WO2023100862A1 - Pressure-sensitive adhesive and/or adhesive - Google Patents
Pressure-sensitive adhesive and/or adhesive Download PDFInfo
- Publication number
- WO2023100862A1 WO2023100862A1 PCT/JP2022/043958 JP2022043958W WO2023100862A1 WO 2023100862 A1 WO2023100862 A1 WO 2023100862A1 JP 2022043958 W JP2022043958 W JP 2022043958W WO 2023100862 A1 WO2023100862 A1 WO 2023100862A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pressure
- polymer
- sensitive adhesive
- adhesive layer
- mass
- Prior art date
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 191
- 239000000853 adhesive Substances 0.000 title claims abstract description 103
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 103
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- 239000012790 adhesive layer Substances 0.000 description 33
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- 238000003860 storage Methods 0.000 description 30
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- 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
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
Definitions
- the present invention relates to a pressure-sensitive adhesive and/or an adhesive, more specifically, a pressure-sensitive adhesive layer capable of exhibiting stickiness, an adhesive layer capable of exhibiting adhesiveness, and a composition capable of forming the pressure-sensitive adhesive layer (adhesive and a composition capable of forming the adhesive layer (adhesive composition).
- optical devices such as displays
- thin and flexible displays typified by OLED are constructed by laminating a plurality of optical films and thin layer devices.
- a device such as a pressure-sensitive sensor that requires flexibility is constructed by laminating a pressure-sensitive member and a substrate (Patent Document 1).
- Liquid curable resins, pressure-sensitive adhesives, and adhesives are selected as interlayer fillers in these laminates.
- An adhesive (adhesive, etc.) is preferably used.
- the pressure-sensitive adhesive or the like has a function of dispersing and relieving the stress generated by bending/folding, especially in a flexible member, and it is said that the more flexible the pressure-sensitive adhesive or the like, the more efficiently the function is expressed (Patent Document 2) A flexible adhesive or the like is used.
- the present invention is intended to solve such problems, and its object is to form a pressure-sensitive adhesive and / or adhesive, or the pressure-sensitive adhesive or adhesive that can improve flexibility by external stimulation at any timing.
- An object of the present invention is to provide a pressure-sensitive adhesive and/or an adhesive that can be used.
- the present invention contains a polymer having an irreversible degradable bond in its molecule that is not rebonded after being cleaved by an external stimulus, and/or a compound capable of introducing the irreversible degradable bond into the polymer.
- Adhesives and/or adhesives are provided.
- the adhesive or the like contains the polymer having the irreversibly degradable bond
- the irreversibly degradable bond contained in the polymer is decomposed by an external stimulus.
- the structure of the polymer in the pressure-sensitive adhesive or the like is shredded to improve the flexibility.
- the adhesive or the like contains a compound capable of introducing the reversible degradable bond into the polymer
- the irreversible degradable bond is introduced into the polymer by allowing the compound to act as a monomer component or a cross-linking agent, for example. can do.
- the irreversibly degradable bond is preferably a bond containing a nitrobenzyl group. In this case, it is easy to introduce an irreversible degradable bond into the polymer.
- the polymer is preferably a thermoplastic resin and/or a thermosetting resin.
- a pressure-sensitive adhesive or the like containing a thermoplastic resin is capable of exerting adhesiveness such that it adheres under pressure from the outside, for example.
- a pressure-sensitive adhesive or the like containing a thermosetting resin can be adhered to an adherend by being cured by heating, for example.
- the above polymer is preferably a polymer that forms a network structure by bonding or entanglement between molecules or a polymer that can form the above network structure.
- a pressure-sensitive adhesive or the like having such a structure forms a network structure through polymer-to-polymer bonding or polymer-to-polymer entanglement, and can have an appropriate hardness, and the irreversible degradable bond formed by an external stimulus can be Degradation shreds the polymer structure and improves flexibility.
- the above-mentioned adhesives and the like are preferably used for optical applications.
- the pressure-sensitive adhesive and/or adhesive of the present invention can improve flexibility by applying an external stimulus at any time.
- FIG. 1 shows a schematic cross-sectional view of a release liner-attached pressure-sensitive adhesive sheet or adhesive sheet 10 in which a pressure-sensitive adhesive layer or adhesive layer 1 of the present invention is formed on a release liner 2.
- FIG. 1 shows a schematic cross-sectional view of a release liner-attached pressure-sensitive adhesive sheet or adhesive sheet 10 in which a pressure-sensitive adhesive layer or adhesive layer 1 of the present invention is formed on a release liner 2.
- the term “adhesive” refers to the property that two surfaces adhere to each other and can be peeled off if necessary, based on the cohesive force based on the chemical structure of the composition, when external pressure is applied (e.g., microscopic pressure). say.
- “adhesion” refers to the property of chemically reacting (curing) the composition to form a cured product, which is not intended to be peeled off, and which allows two surfaces to be firmly joined together.
- the "adhesive” may be a layered adhesive layer having no fluidity, and is an adhesive composition having fluidity for forming the adhesive layer. good too.
- the "adhesive” may be a laminar adhesive layer that does not have fluidity, or it may be an adhesive composition that has fluidity for forming the adhesive layer.
- the pressure-sensitive adhesive and/or adhesive of the present invention is a polymer having an irreversible degradable bond in its molecule that is cleaved by an external stimulus and then not rebonded, and/or the irreversible degradable bond can be introduced into the polymer. contains at least a compound
- the polymer may be referred to as "polymer (A)”
- the compound capable of introducing the irreversibly degradable bond into the polymer may be referred to as "compound (B)”.
- compound (A) the compound capable of introducing the irreversibly degradable bond into the polymer
- compound (B) the compound capable of introducing the irreversibly degradable bond into the polymer
- compound (B) the compound capable of introducing the irreversibly degradable bond into the polymer
- “adhesive and/or adhesive” may be referred to as "adhesive or the like”.
- the external stimulus that causes the cleavage reaction of the irreversibly degradable bond is appropriately selected according to the type of the irreversibly degradable bond, and includes active energy ray irradiation, heat, and the like.
- the polymer (A) is a thermosetting resin or an active energy ray-curable resin
- the polymer ( It is preferably an external stimulus that is different from the type of curability when A) has curability.
- the external stimulus is preferably active energy ray irradiation when the polymer (A) is a thermosetting resin, and preferably heat when the polymer (A) is an active energy ray-curable resin.
- the active energy rays are not particularly limited, but include ionizing radiation such as ⁇ -rays, ⁇ -rays, ⁇ -rays, neutron beams and electron beams, ultraviolet light and visible light. Ultraviolet rays are particularly preferred.
- the irradiation energy, irradiation time, irradiation method, etc. of the active energy ray are not particularly limited. Examples of light sources for ultraviolet light or visible light irradiation include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and LED lamps.
- the irreversibly degradable bond a known or commonly used bond can be applied, preferably a bond containing a nitrobenzyl group. In this case, it is easy to introduce an irreversible degradable bond into the polymer.
- the bond containing the nitrobenzyl group is preferably an ester bond formed by nitrobenzyl alcohol (preferably 2-nitrobenzyl alcohol) and a carboxylic acid having a polymerizable functional group.
- Polymer (A) can be obtained using compound (B).
- the compound (B) includes, for example, a monomer component, an oligomer component, a cross-linking agent, etc. having the irreversible degradable bond. That is, the polymer (A) may contain a structural unit derived from a monomer component and/or an oligomer component having an irreversibly degradable bond, and may contain a structural portion derived from the cross-linking agent.
- the compound (B) is a monomer component or an oligomer component
- the polymer (A) having the irreversible bond can be obtained by polymerizing or copolymerizing the above monomer component or oligomer component with another monomer component.
- the irreversibly degradable bond may be present in the portion constituting the side chain of the polymer (A), or may be present in the portion constituting the main chain.
- the side chain is present in the portion constituting the side chain, it is preferable from the viewpoint that stress is less likely to be applied when it is greatly deformed, and the handleability in the actual use temperature range (assuming room temperature) is maintained.
- the molecular weight of the polymer is further reduced after the irreversible degradable bond is cleaved, the flexibility is further improved, and a large change in physical properties can be expressed.
- the compound (B) preferably has a functional group (functional group (L1)) other than the irreversibly degradable bond.
- a functional group (functional group (L1)) other than the irreversibly degradable bond.
- the compound (B) functions as a cross-linking agent.
- the functional group (L1) is a polymerizable functional group
- the compound (B) functions as a monomer component or an oligomer component.
- polymerizable functional groups examples include cationic polymerizable groups, anionic polymerizable groups, and radically polymerizable groups. Among them, a radically polymerizable group is preferred.
- radically polymerizable group examples include radically polymerizable carbon-carbon double bonds such as (meth)acryloyl group and vinyl group.
- a thiol group, a carboxyl group, a hydroxy group, an amino group, an epoxy group, and isocyanate are used from the viewpoint of securing a certain degree of flexibility of the pressure-sensitive adhesive layer with an appropriate crosslinking density. and the like.
- the number of functional groups of the compound (B) increases the molecular weight of the polymer (A) after introduction into the polymer (A), giving the polymer a certain degree of hardness before applying an external stimulus, while reducing the molecular weight of the polymer after cleavage to make it flexible. From the viewpoint of exhibiting properties, the number is preferably two or more. On the other hand, if the number of functional groups increases, it will crosslink with many polymers, making it difficult to obtain the effect of cleaving the irreversibly degradable bond. From the viewpoint, the number of functional groups is preferably 4 or less, more preferably 3 or less.
- a monomer in which a nitrobenzyl group and a polymerizable functional group are bonded via a linking group is preferable.
- the linking group is not particularly limited, an ester bond is preferable.
- a nitrobenzyl-based monomer in which the linking group is an ester bond is sometimes referred to as a "nitrobenzyl ester-based monomer.”
- the nitrobenzyl ester-based monomers include, for example, an esterified product of a compound having a nitrobenzyl alcohol skeleton and a compound having a polymerizable functional group and a carboxy group, or a compound having a nitrophenylacetic acid skeleton and a polymerizable functional group and a hydroxy group.
- Examples include esterified products with compounds having
- Examples of compounds having a nitrobenzyl alcohol skeleton include 2-nitrobenzyl alcohol and 2-nitro-1,3-bis(hydroxymethyl)benzene.
- Examples of compounds having a nitrophenylacetic acid skeleton include 2-nitroisophthalic acid.
- As the nitrobenzyl ester-based monomer 2-nitro-1,3-bis((meth)acryloyloxymethylene)benzene is preferred.
- the nitrobenzyl ester-based monomer is a carboxylic acid having a polymerizable functional group (e.g. (meth) acrylic acid) and a compound having a nitrobenzyl alcohol skeleton to esterify, a compound having a polymerizable functional group and a hydroxy group and a compound having a nitrophenylacetic acid skeleton can be esterified.
- a polymerizable functional group e.g. (meth) acrylic acid
- a compound having a nitrobenzyl alcohol skeleton to esterify e.g. (meth)
- polymer (A) Only one type of polymer (A) may be used, or two or more types may be used. Moreover, a compound (B) may use only 1 type, and may use 2 or more types. Moreover, the pressure-sensitive adhesive or the like of the present invention may contain either one of the polymer (A) and the compound (B), or may contain both.
- the content ratio of one or more selected from the group consisting of the compound (B), the structural unit derived from the compound (B), and the structural part derived from the compound (B) in the pressure-sensitive adhesive or the like of the present invention is applied to impart an external stimulus.
- the total amount of the adhesive etc. of the present invention (excluding components such as organic solvents that do not remain at the time of layer formation) 100% by mass , preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more.
- the amount is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.
- thermoplastic resins examples include thermoplastic resins, thermosetting resins, and active energy ray-curable resins. Among them, thermoplastic resins and thermosetting resins are preferred.
- a pressure-sensitive adhesive or the like (adhesive layer or adhesive layer) containing a thermoplastic resin can exhibit adhesiveness such that it adheres under pressure from the outside, for example.
- An adhesive or the like (adhesive layer or adhesive layer) containing a thermosetting resin can be adhered to an adherend by curing, for example, by heating.
- thermosetting resin examples include both resins having thermosetting properties (thermosetting resins) and resins obtained by curing the above thermosetting resins.
- the thermosetting resin has a thermosetting functional group.
- the number of thermosetting functional groups in the thermosetting resin is preferably 2 or more (for example, 2 to 4).
- thermosetting resin examples include phenol-based resin, epoxy-based resin, urethane-based resin, melamine-based resin, and alkyd-based resin.
- thermoplastic resin examples include polystyrene-based resin, vinyl acetate-based resin, polyester-based resin, polyolefin-based resin (polyethylene-based resin, polypropylene-based resin composition, etc.), polyimide-based resin, acrylic-based resin, and the like.
- acrylic resins are preferable because they can impart cohesion and appropriate flexibility to adhesives and the like.
- acrylic resin designs There are various types of acrylic resin designs depending on the purpose. Accordingly, it is preferable to appropriately select the monomer species, copolymerization composition ratio, molecular weight, molecular weight distribution, cross-linking agent, compounding composition ratio, and the like.
- An acrylic resin is a resin containing an acrylic monomer (a monomer having a (meth)acryloyl group in the molecule) as a monomer component that constitutes the resin. That is, the acrylic resin contains structural units derived from acrylic monomers.
- the acrylic resin is preferably a polymer containing a (meth)acrylic acid alkyl ester as a monomer component constituting the polymer.
- (meth)acrylic means “acrylic” and/or “methacrylic” (one or both of "acrylic” and “methacrylic"), and the same applies to others. .
- a (meth)acrylic acid alkyl ester having a linear or branched alkyl group is preferably mentioned.
- 1 type may be used for the said (meth)acrylic-acid alkyl ester, and 2 or more types may be used for it.
- the (meth)acrylic acid alkyl ester having a linear or branched alkyl group is not particularly limited, but examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, Isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) ) isopentyl acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, ( meth) isononyl acrylate, decyl
- (meth)acrylic acid alkyl ester having a linear or branched alkyl group among them, a linear or branched chain having 2 or more carbon atoms (preferably 2 to 18, more preferably 2 to 5) A (meth)acrylic acid alkyl ester having a triangular alkyl group is preferred.
- the content of structural units derived from (meth)acrylic acid alkyl ester in the acrylic resin is preferably 70% by mass or more, more preferably 100% by mass, based on the total amount of the monomer components constituting the acrylic resin. It is 80% by mass or more. The above content is preferably 99% by mass or less, more preferably 98% by mass or less. Of course, depending on the application and required properties, the content ratio of the structural unit derived from the (meth)acrylic acid alkyl ester in the acrylic resin may be and may be less than 70% by mass.
- the acrylic resin contains the (meth)acrylic acid alkyl ester and other monomers (copolymerizable monomers) copolymerizable with the (meth)acrylic acid alkyl ester as monomer components constituting the resin. good too. That is, the acrylic resin may contain a copolymerizable monomer as a structural unit.
- the above copolymerizable monomers may be used alone or in combination of two or more.
- Examples of the copolymerizable monomer include carboxy group-containing monomers, hydroxy group-containing monomers, epoxy group-containing monomers, keto group-containing monomers, alkoxy group-containing monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, vinyl ester-based monomers, vinyl ether-based monomers, isocyanate group-containing monomers, aromatic vinyl compounds, alicyclic monomers, aromatic ring-containing (meth)acrylates, chlorine-containing monomers, nitrogen-containing monomers, and the like.
- the content of structural units derived from copolymerizable monomers in the acrylic resin is preferably 0.1% by mass or more, more preferably 0%, based on the total amount of 100% by mass of the monomer components constituting the acrylic resin. .3% by mass or more.
- the above content is preferably 15% by mass or less, more preferably 10% by mass or less.
- the content ratio of the structural units derived from the copolymerizable monomer in the acrylic resin may be It may be less than 0.1% by mass.
- the polymer (A) is preferably a thermoplastic resin, more preferably an acrylic resin.
- the acrylic resin preferably contains at least an acrylic monomer and a compound (B) as monomer components constituting the resin.
- the content of the thermoplastic resin is not particularly limited. 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and especially Preferably, it is 90% by mass or more.
- the amount of the thermoplastic resin includes the amount of the thermoplastic resin, its raw material monomers, the cross-linking agent, and the structural portion derived from the cross-linking agent.
- the adhesive or the like of the present invention may contain other components other than the components described above, if necessary.
- the other components include resins other than the polymer (A), curing catalysts, cross-linking agents (including polyfunctional (meth)acrylates), cross-linking accelerators, polymerization initiators, tackifying resins (rosin derivatives, polyterpene resins , petroleum resin, oil-soluble phenol, etc.), oligomers, antioxidants, fillers (metal powder, organic fillers, inorganic fillers, etc.), coloring agents (pigments, dyes, etc.), antioxidants, plasticizers, softeners , surfactants, antistatic agents, surface lubricants, leveling agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, particulates, foils, flame retardants, silane coupling agents, ion trapping agents, etc. . Only one kind of each of the other components may be used, or two or more kinds thereof may be used.
- the cross-linking agent is not particularly limited as long as it cross-links the polymer, and includes polyisocyanate compounds, epoxy compounds, polyol compounds (such as polyphenol compounds), aziridine compounds, melamine-based cross-linking agents, and polyfunctional (meth)acrylates.
- polyfunctional (meth)acrylates include bifunctional or higher (meth)acrylic acid esters, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di pentaerythritol hexa(meth)acrylate and the like.
- the pressure-sensitive adhesive or the like of the present invention is a fluid pressure-sensitive adhesive composition or adhesive composition and the case where it is a pressure-sensitive adhesive layer or adhesive layer.
- an adhesive composition and/or an adhesive composition may be called “adhesive composition etc.”.
- an adhesive layer and/or an adhesive layer may be called “adhesive layer etc.”.
- FIG. 1 is a schematic cross-sectional view of one embodiment in which the adhesive or the like of the present invention is an adhesive layer or the like.
- a pressure-sensitive adhesive layer or adhesive layer 1 shown in FIG. 1 is laminated on the release-treated surface of a release liner 2 to form a pressure-sensitive adhesive sheet or adhesive sheet 10 with a release liner.
- the adhesive layer or the like of the present invention is an adhesive layer or the like
- the adhesive layer or the like contains at least the polymer (A). Only one kind of polymer (A) may be used, or two or more kinds thereof may be used.
- the content ratio of one or more selected from the group consisting of structural units derived from the compound (B) and structural units derived from the compound (B) in the polymer (A) is cleaved and shredded after application of an external stimulus.
- the polymer (A) is preferably 0.1 to 15% by mass, more preferably 0.2 to 10% by mass, and still more preferably 0 .5 to 5% by weight, particularly preferably 1 to 3% by weight.
- the entangled polymer is converted into one polymer.
- the content of the polymer (A) in the pressure-sensitive adhesive layer, etc. is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass, with respect to 100% by mass of the total amount of the pressure-sensitive adhesive layer, etc. % or more, particularly preferably 90 mass % or more.
- the content ratio includes the amount of the compound (B) and the structural units derived from the compound (B).
- the amount of the polymer (A) includes the amount of the polymer (A), its raw material monomers, the cross-linking agent, and the structural part derived from the cross-linking agent.
- the content of the cross-linking agent and/or the structural part derived from the cross-linking agent in the pressure-sensitive adhesive layer or the like is preferably 0.1 to 15% by mass, more preferably 0.1 to 15% by mass with respect to 100% by mass of the total amount of the polymer (A). 0.2 to 10% by mass, more preferably 0.5 to 5% by mass, particularly preferably 1 to 3% by mass.
- the content includes the amount of the compound (B) and the structural portion derived from the compound (B).
- the pressure-sensitive adhesive layer and the like may contain components other than the components described above.
- Examples of the above-mentioned other components include those exemplified and explained as other components that may be contained in the pressure-sensitive adhesive or the like of the present invention. Only one kind of each of the other components may be used, or two or more kinds thereof may be used.
- the base polymer forms a network structure in the adhesive layer and the like.
- a network structure refers to a state in which molecules are entangled with each other, or a state in which molecular chains form a long molecule through some bond.
- the polymer (A) is preferably a polymer in which a network structure is formed by bonding or entanglement between molecules.
- a pressure-sensitive adhesive layer or the like having such a configuration forms a network structure through polymer-to-polymer bonding or polymer-to-polymer entanglement, and can have an appropriate degree of hardness. The decomposition of the polymer shreds the polymer structure and improves flexibility.
- Micromolecules are entangled with each other refers to the state in which macromolecules form a network structure without covalent bonds. In order to form such an entangled structure, it is preferable to contain different types of polymers that are unlikely to cause a cross-linking reaction. preferable. Such a configuration is suitable for adhesives or the like that are relatively soft before application of an external stimulus because no covalent bond is involved.
- the state in which the molecular chains form a long molecule through some kind of bond means that the polymer is a single macromolecular polymer.
- Such a structure can form a relatively hard adhesive, etc., because the molecular chains are covalently bonded to each other. Suitable for pressure-sensitive adhesives, etc. with different thicknesses.
- the shear storage modulus (G') of the pressure-sensitive adhesive layer or the like is lowered by irradiation with active energy rays. Flexibility of such a pressure-sensitive adhesive or the like is improved by irradiation with active energy rays. Also, it is preferable that the shear storage modulus (G') does not increase after the decrease.
- the pressure-sensitive adhesive layer or the like preferably has a shear storage modulus (G') of 1.0 ⁇ 10 3 to 1.0 ⁇ 10 8 Pa at 25° C. before application of an external stimulus, more preferably 1. 0 ⁇ 10 4 to 1.0 ⁇ 10 7 Pa, more preferably 1.0 ⁇ 10 4 to 1.0 ⁇ 10 6 Pa, particularly preferably 2.0 ⁇ 10 4 to 1.0 ⁇ 10 5 Pa .
- G' shear storage modulus
- the pressure-sensitive adhesive layer and the like having the above shear storage elastic modulus have appropriate hardness before application of an external stimulus, and are excellent in workability such as production/processing, storage and transportation.
- the pressure-sensitive adhesive layer or the like preferably has a shear storage modulus (G') of 1.0 ⁇ 10 3 to 5.0 ⁇ 10 7 Pa at 50° C. before application of an external stimulus, more preferably 7. 0 ⁇ 10 3 to 1.0 ⁇ 10 6 Pa, more preferably 1.0 ⁇ 10 4 to 1.0 ⁇ 10 5 Pa.
- G' shear storage modulus
- the pressure-sensitive adhesive layer or the like having the above shear storage elastic modulus has an appropriate hardness before applying an external stimulus even when the temperature is slightly increased due to the environment, and is excellent in workability such as manufacturing/processing, storage, and transportation. .
- the pressure-sensitive adhesive layer or the like preferably has a shear storage modulus (G') of 1.0 ⁇ 10 2 to 1.0 ⁇ 10 6 Pa at 85° C. before application of an external stimulus, more preferably 1. 0 ⁇ 10 3 to 1.0 ⁇ 10 5 Pa, more preferably 5.0 ⁇ 10 3 to 1.0 ⁇ 10 5 Pa.
- G' shear storage modulus
- the pressure-sensitive adhesive layer or the like having the above-mentioned shear storage modulus has an appropriate hardness before applying an external stimulus even when applied in a high-temperature environment. Excellent.
