘合剂(即本发明的压敏粘合剂直接起到粘结作用)。
或者，作为本发明的另一种方式，背衬也可由本发明的压敏粘合剂构成；优选的，在该背衬的一侧或两侧，还可设有其它已知的粘合剂。也就是说，本发明的压敏粘合剂(尤其具有泡棉特性的压敏粘合剂)也可作为背衬使用，该背衬可单独存在，从而形成两侧均具有粘性的“胶膜”；或者，也可将该背衬与其它粘合剂一同使用，即在其一侧或两侧还可设有其它已知的粘合剂。
总之，本发明的压敏粘合剂可以作为单独的胶膜(背衬或泡棉)，或也可作为带有其它粘合剂的胶带的背衬，或也可作为粘合剂附在其它背衬上。
为方便胶带的使用，其中还可设有离型膜或离型纸，用于避免不使用时的意外粘结。具体的，离型膜或离型纸的形式是公知且多样的，如有机硅涂布的牛皮纸、格拉辛纸、淋塑牛皮纸、聚(对苯二甲酸乙二酯)等。其中，当由压敏粘合剂构成的胶膜直接与离型膜或离型纸接触时，也可直接将压敏粘合剂形成在离型膜或离型纸上。
粘合制品
本发明还提供一种粘合制品，其包括第一部件，第一部件的至少部分表面上粘结有上述的压敏粘合剂。
也就是说，本发明提供一种粘合制品，其包括上述的压敏粘合剂，从而该粘合制品可通过上述压敏粘合剂与其它产品相互粘结，或者粘合制品中的多个部件可通过上述压敏粘合剂粘结在一起。
优选的，以上粘合制品还包括第二部件，第一部件和第二部件通过上述压敏粘合剂粘结在一起。
也就是说，粘合制品中的多个部件可由上述的压敏粘合剂粘结在一起的。其中，如前所述，压敏粘合剂可以作为单独的胶膜(背衬或泡棉)，或也可作为带有其它粘合剂的胶带的背衬，或也可作为粘合剂附在其它背衬上。
优选的，以上粘合制品为移动终端、平板电脑、笔记本电脑中的任意一种；第一部件为壳体；第二部件为显示面板。
也就是说，本发明的压敏粘合剂优选用于将移动终端(手机)、平板电脑、笔记本电脑等的显示面板与壳体粘结在一起。这是因为这些产品往往比较容易意外跌落，从而其中的压敏粘合剂的抗跌落性能是比较重要的。
当然，以上描述不是对粘合制品具体形式限定，只要包括上述的压敏粘合剂的产品都属于粘合制品。
本发明的具体实施方式
本发明的实施例提供一种可固化组合物，其中，包括：
单体组分，包括至少两种可聚合单体，所述可聚合单体包括非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体；
至少一种嵌段共聚物，所述嵌段共聚物属于弹性体，其包括至少两个分别位于两端的A嵌段和至少一个位于中间的B嵌段；其中，所述A嵌段由甲基丙烯酸酯单体聚合形成，所述B嵌段由丙烯酸酯单体聚合形成。
优选的，所述嵌段共聚物为A嵌段-B嵌段-A嵌段结构的三嵌段共聚物。
优选的，所述A嵌段由甲基丙烯酸烷基酯单体聚合形成；所述B嵌段由丙烯酸烷基酯单体聚合形成。
优选的，所述甲基丙烯酸烷基酯单体的烷基的碳原子数在1个至6个之间；所述丙烯酸烷基酯单体的烷基的碳原子数在3个至20个之间；且所述甲基丙烯酸烷基酯单体的烷基的碳原子数小于所述丙烯酸烷基酯单体的烷基的碳原子。
进一步优选的，所述甲基丙烯酸烷基酯单体为甲基丙烯酸甲酯单体；所述丙烯酸烷基酯单体为丙烯酸正丁酯单体。
优选的，所述嵌段共聚物的重均分子量在2000道尔顿至500000道尔顿之间。
进一步优选的，所述嵌段共聚物的重均分子量在40000道尔顿至120000道尔顿之间。
优选的，在所述嵌段共聚物中，所述A嵌段的重量百分含量在5％至50％之间；所述B嵌段的重量百分含量在50％至95％之间。
进一步优选的，在所述嵌段共聚物中，所述A嵌段的重量百分含量在20％至30％之间；所述B嵌段的重量百分含量在70％至80％之间。
优选的，所述可固化组合物还包括：(甲基)丙烯酸酯共聚物，其由包括至少两种可聚合单体的原料共聚形成，所述可聚合单体包括：非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体；所述(甲基)丙烯酸酯共聚物的重均分子量在500000道尔顿至10000000道尔顿之间。