- the pressure-sensitive adhesive layer or the like preferably has a shear storage modulus (G') of 1.0 ⁇ 10 2 to 5.0 ⁇ 10 6 Pa at 25° C. after application of an external stimulus, more preferably 1. 0 ⁇ 10 3 to 5.0 ⁇ 10 5 Pa, more preferably 3.0 ⁇ 10 3 to 1.0 ⁇ 10 5 Pa, particularly preferably 5.0 ⁇ 10 3 to 5.0 ⁇ 10 4 Pa .
- G' shear storage modulus
- the pressure-sensitive adhesive layer or the like of the present invention is more excellent in flexibility after application of an external stimulus, and is more excellent in step followability, adhesiveness, and the like.
- the pressure-sensitive adhesive layer or the like preferably has a shear storage modulus (G') of 1.0 ⁇ 10 2 to 1.0 ⁇ 10 6 Pa at 50° C. after application of an external stimulus, more preferably 5. 0 ⁇ 10 2 to 3.0 ⁇ 10 5 Pa, more preferably 1.0 ⁇ 10 3 to 1.0 ⁇ 10 5 Pa, particularly preferably 2.0 ⁇ 10 3 to 8.0 ⁇ 10 4 Pa .
- G' shear storage modulus
- the shear storage elastic modulus is within the above range, after application of an external stimulus, for example, when the temperature is slightly increased due to the environment, the flexibility, step conformability, adhesion, etc. are superior.
- the pressure-sensitive adhesive layer or the like preferably has a shear storage modulus (G′) at 85° C. after application of an external stimulus of 1.0 ⁇ 10 2 to 8.0 ⁇ 10 5 Pa, more preferably 3. 0 ⁇ 10 2 to 1.0 ⁇ 10 5 Pa, more preferably 5.0 ⁇ 10 2 to 1.0 ⁇ 10 5 Pa, particularly preferably 1.0 ⁇ 10 2 to 7.0 ⁇ 10 4 Pa .
- G′ shear storage modulus
- the shear storage elastic modulus is within the above range, after application of an external stimulus, for example, when subjected to a high-temperature environment, the film is more excellent in flexibility, step followability, adhesion, and the like.
- the pressure-sensitive adhesive layer or the like has a ratio of the shear storage modulus (G') at 25 ° C. before applying an external stimulus to the shear storage modulus (G') at 25 ° C. after applying an external stimulus [after applying an external stimulus/external stimulus before application] is preferably less than 0.95 (eg, 0.01 or more and less than 0.95), more preferably 0.8 or less (eg, 0.05 to 0.8), still more preferably 0.7 or less (eg 0.1 to 0.7), particularly preferably 0.6 or less (eg 0.2 to 0.6). In this case, there is a tendency that the flexibility, step followability, and adhesion of the pressure-sensitive adhesive layer, etc. at around room temperature before and after the application of the external stimulus change more greatly.
- the pressure-sensitive adhesive layer or the like has a ratio of the shear storage modulus (G ') at 50 ° C. before applying an external stimulus to the shear storage modulus (G ') at 50 ° C. after applying an external stimulus [after applying an external stimulus/external stimulus before application] is preferably less than 0.95 (eg, 0.01 or more and less than 0.95), more preferably 0.8 or less (eg, 0.05 to 0.8), still more preferably 0.7 or less (eg 0.1 to 0.7), particularly preferably 0.6 or less (eg 0.2 to 0.6). In this case, there is a tendency that the flexibility, step followability, and adhesiveness of the pressure-sensitive adhesive layer, etc. at around 50° C. change more significantly before and after applying an external stimulus.
- the pressure-sensitive adhesive layer or the like has a ratio of the shear storage modulus (G') at 85 ° C. before applying an external stimulus to the shear storage modulus (G') at 85 ° C. after applying an external stimulus [after applying an external stimulus/external stimulus before application] is preferably less than 0.95 (eg, 0.01 or more and less than 0.95), more preferably 0.8 or less (eg, 0.05 to 0.8), still more preferably 0.7 or less (eg 0.1 to 0.7), particularly preferably 0.6 or less (eg 0.2 to 0.6). In this case, there is a tendency that the flexibility, step followability, and adhesion of the pressure-sensitive adhesive layer, etc. under high-temperature environments change more significantly before and after the application of the external stimulus.
- the pressure-sensitive adhesive layer, etc. of the present invention have the property that the hardness is reduced by an external stimulus.
- the hardness does not increase after reduction.
- Such a pressure-sensitive adhesive layer or the like does not increase in hardness in a state where the pressure-sensitive adhesive layer or the like is adhered or adhered to a member, and maintains flexibility.
- the hardness is preferably Young's modulus, which is measured, for example, with a tensile compression tester. That is, it is preferable that the pressure-sensitive adhesive layer or the like of the present invention has a property that Young's modulus is reduced by an external stimulus.
- the Young's modulus of the pressure-sensitive adhesive layer or the like after application of the external stimulus is lower than that before the application of the external stimulus.
- Such a pressure-sensitive adhesive layer or the like is excellent in handleability before application of an external stimulus, and excellent in flexibility, impact resistance, and shape deformability in a high speed range after application of an external stimulus.
- the Young's modulus (E1) of the pressure-sensitive adhesive layer and the like before application of an external stimulus is preferably 200 MPa or less (eg, 0.03 to 200 MPa).
- the pressure-sensitive adhesive layer or the like preferably has a Young's modulus (E2) of 50 MPa or less (eg, 0.001 to 50 MPa) after application of an external stimulus.
- the pressure-sensitive adhesive layer or the like having the above Young's modulus has an appropriate hardness before application of an external stimulus, and is excellent in workability such as manufacturing/processing, storage and transportation.
- the pressure-sensitive adhesive layer or the like having the above Young's modulus is excellent in flexibility after application of an external stimulus, and is more excellent in step followability, adhesiveness, and the like.
- the pressure-sensitive adhesive layer preferably has a Young's modulus (E1) of 0.03 to 1.5 MPa, more preferably 0.05 to 1.0 MPa, still more preferably 0.1 to 0 .8 MPa.
- E1 Young's modulus
- the pressure-sensitive adhesive layer having the above Young's modulus (E1) has appropriate hardness before application of an external stimulus and is superior in handleability.
- the pressure-sensitive adhesive layer preferably has a Young's modulus (E2) of less than 1.0 MPa (for example, 0.001 MPa or more and less than 1.0 MPa), more preferably 0.5 MPa or less (for example, 0.001 MPa or more and less than 1.0 MPa) after application of an external stimulus. 005 to 0.5 MPa), more preferably 0.3 MPa or less (for example, 0.01 to 0.3 MPa).
- E2 Young's modulus
- the pressure-sensitive adhesive layer having the above Young's modulus is excellent in flexibility after application of an external stimulus, and is more excellent in step followability, adhesion, and the like.
- the pressure-sensitive adhesive layer or the like has a ratio [Young's modulus (E2)/Young's modulus (E1)] of Young's modulus (E1) before applying an external stimulus to Young's modulus (E2) after applying an external stimulus is less than 0.95 ( For example, 0.1 or more and less than 0.95), more preferably 0.8 or less (eg, 0.2 to 0.8), still more preferably 0.7 or less (eg, 0.3 to 0.7 ). In this case, there is a tendency that the flexibility, step followability, and adhesion of the pressure-sensitive adhesive layer, etc., change more significantly before and after the application of the external stimulus.
- the pressure-sensitive adhesive layer, etc. of the present invention have the property of reducing stress due to an external stimulus.
- the stress does not increase after reduction.
- Such a pressure-sensitive adhesive layer or the like does not increase stress in a state in which the pressure-sensitive adhesive layer or the like is adhered or adhered to a member, and maintains its flexibility.
- the stress examples include the stress (distortion stress) when pulled at an arbitrary magnification, which is measured by a tension/compression tester.
- the stress (distortion stress) when pulled at the above-mentioned specific magnification may be reduced as long as the stress (distortion stress) when pulled at at least one magnification is reduced.
- the strain stress at at least one of the tensile ratios of 100 to 500% is reduced, and the strain at one or more tensile ratios selected from the group consisting of 100%, 200%, 300%, and 500%.
- a reduction in stress is particularly preferred. Preferred ranges of stress at each tensile magnification are described below, and these values are preferred ranges when no breakage occurs at each tensile magnification.
- the pressure-sensitive adhesive layer or the like has a ratio [S2 ( 100)/S1(100)] is preferably less than 0.95 (for example, 0.1 or more and less than 0.95), more preferably 0.9 or less, still more preferably 0.8 or less.
- a ratio [S2 ( 100)/S1(100)] is preferably less than 0.95 (for example, 0.1 or more and less than 0.95), more preferably 0.9 or less, still more preferably 0.8 or less.
- the pressure-sensitive adhesive layer or the like preferably has a stress (100% strain stress) (S1(100)) of 0.01 MPa or more (for example, 0.01 to 10 MPa) before application of an external stimulus, more preferably 0.01 MPa or more (for example, 0.01 to 10 MPa).
- a stress (100% strain stress) S1(100)
- 0.01 MPa or more for example, 0.01 to 10 MPa
- 03 MPa or more eg 0.03 to 6 MPa
- more preferably 0.05 MPa or more eg 0.05 to 3 MPa.
- Such a pressure-sensitive adhesive layer or the like is even more excellent in flexibility after application of an external stimulus.
- the pressure-sensitive adhesive layer or the like preferably has a stress (100% strain stress) (S2(100)) after application of an external stimulus of 10 MPa or less (eg, 0.01 to 10 MPa), more preferably 6 MPa or less (eg, 0.02 to 6 MPa), more preferably 3 MPa or less (for example, 0.03 to 3 MPa).
- a stress (100% strain stress) S2(100)
- Such a pressure-sensitive adhesive layer or the like is even more excellent in flexibility after application of an external stimulus.
- the pressure-sensitive adhesive layer or the like has a ratio [S2 ( 200)/S1(200)] is preferably less than 0.95 (for example, 0.1 or more and less than 0.95), more preferably 0.8 or less, still more preferably 0.7 or less.
- a ratio [S2 ( 200)/S1(200)] is preferably less than 0.95 (for example, 0.1 or more and less than 0.95), more preferably 0.8 or less, still more preferably 0.7 or less.
- the pressure-sensitive adhesive layer or the like preferably has a stress (200% strain stress) (S1(200)) of 0.03 MPa or more (for example, 0.03 to 10 MPa) before application of an external stimulus, and more preferably 0.03 MPa or more (for example, 0.03 to 10 MPa).
- 04 MPa or more eg, 0.04 to 4 MPa
- 0.06 MPa eg, 0.06 to 2 MPa
- Such a pressure-sensitive adhesive layer or the like is even more excellent in flexibility after application of an external stimulus.
- the pressure-sensitive adhesive layer or the like preferably has a stress (200% strain stress) (S2(200)) after application of an external stimulus of 10 MPa or less (eg, 0.01 to 10 MPa), more preferably 4 MPa or less (eg, 0.03 to 4 MPa), more preferably 2 MPa or less (for example, 0.04 to 2 MPa).
- S2(200) stress (200% strain stress
- Such a pressure-sensitive adhesive layer or the like is even more excellent in flexibility after application of an external stimulus.
- the pressure-sensitive adhesive layer or the like has a ratio [S2 ( 300)/S1(300)] is preferably less than 0.95 (for example, 0.1 or more and less than 0.95), more preferably 0.8 or less, still more preferably 0.7 or less.
- a pressure-sensitive adhesive layer or the like shows that the tensile stress is reduced by applying an external stimulus, and is suitable for relatively low-load applications such as foldable members.
- the pressure-sensitive adhesive layer or the like preferably has a stress (300% strain stress) (S1(300)) of 0.03 MPa or more (for example, 0.03 to 10 MPa) before application of an external stimulus, more preferably 0. 05 MPa or more (eg 0.05 to 4 MPa), more preferably 0.07 MPa or more (eg 0.07 to 2 MPa).
- a stress (300% strain stress) S1(300)
- 0.03 MPa or more for example, 0.03 to 10 MPa
- an external stimulus more preferably 0. 05 MPa or more (eg 0.05 to 4 MPa)
- 0.07 MPa or more eg 0.07 to 2 MPa.
- the pressure-sensitive adhesive layer or the like preferably has a stress (300% strain stress) (S2(300)) after application of an external stimulus of 10 MPa or less (eg, 0.01 to 10 MPa), more preferably 4 MPa or less (eg, 0.03 to 4 MPa), more preferably 2 MPa or less (for example, 0.04 to 2 MPa).
- a stress (300% strain stress) S2(300)
- Such a pressure-sensitive adhesive layer or the like is even more excellent in flexibility after application of an external stimulus.
- the pressure-sensitive adhesive layer or the like has a ratio [S2 ( 500)/S1(500)] is preferably less than 0.95 (for example, 0.1 or more and less than 0.95), more preferably 0.8 or less, still more preferably 0.7 or less.
- a pressure-sensitive adhesive layer or the like shows that a relatively strong tensile stress is reduced by applying an external stimulus, and the repulsive force when pulled is particularly low, and a folding type (especially a winding type such as a rollable) member etc. Suitable for relatively high load applications.
- the pressure-sensitive adhesive layer or the like preferably has a stress (500% strain stress) (S1(500)) of 0.05 MPa or more (eg, 0.05 to 10 MPa) before application of an external stimulus, more preferably 0 0.07 MPa or more (eg, 0.07 to 4 MPa), more preferably 0.1 MPa or more (eg, 0.1 to 2 MPa).
- a stress-sensitive adhesive layer or the like is even more excellent in flexibility after application of an external stimulus.
- the pressure-sensitive adhesive layer or the like preferably has a stress (500% strain stress) (S2(500)) after application of an external stimulus of 10 MPa or less (eg, 0.01 to 10 MPa), more preferably 4 MPa or less (eg, 0.03 to 4 MPa), more preferably 2 MPa or less (for example, 0.04 to 2 MPa).
- S2(500) stress (500% strain stress)
- Such a pressure-sensitive adhesive layer or the like is even more excellent in flexibility after application of an external stimulus.
- the pressure-sensitive adhesive layer and the like of the present invention may have the property of reducing the peak strength (stress peak strength) in the stress-strain curve and the stress at break due to an external stimulus. It is preferable that the stress peak strength and the stress at break do not increase after reduction.
- the pressure-sensitive adhesive layer or the like preferably has a peak strength (stress peak strength) of 0.07 MPa or more, more preferably 0.1 MPa or more, and still more preferably 0.2 MPa in a stress-strain curve before application of an external stimulus. That's it.
- stress peak strength is 0.07 MPa or more
- the pressure-sensitive adhesive layer or the like has appropriate hardness before application of an external stimulus, and is excellent in workability such as manufacturing/processing, storage and transportation.
- the pressure-sensitive adhesive layer or the like preferably has a peak strength (stress peak strength) in a stress-strain curve after application of an external stimulus of 0.01 to 1.0 MPa, more preferably 0.03 to 0.8 MPa. More preferably, it is 0.04 to 0.5 MPa.
- stress peak intensity is within the above range, the flexibility, step conformability, adhesion, etc. are more excellent after application of an external stimulus.
- the ratio of the peak intensity in the stress-strain curve before applying the external stimulus to the peak intensity in the stress-strain curve after applying the external stimulus [after applying the external stimulus/before applying the external stimulus] is 0.5. It is preferably less than 95 (eg, 0.05 or more and less than 0.95), more preferably 0.8 or less (eg, 0.1 to 0.8), still more preferably 0.7 or less (eg, 0.3 to 0.7). In this case, there is a tendency that the flexibility, step followability, and adhesion of the pressure-sensitive adhesive layer, etc., change more significantly before and after the application of the external stimulus.
- the thickness of the adhesive layer, etc. is not particularly limited, but is, for example, about 5 to 250 ⁇ m, more preferably 7 to 200 ⁇ m, even more preferably 10 to 100 ⁇ m, and particularly preferably 10 to 50 ⁇ m.
- the release liner protects the pressure-sensitive adhesive surface and/or the adhesive surface with which the pressure-sensitive adhesive layer and the like are in contact until use, and is peeled off when the pressure-sensitive adhesive layer and the like is used.
- base materials for the release liner include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, poly Butylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene/(meth)acrylic acid copolymer film, ethylene/(meth)acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, A fluorine resin film etc. are mentioned. Moreover, these crosslinked films are also mentioned. Furthermore, a laminated film of these may be used.
- the release surface of the release liner (especially the surface in contact with the pressure-sensitive adhesive layer, etc.) is preferably subjected to a release treatment.
- release agents used in the release treatment include alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents.
- the thickness of the release liner is not particularly limited, it is, for example, about 20 to 150 ⁇ m.
- the pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive composition. Also, the adhesive layer is formed from the adhesive composition.
- the pressure-sensitive adhesive composition and the like preferably contain at least a base polymer and/or a raw material monomer thereof.
- the base polymer is polymer (A) and/or other polymers (that is, polymers without irreversible degradable bonds). Only one type of the base polymer may be used, or two or more types may be used.
- the adhesive composition or the like further contains the compound (B).
- the base polymer preferably contains the polymer (A), and more preferably contains the polymer (A) and the other polymer.
- the polymer (A) is preferably a curable resin.
- the curability of the curable resin is appropriately selected according to the type of the irreversibly decomposable bond, and when the irreversibly decomposable bond can be cleaved by active energy rays, it is preferably a thermosetting resin.
- the polymer (A), which is the curable resin, is preferably a resin (prepolymer) having a polymerizable functional group.
- a resin (prepolymer) having a polymerizable functional group when the polymer (A) has a polymerizable functional group, when forming an adhesive layer or the like, polymerization of the polymerizable functional groups proceeds by heat or active energy ray irradiation after application of the adhesive composition or the like. , can form a network structure by entangling with other polymers. That is, the polymer (A) is preferably a polymer capable of forming the above network structure. Only one kind of the other polymers may be used, or two or more kinds thereof may be used.
- the adhesive composition or the like further contains the compound (B).
- a monomer component (monomer component (C)) having reactivity with the compound (B) may be further included.
- Compound (B) has reactivity with the other polymer and/or monomer component (C).
- the compound (B) has reactivity with the other polymer
- the other polymer and the compound (B) react with heat or active energy ray irradiation in the pressure-sensitive adhesive layer or the like to form, for example, a polymer chain
- the polymer chain and the other polymer combine to form a network structure, and a pressure-sensitive adhesive layer or the like containing the polymer (A) is obtained.
- the compound (B) and the monomer component (C) react with heat or active energy ray irradiation in the pressure-sensitive adhesive layer or the like to form, for example, a polymer chain.
- the polymer chains and the above-mentioned other polymers are entangled to form a network structure, and a pressure-sensitive adhesive layer or the like containing the polymer (A) is obtained.
- the compound (B) is incorporated into the base polymer when the raw material monomer is polymerized to form the polymer (A).
- the raw material monomer is polymerized to form the other polymer, which is then reacted with compound (B) to form polymer (A).
- the above-mentioned pressure-sensitive adhesive composition mainly includes (i) a pressure-sensitive adhesive composition containing the polymer (A), (ii) a pressure-sensitive adhesive composition containing the polymer (A) and the other polymer, and (iii) the above Other polymers, compound (B), pressure-sensitive adhesive composition containing monomer component (C) as necessary, (iv) raw material monomer, compound (B), pressure-sensitive adhesive containing monomer component (C) as necessary composition and the like.
- the polymer (A) may be a reaction product of the other polymer, the compound (B), and the monomer component (C), or a reaction product of the other polymer with the other polymer and the compound (a). It may also be a polymer comprising (especially entangled). Moreover, when the base polymer contains polymer (A), the pressure-sensitive adhesive layer and the like may contain unreacted compound (B) and/or unreacted monomer component (C).
- the base polymer examples include the thermoplastic resin, the thermosetting resin, the active energy ray-curable resin, and the like.
- the polymer (A) as the base polymer is preferably a curable resin, more preferably a thermosetting resin.
- Thermoplastic resins are preferable as the other polymers.
- a pressure-sensitive adhesive layer or the like containing a thermoplastic resin is capable of exerting adhesiveness such that it adheres under pressure from the outside, for example.
- a pressure-sensitive adhesive composition containing a thermosetting resin can form a network structure, for example, by being cured by heating.
- the other polymer may be a curable resin, and in this case, the polymer (A), which is also a curable resin, and the other polymer form a bond between the two resins by heat, active energy ray irradiation, or the like. It becomes possible to form a network structure.
- the compound (B) includes a monomer component, an oligomer component, a cross-linking agent, and the like having the irreversibly degradable bond.
- the monomer component that is, the compound having the polymerizable functional group
- the nitrobenzyl-based monomer is more preferred
- the nitrobenzyl ester-based monomer is even more preferred.
- the content of the polymer (A) in the base polymer is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, more preferably 40 to 90% by mass, relative to the total amount (100% by mass) of the base polymer. 60% by mass.
- the content is 10% by mass or more, a sufficient amount of the irreversible degradable bond is cleaved by an external stimulus.
- the content is 90% by mass or less, appropriate tackiness and/or adhesiveness can be maintained even after application of an external stimulus.
- the content of the other polymer in the base polymer is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, more preferably 40 to 90% by mass, relative to the total amount (100% by mass) of the base polymer. 60% by mass.
- the above content is 10% by mass or more, appropriate tackiness and/or adhesiveness can be maintained even after application of an external stimulus.
- the polymer (A) can be sufficiently blended, whereby the irreversible degradable bond is cleaved in a sufficient amount by an external stimulus.
- the content of structural units derived from the compound (B) in the polymer (A) is preferably 0.2 to 30% by mass, more preferably 0.5 to 30% by mass, with respect to 100% by mass of the total amount of the polymer (A). 15% by mass, more preferably 0.8 to 10% by mass.
- the content of the compound (B) in all the monomer components constituting the polymer (A) is preferably within the above range.
- the content of structural units derived from acrylic monomers in the polymer (A) is 70 to 99.8 with respect to 100% by mass of the total amount of the polymer (A). % by mass is preferable, more preferably 85 to 99.5% by mass, and still more preferably 90 to 99.2% by mass.
- the pressure-sensitive adhesive composition or the like contains a raw material monomer that constitutes the base polymer, the content of the acrylic monomer in all the monomer components that constitute the polymer (A) is preferably within the above range.
- the content of structural units derived from the compound (B) in the base polymer is 100% by mass in the total amount of the base polymer in order to exhibit sufficient flexibility by being cleaved and shredded after application of an external stimulus. is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. Moreover, in order to make the crosslink density appropriate and to impart appropriate flexibility to the resin before applying an external stimulus, the amount is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.
- the pressure-sensitive adhesive composition or the like contains raw material monomers constituting the base polymer, the content of the compound (B) in all the monomer components constituting the base polymer is preferably within the above range.
- the content of structural units derived from acrylic monomers in the base polymer is preferably 85 to 99.9% by mass with respect to 100% by mass of the total amount of the base polymer. , more preferably 90 to 99.8% by mass, more preferably 95 to 99.5% by mass.
- the pressure-sensitive adhesive composition or the like contains a raw material monomer constituting the base polymer, the content of the acrylic monomer in all the monomer components constituting the base polymer is preferably within the above range.
- the adhesive composition and the like may contain other components other than the components described above.
- examples of the above-mentioned other components include those exemplified and explained as other components that may be contained in the above-described pressure-sensitive adhesive of the present invention, and solvents such as organic solvents. Only one kind of each of the other components may be used, or two or more kinds thereof may be used.
- the content of the base polymer in the pressure-sensitive adhesive composition, etc. is 50% by mass or more with respect to 100% by mass of the total amount of the pressure-sensitive adhesive composition, etc. (excluding components such as organic solvents that do not remain during layer formation). is preferred, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
- the pressure-sensitive adhesive sheet with a release liner or adhesive sheet 10 shown in FIG. 1 can be produced by the following method. After forming a coating layer by applying a pressure-sensitive adhesive composition or the like for forming the pressure-sensitive adhesive layer or the like 1 to the base material layer or the release-treated surface of the release liner 2 that has been subjected to the release treatment, the solvent is removed by heating, or It can be prepared by hardening the coating layer by heat curing or curing by irradiation with active energy rays. In addition, when performing active energy ray irradiation, it is performed after bonding a separate release liner on the coating layer.
- the adhesive composition and the like may be in any form as long as it does not impair the effects of the present invention.
- the pressure-sensitive adhesive composition may be emulsion type, solvent type (solution type), heat melting type (hot melt type), or the like.
- the solvent type is preferable because it is easy to obtain a pressure-sensitive adhesive layer with excellent productivity.
- the adhesive layer or the like is formed by heating when the coating layer is solidified.
- the pressure-sensitive adhesive composition or the like contains the other polymer and/or raw material monomer and the compound (B)
- the raw material monomer is optionally removed by heating or active energy ray irradiation when solidifying the coating layer. is polymerized, and the compound (B) forms a bond with the polymer of the raw material monomers and the above-mentioned other polymer to form the polymer (A), and at the same time, the pressure-sensitive adhesive layer and the like are formed.
- the pressure-sensitive adhesive layer and the like may be heated or irradiated with an active energy ray, or when the polymer (A) is a curable resin, a curing treatment may be performed.
- the pressure-sensitive adhesive sheet with a release liner or adhesive sheet 10 shown in FIG. 1 is obtained.
- the use of the adhesive, etc. of the present invention is not particularly limited, and it can be used for any purpose.
- the pressure-sensitive adhesive or the like of the present invention can be used, for example, for optical applications, that is, for bonding to optical members.
- the pressure-sensitive adhesive or the like of the present invention is used, for example, in optical members such as electrical and electronic equipment, when various members or parts are attached (mounted) to a predetermined portion (for example, a housing or the like).
- electrical/electronic equipment refers to equipment corresponding to at least one of electric equipment and electronic equipment.
- Examples of the electric/electronic devices include image display devices such as liquid crystal displays, electroluminescence displays, and plasma displays, and mobile electronic devices.
- Examples of the image display device include an image display device in the portable electronic device, a display (roll display) inside and outside a vehicle such as a train or a bus, and the like.
- Examples of the portable electronic devices include mobile phones, smartphones, tablet computers, notebook computers, and various wearable devices (for example, wrist wear types that are worn on the wrist like wristwatches, clips, straps, etc. that are attached to a part of the body) Modular type to be worn, eyewear type including eyeglass type (monocular type and binocular type, including head-mounted type), clothing type that can be attached to shirts, socks, hats, etc.
- wearable devices for example, wrist wear types that are worn on the wrist like wristwatches, clips, straps, etc. that are attached to a part of the body
- Modular type to be worn for example, wrist wear types that are worn on the wrist like wristwatches, clips, straps, etc. that are attached to a part of the body
- eyewear type including eyeglass type (monocular type and binocular type, including head-mounted type)
- clothing type that can be attached to shirts, socks, hats, etc.
- the term “portable” means not only being able to be carried but also having a level of portability that allows individuals (standard adults) to relatively easily carry it. shall mean.
- the adhesive, etc. of the present invention can improve flexibility by applying an external stimulus at any time. For this reason, during manufacturing, processing, storage, transportation, etc., it can be made to have a certain degree of hardness and be excellent in handleability. For example, at the time of cutting with a punching blade, it is possible to prevent paste from overflowing, lack of glue, and process contamination caused by these. In addition, the glue is less likely to ooze out due to its own weight during storage, and less likely to cause glue chipping due to vibration or contact during transportation. By improving the flexibility when used by being attached to a member, the adhesive strength, adhesive strength (adhesive strength), bendability, foldability, bending resistance, etc. can be improved. In addition, since the pressure-sensitive adhesive layer or the like of the present invention contains a polymer having an irreversible degradable bond in the molecule, it is possible to change the adhesive force and adhesion force by an external stimulus.
- a pressure-sensitive adhesive layer and/or a pressure-sensitive adhesive sheet can be obtained using the pressure-sensitive adhesive layer or the like of the present invention.
- an adhesive sheet and/or an adhesive sheet may be called “adhesive sheet etc.”.
- the pressure-sensitive adhesive sheet or the like may be a so-called “substrate-less type” pressure-sensitive adhesive sheet or the like that does not have a substrate (substrate layer), or may be a type pressure-sensitive adhesive sheet or the like that has a substrate.
- a "substrate-less type" pressure-sensitive adhesive sheet or the like may be referred to as a "substrate-less pressure-sensitive adhesive sheet or the like”
- a type pressure-sensitive adhesive sheet or the like having a substrate may be referred to as a "substrate-attached pressure-sensitive adhesive sheet or the like.”
- the substrate-less pressure-sensitive adhesive sheet or the like include, for example, a double-sided pressure-sensitive adhesive sheet or the like consisting only of the pressure-sensitive adhesive layer of the present invention, or the pressure-sensitive adhesive layer of the present invention and other pressure-sensitive adhesive layers (such as the pressure-sensitive adhesive layer of the present invention).
- a double-sided pressure-sensitive adhesive sheet made of a pressure-sensitive adhesive layer, etc., other than the above) may be mentioned.
- the adhesive sheet with a substrate or the like is a pressure-sensitive adhesive sheet or the like containing a substrate and the adhesive layer or the like of the present invention formed on at least one surface of the substrate.
- Examples include a double-sided pressure-sensitive adhesive sheet having a layer or the like and having another pressure-sensitive adhesive layer or the like on the other side.
- base material refers to a support, and when using (sticking) an adhesive sheet or the like on an adherend, This is the part where A release liner that is peeled off when using (sticking) an adhesive sheet or the like is not included in the base material.
- the substrate is not particularly limited.
- Various optical films such as a retardation plate can be used.
- the base material include porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and the like.
- Plastic film Materials for the plastic film include, for example, polyester resins such as polyethylene terephthalate (PET), acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate, triacetyl cellulose (TAC), polysulfone, polyarylate, polyimide, Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, ethylene-propylene copolymer, trade name “Arton” (cyclic olefin polymer, manufactured by JSR Corporation), trade name “Zeonor” (cyclic olefin polymer, Nippon Zeon Co., Ltd.) company) and other plastic materials such as cyclic olefin polymers. These plastic materials may be used alone or in combination of two or more.
- PET polyethylene terephthalate
- PMMA polymethyl methacrylate
- TAC triacetyl cellulose
- Polysulfone polyarylate
- Polyimide Polyvinyl chloride
- Polyvinyl acetate
- the thickness of the base material is not particularly limited, it is preferably 10 to 150 ⁇ m, more preferably 15 to 125 ⁇ m, still more preferably 25 to 100 ⁇ m.
- the substrate may have either a single-layer structure or a multilayer structure.
- the surface of the substrate may be appropriately subjected to known and commonly used surface treatments such as physical treatments such as corona discharge treatment and plasma treatment, and chemical treatments such as undercoating treatment.
- the adhesive sheet, etc. may be provided with a release liner on the surface (adhesive surface or adhesive surface) of the adhesive layer, etc. until use.
- a release liner on the surface (adhesive surface or adhesive surface) of the adhesive layer, etc. until use.
- each adhesive surface or adhesive surface may be protected by two release liners, or one release liner having release surfaces on both sides. may be protected in the form of being wound into a roll (wound body).
- a release liner is used as a protective material such as a pressure-sensitive adhesive layer, and is peeled off when applied to an adherend.
- the pressure-sensitive adhesive sheet or the like is a substrate-less pressure-sensitive adhesive sheet or the like
- the release liner also serves as a support for the pressure-sensitive adhesive layer and the like. Note that the release liner does not necessarily have to be provided.
- Preparation example 3 Synthesis of acrylic polymer P1
- a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube 95 parts by mass of n-butyl acrylate (BA), 5 parts by mass of acrylic acid (AA), and 0.2 of AIBN as a polymerization initiator.
- a mixture containing parts by mass and 122 parts by mass of ethyl acetate as a solvent was stirred at 60° C. for 7 hours under a nitrogen atmosphere to carry out a polymerization reaction.
- a polymer solution containing the acrylic polymer P1 was obtained.
- the weight average molecular weight (Mw) of the acrylic polymer P1 in this polymer solution was 600,000.
- Example 1 Synthesis of acrylic polymer P2
- BA butyl acrylate
- C12TCSS trade name "manufactured by Nippon Terpene Chemical Co., Ltd.”
- AIBN 2,2'-azobisisobutyronitrile
- a mixture containing parts by mass and 301 parts by mass of ethyl acetate as a solvent was stirred at 60° C. for 6 hours under a nitrogen atmosphere to carry out a polymerization reaction.
- a polymer solution containing acrylic polymer P2 (corresponding to polymer (A)), which is a prepolymer having acryloyl groups, was
- the pressure-sensitive adhesive composition was applied to the release-treated surface of a polyethylene terephthalate film (trade name: "MRF38", manufactured by Mitsubishi Chemical Corporation) with a silicone-based release agent, and the thickness of the pressure-sensitive adhesive layer after drying was was applied so as to have a thickness of 25 ⁇ m, allowed to stand at room temperature for 5 minutes, and then dried at 130° C. for 3 minutes.
- a pressure-sensitive adhesive sheet was obtained by sufficiently volatilizing and removing ethyl acetate contained as a solvent.
- Comparative example 1 Synthesis of acrylic polymer P3 95 parts by mass of butyl acrylate (BA), 5 parts by mass of 1,6-hexanediol diacrylate, and a commercial product as a chain transfer agent were placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube.
- Name "C12TCSS” manufactured by Nippon Terpene Chemical Co., Ltd.
- AIBN 2,2'-azobisisobutyronitrile
- AIBN 2,2'-azobisisobutyronitrile
- a pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1, except that the pressure-sensitive adhesive composition prepared above was used.
- Comparative example 2 Synthesis of acrylic polymer P4
- BA butyl acrylate
- C12TCSS trade name "manufactured by Nippon Terpene Chemical Co., Ltd.”
- a mixture containing 2.83 parts by mass, 0.28 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator, and 301 parts by mass of ethyl acetate as a solvent was heated at 60°C for 6 hours. , and stirred under a nitrogen atmosphere to carry out a polymerization reaction.
- AIBN 2,2'-azobisisobutyronitrile
- a pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1, except that the pressure-sensitive adhesive composition prepared above was used.
- UV irradiation For the adhesive sheets obtained in Examples and Comparative Examples, a release liner was further attached to the exposed adhesive surface, and a UV-LED irradiation device manufactured by Quark Technology Co., Ltd. (model number "QEL-350-RU6W-CW -MY”), a UV-LED lamp with a wavelength of 365 nm was used as a light source, and ultraviolet irradiation was performed with an integrated irradiation light amount of 8000 mJ/cm 2 in the wavelength range of 320 to 390 nm.
- Shear storage modulus Adhesive sheets were laminated to prepare a sample for measurement with a thickness of about 1.0 mm, and subjected to the following conditions using "Advanced Rheometric Expansion System (ARES)" manufactured by Rheometric Scientific. A dynamic viscoelasticity measurement was performed by Then, the shear storage elastic moduli at 25°C, 50°C and 80°C were calculated.
- Deformation mode Torsion Measurement frequency: 1Hz Heating rate: 5°C/min Measurement temperature: -50 to 150°C Shape: Parallel plate 8.0mm ⁇
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Abstract
Provided are a pressure-sensitive adhesive and/or an adhesive having flexibility that can be improved by an external stimulus at any time, or a pressure-sensitive adhesive and/or adhesive that can form said pressure-sensitive adhesive and adhesive. Provided is a pressure-sensitive adhesive and/or adhesive that contains: a polymer that has, in the molecules thereof, an irreversibly degradable bond that is broken by an external stimulus and does not subsequently re-bond; and/or a compound that can introduce the irreversibly degradable bond to the polymer. The irreversibly degradable bond preferably includes a nitrobenzyl group.
Description
本発明は、粘着剤および／または接着剤、より具体的には、粘着性を発揮し得る粘着剤層、接着性を発揮し得る接着剤層、上記粘着剤層を形成可能な組成物（粘着剤組成物）、および、上記接着剤層を形成可能な組成物（接着剤組成物）に関する。
The present invention relates to a pressure-sensitive adhesive and/or an adhesive, more specifically, a pressure-sensitive adhesive layer capable of exhibiting stickiness, an adhesive layer capable of exhibiting adhesiveness, and a composition capable of forming the pressure-sensitive adhesive layer (adhesive and a composition capable of forming the adhesive layer (adhesive composition).
ディスプレイ等の光学デバイスの中でも、ＯＬＥＤに代表される薄型、可撓性ディスプレイは、複数の光学用フィルムや薄層デバイスが積層された状態で構成される。また、感圧センサなどの可撓性を要求されるデバイスは、感圧部材と基板が積層された状態で構成される（特許文献１）。これらの積層体における層間充填剤には、液状硬化樹脂や粘着剤、接着剤が選択され、作業性の向上、硬化収縮による反り、応力分散による可撓性の向上などの観点から、粘着剤や接着剤（粘着剤等）が好ましく用いられている。
Among optical devices such as displays, thin and flexible displays typified by OLED are constructed by laminating a plurality of optical films and thin layer devices. A device such as a pressure-sensitive sensor that requires flexibility is constructed by laminating a pressure-sensitive member and a substrate (Patent Document 1). Liquid curable resins, pressure-sensitive adhesives, and adhesives are selected as interlayer fillers in these laminates. An adhesive (adhesive, etc.) is preferably used.
上記粘着剤等は、特に可撓性部材において、折り曲げ・折り畳みで生じる応力を分散・緩和する機能を担い、該機能は粘着剤等が柔軟であるほど効率的に発現されるとされ（特許文献２）、柔軟な粘着剤等が使用される。
The pressure-sensitive adhesive or the like has a function of dispersing and relieving the stress generated by bending/folding, especially in a flexible member, and it is said that the more flexible the pressure-sensitive adhesive or the like, the more efficiently the function is expressed (Patent Document 2) A flexible adhesive or the like is used.
一方で、柔軟な粘着剤等は僅かな応力でも大きく変形し、例えば打ち抜き刃での切り抜き時に、糊はみだし、糊欠け、これらに起因した工程汚染などが生じるなど、粘着剤等を製造・加工する時点で問題が生じることがある。加えて、このような粘着剤等では保管時には自重で糊はみだしが、運搬時には振動・接触による糊欠けなどの問題が生じることもある。
On the other hand, flexible adhesives, etc., can be greatly deformed even with a small amount of stress. Problems can arise at times. In addition, such an adhesive or the like may cause problems such as the paste oozing out due to its own weight during storage, and the paste being chipped due to vibration or contact during transportation.
このため、製造・加工、保管、運搬等の際にはある程度の硬さを有し、部材へ使用する際には柔軟性を有する粘着剤や接着剤が求められている。
Therefore, there is a demand for pressure-sensitive adhesives and adhesives that have a certain degree of hardness during manufacturing, processing, storage, transportation, etc., and that have flexibility when used for components.
本発明はこのような課題を解決するためのものであって、その目的は任意のタイミングで外部刺激により柔軟性が向上し得る粘着剤および／または接着剤、または当該粘着剤や接着剤を形成し得る粘着剤および／または接着剤を提供することにある。
The present invention is intended to solve such problems, and its object is to form a pressure-sensitive adhesive and / or adhesive, or the pressure-sensitive adhesive or adhesive that can improve flexibility by external stimulation at any timing. An object of the present invention is to provide a pressure-sensitive adhesive and/or an adhesive that can be used.
本発明者らは、上記課題を解決するため、鋭意努力した結果、外部刺激により非可逆的に開裂する結合を有するポリマーを含む粘着剤層および接着剤層によれば、任意のタイミングで外部刺激により柔軟性が向上することを見出した。本発明は、これらの知見に基づいて完成されたものである。
In order to solve the above problems, the present inventors made diligent efforts, and as a result, according to the pressure-sensitive adhesive layer and adhesive layer containing a polymer having a bond that is irreversibly cleaved by an external stimulus, an external stimulus can be applied at any time. It was found that the flexibility is improved by The present invention has been completed based on these findings.
すなわち、本発明は、外部刺激により結合が開裂しその後再結合しない非可逆分解性結合を分子内に有するポリマー、および／または、上記非可逆分解性結合をポリマーに導入可能な化合物を含有する、粘着剤および／または接着剤（粘着剤等）を提供する。
That is, the present invention contains a polymer having an irreversible degradable bond in its molecule that is not rebonded after being cleaved by an external stimulus, and/or a compound capable of introducing the irreversible degradable bond into the polymer. Adhesives and/or adhesives (such as adhesives) are provided.
上記粘着剤等が上記非可逆分解性結合を有するポリマーを含有する場合、外部刺激によって上記ポリマーに含まれる上記非可逆分解性結合が分解する。これにより、粘着剤等におけるポリマーの構造が細断され、柔軟性が向上する。また、上記粘着剤等が上記ポリマーに上記可逆分解性結合を導入可能な化合物を含む場合、上記化合物を例えばモノマー成分や架橋剤として作用させることで上記ポリマー中に上記非可逆分解性結合を導入することができる。
When the adhesive or the like contains the polymer having the irreversibly degradable bond, the irreversibly degradable bond contained in the polymer is decomposed by an external stimulus. As a result, the structure of the polymer in the pressure-sensitive adhesive or the like is shredded to improve the flexibility. Further, when the adhesive or the like contains a compound capable of introducing the reversible degradable bond into the polymer, the irreversible degradable bond is introduced into the polymer by allowing the compound to act as a monomer component or a cross-linking agent, for example. can do.
上記非可逆分解性結合はニトロベンジル基を含む結合であることが好ましい。この場合、ポリマーに非可逆分解性結合を導入することが容易である。
The irreversibly degradable bond is preferably a bond containing a nitrobenzyl group. In this case, it is easy to introduce an irreversible degradable bond into the polymer.
上記ポリマーは熱可塑性樹脂および／または熱硬化型樹脂であることが好ましい。熱可塑性樹脂を含有する粘着剤等は例えば外部からの圧力で密着する粘着性を発揮することが可能となる。熱硬化型樹脂を含有する粘着剤等は、例えば加熱により硬化することで被着体と接着することができる。
The polymer is preferably a thermoplastic resin and/or a thermosetting resin. A pressure-sensitive adhesive or the like containing a thermoplastic resin is capable of exerting adhesiveness such that it adheres under pressure from the outside, for example. A pressure-sensitive adhesive or the like containing a thermosetting resin can be adhered to an adherend by being cured by heating, for example.
上記ポリマーは結合または分子同士の絡み合いによりネットワーク構造を形成されたポリマーまたは上記ネットワーク構造を形成し得るポリマーであることが好ましい。このような構成を有する粘着剤等はポリマー同士の結合若しくはポリマー同士の絡み合いによってネットワーク構造を形成し、適度な硬さを有することが可能であり、外部刺激によって形成された非可逆分解性結合が分解することにより、ポリマー構造が細断され、柔軟性が向上する。
The above polymer is preferably a polymer that forms a network structure by bonding or entanglement between molecules or a polymer that can form the above network structure. A pressure-sensitive adhesive or the like having such a structure forms a network structure through polymer-to-polymer bonding or polymer-to-polymer entanglement, and can have an appropriate hardness, and the irreversible degradable bond formed by an external stimulus can be Degradation shreds the polymer structure and improves flexibility.
上記粘着剤等は光学用途に好ましく使用される。
The above-mentioned adhesives and the like are preferably used for optical applications.
本発明の粘着剤および／または接着剤は、任意のタイミングで外部刺激の付与により柔軟性を向上することが可能である。
The pressure-sensitive adhesive and/or adhesive of the present invention can improve flexibility by applying an external stimulus at any time.
［粘着剤、接着剤］
本明細書において、「粘着」は、外部からの感圧（例えば微小な圧力）によって、組成物が有する化学構造に基づく凝集力に基づき、２つの面が密着し、必要により剥離できる性質に関することを言う。これに対して、「接着」は、組成物が化学反応（硬化）して、硬化物を生成し、剥離を予定しておらず、２つの面が強固に接合できる性質に関することを言う。また、本明細書において、「粘着剤」は、流動性を有しない層状の粘着剤層であってもよく、上記粘着剤層を形成するための、流動性を有する粘着剤組成物であってもよい。同様に、「接着剤」は、流動性を有しない層状の接着剤層であってもよく、上記接着剤層を形成するための、流動性を有する接着剤組成物であってもよい。 [Adhesives, Adhesives]
As used herein, the term "adhesive" refers to the property that two surfaces adhere to each other and can be peeled off if necessary, based on the cohesive force based on the chemical structure of the composition, when external pressure is applied (e.g., microscopic pressure). say. On the other hand, "adhesion" refers to the property of chemically reacting (curing) the composition to form a cured product, which is not intended to be peeled off, and which allows two surfaces to be firmly joined together. Further, in the present specification, the "adhesive" may be a layered adhesive layer having no fluidity, and is an adhesive composition having fluidity for forming the adhesive layer. good too. Similarly, the "adhesive" may be a laminar adhesive layer that does not have fluidity, or it may be an adhesive composition that has fluidity for forming the adhesive layer.
本明細書において、「粘着」は、外部からの感圧（例えば微小な圧力）によって、組成物が有する化学構造に基づく凝集力に基づき、２つの面が密着し、必要により剥離できる性質に関することを言う。これに対して、「接着」は、組成物が化学反応（硬化）して、硬化物を生成し、剥離を予定しておらず、２つの面が強固に接合できる性質に関することを言う。また、本明細書において、「粘着剤」は、流動性を有しない層状の粘着剤層であってもよく、上記粘着剤層を形成するための、流動性を有する粘着剤組成物であってもよい。同様に、「接着剤」は、流動性を有しない層状の接着剤層であってもよく、上記接着剤層を形成するための、流動性を有する接着剤組成物であってもよい。 [Adhesives, Adhesives]
As used herein, the term "adhesive" refers to the property that two surfaces adhere to each other and can be peeled off if necessary, based on the cohesive force based on the chemical structure of the composition, when external pressure is applied (e.g., microscopic pressure). say. On the other hand, "adhesion" refers to the property of chemically reacting (curing) the composition to form a cured product, which is not intended to be peeled off, and which allows two surfaces to be firmly joined together. Further, in the present specification, the "adhesive" may be a layered adhesive layer having no fluidity, and is an adhesive composition having fluidity for forming the adhesive layer. good too. Similarly, the "adhesive" may be a laminar adhesive layer that does not have fluidity, or it may be an adhesive composition that has fluidity for forming the adhesive layer.
本発明の粘着剤および／または接着剤は、外部刺激により結合が開裂しその後再結合しない非可逆分解性結合を分子内に有するポリマー、および／または、上記非可逆分解性結合をポリマーに導入可能な化合物を少なくとも含有する。なお、本明細書において、上記ポリマーを「ポリマー（Ａ）」、上記非可逆分解性結合をポリマーに導入可能な化合物を「化合物（Ｂ）」と称する場合がある。なお、本明細書において、「粘着剤および／または接着剤」を「粘着剤等」と称する場合がある。
The pressure-sensitive adhesive and/or adhesive of the present invention is a polymer having an irreversible degradable bond in its molecule that is cleaved by an external stimulus and then not rebonded, and/or the irreversible degradable bond can be introduced into the polymer. contains at least a compound In this specification, the polymer may be referred to as "polymer (A)", and the compound capable of introducing the irreversibly degradable bond into the polymer may be referred to as "compound (B)". In this specification, "adhesive and/or adhesive" may be referred to as "adhesive or the like".