进一步优选的，所述单体组分和所述(甲基)丙烯酸酯共聚物构成浆液聚合物；所述浆液聚合物由包括至少两种可聚合单体的原料部分共聚形成，所述可聚合单体包括非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体。
进一步优选的，用于形成所述浆液聚合物的可聚合单体中，所述非叔醇的(甲基)丙烯酸酯单体的重量百分含量在50％至99.5％之间；所述酸官能的具有至少一个烯键的非酯不饱和单体的重量百分含量在0.5％至15％之间。
进一步优选的，用于形成所述浆液聚合物的可聚合单体中，所述非叔 醇的(甲基)丙烯酸酯单体的重量百分含量在95％至99.5％之间；所述酸官能的具有至少一个烯键的非酯不饱和单体的重量百分含量在0.5％至5％之间。
进一步优选的，用于形成所述浆液聚合物的可聚合单体还包括：非酸官能的烯键式不饱和极性单体，其重量百分含量小于或等于45％；且所述非酸官能的烯键式不饱和极性单体不同于所述非叔醇的(甲基)丙烯酸酯单体；和/或乙烯基单体，其重量百分含量小于或等于5％；且所述乙烯基单体不同于所述非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体、非酸官能的烯键式不饱和极性单体。
进一步优选的，在用于形成所述浆液聚合物的可聚合单体中，已发生共聚而形成所述(甲基)丙烯酸酯共聚物的可聚合单体的重量百分含量在1％至30％之间；所述浆液聚合物在22℃的粘度在500厘泊至10000厘泊之间。
进一步优选的，相对于单体组分和用于形成所述(甲基)丙烯酸酯共聚物的可聚合单体的总重量，所述弹性体的重量比例在0.1％至55％之间。
进一步优选的，相对于单体组分和用于形成所述(甲基)丙烯酸酯共聚物的可聚合单体的总重量，所述弹性体的重量比例在0.5％至30％之间。
进一步优选的，相对于单体组分和用于形成所述(甲基)丙烯酸酯共聚物的可聚合单体的总重量，所述弹性体的重量比例在0.5％至20％之间。
优选的，所述单体组分还包括：非酸官能的烯键式不饱和极性单体；且所述非酸官能的烯键式不饱和极性单体不同于所述非叔醇的(甲基)丙烯酸酯单体；和/或乙烯基单体；且所述乙烯基单体不同于所述非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体、非酸官能的烯键式不饱和极性单体。
优选的，所述可固化组合物还包括：光引发剂；和/或交联剂。
优选的，所述可固化组合物还包括以下组分中的任意一种或多种：增粘树脂；黑色颜料；已膨胀的聚合物微球。
本发明的实施例还提供一种压敏粘合剂，由可固化组合物固化形成，其中，所述可固化组合物包括：
单体组分，包括至少两种可聚合单体，所述可聚合单体包括非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体；
至少一种嵌段共聚物，所述嵌段共聚物属于弹性体，其包括至少两个分别位于两端的A嵌段和至少一个位于中间的B嵌段；其中，所述A嵌段由甲基丙烯酸酯单体聚合形成，所述B嵌段由丙烯酸酯单体聚合形成。
本发明的实施例还提供一种胶带，包括压敏粘合剂，所述压敏粘合剂由可固化组合物固化形成，其中，所述可固化组合物包括：
单体组分，包括至少两种可聚合单体，所述可聚合单体包括非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体；
至少一种嵌段共聚物，所述嵌段共聚物属于弹性体，其包括至少两个分别位于两端的A嵌段和至少一个位于中间的B嵌段；其中，所述A嵌段由甲基丙烯酸酯单体聚合形成，所述B嵌段由丙烯酸酯单体聚合形成。
优选的，所述胶带包括背衬，以及设于所述背衬至少一侧的所述压敏粘合剂；或所述胶带包括由所述压敏粘合剂构成的背衬。
本发明的实施例还提供一种粘合制品，包括第一部件，所述第一部件的至少部分表面上粘结有压敏粘合剂，所述压敏粘合剂由可固化组合物固化形成，其中，所述可固化组合物包括：
单体组分，包括至少两种可聚合单体，所述可聚合单体包括非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体；
至少一种嵌段共聚物，所述嵌段共聚物属于弹性体，其包括至少两个分别位于两端的A嵌段和至少一个位于中间的B嵌段；其中，所述A嵌段由甲基丙烯酸酯单体聚合形成，所述B嵌段由丙烯酸酯单体聚合形成。
优选的，所述粘合制品还包括：第二部件，所述第二部件与第一部件通过所述压敏粘合剂粘结在一起。
进一步优选的，所述粘合制品为移动终端、平板电脑、笔记本电脑中的任意一种；所述第一部件为壳体；所述第二部件为显示面板。
具体实施例
下面选用不同的配方和参数，制备不同的可固化组合物、压敏粘合剂、胶带作为实施例和对比例，以示例性的说明本发明。
1、物料情况
本发明各对比例和实施例中实际使用的物料如下表所示：
表1第一部分、各实施例中使用的物料情况表
Figure PCTCN2015097364-appb-000001
表1第二部分、各实施例中使用的物料情况表
Figure PCTCN2015097364-appb-000002
2、测试方法
对各对比例和实施例的可固化组合物、压敏粘合剂、胶带等，要进行一些测试以确定其性能，其具体测试方法包括：
1)单体转化率测试
浆液聚合物的单体转化率通过减重法测试，其具体包括：称取一定重量的被测物置于铝盘中，在强制对流的烘箱中于105±3℃的温度下烘烤60±30分钟，从而将未聚合的可聚合单体蒸发，取出剩余物并冷却5分钟后进行称量，按照以下公式计算单体转化率：
转化率％＝100×(M1-M2)/M1；
其中，M1是烘烤前被测物的总重量，M2是烘烤后被测物(剩余物)的总重量，M1和M2均不包括铝盘的重量。
2)重均分子量测试
重均分子量的具体测试方法包括：称取0.1克样品置于5毫升的样品瓶中，加入3毫升四氢呋喃(TEDIA有限公司，俄亥俄州，美国)进行溶解；将溶液用0.45微米孔径的过滤膜进行过滤后加入样品瓶中；用色谱仪(Waters公司，马里兰州，美国)进行测试，所得色谱柱使用标准已知重均分子量聚苯乙烯进行标定并通过线性最小二乘法分析建立标定曲线，从而最终得到重均分子量。
3)抗跌落性能测试
抗跌落性能的测试包括以下步骤：
(1)样品制备：取两块聚甲基丙烯酸甲酯(PMMA)材质的板材(以下简称PMMA板)，其尺寸是108毫米×57毫米×6毫米，重量为38克；用异丙醇(购自国药集团化学试剂有限公司，上海市，中国)将PMMA板擦拭三遍，并确保溶剂完全挥发；用裁切刀从待测胶带上小心裁取两条1.5毫米×150毫米的胶带，扯去其中一面的离型纸，沿与PMMA板宽度平行的方向将它们分别贴在距PMMA板两边缘5毫米处，并用橡胶辊小心压合，避免粘合面间气泡，裁去胶带多余部分；扯去两条胶带另一侧的离型纸，取另一片PMMA板，将两块PMMA板四边对齐的用两条胶带贴合在一起；将4公斤重的重块(与PMMA板相同面积)放置PMMA板上持续30秒钟；将样品在23±2℃的温度和50±5％的相对湿度的条件下放置24小时，得到如图1所示的样品，用于进行测试。
(2)测试：将样品按照PMMA板与地面平行的方式放置，之后使其从2米的高度跌落到水泥地上，重复以上过程(每次不区分正反)，至两PMMA板彻底分离时为失效，记录失效时的跌落次数(每个胶带样品测试三次取平均值)，并记录失效模式。失效模式中：PO表示胶带与PMMA板分开，FS表示胶带的背衬(泡棉)层中间分开，NT表示无法测试，N/A表示没有相应结果；其中，若跌落100次后仍未失效，则不再继续测试，失效次数记为100次，失效模式记为N/A。
3、浆液聚合物的具体制备方法