上記非可逆分解性結合の開裂反応を引き起こす外部刺激は、上記非可逆分解性結合の種類に応じて適宜選択され、活性エネルギー線照射、熱などが挙げられる。特に、ポリマー（Ａ）が熱硬化型樹脂または活性エネルギー線硬化型樹脂である場合の熱硬化反応または活性エネルギー線硬化反応と上記開裂とを別々で生じさせることが可能である観点から、ポリマー（Ａ）が硬化性を有する場合の硬化性の種類とは異なる外部刺激であることが好ましい。上記外部刺激は、具体的には、ポリマー（Ａ）が熱硬化型樹脂である場合は活性エネルギー線照射が好ましく、ポリマー（Ａ）が活性エネルギー線硬化型樹脂である場合は熱が好ましい。
The external stimulus that causes the cleavage reaction of the irreversibly degradable bond is appropriately selected according to the type of the irreversibly degradable bond, and includes active energy ray irradiation, heat, and the like. In particular, when the polymer (A) is a thermosetting resin or an active energy ray-curable resin, the polymer ( It is preferably an external stimulus that is different from the type of curability when A) has curability. Specifically, the external stimulus is preferably active energy ray irradiation when the polymer (A) is a thermosetting resin, and preferably heat when the polymer (A) is an active energy ray-curable resin.
上記活性エネルギー線としては特に限定されないが、α線、β線、γ線、中性子線、電子線等の電離性放射線や、紫外光、可視光などが挙げられる。特に、紫外線が好ましい。活性エネルギー線の照射エネルギー、照射時間、照射方法などは特に限定されない。また、紫外光または可視光照射用の光源としては、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、メタルハライドランプ、ＬＥＤランプなどが挙げられる。
The active energy rays are not particularly limited, but include ionizing radiation such as α-rays, β-rays, γ-rays, neutron beams and electron beams, ultraviolet light and visible light. Ultraviolet rays are particularly preferred. The irradiation energy, irradiation time, irradiation method, etc. of the active energy ray are not particularly limited. Examples of light sources for ultraviolet light or visible light irradiation include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and LED lamps.
上記非可逆分解性結合としては、公知乃至慣用の結合を適用することができ、好ましくはニトロベンジル基を含む結合である。この場合、ポリマーに非可逆分解性結合を導入することが容易である。上記ニトロベンジル基を含む結合としては、ニトロベンジルアルコール（好ましくは２－ニトロベンジルアルコール）と重合性官能基を有するカルボン酸とで形成されるエステル結合が好ましい。
As the irreversibly degradable bond, a known or commonly used bond can be applied, preferably a bond containing a nitrobenzyl group. In this case, it is easy to introduce an irreversible degradable bond into the polymer. The bond containing the nitrobenzyl group is preferably an ester bond formed by nitrobenzyl alcohol (preferably 2-nitrobenzyl alcohol) and a carboxylic acid having a polymerizable functional group.
ポリマー（Ａ）は化合物（Ｂ）を用いて得ることができる。化合物（Ｂ）としては、例えば、上記非可逆分解性結合を有する、モノマー成分、オリゴマー成分、架橋剤などが挙げられる。すなわち、ポリマー（Ａ）は、非可逆分解性結合を有するモノマー成分および／またはオリゴマー成分に由来する構成単位を含んでいてもよく、上記架橋剤に由来する構造部を含んでいてもよい。化合物（Ｂ）がモノマー成分やオリゴマー成分である場合、上記モノマー成分やオリゴマー成分を重合または他のモノマー成分と共重合することで上記非可逆分解性結合を有するポリマー（Ａ）が得られる。
Polymer (A) can be obtained using compound (B). The compound (B) includes, for example, a monomer component, an oligomer component, a cross-linking agent, etc. having the irreversible degradable bond. That is, the polymer (A) may contain a structural unit derived from a monomer component and/or an oligomer component having an irreversibly degradable bond, and may contain a structural portion derived from the cross-linking agent. When the compound (B) is a monomer component or an oligomer component, the polymer (A) having the irreversible bond can be obtained by polymerizing or copolymerizing the above monomer component or oligomer component with another monomer component.
化合物（Ｂ）がモノマー成分やオリゴマー成分である場合、上記非可逆分解性結合は、ポリマー（Ａ）において側鎖を構成する部分に有してもよく、主鎖を構成する部分に有していてもよい。側鎖を構成する部分に有する場合、大きく変形させた際に応力がかかりにくく、かつ実使用温度域（室温を想定）におけるハンドリング性を維持する、という観点で好ましい。一方で、主鎖を構成する部分に有する場合、上記非可逆分解性結合の開裂後においてポリマーの分子量をより低下させ、柔軟性がより向上し大幅な物性変化を発現できる、という観点で好ましい。
When the compound (B) is a monomer component or an oligomer component, the irreversibly degradable bond may be present in the portion constituting the side chain of the polymer (A), or may be present in the portion constituting the main chain. may When the side chain is present in the portion constituting the side chain, it is preferable from the viewpoint that stress is less likely to be applied when it is greatly deformed, and the handleability in the actual use temperature range (assuming room temperature) is maintained. On the other hand, when it is contained in the portion constituting the main chain, it is preferable from the viewpoint that the molecular weight of the polymer is further reduced after the irreversible degradable bond is cleaved, the flexibility is further improved, and a large change in physical properties can be expressed.
化合物（Ｂ）は、上記非可逆分解性結合以外の官能基（官能基（Ｌ１））を有することが好ましい。官能基（Ｌ１）を２以上有する場合、化合物（Ｂ）は架橋剤として機能する。また、官能基（Ｌ１）が重合性官能基である場合、化合物（Ｂ）はモノマー成分またはオリゴマー成分として機能する。
The compound (B) preferably has a functional group (functional group (L1)) other than the irreversibly degradable bond. When having two or more functional groups (L1), the compound (B) functions as a cross-linking agent. Moreover, when the functional group (L1) is a polymerizable functional group, the compound (B) functions as a monomer component or an oligomer component.
上記重合性官能基としては、カチオン重合性基、アニオン重合性基、ラジカル重合性基が挙げられる。中でも、ラジカル重合性基が好ましい。上記ラジカル重合性基としては、（メタ）アクリロイル基、ビニル基等のラジカル重合性炭素－炭素二重結合などが挙げられる。
Examples of the polymerizable functional groups include cationic polymerizable groups, anionic polymerizable groups, and radically polymerizable groups. Among them, a radically polymerizable group is preferred. Examples of the radically polymerizable group include radically polymerizable carbon-carbon double bonds such as (meth)acryloyl group and vinyl group.
上記重合性官能基以外の官能基（Ｌ１）としては、架橋密度を適度として粘着剤層等の柔軟性をある程度確保する観点から、チオール基、カルボキシ基、ヒドロキシ基、アミノ基、エポキシ基、イソシアネート基などが挙げられる。
As the functional group (L1) other than the polymerizable functional group, a thiol group, a carboxyl group, a hydroxy group, an amino group, an epoxy group, and isocyanate are used from the viewpoint of securing a certain degree of flexibility of the pressure-sensitive adhesive layer with an appropriate crosslinking density. and the like.
化合物（Ｂ）の官能基数は、ポリマー（Ａ）への導入後においてより高分子量化させ外部刺激の付与前にポリマーに一定の硬さを与えつつ、開裂後においてポリマーの分子量をより低下させ柔軟性を発揮させる観点から、２個以上であることが好ましい。一方で、官能基数が多くなると、多くのポリマーと架橋することとなり、非可逆分解性結合の開裂による効果が得られにくくなるため、架橋密度を適度として粘着剤層等の柔軟性をある程度確保する観点から、官能基数は４個以下が好ましく、より好ましくは３個以下である。
The number of functional groups of the compound (B) increases the molecular weight of the polymer (A) after introduction into the polymer (A), giving the polymer a certain degree of hardness before applying an external stimulus, while reducing the molecular weight of the polymer after cleavage to make it flexible. From the viewpoint of exhibiting properties, the number is preferably two or more. On the other hand, if the number of functional groups increases, it will crosslink with many polymers, making it difficult to obtain the effect of cleaving the irreversibly degradable bond. From the viewpoint, the number of functional groups is preferably 4 or less, more preferably 3 or less.
化合物（Ｂ）としては、ニトロベンジル基と重合性官能基とが連結基を介して結合したモノマー（ニトロベンジル系モノマー）が好ましい。上記連結基としては、特に限定されないが、エステル結合が好ましい。上記連結基がエステル結合であるニトロベンジル系モノマーを「ニトロベンジルエステル系モノマー」と称する場合がある。上記ニトロベンジルエステル系モノマーとしては、例えば、ニトロベンジルアルコール骨格を有する化合物と重合性官能基およびカルボキシ基を有する化合物とのエステル化物や、ニトロフェニル酢酸骨格を有する化合物と重合性官能基およびヒドロキシ基を有する化合物とのエステル化物などが挙げられる。
As the compound (B), a monomer in which a nitrobenzyl group and a polymerizable functional group are bonded via a linking group (nitrobenzyl-based monomer) is preferable. Although the linking group is not particularly limited, an ester bond is preferable. A nitrobenzyl-based monomer in which the linking group is an ester bond is sometimes referred to as a "nitrobenzyl ester-based monomer." Examples of the nitrobenzyl ester-based monomers include, for example, an esterified product of a compound having a nitrobenzyl alcohol skeleton and a compound having a polymerizable functional group and a carboxy group, or a compound having a nitrophenylacetic acid skeleton and a polymerizable functional group and a hydroxy group. Examples include esterified products with compounds having
上記ニトロベンジルアルコール骨格を有する化合物としては２－ニトロベンジルアルコール、２－ニトロ－１，３－ビス（ヒドロキシメチル）ベンゼンが挙げられる。上記ニトロフェニル酢酸骨格を有する化合物としては２－ニトロイソフタル酸が挙げられる。上記ニトロベンジルエステル系モノマーとしては、２－ニトロ－１，３－ビス（（メタ）アクリロイルオキシメチレン）ベンゼンが好ましい。
Examples of compounds having a nitrobenzyl alcohol skeleton include 2-nitrobenzyl alcohol and 2-nitro-1,3-bis(hydroxymethyl)benzene. Examples of compounds having a nitrophenylacetic acid skeleton include 2-nitroisophthalic acid. As the nitrobenzyl ester-based monomer, 2-nitro-1,3-bis((meth)acryloyloxymethylene)benzene is preferred.
上記ニトロベンジルエステル系モノマーは、重合性官能基を有するカルボン酸（例えば（メタ）アクリル酸）とニトロベンジルアルコール骨格を有する化合物とをエステル化させることや、重合性官能基およびヒドロキシ基を有する化合物とニトロフェニル酢酸骨格を有する化合物とをエステル化させることで作製することができる。
The nitrobenzyl ester-based monomer is a carboxylic acid having a polymerizable functional group (e.g. (meth) acrylic acid) and a compound having a nitrobenzyl alcohol skeleton to esterify, a compound having a polymerizable functional group and a hydroxy group and a compound having a nitrophenylacetic acid skeleton can be esterified.
ポリマー（Ａ）は、一種のみを使用してもよいし、二種以上を使用してもよい。また、化合物（Ｂ）は、一種のみを使用してもよいし、二種以上を使用してもよい。また、本発明の粘着剤等は、ポリマー（Ａ）および化合物（Ｂ）のいずれか一方のみを含んでいてもよく、両方を含んでいてもよい。
Only one type of polymer (A) may be used, or two or more types may be used. Moreover, a compound (B) may use only 1 type, and may use 2 or more types. Moreover, the pressure-sensitive adhesive or the like of the present invention may contain either one of the polymer (A) and the compound (B), or may contain both.
本発明の粘着剤等中の化合物（Ｂ）、化合物（Ｂ）に由来する構成単位、および化合物（Ｂ）に由来する構造部からなる群より選択される１以上の含有割合は、外部刺激付与後に開裂し、細断されることで充分な柔軟性を発揮させるために、本発明の粘着剤等の総量（但し、有機溶媒等の層形成時に残存しない成分は除く）１００質量％に対して、０．１質量％以上が好ましく、より好ましくは０．２質量％以上、さらに好ましくは０．５質量％以上、特に好ましくは１質量％以上である。また、架橋密度を適度とし外部刺激付与前において樹脂に適度な柔軟性を付与するため、１５質量％以下が好ましく、より好ましくは１０質量％以下、さらに好ましくは５質量％以下である。
The content ratio of one or more selected from the group consisting of the compound (B), the structural unit derived from the compound (B), and the structural part derived from the compound (B) in the pressure-sensitive adhesive or the like of the present invention is applied to impart an external stimulus. In order to exhibit sufficient flexibility by being cleaved and shredded later, the total amount of the adhesive etc. of the present invention (excluding components such as organic solvents that do not remain at the time of layer formation) 100% by mass , preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. Also, in order to make the crosslink density appropriate and to impart appropriate flexibility to the resin before applying an external stimulus, the amount is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.
ポリマー（Ａ）としては、熱可塑性樹脂、熱硬化型樹脂、活性エネルギー線硬化型樹脂などが挙げられる。中でも、熱可塑性樹脂、熱硬化型樹脂が好ましい。熱可塑性樹脂を含有する粘着剤等（粘着剤層または接着剤層）は例えば外部からの圧力で密着する粘着性を発揮することが可能となる。熱硬化型樹脂を含有する粘着剤等（粘着剤層または接着剤層）は、例えば加熱により硬化することで被着体と接着することができる。
Examples of the polymer (A) include thermoplastic resins, thermosetting resins, and active energy ray-curable resins. Among them, thermoplastic resins and thermosetting resins are preferred. A pressure-sensitive adhesive or the like (adhesive layer or adhesive layer) containing a thermoplastic resin can exhibit adhesiveness such that it adheres under pressure from the outside, for example. An adhesive or the like (adhesive layer or adhesive layer) containing a thermosetting resin can be adhered to an adherend by curing, for example, by heating.
上記熱硬化型樹脂としては熱硬化性を有する樹脂（熱硬化性樹脂）および上記熱硬化性樹脂を硬化して得られる樹脂の両方が挙げられる。上記熱硬化性樹脂は熱硬化性の官能基を有する。上記熱硬化性樹脂における熱硬化性の官能基数は、２以上（例えば２～４）が好ましい。上記熱硬化型樹脂としては、例えば、フェノール系樹脂、エポキシ系樹脂、ウレタン系樹脂、メラミン系樹脂、アルキド系樹脂などが挙げられる。
Examples of the thermosetting resin include both resins having thermosetting properties (thermosetting resins) and resins obtained by curing the above thermosetting resins. The thermosetting resin has a thermosetting functional group. The number of thermosetting functional groups in the thermosetting resin is preferably 2 or more (for example, 2 to 4). Examples of the thermosetting resin include phenol-based resin, epoxy-based resin, urethane-based resin, melamine-based resin, and alkyd-based resin.
上記熱可塑性樹脂としては、例えば、ポリスチレン系樹脂、酢酸ビニル系樹脂、ポリエステル系樹脂、ポリオレフィン系樹脂（ポリエチレン系樹脂、ポリプロピレン系樹脂組成物等）、ポリイミド系樹脂、アクリル系樹脂などが挙げられる。中でも、粘着剤等に凝集力と適度な柔軟性を付与できるため、アクリル系樹脂が好ましい。
Examples of the thermoplastic resin include polystyrene-based resin, vinyl acetate-based resin, polyester-based resin, polyolefin-based resin (polyethylene-based resin, polypropylene-based resin composition, etc.), polyimide-based resin, acrylic-based resin, and the like. Among them, acrylic resins are preferable because they can impart cohesion and appropriate flexibility to adhesives and the like.
アクリル系樹脂の設計は目的に応じて多種多様となり、柔軟性・弾性率などの機械物性、ガラス転移点などの熱物性、粘着力・密着力などの粘着剤等特有の特性値の目的値に応じて、モノマー種、共重合組成比、分子量、分子量分布、架橋剤、配合組成比などを適宜選択することが好ましい。
There are various types of acrylic resin designs depending on the purpose. Accordingly, it is preferable to appropriately select the monomer species, copolymerization composition ratio, molecular weight, molecular weight distribution, cross-linking agent, compounding composition ratio, and the like.
アクリル系樹脂は、樹脂を構成するモノマー成分として、アクリル系モノマー（分子中に（メタ）アクリロイル基を有するモノマー）を含む樹脂である。すなわち、上記アクリル系樹脂は、アクリル系モノマーに由来する構成単位を含む。上記アクリル系樹脂は、ポリマーを構成するモノマー成分として（メタ）アクリル酸アルキルエステルを含むポリマーであることが好ましい。なお、本明細書において、「（メタ）アクリル」とは、「アクリル」および／または「メタクリル」（「アクリル」および「メタクリル」のうち、いずれか一方または両方）を表し、他も同様である。
An acrylic resin is a resin containing an acrylic monomer (a monomer having a (meth)acryloyl group in the molecule) as a monomer component that constitutes the resin. That is, the acrylic resin contains structural units derived from acrylic monomers. The acrylic resin is preferably a polymer containing a (meth)acrylic acid alkyl ester as a monomer component constituting the polymer. In the present specification, "(meth)acrylic" means "acrylic" and/or "methacrylic" (one or both of "acrylic" and "methacrylic"), and the same applies to others. .
必須のモノマー成分としての上記（メタ）アクリル酸アルキルエステルとしては、直鎖または分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステルが好ましく挙げられる。なお、上記（メタ）アクリル酸アルキルエステルは、一種のみを使用してもよいし、二種以上を使用してもよい。
As the (meth)acrylic acid alkyl ester as an essential monomer component, a (meth)acrylic acid alkyl ester having a linear or branched alkyl group is preferably mentioned. In addition, only 1 type may be used for the said (meth)acrylic-acid alkyl ester, and 2 or more types may be used for it.
直鎖状または分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステルとしては、特に限定されないが、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル（ラウリル（メタ）アクリレート）、（メタ）アクリル酸トリデシル、（メタ）アクリル酸テトラデシル、（メタ）アクリル酸ペンタデシル、（メタ）アクリル酸ヘキサデシル、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸オクタデシル（ステアリル（メタ）アクリレート）、イソステアリル（メタ）アクリレート、（メタ）アクリル酸ノナデシル、（メタ）アクリル酸エイコシルなどの炭素数が１～２０の直鎖または分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステルが挙げられる。
The (meth)acrylic acid alkyl ester having a linear or branched alkyl group is not particularly limited, but examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, Isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) ) isopentyl acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, ( meth) isononyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate, (meth) ) Tetradecyl acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), isostearyl (meth)acrylate, (meth)acrylate (Meth)acrylic acid alkyl esters having a linear or branched alkyl group having 1 to 20 carbon atoms, such as nonadecyl acrylate and eicosyl (meth)acrylate.
直鎖状または分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステルとしては、中でも、炭素数が２以上（好ましくは２～１８、より好ましくは２～５）の直鎖状または分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステルが好ましい。
As the (meth)acrylic acid alkyl ester having a linear or branched alkyl group, among them, a linear or branched chain having 2 or more carbon atoms (preferably 2 to 18, more preferably 2 to 5) A (meth)acrylic acid alkyl ester having a triangular alkyl group is preferred.
上記アクリル系樹脂中の（メタ）アクリル酸アルキルエステルに由来する構成単位の含有割合は、アクリル系樹脂を構成するモノマー成分の総量１００質量％に対して、７０質量％以上が好ましく、より好ましくは８０質量％以上である。上記含有割合は、９９質量％以下が好ましく、より好ましくは９８質量％以下である。なお、もちろん、用途や求められる特性などによっては、アクリル系樹脂中の（メタ）アクリル酸アルキルエステルに由来する構成単位の含有割合は、アクリル系樹脂を構成するモノマー成分の総量１００質量％に対して、７０質量％未満となる場合もある。
The content of structural units derived from (meth)acrylic acid alkyl ester in the acrylic resin is preferably 70% by mass or more, more preferably 100% by mass, based on the total amount of the monomer components constituting the acrylic resin. It is 80% by mass or more. The above content is preferably 99% by mass or less, more preferably 98% by mass or less. Of course, depending on the application and required properties, the content ratio of the structural unit derived from the (meth)acrylic acid alkyl ester in the acrylic resin may be and may be less than 70% by mass.
上記アクリル系樹脂は、樹脂を構成するモノマー成分として、上記（メタ）アクリル酸アルキルエステルとともに、上記（メタ）アクリル酸アルキルエステルと共重合可能な他のモノマー（共重合性モノマー）を含んでいてもよい。すなわち、上記アクリル系樹脂は、構成単位として、共重合性モノマーを含んでいてもよい。上記共重合性モノマーは、一種のみを使用してもよいし、二種以上を使用してもよい。
The acrylic resin contains the (meth)acrylic acid alkyl ester and other monomers (copolymerizable monomers) copolymerizable with the (meth)acrylic acid alkyl ester as monomer components constituting the resin. good too. That is, the acrylic resin may contain a copolymerizable monomer as a structural unit. The above copolymerizable monomers may be used alone or in combination of two or more.
上記共重合性モノマーとしては、例えば、カルボキシ基含有モノマー、ヒドロキシ基含有モノマー、エポキシ基含有モノマー、ケト基含有モノマー、アルコキシ基含有モノマー、スルホン酸基含有モノマー、リン酸基含有モノマー、ビニルエステル系モノマー、ビニルエーテル系モノマー、イソシアネート基含有モノマー、芳香族ビニル化合物、脂環式モノマー、芳香族性環含有（メタ）アクリレート、塩素含有モノマー、窒素含有モノマーなどが挙げられる。
Examples of the copolymerizable monomer include carboxy group-containing monomers, hydroxy group-containing monomers, epoxy group-containing monomers, keto group-containing monomers, alkoxy group-containing monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, vinyl ester-based monomers, vinyl ether-based monomers, isocyanate group-containing monomers, aromatic vinyl compounds, alicyclic monomers, aromatic ring-containing (meth)acrylates, chlorine-containing monomers, nitrogen-containing monomers, and the like.
上記アクリル系樹脂中の共重合性モノマーに由来する構成単位の含有割合は、アクリル系樹脂を構成するモノマー成分の総量１００質量％に対して、０．１質量％以上が好ましく、より好ましくは０．３質量％以上である。上記含有割合は、１５質量％以下が好ましく、より好ましくは１０質量％以下である。なお、もちろん、用途や求められる特性などによっては、上記アクリル系樹脂中の共重合性モノマーに由来する構成単位の含有割合は、アクリル系樹脂を構成するモノマー成分の総量１００質量％に対して、０．１質量％未満であってもよい。
The content of structural units derived from copolymerizable monomers in the acrylic resin is preferably 0.1% by mass or more, more preferably 0%, based on the total amount of 100% by mass of the monomer components constituting the acrylic resin. .3% by mass or more. The above content is preferably 15% by mass or less, more preferably 10% by mass or less. Of course, depending on the application and required properties, the content ratio of the structural units derived from the copolymerizable monomer in the acrylic resin may be It may be less than 0.1% by mass.