浆液聚合物是可固化组合物中的组分之一，本发明中按照以下方法制备浆液聚合物，以作为可固化组合物的原料。浆液聚合物的具体制备方法包括：按下表所列的单体种类和重量向1夸脱的广口玻璃瓶中加料，并加入光引发剂IRGACURE 651，其中相对于100重量份的用于浆液聚合物的可聚合单体，此时加入的IRGACURE 651为0.04重量份(后续还有部分光引发剂直接加入可固化组合物中)；在磁力搅拌下用氮气净化原料15分钟，然后将其暴露于低强度紫外光源(波长365纳米，强度1.5毫瓦/平方厘米) 的照射下，不断测试其粘度，直至得到室温下粘度在500厘泊至7000厘泊的浆液聚合物S1-S5。
表2、浆液聚合物的可聚合单体原料(用量均为重量份)及重均分子量(道尔顿)
编号 2-EHA BA NNDMAA IBxA AA αMS 重均分子量
S1 96 无 无 无 4 无 1798000
S2 90 无 无 无 10 无 4256000
S3 87.5 无 无 无 12.5 无 6525000
S4 64.5 无 35 无 0.5 无 2783000
S5 49 32 无 12 6.5 0.5 1162000
其中，为结果的可比性，每种浆液聚合物的单体原料的总量均取100重量份，而后续各实施例和对比例中选用的浆液聚合物也均是用100重量份的可聚合单体制备的，而其它物质的用量也均是以其为标准的。
4、实施例和对比例
下面按照不同的配方制备各实施例和对比例的可固化组合物，并用其形成压敏粘合剂、胶带以测试性能。
1)对比例C1-C6和实施例1-14
在1夸脱广口玻璃瓶中加入由100重量份的可聚合单体形成的S1浆液聚合物，之后按照下表加入其它原料，避光搅拌至均匀溶解，形成对比例C1-C5和实施例1-14的可固化组合物。
其中，表中的光引发剂IRGACURE 651是指直接加入可固化组合物中的光引发剂，其与上述加入到浆液聚合物原料中的光引发剂(0.04重量份)共同构成以上光引发剂成分，以下其它实施例的光引发剂与此处相同。
表3、对比例C1-C5和实施例1-14的可固化组合物的组成(用量均为重量份)
Figure PCTCN2015097364-appb-000003
将以上各实施例的可固化组合物涂布于厚度0.05毫米的两张CP Film T10 PET(购自Solutia公司，田纳西州，美国)透明离型膜的离型面之间，控制胶膜厚度为0.15毫米，利用前述低强度紫外光(365纳米，1.5毫瓦/平方厘米)照射5分钟至10分钟，得到胶膜。其中，为提高压敏胶带的操作性能，对比例C1-C4、实施例1-9的可固化组合物涂布时，在其中添加一层Cerex23030尼龙织物(Cerex高性能纤维有限公司，佛罗里达州，美国)作为背衬。
在上述胶膜两侧各刷涂一层底涂剂，底涂剂为溶质重量百分含量10％的溶液，其中，溶质为Macromelt 6240(汉高公司，杜塞尔多夫，德国)，溶剂包括：47.5重量份异丙醇(国药集团化学试剂有限公司，上海，中国)，47.5重量份正丙醇(国药集团化学试剂有限公司，上海，中国)，5重量份水。在80℃下干燥10分钟后可得到厚度为5微米至10微米的底涂层。在两侧的底涂层上分别覆合厚度为0.05毫米的常规压敏胶带9482PC(3M公司， 明尼苏达州，美国)，使用2公斤重的橡胶辊手工压合后，制备得到总厚度为0.25毫米的双面胶带。
也就是说，以上制得的胶带主要包括两种不同的结构：第一种(对比例C1-C4、实施例1-9)是在尼龙背衬(Cerex23030)上依次设有本发明的压敏粘合剂的和现有粘合剂(压敏胶带9482PC)；第二种(对比例C5、实施例10-14)是在本发明压敏粘合剂的背衬上设有现有粘合剂(压敏胶带9482PC)。
另外，对于实施例2的压敏粘合剂，还制备了一个未设置压敏胶带9482PC的样品(当然也不用底涂剂)，即其为尼龙背衬上仅设有本发明的压敏粘合剂(记为“单粘合剂层”)。
另外，对于实施例2的压敏粘合剂，还制备了一个未设置压敏胶带9482PC和尼龙背衬的样品(当然也不用底涂剂)，即其为单纯的本发明的压敏粘合剂的胶膜(记为“胶膜”)。
另外，对于实施例7的压敏粘合剂，还制备了一个仅单面设有压敏胶带9482PC(当然也单面才有底涂剂)的样品(记为“单面贴胶”)，即其另一面的表面为本发明的压敏粘合剂。
另外，对于实施例7的压敏粘合剂，还制备了一个未设置压敏胶带9482PC和尼龙背衬的样品(当然也不用底涂剂)，即其为单纯的本发明的压敏粘合剂的胶膜(记为“胶膜”)。
另外，还增加对比例C6，其包括：在厚度为0.15毫米的黑色聚乙烯(PE)泡棉(湖北祥源新材科技有限公司，孝感市，湖北省，中国)两侧分别覆合压敏胶带9482PC，贴合前对泡棉进行双面电晕处理(Softal电晕机，汉堡，德国)，使表面能大于52达因/厘米，并使用重量为2公斤的橡胶辊手工压合，确保胶膜和聚乙烯泡棉之间完全贴合。
将以上各样品在23±2℃的温度和50±5％的相对湿度的条件下放置24小时后，进行抗跌落性能测试，其结果如下表：
表4、对比例C1-C6和实施例1-14的抗跌落性能测试结果
编号 失效次数 失效模式
C1 16 PO
C2 15 PO
C3 12 PO
C4 39 PO
C5 NT N/A
C6 4 FS
1 52 PO
2 82 PO
2(单粘合剂层) 83 PO
2(胶膜) 83 PO
3 100 N/A
4 100 N/A
5 100 N/A
6 NT N/A
7 100 N/A
7(单面贴胶) 100 N/A
7(胶膜) 100 N/A
8 83 PO
9 100 N/A
10 100 N/A
11 100 N/A
12 100 N/A
13 100 N/A
14 63 PO
其中，对比例C5和实施例6的可固化组合物中，嵌段共聚物(弹性体)最终也没能完全溶解，从而不能形成均匀产品，因此并未测试其性能。
从以上结果中可以看出，相对于没有添加嵌段共聚物的对比例C1-C2、添加了常规苯乙烯嵌段共聚物的对比例C3-C5、使用聚乙烯泡棉的对比例C6等，本发明各实施例的压敏粘合剂的抗跌落性能均明显提高，其中多数都是跌落100次后仍未破坏。
2)对比例C7、C8和实施例15、16
在1夸脱广口玻璃瓶中加入由100重量份的可聚合单体形成的S2浆液聚合物，之后按照下表加入其它原料，避光搅拌至均匀溶解，形成对比例C7和实施例15、16的可固化组合物。
表5、对比例C7和实施例15、16的可固化组合物的组成(用量均为重量份)
Figure PCTCN2015097364-appb-000004
将可固化组合物涂布于厚度为0.05毫米的两张CP Film T10 PET透明离型膜的离型面之间，控制胶膜厚度为0.1毫米，利用前述低强度紫外光辐照5分钟至10分钟，得到胶膜。
按照上述方法在胶膜两侧各形成一层底涂层。在两侧的底涂层上分别覆合厚度为0.025毫米的压敏胶带9458(3M公司，明尼苏达州，美国)，使用2公斤重的橡胶辊手工压合后，制备得到总厚度为0.15毫米的双面胶带。
另外，还增加对比例C8，其包括：按照以上方法对厚度为0.1毫米的黑色聚乙烯泡棉(湖北祥源新材科技有限公司，孝感市，湖北省，中国)进行电晕处理，之后在其两侧分别覆合压敏胶带9458。
将以上各样品在23±2℃的温度和50±5％的相对湿度的条件下放置24小时后，进行抗跌落性能测试，其结果如下表：
表6、对比例C7、C8和实施例15、16的抗跌落性能测试结果
编号 失效次数 失效模式
C7 2 PO
C8 2 FS
15 13 PO
16* NT N/A
其中，实施例16的可固化组合物中，嵌段共聚物(弹性体)最终也没能完全溶解，从而不能形成均匀产品，因此并未测试其性能。
从以上结果中可以看出，在添加了本发明特定的嵌段共聚物(弹性体)后，可大幅提高压敏粘合剂的抗跌落性能。
3)对比例C9和实施例17、18
在1夸脱广口玻璃瓶中加入由100重量份的可聚合单体形成的S3浆液聚合物，之后按照下表加入其它原料，避光搅拌至均匀溶解，形成对比例C9和实施例17、18的可固化组合物。