ポリマー（Ａ）は、熱可塑性樹脂が好ましく、より好ましくはアクリル系樹脂である。ポリマー（Ａ）がアクリル系樹脂である場合、当該アクリル系樹脂は、樹脂を構成するモノマー成分として、アクリル系モノマーおよび化合物（Ｂ）を少なくとも含む樹脂であることが好ましい。
The polymer (A) is preferably a thermoplastic resin, more preferably an acrylic resin. When the polymer (A) is an acrylic resin, the acrylic resin preferably contains at least an acrylic monomer and a compound (B) as monomer components constituting the resin.
上記熱可塑性樹脂を含む場合、上記熱可塑性樹脂の含有割合は、特に限定されないが、粘着剤層等に適度な初期硬さと、外部刺激後の硬さを付与するために、本発明の粘着剤等の総量（但し、有機溶媒等の層形成時に残存しない成分は除く）１００質量％に対して、５０質量％以上が好ましく、より好ましくは７０質量％以上、さらに好ましくは８０質量％以上、特に好ましくは９０質量％以上である。なお、熱可塑性樹脂の量は、熱可塑性樹脂、その原料モノマー、架橋剤、および架橋剤に由来する構造部の量を含む。
When the thermoplastic resin is contained, the content of the thermoplastic resin is not particularly limited. 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and especially Preferably, it is 90% by mass or more. The amount of the thermoplastic resin includes the amount of the thermoplastic resin, its raw material monomers, the cross-linking agent, and the structural portion derived from the cross-linking agent.
本発明の粘着剤等は、必要に応じて上述の各成分以外のその他の成分を含んでいてもよい。上記その他の成分としては、例えば、ポリマー（Ａ）以外の樹脂、硬化触媒、架橋剤（多官能（メタ）アクリレートを含む）、架橋促進剤、重合開始剤、粘着付与樹脂（ロジン誘導体、ポリテルペン樹脂、石油樹脂、油溶性フェノール等）、オリゴマー、老化防止剤、充填剤（金属粉、有機充填剤、無機充填剤等）、着色剤（顔料や染料など）、酸化防止剤、可塑剤、軟化剤、界面活性剤、帯電防止剤、表面潤滑剤、レベリング剤、光安定剤、紫外線吸収剤、重合禁止剤、粒状物、箔状物、難燃剤、シランカップリング剤、イオントラップ剤などが挙げられる。上記その他の成分は、それぞれ、一種のみを使用してもよいし、二種以上を使用してもよい。
The adhesive or the like of the present invention may contain other components other than the components described above, if necessary. Examples of the other components include resins other than the polymer (A), curing catalysts, cross-linking agents (including polyfunctional (meth)acrylates), cross-linking accelerators, polymerization initiators, tackifying resins (rosin derivatives, polyterpene resins , petroleum resin, oil-soluble phenol, etc.), oligomers, antioxidants, fillers (metal powder, organic fillers, inorganic fillers, etc.), coloring agents (pigments, dyes, etc.), antioxidants, plasticizers, softeners , surfactants, antistatic agents, surface lubricants, leveling agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, particulates, foils, flame retardants, silane coupling agents, ion trapping agents, etc. . Only one kind of each of the other components may be used, or two or more kinds thereof may be used.
上記架橋剤としてはポリマーを架橋するものであれば特に限定されないが、ポリイソシアネート化合物、エポキシ化合物、ポリオール化合物（ポリフェノール系化合物など）、アジリジン化合物、メラミン系架橋剤、および多官能（メタ）アクリレートなどが挙げられる。多官能（メタ）アクリレートとしては２官能以上の（メタ）アクリル酸エステルが挙げられ、例えば、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートなどが挙げられる。
The cross-linking agent is not particularly limited as long as it cross-links the polymer, and includes polyisocyanate compounds, epoxy compounds, polyol compounds (such as polyphenol compounds), aziridine compounds, melamine-based cross-linking agents, and polyfunctional (meth)acrylates. is mentioned. Examples of polyfunctional (meth)acrylates include bifunctional or higher (meth)acrylic acid esters, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di pentaerythritol hexa(meth)acrylate and the like.
以下、本発明の粘着剤等が流動性を有する粘着剤組成物または接着剤組成物である場合と粘着剤層または接着剤層である場合とに分けて、好ましい態様についてそれぞれ説明する。なお、本明細書において、粘着剤組成物および／または接着剤組成物を「粘着剤組成物等」と称する場合がある。また、本明細書において、粘着剤層および／または接着剤層を「粘着剤層等」と称する場合がある。
Hereinafter, preferred embodiments will be described separately for the case where the pressure-sensitive adhesive or the like of the present invention is a fluid pressure-sensitive adhesive composition or adhesive composition and the case where it is a pressure-sensitive adhesive layer or adhesive layer. In addition, in this specification, an adhesive composition and/or an adhesive composition may be called "adhesive composition etc.". Moreover, in this specification, an adhesive layer and/or an adhesive layer may be called "adhesive layer etc.".
（粘着剤層、接着剤層）
図１は本発明の粘着剤等が粘着剤層等である場合の一実施形態の断面模式図である。図１に示す粘着剤層または接着剤層１は、はく離ライナー２の離型処理面に積層され、はく離ライナー付き粘着シートまたは接着シート１０が形成されている。 (adhesive layer, adhesive layer)
FIG. 1 is a schematic cross-sectional view of one embodiment in which the adhesive or the like of the present invention is an adhesive layer or the like. A pressure-sensitive adhesive layer oradhesive layer 1 shown in FIG. 1 is laminated on the release-treated surface of a release liner 2 to form a pressure-sensitive adhesive sheet or adhesive sheet 10 with a release liner.
図１は本発明の粘着剤等が粘着剤層等である場合の一実施形態の断面模式図である。図１に示す粘着剤層または接着剤層１は、はく離ライナー２の離型処理面に積層され、はく離ライナー付き粘着シートまたは接着シート１０が形成されている。 (adhesive layer, adhesive layer)
FIG. 1 is a schematic cross-sectional view of one embodiment in which the adhesive or the like of the present invention is an adhesive layer or the like. A pressure-sensitive adhesive layer or
本発明の粘着剤等が粘着剤層等である場合、上記粘着剤等層は、ポリマー（Ａ）を少なくとも含む。ポリマー（Ａ）は、一種のみを使用してもよく、二種以上を使用してもよい。
When the adhesive or the like of the present invention is an adhesive layer or the like, the adhesive layer or the like contains at least the polymer (A). Only one kind of polymer (A) may be used, or two or more kinds thereof may be used.
ポリマー（Ａ）中の化合物（Ｂ）に由来する構成単位および化合物（Ｂ）に由来する構造部からなる群より選択される１以上の含有割合は、外部刺激付与後に開裂し、細断されることで充分な柔軟性を発揮させる観点から、ポリマー（Ａ）の総量１００質量％に対して、０．１～１５質量％が好ましく、より好ましくは０．２～１０質量％、さらに好ましくは０．５～５質量％、特に好ましくは１～３質量％である。なお、本明細書において、二種以上のポリマーが絡み合っている場合は、絡み合ったポリマーを１つのポリマーとして換算する。
The content ratio of one or more selected from the group consisting of structural units derived from the compound (B) and structural units derived from the compound (B) in the polymer (A) is cleaved and shredded after application of an external stimulus. From the viewpoint of exhibiting sufficient flexibility, the polymer (A) is preferably 0.1 to 15% by mass, more preferably 0.2 to 10% by mass, and still more preferably 0 .5 to 5% by weight, particularly preferably 1 to 3% by weight. In addition, in this specification, when two or more types of polymers are entangled, the entangled polymer is converted into one polymer.
上記粘着剤層等中のポリマー（Ａ）の含有割合は、上記粘着剤層等の総量１００質量％に対して、５０質量％以上が好ましく、より好ましくは７０質量％以上、さらに好ましくは８０質量％以上、特に好ましくは９０質量％以上である。なお、化合物（Ｂ）がモノマー成分やオリゴマー成分である場合、上記含有割合には化合物（Ｂ）および化合物（Ｂ）に由来する構成単位の量が含まれる。また、上記ポリマー（Ａ）の量は、ポリマー（Ａ）、その原料モノマー、架橋剤、および架橋剤に由来する構造部の量を含む。
The content of the polymer (A) in the pressure-sensitive adhesive layer, etc. is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass, with respect to 100% by mass of the total amount of the pressure-sensitive adhesive layer, etc. % or more, particularly preferably 90 mass % or more. In addition, when the compound (B) is a monomer component or an oligomer component, the content ratio includes the amount of the compound (B) and the structural units derived from the compound (B). Moreover, the amount of the polymer (A) includes the amount of the polymer (A), its raw material monomers, the cross-linking agent, and the structural part derived from the cross-linking agent.
上記粘着剤層等中の架橋剤および／または架橋剤に由来する構造部の含有量は、ポリマー（Ａ）の総量１００質量％に対して、０．１～１５質量％が好ましく、より好ましくは０．２～１０質量％、さらに好ましくは０．５～５質量％、特に好ましくは１～３質量％である。なお、化合物（Ｂ）が架橋剤である場合、上記含有量には化合物（Ｂ）および化合物（Ｂ）に由来する構造部の量が含まれる。
The content of the cross-linking agent and/or the structural part derived from the cross-linking agent in the pressure-sensitive adhesive layer or the like is preferably 0.1 to 15% by mass, more preferably 0.1 to 15% by mass with respect to 100% by mass of the total amount of the polymer (A). 0.2 to 10% by mass, more preferably 0.5 to 5% by mass, particularly preferably 1 to 3% by mass. In addition, when the compound (B) is a cross-linking agent, the content includes the amount of the compound (B) and the structural portion derived from the compound (B).
上記粘着剤層等は、上述の各成分以外のその他の成分を含んでいてもよい。上記その他の成分としては上述の本発明の粘着剤等が含み得るその他の成分として例示および説明されたものが挙げられる。上記その他の成分は、それぞれ、一種のみを使用してもよいし、二種以上を使用してもよい。
The pressure-sensitive adhesive layer and the like may contain components other than the components described above. Examples of the above-mentioned other components include those exemplified and explained as other components that may be contained in the pressure-sensitive adhesive or the like of the present invention. Only one kind of each of the other components may be used, or two or more kinds thereof may be used.
上記粘着剤層等はベースポリマーがネットワーク構造を形成していることが好ましい。ネットワーク構造とは、分子同士が絡み合っている状態、若しくは分子鎖同士が何らかの結合を介して長大な分子を形成している状態をいう。すなわち、ポリマー（Ａ）は、結合または分子同士の絡み合いによりネットワーク構造を形成されたポリマーであることが好ましい。このような構成を有する粘着剤層等はポリマー同士の結合若しくはポリマー同士の絡み合いによってネットワーク構造を形成し、適度の硬さを有することが可能であり、外部刺激によって形成された非可逆分解性結合が分解することにより、ポリマー構造が細断され、柔軟性が向上する。
It is preferable that the base polymer forms a network structure in the adhesive layer and the like. A network structure refers to a state in which molecules are entangled with each other, or a state in which molecular chains form a long molecule through some bond. That is, the polymer (A) is preferably a polymer in which a network structure is formed by bonding or entanglement between molecules. A pressure-sensitive adhesive layer or the like having such a configuration forms a network structure through polymer-to-polymer bonding or polymer-to-polymer entanglement, and can have an appropriate degree of hardness. The decomposition of the polymer shreds the polymer structure and improves flexibility.
分子同士が絡み合っているとは、高分子同士が共有結合を介さずにネットワーク構造を形成している状態を示す。このような絡み合い構造を形成するには、種類の異なる相互に架橋反応を起こしづらいポリマーを含有することが好ましく、作製が容易である観点から熱可塑性樹脂同士が絡み合い構造を形成している状態が好ましい。このような構成は、共有結合を介さない分、外部刺激付与前に比較的柔軟な粘着剤等に適する。
"Molecules are entangled with each other" refers to the state in which macromolecules form a network structure without covalent bonds. In order to form such an entangled structure, it is preferable to contain different types of polymers that are unlikely to cause a cross-linking reaction. preferable. Such a configuration is suitable for adhesives or the like that are relatively soft before application of an external stimulus because no covalent bond is involved.
上記分子鎖同士が何らかの結合を介して長大な分子を形成している状態とは、単一高分子による重合ポリマーであることを示す。このような長大な分子を形成するには、単一のポリマーを含有することが好ましく、上述の熱硬化型樹脂を含有していることが好ましい。このような構成は分子鎖が長大に共有結合していることから、比較的硬い粘着剤等を形成でき、また、外部刺激によって切断される部位も増加することから、より外部刺激前後で柔軟性に差のある粘着剤等に適する。
The state in which the molecular chains form a long molecule through some kind of bond means that the polymer is a single macromolecular polymer. In order to form such long and large molecules, it is preferable to contain a single polymer, and it is preferable to contain the thermosetting resin described above. Such a structure can form a relatively hard adhesive, etc., because the molecular chains are covalently bonded to each other. Suitable for pressure-sensitive adhesives, etc. with different thicknesses.
上記粘着剤層等は活性エネルギー線照射によってせん断貯蔵弾性率（Ｇ’）が低下することが好ましい。このような粘着剤等は活性エネルギー線照射によって柔軟性が向上する。また、上記せん断貯蔵弾性率（Ｇ’）は上記低下後において増加しないことが好ましい。
It is preferable that the shear storage modulus (G') of the pressure-sensitive adhesive layer or the like is lowered by irradiation with active energy rays. Flexibility of such a pressure-sensitive adhesive or the like is improved by irradiation with active energy rays. Also, it is preferable that the shear storage modulus (G') does not increase after the decrease.
上記粘着剤層等は、外部刺激付与前の２５℃におけるせん断貯蔵弾性率（Ｇ’）が、１．０×１０3～１．０×１０8Ｐａであることが好ましく、より好ましくは１．０×１０4～１．０×１０7Ｐａ、さらに好ましくは１．０×１０4～１．０×１０6Ｐａ、特に好ましくは２．０×１０4～１．０×１０5Ｐａである。上記せん断貯蔵弾性率を有する粘着剤層等は外部刺激付与前において適度な硬さを有し、製造・加工、保管、運搬等の作業性に優れる。
The pressure-sensitive adhesive layer or the like preferably has a shear storage modulus (G') of 1.0×10 3 to 1.0×10 8 Pa at 25° C. before application of an external stimulus, more preferably 1. 0×10 4 to 1.0×10 7 Pa, more preferably 1.0×10 4 to 1.0×10 6 Pa, particularly preferably 2.0×10 4 to 1.0×10 5 Pa . The pressure-sensitive adhesive layer and the like having the above shear storage elastic modulus have appropriate hardness before application of an external stimulus, and are excellent in workability such as production/processing, storage and transportation.
上記粘着剤層等は、外部刺激付与前の５０℃におけるせん断貯蔵弾性率（Ｇ’）が、１．０×１０3～５．０×１０7Ｐａであることが好ましく、より好ましくは７．０×１０3～１．０×１０6Ｐａ、さらに好ましくは１．０×１０4～１．０×１０5Ｐａである。上記せん断貯蔵弾性率を有する粘着剤層等は例えば環境により多少昇温した場合であっても外部刺激付与前において適度な硬さを有し、製造・加工、保管、運搬等の作業性に優れる。
The pressure-sensitive adhesive layer or the like preferably has a shear storage modulus (G') of 1.0×10 3 to 5.0×10 7 Pa at 50° C. before application of an external stimulus, more preferably 7. 0×10 3 to 1.0×10 6 Pa, more preferably 1.0×10 4 to 1.0×10 5 Pa. The pressure-sensitive adhesive layer or the like having the above shear storage elastic modulus has an appropriate hardness before applying an external stimulus even when the temperature is slightly increased due to the environment, and is excellent in workability such as manufacturing/processing, storage, and transportation. .
上記粘着剤層等は、外部刺激付与前の８５℃におけるせん断貯蔵弾性率（Ｇ’）が、１．０×１０2～１．０×１０6Ｐａであることが好ましく、より好ましくは１．０×１０3～１．０×１０5Ｐａ、さらに好ましくは５．０×１０3～１．０×１０5Ｐａである。上記せん断貯蔵弾性率を有する粘着剤層等は例えば高温環境下に付された場合であっても外部刺激付与前において適度な硬さを有し、製造・加工、保管、運搬等の作業性により優れる。
The pressure-sensitive adhesive layer or the like preferably has a shear storage modulus (G') of 1.0×10 2 to 1.0×10 6 Pa at 85° C. before application of an external stimulus, more preferably 1. 0×10 3 to 1.0×10 5 Pa, more preferably 5.0×10 3 to 1.0×10 5 Pa. The pressure-sensitive adhesive layer or the like having the above-mentioned shear storage modulus has an appropriate hardness before applying an external stimulus even when applied in a high-temperature environment. Excellent.
上記粘着剤層等は、外部刺激付与後の２５℃におけるせん断貯蔵弾性率（Ｇ’）が、１．０×１０2～５．０×１０6Ｐａであることが好ましく、より好ましくは１．０×１０3～５．０×１０5Ｐａ、さらに好ましくは３．０×１０3～１．０×１０5Ｐａ、特に好ましくは５．０×１０3～５．０×１０4Ｐａである。上記せん断貯蔵弾性率が上記範囲内であると、本発明の粘着剤層等は外部刺激付与後において柔軟性により優れ、段差追従性、密着性などがより優れる。
The pressure-sensitive adhesive layer or the like preferably has a shear storage modulus (G') of 1.0×10 2 to 5.0×10 6 Pa at 25° C. after application of an external stimulus, more preferably 1. 0×10 3 to 5.0×10 5 Pa, more preferably 3.0×10 3 to 1.0×10 5 Pa, particularly preferably 5.0×10 3 to 5.0×10 4 Pa . When the shear storage elastic modulus is within the above range, the pressure-sensitive adhesive layer or the like of the present invention is more excellent in flexibility after application of an external stimulus, and is more excellent in step followability, adhesiveness, and the like.
上記粘着剤層等は、外部刺激付与後の５０℃におけるせん断貯蔵弾性率（Ｇ’）が、１．０×１０2～１．０×１０6Ｐａであることが好ましく、より好ましくは５．０×１０2～３．０×１０5Ｐａ、さらに好ましくは１．０×１０3～１．０×１０5Ｐａ、特に好ましくは２．０×１０3～８．０×１０4Ｐａである。上記せん断貯蔵弾性率が上記範囲内であると、外部刺激付与後では、例えば環境により多少昇温した場合において柔軟性により優れ、段差追従性、密着性などがより優れる。
The pressure-sensitive adhesive layer or the like preferably has a shear storage modulus (G') of 1.0×10 2 to 1.0×10 6 Pa at 50° C. after application of an external stimulus, more preferably 5. 0×10 2 to 3.0×10 5 Pa, more preferably 1.0×10 3 to 1.0×10 5 Pa, particularly preferably 2.0×10 3 to 8.0×10 4 Pa . When the shear storage elastic modulus is within the above range, after application of an external stimulus, for example, when the temperature is slightly increased due to the environment, the flexibility, step conformability, adhesion, etc. are superior.
上記粘着剤層等は、外部刺激付与後の８５℃におけるせん断貯蔵弾性率（Ｇ’）が、１．０×１０2～８．０×１０5Ｐａであることが好ましく、より好ましくは３．０×１０2～１．０×１０5Ｐａ、さらに好ましくは５．０×１０2～１．０×１０5Ｐａ、特に好ましくは１．０×１０2～７．０×１０4Ｐａである。上記せん断貯蔵弾性率が上記範囲内であると、外部刺激付与後では、例えば高温環境下に付された場合において柔軟性により優れ、段差追従性、密着性などがより優れる。
The pressure-sensitive adhesive layer or the like preferably has a shear storage modulus (G′) at 85° C. after application of an external stimulus of 1.0×10 2 to 8.0×10 5 Pa, more preferably 3. 0×10 2 to 1.0×10 5 Pa, more preferably 5.0×10 2 to 1.0×10 5 Pa, particularly preferably 1.0×10 2 to 7.0×10 4 Pa . When the shear storage elastic modulus is within the above range, after application of an external stimulus, for example, when subjected to a high-temperature environment, the film is more excellent in flexibility, step followability, adhesion, and the like.
上記粘着剤層等は、外部刺激付与前の２５℃におけるせん断貯蔵弾性率（Ｇ’）と外部刺激付与後の２５℃におけるせん断貯蔵弾性率（Ｇ’）の比［外部刺激付与後／外部刺激付与前］が、０．９５未満（例えば０．０１以上０．９５未満）であることが好ましく、より好ましくは０．８以下（例えば０．０５～０．８）、さらに好ましくは０．７以下（例えば０．１～０．７）、特に好ましくは０．６以下（例えば０．２～０．６）である。この場合、外部刺激付与前後において常温付近における粘着剤層等の柔軟性、段差追従性、密着性がより大きく変化する傾向にある。
The pressure-sensitive adhesive layer or the like has a ratio of the shear storage modulus (G') at 25 ° C. before applying an external stimulus to the shear storage modulus (G') at 25 ° C. after applying an external stimulus [after applying an external stimulus/external stimulus before application] is preferably less than 0.95 (eg, 0.01 or more and less than 0.95), more preferably 0.8 or less (eg, 0.05 to 0.8), still more preferably 0.7 or less (eg 0.1 to 0.7), particularly preferably 0.6 or less (eg 0.2 to 0.6). In this case, there is a tendency that the flexibility, step followability, and adhesion of the pressure-sensitive adhesive layer, etc. at around room temperature before and after the application of the external stimulus change more greatly.
上記粘着剤層等は、外部刺激付与前の５０℃におけるせん断貯蔵弾性率（Ｇ’）と外部刺激付与後の５０℃におけるせん断貯蔵弾性率（Ｇ’）の比［外部刺激付与後／外部刺激付与前］が、０．９５未満（例えば０．０１以上０．９５未満）であることが好ましく、より好ましくは０．８以下（例えば０．０５～０．８）、さらに好ましくは０．７以下以下（例えば０．１～０．７）、特に好ましくは０．６以下（例えば０．２～０．６）である。この場合、外部刺激付与前後において５０℃付近における粘着剤層等の柔軟性、段差追従性、密着性がより大きく変化する傾向にある。
The pressure-sensitive adhesive layer or the like has a ratio of the shear storage modulus (G ') at 50 ° C. before applying an external stimulus to the shear storage modulus (G ') at 50 ° C. after applying an external stimulus [after applying an external stimulus/external stimulus before application] is preferably less than 0.95 (eg, 0.01 or more and less than 0.95), more preferably 0.8 or less (eg, 0.05 to 0.8), still more preferably 0.7 or less (eg 0.1 to 0.7), particularly preferably 0.6 or less (eg 0.2 to 0.6). In this case, there is a tendency that the flexibility, step followability, and adhesiveness of the pressure-sensitive adhesive layer, etc. at around 50° C. change more significantly before and after applying an external stimulus.
上記粘着剤層等は、外部刺激付与前の８５℃におけるせん断貯蔵弾性率（Ｇ’）と外部刺激付与後の８５℃におけるせん断貯蔵弾性率（Ｇ’）の比［外部刺激付与後／外部刺激付与前］が、０．９５未満（例えば０．０１以上０．９５未満）であることが好ましく、より好ましくは０．８以下（例えば０．０５～０．８）、さらに好ましくは０．７以下（例えば０．１～０．７）、特に好ましくは０．６以下（例えば０．２～０．６）である。この場合、外部刺激付与前後において高温環境下における粘着剤層等の柔軟性、段差追従性、密着性がより大きく変化する傾向にある。
The pressure-sensitive adhesive layer or the like has a ratio of the shear storage modulus (G') at 85 ° C. before applying an external stimulus to the shear storage modulus (G') at 85 ° C. after applying an external stimulus [after applying an external stimulus/external stimulus before application] is preferably less than 0.95 (eg, 0.01 or more and less than 0.95), more preferably 0.8 or less (eg, 0.05 to 0.8), still more preferably 0.7 or less (eg 0.1 to 0.7), particularly preferably 0.6 or less (eg 0.2 to 0.6). In this case, there is a tendency that the flexibility, step followability, and adhesion of the pressure-sensitive adhesive layer, etc. under high-temperature environments change more significantly before and after the application of the external stimulus.
本発明の粘着剤層等は外部刺激により硬さが低減する性質を有することが好ましい。上記硬さは低減後において増加しないことが好ましい。このような粘着剤層等は、粘着剤層等を部材へ粘着または接着した状態において硬さが増加することがなく、柔軟性が持続する。
It is preferable that the pressure-sensitive adhesive layer, etc. of the present invention have the property that the hardness is reduced by an external stimulus. Preferably, the hardness does not increase after reduction. Such a pressure-sensitive adhesive layer or the like does not increase in hardness in a state where the pressure-sensitive adhesive layer or the like is adhered or adhered to a member, and maintains flexibility.
上記硬さは、例えば引張圧縮試験機で測定される、ヤング率が好ましい。すなわち、本発明の粘着剤層等は、外部刺激によりヤング率が低減する性質を有することが好ましい。
The hardness is preferably Young's modulus, which is measured, for example, with a tensile compression tester. That is, it is preferable that the pressure-sensitive adhesive layer or the like of the present invention has a property that Young's modulus is reduced by an external stimulus.
すなわち、上記粘着剤層等は外部刺激付与前のヤング率と比較して、外部刺激付与後のヤング率が低値であることが好ましい。このような粘着剤層等は外部刺激の付与前において取り扱い性に優れ、外部刺激の付与後において、柔軟性、耐衝撃性、および高速域での形状変形性により優れる。
That is, it is preferable that the Young's modulus of the pressure-sensitive adhesive layer or the like after application of the external stimulus is lower than that before the application of the external stimulus. Such a pressure-sensitive adhesive layer or the like is excellent in handleability before application of an external stimulus, and excellent in flexibility, impact resistance, and shape deformability in a high speed range after application of an external stimulus.
上記粘着剤層等は、外部刺激付与前のヤング率（Ｅ１）が、２００ＭＰａ以下（例えば０．０３～２００ＭＰａ）であることが好ましい。また、上記粘着剤層等は、外部刺激付与後のヤング率（Ｅ２）が、５０ＭＰａ以下（例えば０．００１～５０ＭＰａ）であることが好ましい。上記ヤング率を有する粘着剤層等は外部刺激付与前において適度な硬さを有し、製造・加工、保管、運搬等の作業性により優れる。また、上記ヤング率を有する粘着剤層等は外部刺激付与後において柔軟性に優れ、段差追従性、密着性などがより優れる。
The Young's modulus (E1) of the pressure-sensitive adhesive layer and the like before application of an external stimulus is preferably 200 MPa or less (eg, 0.03 to 200 MPa). The pressure-sensitive adhesive layer or the like preferably has a Young's modulus (E2) of 50 MPa or less (eg, 0.001 to 50 MPa) after application of an external stimulus. The pressure-sensitive adhesive layer or the like having the above Young's modulus has an appropriate hardness before application of an external stimulus, and is excellent in workability such as manufacturing/processing, storage and transportation. Moreover, the pressure-sensitive adhesive layer or the like having the above Young's modulus is excellent in flexibility after application of an external stimulus, and is more excellent in step followability, adhesiveness, and the like.
上記粘着剤層は、外部刺激付与前のヤング率（Ｅ１）が、０．０３～１．５ＭＰａであることが好ましく、より好ましくは０．０５～１．０ＭＰａ、さらに好ましくは０．１～０．８ＭＰａである。上記ヤング率（Ｅ１）を有する粘着剤層は外部刺激付与前において適度な硬さを有し、取り扱い性により優れる。
The pressure-sensitive adhesive layer preferably has a Young's modulus (E1) of 0.03 to 1.5 MPa, more preferably 0.05 to 1.0 MPa, still more preferably 0.1 to 0 .8 MPa. The pressure-sensitive adhesive layer having the above Young's modulus (E1) has appropriate hardness before application of an external stimulus and is superior in handleability.
上記粘着剤層は、外部刺激付与後のヤング率（Ｅ２）が、１．０ＭＰａ未満（例えば０．００１ＭＰａ以上１．０ＭＰａ未満）であることが好ましく、より好ましくは０．５ＭＰａ以下（例えば０．００５～０．５ＭＰａ）、さらに好ましくは０．３ＭＰａ以下（例えば０．０１～０．３ＭＰａ）である。上記ヤング率を有する粘着剤層は外部刺激付与後において柔軟性に優れ、段差追従性、密着性などがより優れる。
The pressure-sensitive adhesive layer preferably has a Young's modulus (E2) of less than 1.0 MPa (for example, 0.001 MPa or more and less than 1.0 MPa), more preferably 0.5 MPa or less (for example, 0.001 MPa or more and less than 1.0 MPa) after application of an external stimulus. 005 to 0.5 MPa), more preferably 0.3 MPa or less (for example, 0.01 to 0.3 MPa). The pressure-sensitive adhesive layer having the above Young's modulus is excellent in flexibility after application of an external stimulus, and is more excellent in step followability, adhesion, and the like.
上記粘着剤層等は、外部刺激付与前のヤング率（Ｅ１）と外部刺激付与後のヤング率（Ｅ２）の比［ヤング率（Ｅ２）／ヤング率（Ｅ１）］が、０．９５未満（例えば０．１以上０．９５未満）であることが好ましく、より好ましくは０．８以下（例えば０．２～０．８）、さらに好ましくは０．７以下（例えば０．３～０．７）である。この場合、外部刺激付与前後において粘着剤層等の柔軟性、段差追従性、密着性がより大きく変化する傾向にある。
The pressure-sensitive adhesive layer or the like has a ratio [Young's modulus (E2)/Young's modulus (E1)] of Young's modulus (E1) before applying an external stimulus to Young's modulus (E2) after applying an external stimulus is less than 0.95 ( For example, 0.1 or more and less than 0.95), more preferably 0.8 or less (eg, 0.2 to 0.8), still more preferably 0.7 or less (eg, 0.3 to 0.7 ). In this case, there is a tendency that the flexibility, step followability, and adhesion of the pressure-sensitive adhesive layer, etc., change more significantly before and after the application of the external stimulus.
本発明の粘着剤層等は外部刺激により応力が低減する性質を有することが好ましい。上記応力は低減後において増加しないことが好ましい。このような粘着剤層等は、粘着剤層等を部材へ粘着または接着した状態において応力が増加することがなく、柔軟性が持続する。
It is preferable that the pressure-sensitive adhesive layer, etc. of the present invention have the property of reducing stress due to an external stimulus. Preferably, the stress does not increase after reduction. Such a pressure-sensitive adhesive layer or the like does not increase stress in a state in which the pressure-sensitive adhesive layer or the like is adhered or adhered to a member, and maintains its flexibility.
上記応力としては、例えば張圧縮試験機で測定される、任意の倍率で引っ張ったときの応力（歪み応力）が挙げられる。上記特定の倍率で引っ張ったときの応力（歪み応力）は、少なくとも１つの倍率で引っ張ったときの応力（歪み応力）が低減するものであればよい。中でも、引張倍率１００～５００％のうちの少なくとも１点における歪み応力が低減することが好ましく、１００％、２００％、３００％、および５００％からなる群より選択される１以上の引張倍率において歪み応力が低減することが特に好ましい。以下、各引張倍率における応力の好ましい範囲を記載するが、これらの値は各引張倍率において破断しない場合の好ましい範囲である。
Examples of the stress include the stress (distortion stress) when pulled at an arbitrary magnification, which is measured by a tension/compression tester. The stress (distortion stress) when pulled at the above-mentioned specific magnification may be reduced as long as the stress (distortion stress) when pulled at at least one magnification is reduced. Among them, it is preferable that the strain stress at at least one of the tensile ratios of 100 to 500% is reduced, and the strain at one or more tensile ratios selected from the group consisting of 100%, 200%, 300%, and 500%. A reduction in stress is particularly preferred. Preferred ranges of stress at each tensile magnification are described below, and these values are preferred ranges when no breakage occurs at each tensile magnification.
上記粘着剤層等は、外部刺激付与前の応力（１００％歪み応力）（Ｓ１（１００））と、外部刺激付与後の応力（１００％歪み応力）（Ｓ２（１００））の比［Ｓ２（１００）／Ｓ１（１００）］が、０．９５未満（例えば０．１以上０．９５未満）であることが好ましく、より好ましくは０．９以下、さらに好ましくは０．８以下である。このような粘着剤層等は、外部刺激付与により比較的弱い引張応力がさらに低減されたことを示し、引っ張った際の反発力が低く、折り畳み式の部材などの比較的低荷重の用途に適する。
The pressure-sensitive adhesive layer or the like has a ratio [S2 ( 100)/S1(100)] is preferably less than 0.95 (for example, 0.1 or more and less than 0.95), more preferably 0.9 or less, still more preferably 0.8 or less. Such an adhesive layer or the like shows that the relatively weak tensile stress is further reduced by applying an external stimulus, and the repulsive force when pulled is low, making it suitable for relatively low load applications such as foldable members. .
上記粘着剤層等は、外部刺激付与前の応力（１００％歪み応力）（Ｓ１（１００））が、０．０１ＭＰａ以上（例えば０．０１～１０ＭＰａ）であることが好ましく、より好ましくは０．０３ＭＰａ以上（例えば０．０３～６ＭＰａ）、さらに好ましくは０．０５ＭＰａ以上（例えば０．０５～３ＭＰａ）である。このような粘着剤層等は、外部刺激付与後において柔軟性がよりいっそう優れる。
The pressure-sensitive adhesive layer or the like preferably has a stress (100% strain stress) (S1(100)) of 0.01 MPa or more (for example, 0.01 to 10 MPa) before application of an external stimulus, more preferably 0.01 MPa or more (for example, 0.01 to 10 MPa). 03 MPa or more (eg 0.03 to 6 MPa), more preferably 0.05 MPa or more (eg 0.05 to 3 MPa). Such a pressure-sensitive adhesive layer or the like is even more excellent in flexibility after application of an external stimulus.
上記粘着剤層等は、外部刺激付与後の応力（１００％歪み応力）（Ｓ２（１００））が、１０ＭＰａ以下（例えば０．０１～１０ＭＰａ）であることが好ましく、より好ましくは６ＭＰａ以下（例えば０．０２～６ＭＰａ）、さらに好ましくは３ＭＰａ以下（例えば０．０３～３ＭＰａ）である。このような粘着剤層等は、外部刺激付与後において柔軟性がよりいっそう優れる。
The pressure-sensitive adhesive layer or the like preferably has a stress (100% strain stress) (S2(100)) after application of an external stimulus of 10 MPa or less (eg, 0.01 to 10 MPa), more preferably 6 MPa or less (eg, 0.02 to 6 MPa), more preferably 3 MPa or less (for example, 0.03 to 3 MPa). Such a pressure-sensitive adhesive layer or the like is even more excellent in flexibility after application of an external stimulus.
上記粘着剤層等は、外部刺激付与前の応力（２００％歪み応力）（Ｓ１（２００））と、外部刺激付与後の応力（２００％歪み応力）（Ｓ２（２００））の比［Ｓ２（２００）／Ｓ１（２００）］が、０．９５未満（例えば０．１以上０．９５未満）であることが好ましく、より好ましくは０．８以下、さらに好ましくは０．７以下である。このような粘着剤層等は、外部刺激付与により比較的弱い引張応力がさらに軽減されたことを示し、折り畳み式の部材などの比較的低荷重の用途に適する。
The pressure-sensitive adhesive layer or the like has a ratio [S2 ( 200)/S1(200)] is preferably less than 0.95 (for example, 0.1 or more and less than 0.95), more preferably 0.8 or less, still more preferably 0.7 or less. Such an adhesive layer or the like shows that the relatively weak tensile stress is further reduced by applying an external stimulus, and is suitable for relatively low-load applications such as foldable members.
上記粘着剤層等は、外部刺激付与前の応力（２００％歪み応力）（Ｓ１（２００））が、０．０３ＭＰａ以上（例えば０．０３～１０ＭＰａ）であることが好ましく、より好ましくは０．０４ＭＰａ以上（例えば０．０４～４ＭＰａ）、さらに好ましくは０．０６ＭＰａ以上（例えば０．０６～２ＭＰａ）である。このような粘着剤層等は、外部刺激付与後において柔軟性がよりいっそう優れる。
The pressure-sensitive adhesive layer or the like preferably has a stress (200% strain stress) (S1(200)) of 0.03 MPa or more (for example, 0.03 to 10 MPa) before application of an external stimulus, and more preferably 0.03 MPa or more (for example, 0.03 to 10 MPa). 04 MPa or more (eg, 0.04 to 4 MPa), more preferably 0.06 MPa or more (eg, 0.06 to 2 MPa). Such a pressure-sensitive adhesive layer or the like is even more excellent in flexibility after application of an external stimulus.
上記粘着剤層等は、外部刺激付与後の応力（２００％歪み応力）（Ｓ２（２００））が、１０ＭＰａ以下（例えば０．０１～１０ＭＰａ）であることが好ましく、より好ましくは４ＭＰａ以下（例えば０．０３～４ＭＰａ）、さらに好ましくは２ＭＰａ以下（例えば０．０４～２ＭＰａ）である。このような粘着剤層等は、外部刺激付与後において柔軟性がよりいっそう優れる。
The pressure-sensitive adhesive layer or the like preferably has a stress (200% strain stress) (S2(200)) after application of an external stimulus of 10 MPa or less (eg, 0.01 to 10 MPa), more preferably 4 MPa or less (eg, 0.03 to 4 MPa), more preferably 2 MPa or less (for example, 0.04 to 2 MPa). Such a pressure-sensitive adhesive layer or the like is even more excellent in flexibility after application of an external stimulus.
上記粘着剤層等は、外部刺激付与前の応力（３００％歪み応力）（Ｓ１（３００））と、外部刺激付与後の応力（３００％歪み応力）（Ｓ２（３００））の比［Ｓ２（３００）／Ｓ１（３００）］が、０．９５未満（例えば０．１以上０．９５未満）であることが好ましく、より好ましくは０．８以下、さらに好ましくは０．７以下である。このような粘着剤層等は、外部刺激付与により引張応力が軽減されたことを示し、折り畳み式の部材などの比較的低荷重の用途に適する。
The pressure-sensitive adhesive layer or the like has a ratio [S2 ( 300)/S1(300)] is preferably less than 0.95 (for example, 0.1 or more and less than 0.95), more preferably 0.8 or less, still more preferably 0.7 or less. Such a pressure-sensitive adhesive layer or the like shows that the tensile stress is reduced by applying an external stimulus, and is suitable for relatively low-load applications such as foldable members.
上記粘着剤層等は、外部刺激付与前の応力（３００％歪み応力）（Ｓ１（３００））が、０．０３ＭＰａ以上（例えば０．０３～１０ＭＰａ）であることが好ましく、より好ましくは０．０５ＭＰａ以上（例えば０．０５～４ＭＰａ）、さらに好ましくは０．０７ＭＰａ以上（例えば０．０７～２ＭＰａ）である。このような粘着剤層等は、外部刺激付与後において柔軟性がよりいっそう優れる。
The pressure-sensitive adhesive layer or the like preferably has a stress (300% strain stress) (S1(300)) of 0.03 MPa or more (for example, 0.03 to 10 MPa) before application of an external stimulus, more preferably 0. 05 MPa or more (eg 0.05 to 4 MPa), more preferably 0.07 MPa or more (eg 0.07 to 2 MPa). Such a pressure-sensitive adhesive layer or the like is even more excellent in flexibility after application of an external stimulus.
上記粘着剤層等は、外部刺激付与後の応力（３００％歪み応力）（Ｓ２（３００））が、１０ＭＰａ以下（例えば０．０１～１０ＭＰａ）であることが好ましく、より好ましくは４ＭＰａ以下（例えば０．０３～４ＭＰａ）、さらに好ましくは２ＭＰａ以下（例えば０．０４～２ＭＰａ）である。このような粘着剤層等は、外部刺激付与後において柔軟性がよりいっそう優れる。
The pressure-sensitive adhesive layer or the like preferably has a stress (300% strain stress) (S2(300)) after application of an external stimulus of 10 MPa or less (eg, 0.01 to 10 MPa), more preferably 4 MPa or less (eg, 0.03 to 4 MPa), more preferably 2 MPa or less (for example, 0.04 to 2 MPa). Such a pressure-sensitive adhesive layer or the like is even more excellent in flexibility after application of an external stimulus.
上記粘着剤層等は、外部刺激付与前の応力（５００％歪み応力）（Ｓ１（５００））と、外部刺激付与後の応力（５００％歪み応力）（Ｓ２（５００））の比［Ｓ２（５００）／Ｓ１（５００）］が、０．９５未満（例えば０．１以上０．９５未満）であることが好ましく、より好ましくは０．８以下、さらに好ましくは０．７以下である。このような粘着剤層等は、外部刺激付与により比較的強い引張応力が軽減されたことを示し、引っ張った際の反発力が特に低く、折り畳み式（特に、ローラブル等の巻き付ける方式）の部材などの比較的高荷重の用途に適する。
The pressure-sensitive adhesive layer or the like has a ratio [S2 ( 500)/S1(500)] is preferably less than 0.95 (for example, 0.1 or more and less than 0.95), more preferably 0.8 or less, still more preferably 0.7 or less. Such a pressure-sensitive adhesive layer or the like shows that a relatively strong tensile stress is reduced by applying an external stimulus, and the repulsive force when pulled is particularly low, and a folding type (especially a winding type such as a rollable) member etc. Suitable for relatively high load applications.
上記の粘着剤層等は、外部刺激付与前の応力（５００％歪み応力）（Ｓ１（５００））が、０．０５ＭＰａ以上（例えば０．０５～１０ＭＰａ）であることが好ましく、より好ましくは０．０７ＭＰａ以上（例えば０．０７～４ＭＰａ）、さらに好ましくは０．１ＭＰａ以上（例えば０．１～２ＭＰａ）である。このような粘着剤層等は、外部刺激付与後において柔軟性がよりいっそう優れる。
The pressure-sensitive adhesive layer or the like preferably has a stress (500% strain stress) (S1(500)) of 0.05 MPa or more (eg, 0.05 to 10 MPa) before application of an external stimulus, more preferably 0 0.07 MPa or more (eg, 0.07 to 4 MPa), more preferably 0.1 MPa or more (eg, 0.1 to 2 MPa). Such a pressure-sensitive adhesive layer or the like is even more excellent in flexibility after application of an external stimulus.
上記粘着剤層等は、外部刺激付与後の応力（５００％歪み応力）（Ｓ２（５００））が、１０ＭＰａ以下（例えば０．０１～１０ＭＰａ）であることが好ましく、より好ましくは４ＭＰａ以下（例えば０．０３～４ＭＰａ）、さらに好ましくは２ＭＰａ以下（例えば０．０４～２ＭＰａ）である。このような粘着剤層等は、外部刺激付与後において柔軟性がよりいっそう優れる。
The pressure-sensitive adhesive layer or the like preferably has a stress (500% strain stress) (S2(500)) after application of an external stimulus of 10 MPa or less (eg, 0.01 to 10 MPa), more preferably 4 MPa or less (eg, 0.03 to 4 MPa), more preferably 2 MPa or less (for example, 0.04 to 2 MPa). Such a pressure-sensitive adhesive layer or the like is even more excellent in flexibility after application of an external stimulus.
また、本発明の粘着剤層等は、外部刺激により、応力－ひずみ曲線におけるピーク強度（応力ピーク強度）や破断点応力が低減する性質を有していてもよい。上記応力ピーク強度や破断点応力は低減後において増加しないことが好ましい。
In addition, the pressure-sensitive adhesive layer and the like of the present invention may have the property of reducing the peak strength (stress peak strength) in the stress-strain curve and the stress at break due to an external stimulus. It is preferable that the stress peak strength and the stress at break do not increase after reduction.
上記粘着剤層等は、外部刺激付与前の応力－ひずみ曲線におけるピーク強度（応力ピーク強度）が、０．０７ＭＰａ以上であることが好ましく、より好ましくは０．１ＭＰａ以上、さらに好ましくは０．２ＭＰａ以上である。上記応力ピーク強度が０．０７ＭＰａ以上であると、粘着剤層等は外部刺激付与前において適度な硬さを有し、製造・加工、保管、運搬等の作業性に優れる。
The pressure-sensitive adhesive layer or the like preferably has a peak strength (stress peak strength) of 0.07 MPa or more, more preferably 0.1 MPa or more, and still more preferably 0.2 MPa in a stress-strain curve before application of an external stimulus. That's it. When the stress peak strength is 0.07 MPa or more, the pressure-sensitive adhesive layer or the like has appropriate hardness before application of an external stimulus, and is excellent in workability such as manufacturing/processing, storage and transportation.
上記粘着剤層等は、外部刺激付与後の応力－ひずみ曲線におけるピーク強度（応力ピーク強度）が、０．０１～１．０ＭＰａであることが好ましく、より好ましくは０．０３～０．８ＭＰａ、さらに好ましくは０．０４～０．５ＭＰａである。上記応力ピーク強度が上記範囲内であると、外部刺激付与後では柔軟性により優れ、段差追従性、密着性などがより優れる。
The pressure-sensitive adhesive layer or the like preferably has a peak strength (stress peak strength) in a stress-strain curve after application of an external stimulus of 0.01 to 1.0 MPa, more preferably 0.03 to 0.8 MPa. More preferably, it is 0.04 to 0.5 MPa. When the stress peak intensity is within the above range, the flexibility, step conformability, adhesion, etc. are more excellent after application of an external stimulus.
上記粘着剤層等は、外部刺激付与前の応力－ひずみ曲線におけるピーク強度と、外部刺激付与後の応力－ひずみ曲線におけるピーク強度の比［外部刺激付与後／外部刺激付与前］が、０．９５未満（例えば０．０５以上０．９５未満）であることが好ましく、より好ましくは０．８以下（例えば０．１～０．８）、さらに好ましくは０．７以下（例えば０．３～０．７）である。この場合、外部刺激付与前後において粘着剤層等の柔軟性、段差追従性、密着性がより大きく変化する傾向にある。
In the pressure-sensitive adhesive layer, etc., the ratio of the peak intensity in the stress-strain curve before applying the external stimulus to the peak intensity in the stress-strain curve after applying the external stimulus [after applying the external stimulus/before applying the external stimulus] is 0.5. It is preferably less than 95 (eg, 0.05 or more and less than 0.95), more preferably 0.8 or less (eg, 0.1 to 0.8), still more preferably 0.7 or less (eg, 0.3 to 0.7). In this case, there is a tendency that the flexibility, step followability, and adhesion of the pressure-sensitive adhesive layer, etc., change more significantly before and after the application of the external stimulus.