表7、对比例C9和实施例17、18的可固化组合物的组成(用量均为重量份)
Figure PCTCN2015097364-appb-000005
将可固化组合物涂布于厚度为0.05毫米的两张CP Film T10 PET透明离型膜的离型面之间，控制胶膜厚度为0.2毫米，利用前述低强度紫外光辐照5分钟至10分钟，得到胶膜。
按照上述方法在胶膜两侧各形成一层底涂层。在两侧的底涂层上分别覆合厚度为0.05毫米的压敏胶带467MP(3M公司，明尼苏达州，美国)，使用2公斤重的橡胶辊手工压合后，制备得到总厚度为0.3毫米的双面胶带。
将以上各样品在23±2℃的温度和50±5％的相对湿度的条件下放置24小时后，进行抗跌落性能测试，其结果如下表：
表8、对比例C9和实施例17、18的抗跌落性能测试结果
编号 失效次数 失效模式
C9 1 PO
17 3 PO
18 13 PO
从以上结果中可以看出，在添加了本发明特定的嵌段共聚物(弹性体)后，可大幅提高压敏粘合剂的抗跌落性能。
4)对比例C10和实施例19-22
在1夸脱广口玻璃瓶中加入由100重量份的可聚合单体形成的S4浆液聚合物，之后按照下表加入其它原料，避光搅拌至均匀溶解，形成对比例C10和实施例19-22的可固化组合物。
表9、对比例C10和实施例21-24的可固化组合物的组成(用量均为重量份)
Figure PCTCN2015097364-appb-000006
将可固化组合物涂布于厚度为0.05毫米的两张CP Film T10 PET透明 离型膜的离型面之间，控制胶膜厚度为0.25毫米，利用前述低强度紫外光辐照5分钟至10分钟，得到胶膜。
按照上述方法在胶膜两侧各形成一层底涂层。在两侧的底涂层上分别覆合厚度为0.05毫米的压敏胶带467MP(3M公司，明尼苏达州，美国)，使用2公斤重的橡胶辊手工压合后，制备得到总厚度为0.35毫米的双面胶带。
将以上各样品在23±2℃的温度和50±5％的相对湿度的条件下放置24小时后，进行抗跌落性能测试，其结果如下表：
表10、对比例C10和实施例19-22的抗跌落性能测试结果
编号 失效次数 失效模式
C10 1 PO
19 3 PO
20 4 PO
21 16 PO
22 NT N/A
其中，实施例22的可固化组合物中，嵌段共聚物(弹性体)最终也没能完全溶解，从而不能形成均匀产品，因此并未测试其性能。
从以上结果中可以看出，在添加了本发明特定的嵌段共聚物(弹性体)后，可大幅提高压敏粘合剂的抗跌落性能。
5)对比例C11、C12和实施例23、24
在1夸脱广口玻璃瓶中加入由100重量份的可聚合单体形成的S5浆液聚合物，之后按照下表加入其它原料，避光搅拌至均匀溶解，形成对比例C11、C12和实施例23、24的可固化组合物。
表11、对比例C11、C12和实施例23、24的可固化组合物的组成(用量均为重量份)
Figure PCTCN2015097364-appb-000007
将可固化组合物涂布于厚度为0.05毫米的两张CP Film T10 PET透明离型膜的离型面之间，控制胶膜厚度为0.3毫米，利用前述低强度紫外光辐照5分钟至10分钟，得到胶膜。
按照上述方法在胶膜两侧各形成一层底涂层。在两侧的底涂层上分别 覆合厚度为0.05毫米的压敏胶带467MP和9482PC(3M公司，明尼苏达州，美国)，使用2公斤重的橡胶辊手工压合后，制备得到总厚度为0.4毫米的双面胶带。
将以上各样品在23±2℃的温度和50±5％的相对湿度的条件下放置24小时后，进行抗跌落性能测试，其结果如下表：
表12、对比例C11、C12和实施例23、24的抗跌落性能测试结果
编号 失效次数 失效模式
C11 3 PO
C12 5 PO
23 28 PO
24 32 PO
从以上结果中可以看出，在添加了本发明特定的嵌段共聚物(弹性体)后，可大幅提高压敏粘合剂的抗跌落性能。