上記粘着剤層等の厚さは、特に限定されないが、例えば５～２５０μｍ程度であり、より好ましくは７～２００μｍ、さらに好ましくは１０～１００μｍ、特に好ましくは１０～５０μｍである。
The thickness of the adhesive layer, etc. is not particularly limited, but is, for example, about 5 to 250 μm, more preferably 7 to 200 μm, even more preferably 10 to 100 μm, and particularly preferably 10 to 50 μm.
（はく離ライナー）
はく離ライナーは、上記粘着剤層等の使用時まで接する粘着面および／または接着面を保護するものであり、上記粘着剤層等を使用するときに剥離される。 (Release liner)
The release liner protects the pressure-sensitive adhesive surface and/or the adhesive surface with which the pressure-sensitive adhesive layer and the like are in contact until use, and is peeled off when the pressure-sensitive adhesive layer and the like is used.
はく離ライナーは、上記粘着剤層等の使用時まで接する粘着面および／または接着面を保護するものであり、上記粘着剤層等を使用するときに剥離される。 (Release liner)
The release liner protects the pressure-sensitive adhesive surface and/or the adhesive surface with which the pressure-sensitive adhesive layer and the like are in contact until use, and is peeled off when the pressure-sensitive adhesive layer and the like is used.
上記はく離ライナーの基材としては、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン酢酸ビニルフィルム、アイオノマー樹脂フィルム、エチレン・（メタ）アクリル酸共重合体フィルム、エチレン・（メタ）アクリル酸エステル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリイミドフィルム、フッ素樹脂フィルムなどが挙げられる。また、これらの架橋フィルムも挙げられる。さらに、これらの積層フィルムであってもよい。
Examples of base materials for the release liner include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, poly Butylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene/(meth)acrylic acid copolymer film, ethylene/(meth)acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, A fluorine resin film etc. are mentioned. Moreover, these crosslinked films are also mentioned. Furthermore, a laminated film of these may be used.
上記はく離ライナーの剥離面（特に上記粘着剤層等と接する面）には、剥離処理が施されていることが好ましい。剥離処理に使用される剥離剤としては、例えば、アルキッド系、シリコーン系、フッ素系、不飽和ポリエステル系、ポリオレフィン系、ワックス系の剥離剤が挙げられる。
The release surface of the release liner (especially the surface in contact with the pressure-sensitive adhesive layer, etc.) is preferably subjected to a release treatment. Examples of release agents used in the release treatment include alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents.
上記はく離ライナーの厚さは、特に限定されないが、例えば２０～１５０μｍ程度である。
Although the thickness of the release liner is not particularly limited, it is, for example, about 20 to 150 μm.
（粘着剤組成物、接着剤組成物）
上記粘着剤層は上記粘着剤組成物から形成される。また、上記接着剤層は上記接着剤組成物から形成される。上記粘着剤組成物等は、ベースポリマーおよび／またはその原料モノマーを少なくとも含むことが好ましい。上記ベースポリマーは、ポリマー（Ａ）および／またはその他のポリマー（すなわち非可逆分解性結合を有しないポリマー）である。上記ベースポリマーは、一種のみを使用してもよく、二種以上を使用してもよい。 (Adhesive composition, adhesive composition)
The pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive composition. Also, the adhesive layer is formed from the adhesive composition. The pressure-sensitive adhesive composition and the like preferably contain at least a base polymer and/or a raw material monomer thereof. The base polymer is polymer (A) and/or other polymers (that is, polymers without irreversible degradable bonds). Only one type of the base polymer may be used, or two or more types may be used.
上記粘着剤層は上記粘着剤組成物から形成される。また、上記接着剤層は上記接着剤組成物から形成される。上記粘着剤組成物等は、ベースポリマーおよび／またはその原料モノマーを少なくとも含むことが好ましい。上記ベースポリマーは、ポリマー（Ａ）および／またはその他のポリマー（すなわち非可逆分解性結合を有しないポリマー）である。上記ベースポリマーは、一種のみを使用してもよく、二種以上を使用してもよい。 (Adhesive composition, adhesive composition)
The pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive composition. Also, the adhesive layer is formed from the adhesive composition. The pressure-sensitive adhesive composition and the like preferably contain at least a base polymer and/or a raw material monomer thereof. The base polymer is polymer (A) and/or other polymers (that is, polymers without irreversible degradable bonds). Only one type of the base polymer may be used, or two or more types may be used.
上記ベースポリマーが上記その他のポリマーである場合、上記粘着剤組成物等は、さらに化合物（Ｂ）を含む。上記ベースポリマーは、中でも、ポリマー（Ａ）を含むことが好ましく、ポリマー（Ａ）および上記その他のポリマーを含むことがより好ましい。また、ポリマー（Ａ）は硬化性樹脂であることが好ましい。上記硬化性樹脂の硬化性は非可逆分解性結合の種類に応じて適宜選択され、非可逆分解性結合が活性エネルギー線により開裂可能である場合は熱硬化性樹脂であることが好ましい。
When the base polymer is the other polymer, the adhesive composition or the like further contains the compound (B). Among others, the base polymer preferably contains the polymer (A), and more preferably contains the polymer (A) and the other polymer. Also, the polymer (A) is preferably a curable resin. The curability of the curable resin is appropriately selected according to the type of the irreversibly decomposable bond, and when the irreversibly decomposable bond can be cleaved by active energy rays, it is preferably a thermosetting resin.
上記硬化性樹脂であるポリマー（Ａ）は重合性官能基を有する樹脂（プレポリマー）であることが好ましい。ポリマー（Ａ）が重合性官能基を有する場合、粘着剤層等を形成する際、粘着剤組成物等の塗布後において熱や活性エネルギー線照射により重合性官能基同士の重合が進行することで、上記その他のポリマーと絡み合うことによりネットワーク構造を形成することができる。すなわち、ポリマー（Ａ）は、上記ネットワーク構造を形成し得るポリマーであることが好ましい。上記その他のポリマーは、一種のみを使用してもよく、二種以上を使用してもよい。
The polymer (A), which is the curable resin, is preferably a resin (prepolymer) having a polymerizable functional group. When the polymer (A) has a polymerizable functional group, when forming an adhesive layer or the like, polymerization of the polymerizable functional groups proceeds by heat or active energy ray irradiation after application of the adhesive composition or the like. , can form a network structure by entangling with other polymers. That is, the polymer (A) is preferably a polymer capable of forming the above network structure. Only one kind of the other polymers may be used, or two or more kinds thereof may be used.
上記ベースポリマーが上記その他のポリマーである場合、上記粘着剤組成物等は、さらに化合物（Ｂ）を含む。また、この場合、さらに化合物（Ｂ）と反応性を有するモノマー成分（モノマー成分（Ｃ））を含んでいてもよい。化合物（Ｂ）は、上記その他のポリマーおよび／またはモノマー成分（Ｃ）と反応性を有する。化合物（Ｂ）が上記その他のポリマーと反応性を有する場合、粘着剤層等において熱や活性エネルギー線照射などにより上記その他のポリマーと化合物（Ｂ）とが反応して例えばポリマー鎖を形成し、上記ポリマー鎖と上記その他のポリマーとが結合してネットワーク構造を形成し、ポリマー（Ａ）を含む粘着剤層等が得られる。化合物（Ｂ）およびモノマー成分（Ｃ）を含む場合、粘着剤層等において熱や活性エネルギー線照射などにより化合物（Ｂ）とモノマー成分（Ｃ）とが反応して例えばポリマー鎖を形成し、上記ポリマー鎖と上記その他のポリマーとが絡み合ってネットワーク構造を形成し、ポリマー（Ａ）を含む粘着剤層等が得られる。
When the base polymer is the other polymer, the adhesive composition or the like further contains the compound (B). Moreover, in this case, a monomer component (monomer component (C)) having reactivity with the compound (B) may be further included. Compound (B) has reactivity with the other polymer and/or monomer component (C). When the compound (B) has reactivity with the other polymer, the other polymer and the compound (B) react with heat or active energy ray irradiation in the pressure-sensitive adhesive layer or the like to form, for example, a polymer chain, The polymer chain and the other polymer combine to form a network structure, and a pressure-sensitive adhesive layer or the like containing the polymer (A) is obtained. When the compound (B) and the monomer component (C) are included, the compound (B) and the monomer component (C) react with heat or active energy ray irradiation in the pressure-sensitive adhesive layer or the like to form, for example, a polymer chain. The polymer chains and the above-mentioned other polymers are entangled to form a network structure, and a pressure-sensitive adhesive layer or the like containing the polymer (A) is obtained.
上記粘着剤組成物等が上記原料モノマーを含む場合、上記原料モノマーを重合させる際に化合物（Ｂ）がベースポリマー内に取り込まれ、ポリマー（Ａ）が形成される。あるいは、上記原料モノマーを重合させて上記その他のポリマーを形成し、その後化合物（Ｂ）と反応させてポリマー（Ａ）が形成される。
When the adhesive composition or the like contains the raw material monomer, the compound (B) is incorporated into the base polymer when the raw material monomer is polymerized to form the polymer (A). Alternatively, the raw material monomer is polymerized to form the other polymer, which is then reacted with compound (B) to form polymer (A).
上記粘着剤組成物等としては、主として、（ｉ）ポリマー（Ａ）を含む粘着剤組成物等、（ii）ポリマー（Ａ）および上記その他のポリマーを含む粘着剤組成物等、（iii）上記その他のポリマー、化合物（Ｂ）、必要に応じてモノマー成分（Ｃ）を含む粘着剤組成物等、（iv）原料モノマー、化合物（Ｂ）、必要に応じてモノマー成分（Ｃ）を含む粘着剤組成物等が挙げられる。
The above-mentioned pressure-sensitive adhesive composition mainly includes (i) a pressure-sensitive adhesive composition containing the polymer (A), (ii) a pressure-sensitive adhesive composition containing the polymer (A) and the other polymer, and (iii) the above Other polymers, compound (B), pressure-sensitive adhesive composition containing monomer component (C) as necessary, (iv) raw material monomer, compound (B), pressure-sensitive adhesive containing monomer component (C) as necessary composition and the like.
よって、ポリマー（Ａ）は、上記その他のポリマー、化合物（Ｂ）、およびモノマー成分（Ｃ）の反応物であってもよく、上記その他のポリマーと上記その他のポリマーおよび化合物（ａ）の反応物とを含む（特に、絡み合った）ポリマーであってもよい。また、上記ベースポリマーがポリマー（Ａ）を含む場合、上記粘着剤層等は、未反応の化合物（Ｂ）および／または未反応のモノマー成分（Ｃ）を含み得る。
Therefore, the polymer (A) may be a reaction product of the other polymer, the compound (B), and the monomer component (C), or a reaction product of the other polymer with the other polymer and the compound (a). It may also be a polymer comprising (especially entangled). Moreover, when the base polymer contains polymer (A), the pressure-sensitive adhesive layer and the like may contain unreacted compound (B) and/or unreacted monomer component (C).
上記ベースポリマーとしては、上記熱可塑性樹脂、上記熱硬化性樹脂、上記活性エネルギー線硬化性樹脂などが挙げられる。上記ベースポリマーとしてのポリマー（Ａ）は、中でも、硬化性樹脂が好ましく、より好ましくは熱硬化性樹脂である。上記その他のポリマーとしては、熱可塑性樹脂が好ましい。熱可塑性樹脂を含有する粘着剤層等は例えば外部からの圧力で密着する粘着性を発揮することが可能となる。熱硬化性樹脂を含有する粘着剤組成物等は、例えば加熱により硬化することでネットワーク構造を形成することができる。なお、上記その他のポリマーは硬化性樹脂であってもよく、この場合、同じく硬化性樹脂であるポリマー（Ａ）と上記その他のポリマーとで熱や活性エネルギー線照射などにより両樹脂で結合を形成し、ネットワーク構造を形成することが可能となる。
Examples of the base polymer include the thermoplastic resin, the thermosetting resin, the active energy ray-curable resin, and the like. The polymer (A) as the base polymer is preferably a curable resin, more preferably a thermosetting resin. Thermoplastic resins are preferable as the other polymers. A pressure-sensitive adhesive layer or the like containing a thermoplastic resin is capable of exerting adhesiveness such that it adheres under pressure from the outside, for example. A pressure-sensitive adhesive composition containing a thermosetting resin can form a network structure, for example, by being cured by heating. In addition, the other polymer may be a curable resin, and in this case, the polymer (A), which is also a curable resin, and the other polymer form a bond between the two resins by heat, active energy ray irradiation, or the like. It becomes possible to form a network structure.
化合物（Ｂ）としては、上述のように、上記非可逆分解性結合を有する、モノマー成分、オリゴマー成分、架橋剤などが挙げられる。中でも、モノマー成分（すなわち上記重合性官能基を有する化合物）が好ましく、より好ましくは上記ニトロベンジル系モノマー、さらに好ましくは上記ニトロベンジルエステル系モノマーである。
As described above, the compound (B) includes a monomer component, an oligomer component, a cross-linking agent, and the like having the irreversibly degradable bond. Among them, the monomer component (that is, the compound having the polymerizable functional group) is preferred, the nitrobenzyl-based monomer is more preferred, and the nitrobenzyl ester-based monomer is even more preferred.
上記ベースポリマー中のポリマー（Ａ）の含有割合は、上記ベースポリマーの総量（１００質量％）に対して、１０～９０質量％が好ましく、より好ましくは３０～７０質量％、さらに好ましくは４０～６０質量％である。上記含有割合が１０質量％以上であると、外部刺激により非可逆分解性結合が充分な量で開裂する。上記含有割合が９０質量％以下であると、外部刺激付与後であっても適度な粘着性および／または接着性を維持することができる。
The content of the polymer (A) in the base polymer is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, more preferably 40 to 90% by mass, relative to the total amount (100% by mass) of the base polymer. 60% by mass. When the content is 10% by mass or more, a sufficient amount of the irreversible degradable bond is cleaved by an external stimulus. When the content is 90% by mass or less, appropriate tackiness and/or adhesiveness can be maintained even after application of an external stimulus.
上記ベースポリマー中の上記その他のポリマーの含有割合は、上記ベースポリマーの総量（１００質量％）に対して、１０～９０質量％が好ましく、より好ましくは３０～７０質量％、さらに好ましくは４０～６０質量％である。上記含有割合が１０質量％以上であると、外部刺激付与後であっても適度な粘着性および／または接着性を維持することができる。上記含有割合が９０質量％以下であると、ポリマー（Ａ）を充分に配合することができ、これにより外部刺激により非可逆分解性結合が充分な量で開裂する。
The content of the other polymer in the base polymer is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, more preferably 40 to 90% by mass, relative to the total amount (100% by mass) of the base polymer. 60% by mass. When the above content is 10% by mass or more, appropriate tackiness and/or adhesiveness can be maintained even after application of an external stimulus. When the above content is 90% by mass or less, the polymer (A) can be sufficiently blended, whereby the irreversible degradable bond is cleaved in a sufficient amount by an external stimulus.
ポリマー（Ａ）中の化合物（Ｂ）に由来する構成単位の含有割合は、ポリマー（Ａ）の総量１００質量％に対して、０．２～３０質量％が好ましく、より好ましくは０．５～１５質量％、さらに好ましくは０．８～１０質量％である。上記粘着剤組成物等がベースポリマーを構成する原料モノマーを含む場合、ポリマー（Ａ）を構成する全モノマー成分中の化合物（Ｂ）の含有割合が上記範囲内であることが好ましい。
The content of structural units derived from the compound (B) in the polymer (A) is preferably 0.2 to 30% by mass, more preferably 0.5 to 30% by mass, with respect to 100% by mass of the total amount of the polymer (A). 15% by mass, more preferably 0.8 to 10% by mass. When the pressure-sensitive adhesive composition or the like contains raw material monomers constituting the base polymer, the content of the compound (B) in all the monomer components constituting the polymer (A) is preferably within the above range.
ポリマー（Ａ）が上記アクリル系樹脂である場合、ポリマー（Ａ）中のアクリル系モノマーに由来する構成単位の含有割合は、ポリマー（Ａ）の総量１００質量％に対して、７０～９９．８質量％が好ましく、より好ましくは８５～９９．５質量％、さらに好ましくは９０～９９．２質量％である。上記粘着剤組成物等がベースポリマーを構成する原料モノマーを含む場合、ポリマー（Ａ）を構成する全モノマー成分中のアクリル系モノマーの含有割合が上記範囲内であることが好ましい。
When the polymer (A) is the above acrylic resin, the content of structural units derived from acrylic monomers in the polymer (A) is 70 to 99.8 with respect to 100% by mass of the total amount of the polymer (A). % by mass is preferable, more preferably 85 to 99.5% by mass, and still more preferably 90 to 99.2% by mass. When the pressure-sensitive adhesive composition or the like contains a raw material monomer that constitutes the base polymer, the content of the acrylic monomer in all the monomer components that constitute the polymer (A) is preferably within the above range.
上記ベースポリマー中の化合物（Ｂ）に由来する構成単位の含有割合は、外部刺激付与後に開裂し、細断されることで充分な柔軟性を発揮させるために、上記ベースポリマーの総量１００質量％に対して、０．１質量％以上が好ましく、より好ましくは０．２質量％以上、さらに好ましくは０．５質量％以上、特に好ましくは１質量％以上である。また、架橋密度を適度とし外部刺激付与前において樹脂に適度な柔軟性を付与するため、１５質量％以下が好ましく、より好ましくは１０質量％以下、さらに好ましくは５質量％以下である。上記粘着剤組成物等がベースポリマーを構成する原料モノマーを含む場合、ベースポリマーを構成する全モノマー成分中の化合物（Ｂ）の含有割合が上記範囲内であることが好ましい。
The content of structural units derived from the compound (B) in the base polymer is 100% by mass in the total amount of the base polymer in order to exhibit sufficient flexibility by being cleaved and shredded after application of an external stimulus. is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. Moreover, in order to make the crosslink density appropriate and to impart appropriate flexibility to the resin before applying an external stimulus, the amount is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. When the pressure-sensitive adhesive composition or the like contains raw material monomers constituting the base polymer, the content of the compound (B) in all the monomer components constituting the base polymer is preferably within the above range.
上記ベースポリマーが上記アクリル系樹脂である場合、上記ベースポリマー中のアクリル系モノマーに由来する構成単位の含有割合は、ベースポリマーの総量１００質量％に対して、８５～９９．９質量％が好ましく、より好ましくは９０～９９．８質量％、さらに好ましくは９５～９９．５質量％である。上記粘着剤組成物等がベースポリマーを構成する原料モノマーを含む場合、ベースポリマーを構成する全モノマー成分中のアクリル系モノマーの含有割合が上記範囲内であることが好ましい。
When the base polymer is the acrylic resin, the content of structural units derived from acrylic monomers in the base polymer is preferably 85 to 99.9% by mass with respect to 100% by mass of the total amount of the base polymer. , more preferably 90 to 99.8% by mass, more preferably 95 to 99.5% by mass. When the pressure-sensitive adhesive composition or the like contains a raw material monomer constituting the base polymer, the content of the acrylic monomer in all the monomer components constituting the base polymer is preferably within the above range.
上記粘着剤組成物等は、上述の各成分以外のその他の成分を含んでいてもよい。上記その他の成分としては上述の本発明の粘着剤等が含み得るその他の成分として例示および説明されたものや、有機溶媒等の溶媒が挙げられる。上記その他の成分は、それぞれ、一種のみを使用してもよいし、二種以上を使用してもよい。
The adhesive composition and the like may contain other components other than the components described above. Examples of the above-mentioned other components include those exemplified and explained as other components that may be contained in the above-described pressure-sensitive adhesive of the present invention, and solvents such as organic solvents. Only one kind of each of the other components may be used, or two or more kinds thereof may be used.
上記粘着剤組成物等中のベースポリマーの含有割合は、上記粘着剤組成物等の総量（但し、有機溶媒等の層形成時に残存しない成分は除く）１００質量％に対して、５０質量％以上が好ましく、より好ましくは７０質量％以上、さらに好ましくは８０質量％以上、特に好ましくは９０質量％以上である。
The content of the base polymer in the pressure-sensitive adhesive composition, etc. is 50% by mass or more with respect to 100% by mass of the total amount of the pressure-sensitive adhesive composition, etc. (excluding components such as organic solvents that do not remain during layer formation). is preferred, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
本発明の粘着剤等の製造方法の一実施形態について説明する。例えば、図１に示すはく離ライナー付き粘着シートまたは接着シート１０は、下記の方法で作製することができる。基材層や離型処理が施されたはく離ライナー２の離型処理面に、粘着剤層等１を形成する粘着剤組成物等を塗布して塗布層を形成した後、加熱による脱溶媒や熱硬化、あるいは活性エネルギー線照射による硬化を行い、当該塗布層を固化させることによって作製することができる。なお、活性エネルギー線照射を行う場合、上記塗布層上に別途はく離ライナーを貼り合わせた後に行う。
An embodiment of the method for manufacturing the pressure-sensitive adhesive, etc. of the present invention will be described. For example, the pressure-sensitive adhesive sheet with a release liner or adhesive sheet 10 shown in FIG. 1 can be produced by the following method. After forming a coating layer by applying a pressure-sensitive adhesive composition or the like for forming the pressure-sensitive adhesive layer or the like 1 to the base material layer or the release-treated surface of the release liner 2 that has been subjected to the release treatment, the solvent is removed by heating, or It can be prepared by hardening the coating layer by heat curing or curing by irradiation with active energy rays. In addition, when performing active energy ray irradiation, it is performed after bonding a separate release liner on the coating layer.
上記粘着剤組成物等は、本発明の効果を損なわない限り、いずれの形態であってもよい。例えば、粘着剤組成物等は、エマルジョン型、溶剤型（溶液型）、熱溶融型（ホットメルト型）などであってもよい。中でも、生産性に優れる粘着剤層等が得やすい点より、溶剤型が好ましい。
The adhesive composition and the like may be in any form as long as it does not impair the effects of the present invention. For example, the pressure-sensitive adhesive composition may be emulsion type, solvent type (solution type), heat melting type (hot melt type), or the like. Among them, the solvent type is preferable because it is easy to obtain a pressure-sensitive adhesive layer with excellent productivity.
上記粘着剤組成物等がポリマー（Ａ）を含む場合、上記塗布層を固化させる際の加熱により上記粘着剤層等が形成される。また、上記粘着剤組成物等が上記その他のポリマーおよび／または原料モノマーと化合物（Ｂ）とを含む場合、上記塗布層を固化させる際の加熱や活性エネルギー線照射より、必要に応じて原料モノマーが重合し、化合物（Ｂ）が原料モノマーの重合物や上記その他のポリマーと結合を形成し、ポリマー（Ａ）が形成されると同時に、上記粘着剤層等が形成される。上記粘着剤層等は、その後に加熱や活性エネルギー線照射を行ってもよいし、またポリマー（Ａ）が硬化性樹脂である場合は硬化処理を行ってもよい。このようにして図１に示すはく離ライナー付き粘着シートまたは接着シート１０が得られる。
When the adhesive composition or the like contains the polymer (A), the adhesive layer or the like is formed by heating when the coating layer is solidified. Further, when the pressure-sensitive adhesive composition or the like contains the other polymer and/or raw material monomer and the compound (B), the raw material monomer is optionally removed by heating or active energy ray irradiation when solidifying the coating layer. is polymerized, and the compound (B) forms a bond with the polymer of the raw material monomers and the above-mentioned other polymer to form the polymer (A), and at the same time, the pressure-sensitive adhesive layer and the like are formed. After that, the pressure-sensitive adhesive layer and the like may be heated or irradiated with an active energy ray, or when the polymer (A) is a curable resin, a curing treatment may be performed. Thus, the pressure-sensitive adhesive sheet with a release liner or adhesive sheet 10 shown in FIG. 1 is obtained.