结论
根据以上各实施例和对比例的性能测试，可得出以下的结论：
(1)通过在丙烯酸酯压敏粘合剂中加入一种或多种本发明特定的嵌段共聚物(弹性体)后，可使压敏粘合剂的抗跌落性能获得大幅提高。
(2)在同样情况下，使用其它常规嵌段共聚物(弹性体)的各对比例的抗跌落性能仍远远低于使用本发明特定嵌段共聚物(弹性体)的实施例。这表明，并非随便什么嵌段共聚物(弹性体)都可起到改善压敏粘合剂抗跌落性能的作用。而本发明的特定的嵌段共聚物(弹性体)能改善抗跌落性能的原因可能如下：该嵌段共聚物具有良好的弹性，并且可以很好的与丙烯酸酯压敏粘合剂中的其它组份相互融合，故当其加入后，可在跌落时大量吸收冲击力，从而降低其它位置所受的冲击，提高压敏粘合剂的跌落性能。当然，以上分析并不构成对本发明作用原理的限定。
(3)不论丙烯酸酯压敏粘合剂的其它可选组分(如增粘树脂、黑色颜料、已膨胀的聚合物微球、乙烯基单体、非酸官能的烯键式不饱和极性单体等)的情况如何，使用本发明特定的嵌段共聚物(弹性体)都对压敏粘合剂的抗跌落性能有改善作用。
(4)不论压敏粘合剂以什么形式存在(如作为单独的胶膜或泡棉、作为胶带的背衬、作为胶带背衬上的粘合剂、单面贴胶或双面贴胶、单独使用 或与其它已知粘合剂一起使用等)，其都具有改善的抗跌落性能。
(5)在部分嵌段共聚物(弹性体)含量过高的可固化组合物中，嵌段共聚物不能完全溶解，从而不能形成均匀产品。这表明，可固化组合物中嵌段共聚物(弹性体)的含量有特殊要求，不能过高，且其该含量上限值也与其它组分相关。
(6)使用浆液聚合物S1的各例子整体上具有更好的抗跌落性能。这表明，浆液聚合物的原料具有较高的非叔醇的(甲基)丙烯酸酯单体含量(如在95％至99.5％)和较低的酸官能的具有至少一个烯键的非酯不饱和单体含量(如在0.5％至5％)是比较优选的。这可能是因为，这样的压敏粘合剂整体上具有较低的硬度(或者说更低的玻璃化转变温度)，从而其在相同条件下“更软”，更能吸收跌落时的冲击。
(7)虽然本发明中未对压敏粘合剂的其它性能进行测试。但是，既然该压敏粘合剂能将两个PMMA板牢固的粘结在一起并经历多次跌落，这表明其粘结力不会太差。同时，对于发生失效的实施例，其也都是PO失效方式，而没有FS失效方式(只有对比例才有FS失效方式)，这表明，本发明的压敏粘合剂本身的内聚强度也是足够的。因此，本发明的压敏粘合剂的其它常规性能起码能满足基本的要求。
可以理解的是，以上实施方式仅仅是为了说明本发明的原理而采用的示例性实施方式，然而本发明并不局限于此。对于本领域内的普通技术人员而言，在不脱离本发明的精神和实质的情况下，可以做出各种变型和改进，这些变型和改进也视为本发明的保护范围。

Claims (15)

  1. 一种可固化组合物，其中，包括：
    单体组分，包括至少两种可聚合单体，所述可聚合单体包括非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体；
    至少一种嵌段共聚物，所述嵌段共聚物属于弹性体，其包括至少两个分别位于两端的A嵌段和至少一个位于中间的B嵌段；其中，所述A嵌段由甲基丙烯酸酯单体聚合形成，所述B嵌段由丙烯酸酯单体聚合形成。
  2. 根据权利要求1所述的可固化组合物，其中，
    所述嵌段共聚物为A嵌段-B嵌段-A嵌段结构的三嵌段共聚物。
  3. 根据权利要求1所述的可固化组合物，其中，
    所述A嵌段由甲基丙烯酸烷基酯单体聚合形成；
    所述B嵌段由丙烯酸烷基酯单体聚合形成。
  4. 根据权利要求3所述的可固化组合物，其中，
    所述甲基丙烯酸烷基酯单体为甲基丙烯酸甲酯单体；
    所述丙烯酸烷基酯单体为丙烯酸正丁酯单体。
  5. 根据权利要求1所述的可固化组合物，其中，
    所述嵌段共聚物的重均分子量在2000道尔顿至500000道尔顿之间。
  6. 根据权利要求1所述的可固化组合物，其中，在所述嵌段共聚物中，
    所述A嵌段的重量百分含量在5％至50％之间；
    所述B嵌段的重量百分含量在50％至95％之间。
  7. 根据权利要求1所述的可固化组合物，其中，还包括：
    (甲基)丙烯酸酯共聚物，其由包括至少两种可聚合单体的原料共聚形 成，所述可聚合单体包括：非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体；
    所述(甲基)丙烯酸酯共聚物的重均分子量在500000道尔顿至10000000道尔顿之间。
  8. 根据权利要求7所述的可固化组合物，其中，
    所述单体组分和所述(甲基)丙烯酸酯共聚物构成浆液聚合物；
    所述浆液聚合物由包括至少两种可聚合单体的原料部分共聚形成，所述可聚合单体包括非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体。
  9. 根据权利要求8所述的可固化组合物，其中，用于形成所述浆液聚合物的可聚合单体中，
    所述非叔醇的(甲基)丙烯酸酯单体的重量百分含量在50％至99.5％之间；
    所述酸官能的具有至少一个烯键的非酯不饱和单体的重量百分含量在0.5％至15％之间。
  10. 根据权利要求7所述的可固化组合物，其中，
    相对于单体组分和用于形成所述(甲基)丙烯酸酯共聚物的可聚合单体的总重量，所述弹性体的重量比例在0.1％至55％之间。
  11. 根据权利要求10所述的可固化组合物，其中，
    相对于单体组分和用于形成所述(甲基)丙烯酸酯共聚物的可聚合单体的总重量，所述弹性体的重量比例在0.5％至30％之间。
  12. 根据权利要求1所述的可固化组合物，其中，还包括：
    光引发剂；
    和/或
    交联剂。
  13. 一种压敏粘合剂，由可固化组合物固化形成，其中，所述可固化组合物包括：
    单体组分，包括至少两种可聚合单体，所述可聚合单体包括非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体；
    至少一种嵌段共聚物，所述嵌段共聚物属于弹性体，其包括至少两个分别位于两端的A嵌段和至少一个位于中间的B嵌段；其中，所述A嵌段由甲基丙烯酸酯单体聚合形成，所述B嵌段由丙烯酸酯单体聚合形成。
  14. 一种胶带，包括压敏粘合剂，所述压敏粘合剂由可固化组合物固化形成，其中，所述可固化组合物包括：
    单体组分，包括至少两种可聚合单体，所述可聚合单体包括非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体；
    至少一种嵌段共聚物，所述嵌段共聚物属于弹性体，其包括至少两个分别位于两端的A嵌段和至少一个位于中间的B嵌段；其中，所述A嵌段由甲基丙烯酸酯单体聚合形成，所述B嵌段由丙烯酸酯单体聚合形成。
  15. 一种粘合制品，包括第一部件，所述第一部件的至少部分表面上粘结有压敏粘合剂，所述压敏粘合剂由可固化组合物固化形成，其中，所述可固化组合物包括：
    单体组分，包括至少两种可聚合单体，所述可聚合单体包括非叔醇的(甲基)丙烯酸酯单体、酸官能的具有至少一个烯键的非酯不饱和单体；
    至少一种嵌段共聚物，所述嵌段共聚物属于弹性体，其包括至少两个分别位于两端的A嵌段和至少一个位于中间的B嵌段；其中，所述A嵌段由甲基丙烯酸酯单体聚合形成，所述B嵌段由丙烯酸酯单体聚合形成。
PCT/CN2015/097364 2015-12-15 2015-12-15 可固化组合物、压敏粘合剂、胶带、粘合制品 Ceased WO2017100995A1 (zh)

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