本発明の粘着剤等の用途は特に限定されず、あらゆる用途に使用することができる。本発明の粘着剤等は、例えば光学用途、すなわち光学部材に貼り合わせる用途に使用することができる。本発明の粘着剤等は、例えば、電気電子機器等の光学部材において、各種部材または部品を所定の部位（例えば、筐体等）に取り付ける（装着する）際に用いられる。なお、「電気電子機器」とは、電気機器または電子機器の少なくともいずれかに該当する機器をいう。上記電気電子機器としては、例えば、液晶ディスプレイ、エレクトロルミネッセンスディスプレイ、プラズマディスプレイ等の画像表示装置や、携帯電子機器などが挙げられる。上記画像表示装置としては、上記携帯電子機器における画像表示装置や、電車やバスなどの車両内外のディスプレイ（ロールディスプレイ）などが挙げられる。
The use of the adhesive, etc. of the present invention is not particularly limited, and it can be used for any purpose. The pressure-sensitive adhesive or the like of the present invention can be used, for example, for optical applications, that is, for bonding to optical members. The pressure-sensitive adhesive or the like of the present invention is used, for example, in optical members such as electrical and electronic equipment, when various members or parts are attached (mounted) to a predetermined portion (for example, a housing or the like). It should be noted that "electrical/electronic equipment" refers to equipment corresponding to at least one of electric equipment and electronic equipment. Examples of the electric/electronic devices include image display devices such as liquid crystal displays, electroluminescence displays, and plasma displays, and mobile electronic devices. Examples of the image display device include an image display device in the portable electronic device, a display (roll display) inside and outside a vehicle such as a train or a bus, and the like.
上記携帯電子機器としては、例えば、携帯電話、スマートフォン、タブレット型パソコン、ノート型パソコン、各種ウェアラブル機器（例えば、腕時計のように手首に装着するリストウェア型、クリップやストラップ等で体の一部に装着するモジュラー型、メガネ型（単眼型や両眼型。ヘッドマウント型も含む。）を包含するアイウェア型、シャツや靴下、帽子等に例えばアクセサリの形態で取り付ける衣服型、イヤホンのように耳に取り付けるイヤウェア型等）、デジタルカメラ、デジタルビデオカメラ、音響機器（携帯音楽プレーヤー、ＩＣレコーダー等）、計算機（電卓等）、携帯ゲーム機器、電子辞書、電子手帳、電子書籍、車載用情報機器、携帯ラジオ、携帯テレビ、携帯プリンター、携帯スキャナ、携帯モデムなどが挙げられる。なお、本明細書において「携帯」とは、単に携帯することが可能であるだけでは充分ではなく、個人（標準的な成人）が相対的に容易に持ち運び可能なレベルの携帯性を有することを意味するものとする。
Examples of the portable electronic devices include mobile phones, smartphones, tablet computers, notebook computers, and various wearable devices (for example, wrist wear types that are worn on the wrist like wristwatches, clips, straps, etc. that are attached to a part of the body) Modular type to be worn, eyewear type including eyeglass type (monocular type and binocular type, including head-mounted type), clothing type that can be attached to shirts, socks, hats, etc. in the form of accessories, ears such as earphones earwear type, etc.), digital cameras, digital video cameras, audio equipment (portable music players, IC recorders, etc.), calculators (calculators, etc.), portable game devices, electronic dictionaries, electronic notebooks, electronic books, in-vehicle information equipment, Examples include portable radios, portable televisions, portable printers, portable scanners, and portable modems. In this specification, the term “portable” means not only being able to be carried but also having a level of portability that allows individuals (standard adults) to relatively easily carry it. shall mean.
本発明の粘着剤等は、任意のタイミングで外部刺激の付与により柔軟性を向上することが可能である。このため、製造・加工、保管、運搬等の際にはある程度の硬さを有する状態として取り扱い性に優れることとすることができる。例えば打ち抜き刃での切り抜き時には糊はみだしや糊欠け、これらに起因した工程汚染などを防止することができる。また、保管時には自重で糊はみだしが起こりにくく、運搬時には振動・接触による糊欠けが生じにくい。そして、部材に貼り合わせて使用する際は柔軟性を向上させることで、密着力、接着力（粘着力）、折り曲げ性、折り畳み性、耐屈曲性などに優れることとすることができる。また、本発明の粘着剤層等は、非可逆分解性結合を分子内に有するポリマーを含むため、外部刺激により、密着力や接着力を変動させることができる。
The adhesive, etc. of the present invention can improve flexibility by applying an external stimulus at any time. For this reason, during manufacturing, processing, storage, transportation, etc., it can be made to have a certain degree of hardness and be excellent in handleability. For example, at the time of cutting with a punching blade, it is possible to prevent paste from overflowing, lack of glue, and process contamination caused by these. In addition, the glue is less likely to ooze out due to its own weight during storage, and less likely to cause glue chipping due to vibration or contact during transportation. By improving the flexibility when used by being attached to a member, the adhesive strength, adhesive strength (adhesive strength), bendability, foldability, bending resistance, etc. can be improved. In addition, since the pressure-sensitive adhesive layer or the like of the present invention contains a polymer having an irreversible degradable bond in the molecule, it is possible to change the adhesive force and adhesion force by an external stimulus.
＜粘着シート、接着シート＞
本発明の粘着剤層等を用いて粘着シートおよび／または粘着シートを得ることができる。なお、本明細書において、粘着シートおよび／または粘着シートを「粘着シート等」と称する場合がある。上記粘着シート等は、基材（基材層）を有しない、いわゆる「基材レスタイプ」の粘着シート等であってもよいし、基材を有するタイプの粘着シート等であってもよい。なお、本明細書において、「基材レスタイプ」の粘着シート等を「基材レス粘着シート等」と称する場合があり、基材を有するタイプの粘着シート等を「基材付き粘着シート等」と称する場合がある。上記基材レス粘着シート等としては、例えば、本発明の粘着剤層等のみからなる両面粘着シート等や、本発明の粘着剤層等とその他の粘着剤層等（本発明の粘着剤層等以外の粘着剤層等）からなる両面粘着シート等が挙げられる。また、上記基材付き粘着シート等は、基材と、上記基材の少なくとも一方の面に形成された本発明の粘着剤層等とを含む粘着シート等であり、例えば、基材の片面側に本発明の粘着剤層等を有する片面粘着シート等や、基材の両面側に本発明の粘着剤層等を有する両面粘着シート等や、基材の一方の面側に本発明の粘着剤層等を有し、他方の面側にその他の粘着剤層等を有する両面粘着シートなどが挙げられる。なお、上記の「基材（基材層）」とは、支持体のことであり、粘着シート等を被着体に使用（貼付）する際には、粘着剤層等とともに被着体に貼付される部分である。粘着シート等の使用（貼付）時に剥離されるはく離ライナーは、上記基材に含まれない。 <Adhesive sheet, Adhesive sheet>
A pressure-sensitive adhesive layer and/or a pressure-sensitive adhesive sheet can be obtained using the pressure-sensitive adhesive layer or the like of the present invention. In addition, in this specification, an adhesive sheet and/or an adhesive sheet may be called "adhesive sheet etc.". The pressure-sensitive adhesive sheet or the like may be a so-called "substrate-less type" pressure-sensitive adhesive sheet or the like that does not have a substrate (substrate layer), or may be a type pressure-sensitive adhesive sheet or the like that has a substrate. In this specification, a "substrate-less type" pressure-sensitive adhesive sheet or the like may be referred to as a "substrate-less pressure-sensitive adhesive sheet or the like", and a type pressure-sensitive adhesive sheet or the like having a substrate may be referred to as a "substrate-attached pressure-sensitive adhesive sheet or the like." sometimes referred to as Examples of the substrate-less pressure-sensitive adhesive sheet or the like include, for example, a double-sided pressure-sensitive adhesive sheet or the like consisting only of the pressure-sensitive adhesive layer of the present invention, or the pressure-sensitive adhesive layer of the present invention and other pressure-sensitive adhesive layers (such as the pressure-sensitive adhesive layer of the present invention). A double-sided pressure-sensitive adhesive sheet made of a pressure-sensitive adhesive layer, etc., other than the above) may be mentioned. Further, the adhesive sheet with a substrate or the like is a pressure-sensitive adhesive sheet or the like containing a substrate and the adhesive layer or the like of the present invention formed on at least one surface of the substrate. A single-sided pressure-sensitive adhesive sheet or the like having the pressure-sensitive adhesive layer or the like of the present invention on either side of the substrate, a double-sided pressure-sensitive adhesive sheet or the like having the pressure-sensitive adhesive layer or the like of the present invention on both sides of the substrate, or the pressure-sensitive adhesive of the present invention on one side of the substrate Examples include a double-sided pressure-sensitive adhesive sheet having a layer or the like and having another pressure-sensitive adhesive layer or the like on the other side. In addition, the above-mentioned "base material (base material layer)" refers to a support, and when using (sticking) an adhesive sheet or the like on an adherend, This is the part where A release liner that is peeled off when using (sticking) an adhesive sheet or the like is not included in the base material.
本発明の粘着剤層等を用いて粘着シートおよび／または粘着シートを得ることができる。なお、本明細書において、粘着シートおよび／または粘着シートを「粘着シート等」と称する場合がある。上記粘着シート等は、基材（基材層）を有しない、いわゆる「基材レスタイプ」の粘着シート等であってもよいし、基材を有するタイプの粘着シート等であってもよい。なお、本明細書において、「基材レスタイプ」の粘着シート等を「基材レス粘着シート等」と称する場合があり、基材を有するタイプの粘着シート等を「基材付き粘着シート等」と称する場合がある。上記基材レス粘着シート等としては、例えば、本発明の粘着剤層等のみからなる両面粘着シート等や、本発明の粘着剤層等とその他の粘着剤層等（本発明の粘着剤層等以外の粘着剤層等）からなる両面粘着シート等が挙げられる。また、上記基材付き粘着シート等は、基材と、上記基材の少なくとも一方の面に形成された本発明の粘着剤層等とを含む粘着シート等であり、例えば、基材の片面側に本発明の粘着剤層等を有する片面粘着シート等や、基材の両面側に本発明の粘着剤層等を有する両面粘着シート等や、基材の一方の面側に本発明の粘着剤層等を有し、他方の面側にその他の粘着剤層等を有する両面粘着シートなどが挙げられる。なお、上記の「基材（基材層）」とは、支持体のことであり、粘着シート等を被着体に使用（貼付）する際には、粘着剤層等とともに被着体に貼付される部分である。粘着シート等の使用（貼付）時に剥離されるはく離ライナーは、上記基材に含まれない。 <Adhesive sheet, Adhesive sheet>
A pressure-sensitive adhesive layer and/or a pressure-sensitive adhesive sheet can be obtained using the pressure-sensitive adhesive layer or the like of the present invention. In addition, in this specification, an adhesive sheet and/or an adhesive sheet may be called "adhesive sheet etc.". The pressure-sensitive adhesive sheet or the like may be a so-called "substrate-less type" pressure-sensitive adhesive sheet or the like that does not have a substrate (substrate layer), or may be a type pressure-sensitive adhesive sheet or the like that has a substrate. In this specification, a "substrate-less type" pressure-sensitive adhesive sheet or the like may be referred to as a "substrate-less pressure-sensitive adhesive sheet or the like", and a type pressure-sensitive adhesive sheet or the like having a substrate may be referred to as a "substrate-attached pressure-sensitive adhesive sheet or the like." sometimes referred to as Examples of the substrate-less pressure-sensitive adhesive sheet or the like include, for example, a double-sided pressure-sensitive adhesive sheet or the like consisting only of the pressure-sensitive adhesive layer of the present invention, or the pressure-sensitive adhesive layer of the present invention and other pressure-sensitive adhesive layers (such as the pressure-sensitive adhesive layer of the present invention). A double-sided pressure-sensitive adhesive sheet made of a pressure-sensitive adhesive layer, etc., other than the above) may be mentioned. Further, the adhesive sheet with a substrate or the like is a pressure-sensitive adhesive sheet or the like containing a substrate and the adhesive layer or the like of the present invention formed on at least one surface of the substrate. A single-sided pressure-sensitive adhesive sheet or the like having the pressure-sensitive adhesive layer or the like of the present invention on either side of the substrate, a double-sided pressure-sensitive adhesive sheet or the like having the pressure-sensitive adhesive layer or the like of the present invention on both sides of the substrate, or the pressure-sensitive adhesive of the present invention on one side of the substrate Examples include a double-sided pressure-sensitive adhesive sheet having a layer or the like and having another pressure-sensitive adhesive layer or the like on the other side. In addition, the above-mentioned "base material (base material layer)" refers to a support, and when using (sticking) an adhesive sheet or the like on an adherend, This is the part where A release liner that is peeled off when using (sticking) an adhesive sheet or the like is not included in the base material.
本発明の粘着シート等が基材付き粘着シート等である場合の基材としては、特に限定されないが、例えば、プラスチックフィルム、反射防止（ＡＲ）フィルム、防眩（ＡＧ）フィルム、偏光板、位相差板などの各種光学フィルムが挙げられる。また、上記基材としては、紙、布、不織布等の多孔質材料、ネット、発泡シート、金属箔などが挙げられる。上記プラスチックフィルムなどの素材としては、例えば、ポリエチレンテレフタレート（ＰＥＴ）等のポリエステル系樹脂、ポリメチルメタクリレート（ＰＭＭＡ）等のアクリル系樹脂、ポリカーボネート、トリアセチルセルロース（ＴＡＣ）、ポリサルフォン、ポリアリレート、ポリイミド、ポリ塩化ビニル、ポリ酢酸ビニル、ポリエチレン、ポリプロピレン、エチレン－プロピレン共重合体、商品名「アートン」（環状オレフィン系ポリマー、ＪＳＲ株式会社製）、商品名「ゼオノア」（環状オレフィン系ポリマー、日本ゼオン株式会社製）等の環状オレフィン系ポリマーなどのプラスチック材料が挙げられる。なお、これらのプラスチック材料は、一種のみを用いてもよいし、二種以上を用いてもよい。
When the pressure-sensitive adhesive sheet or the like of the present invention is a pressure-sensitive adhesive sheet or the like with a substrate, the substrate is not particularly limited. Various optical films such as a retardation plate can be used. Examples of the base material include porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and the like. Materials for the plastic film include, for example, polyester resins such as polyethylene terephthalate (PET), acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate, triacetyl cellulose (TAC), polysulfone, polyarylate, polyimide, Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, ethylene-propylene copolymer, trade name “Arton” (cyclic olefin polymer, manufactured by JSR Corporation), trade name “Zeonor” (cyclic olefin polymer, Nippon Zeon Co., Ltd.) company) and other plastic materials such as cyclic olefin polymers. These plastic materials may be used alone or in combination of two or more.
上記基材の厚さは、特に限定されないが、例えば、１０～１５０μｍが好ましく、より好ましくは１５～１２５μｍ、さらに好ましくは２５～１００μｍである。なお、上記基材は単層および複層のいずれの形態を有していてもよい。また、上記基材の表面には、例えば、コロナ放電処理、プラズマ処理等の物理的処理、下塗り処理等の化学的処理などの公知慣用の表面処理が適宜施されていてもよい。
Although the thickness of the base material is not particularly limited, it is preferably 10 to 150 μm, more preferably 15 to 125 μm, still more preferably 25 to 100 μm. In addition, the substrate may have either a single-layer structure or a multilayer structure. In addition, the surface of the substrate may be appropriately subjected to known and commonly used surface treatments such as physical treatments such as corona discharge treatment and plasma treatment, and chemical treatments such as undercoating treatment.
上記粘着シート等は、使用時まで、粘着剤層等の表面（粘着面または接着面）にはく離ライナーが設けられていてもよい。なお、上記粘着シート等が両面粘着シート等である場合の各粘着面または接着面は、２枚のはく離ライナーによりそれぞれ保護されていてもよいし、両面が剥離面となっているはく離ライナー１枚により、ロール状に巻回される形態（巻回体）で保護されていてもよい。はく離ライナーは粘着剤層等の保護材として用いられ、被着体に貼付する際に剥がされる。また、上記粘着シート等が基材レス粘着シート等の場合、はく離ライナーは粘着剤層等の支持体としての役割も担う。なお、剥離ライナーは必ずしも設けられなくてもよい。
The adhesive sheet, etc. may be provided with a release liner on the surface (adhesive surface or adhesive surface) of the adhesive layer, etc. until use. When the adhesive sheet or the like is a double-sided adhesive sheet or the like, each adhesive surface or adhesive surface may be protected by two release liners, or one release liner having release surfaces on both sides. may be protected in the form of being wound into a roll (wound body). A release liner is used as a protective material such as a pressure-sensitive adhesive layer, and is peeled off when applied to an adherend. In addition, when the pressure-sensitive adhesive sheet or the like is a substrate-less pressure-sensitive adhesive sheet or the like, the release liner also serves as a support for the pressure-sensitive adhesive layer and the like. Note that the release liner does not necessarily have to be provided.
以上で説明した実施形態は、本発明の理解を容易にするために記載されたものであって、本発明を限定するために記載されたものではない。
The embodiments described above are described to facilitate understanding of the present invention, and are not described to limit the present invention.
以下に実施例を挙げて本発明をより詳細に説明するが、本発明はこれらの実施例により何ら限定されるものではない。なお、表１に示すプレポリマーを構成する各モノマー成分の数値は質量部である。
Although the present invention will be described in more detail with reference to examples below, the present invention is not limited by these examples. In addition, the numerical value of each monomer component constituting the prepolymer shown in Table 1 is in parts by mass.
調製例１
（ニトロベンジルエステル系モノマー前駆体の合成）
窒素雰囲気下で、５Ｌフラスコに２－ニトロイソフタル酸７２ｇ（３４１ｍｍｏｌ）およびテトラヒドロフラン（ＴＨＦ）４００ｇを入れて混合・撹拌し、２－ニトロイソフタル酸を溶解させた。溶液を２℃まで冷却させて、そこへボランテトラフドロフランコンプレックス（東京化成工業株式会社製）０．９Ｍ（１６２ｍｍｏｌ）を滴下し、室温まで昇温し４８時間撹拌した。その後、メタノールを滴下し、溶媒を減圧留去（５０℃、２５ｍｍＨｇ）し、酢酸エチルで希釈して抽出を行い、有機相を水９００ｇで計３回洗浄を行った。そして、有機相に硫酸マグネシウム７０ｇを加え脱水後、濾過し、酢酸エチルで洗浄した。ろ液の溶媒を減圧留去（５０℃、２５ｍｍＨｇ）し、ニトロベンジルエステル系モノマー前駆体（微黄色結晶）４１ｇを得た。 Preparation example 1
(Synthesis of nitrobenzyl ester-based monomer precursor)
Under a nitrogen atmosphere, 72 g (341 mmol) of 2-nitroisophthalic acid and 400 g of tetrahydrofuran (THF) were placed in a 5 L flask and mixed and stirred to dissolve 2-nitroisophthalic acid. The solution was cooled to 2° C., 0.9 M (162 mmol) of borane tetrahydrofuran complex (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto, the temperature was raised to room temperature, and the mixture was stirred for 48 hours. Thereafter, methanol was added dropwise, the solvent was distilled off under reduced pressure (50° C., 25 mmHg), the residue was diluted with ethyl acetate and extracted, and the organic phase was washed with 900 g of water a total of three times. Then, 70 g of magnesium sulfate was added to the organic phase, dehydrated, filtered, and washed with ethyl acetate. The solvent of the filtrate was distilled off under reduced pressure (50° C., 25 mmHg) to obtain 41 g of a nitrobenzyl ester monomer precursor (pale yellow crystals).
（ニトロベンジルエステル系モノマー前駆体の合成）
窒素雰囲気下で、５Ｌフラスコに２－ニトロイソフタル酸７２ｇ（３４１ｍｍｏｌ）およびテトラヒドロフラン（ＴＨＦ）４００ｇを入れて混合・撹拌し、２－ニトロイソフタル酸を溶解させた。溶液を２℃まで冷却させて、そこへボランテトラフドロフランコンプレックス（東京化成工業株式会社製）０．９Ｍ（１６２ｍｍｏｌ）を滴下し、室温まで昇温し４８時間撹拌した。その後、メタノールを滴下し、溶媒を減圧留去（５０℃、２５ｍｍＨｇ）し、酢酸エチルで希釈して抽出を行い、有機相を水９００ｇで計３回洗浄を行った。そして、有機相に硫酸マグネシウム７０ｇを加え脱水後、濾過し、酢酸エチルで洗浄した。ろ液の溶媒を減圧留去（５０℃、２５ｍｍＨｇ）し、ニトロベンジルエステル系モノマー前駆体（微黄色結晶）４１ｇを得た。 Preparation example 1
(Synthesis of nitrobenzyl ester-based monomer precursor)
Under a nitrogen atmosphere, 72 g (341 mmol) of 2-nitroisophthalic acid and 400 g of tetrahydrofuran (THF) were placed in a 5 L flask and mixed and stirred to dissolve 2-nitroisophthalic acid. The solution was cooled to 2° C., 0.9 M (162 mmol) of borane tetrahydrofuran complex (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto, the temperature was raised to room temperature, and the mixture was stirred for 48 hours. Thereafter, methanol was added dropwise, the solvent was distilled off under reduced pressure (50° C., 25 mmHg), the residue was diluted with ethyl acetate and extracted, and the organic phase was washed with 900 g of water a total of three times. Then, 70 g of magnesium sulfate was added to the organic phase, dehydrated, filtered, and washed with ethyl acetate. The solvent of the filtrate was distilled off under reduced pressure (50° C., 25 mmHg) to obtain 41 g of a nitrobenzyl ester monomer precursor (pale yellow crystals).
調製例２
（ニトロベンジルエステルモノマーの合成）
次に、１Ｌフラスコに上記モノマー前駆体２１．０ｇ（１１５ｍｍｏｌ）、アクリル酸３３．２ｇ（４６０ｍｍｏｌ）、４－ジメチルアミノピリジン（ＤＭＡＰ）９．３ｇ（７６．７ｍｍｏｌ）、およびジクロロメタン２１０ｍＬを入れ、アセトン／氷の混合バスで冷却下、内温５℃以下を維持しながら１－（３－ジメチルアミノプロピル）－３－エチルカルボジイミド塩酸塩（ＥＤＣ塩酸塩）（東京化成工業株式会社製）８４．９ｇ（５７４ｍｍｏｌ）を分割添加し、混合・撹拌して反応を行った。反応終了後、反応液をそのままシリカゲルクロマトグラフィー（展開溶媒：ジクロロメタン）を用いて計２回精製を行った。分取液にヒドロキノンモノメチルエーテル（ＭＥＨＱ）０．００４ｇを添加し、溶媒を減圧留去（３０℃以下、３０ｍｍＨｇ）し、その後氷冷して析出させ、３０℃で減圧乾燥することでニトロベンジルエステルモノマー（２－ニトロ－１，３－ビス（アクリロイルオキシメチレン）ベンゼン、淡黄色結晶）１１．４ｇを得た。ニトロベンジルエステルモノマーは化合物（Ｂ）に相当する。 Preparation example 2
(Synthesis of nitrobenzyl ester monomer)
Next, 21.0 g (115 mmol) of the above monomer precursor, 33.2 g (460 mmol) of acrylic acid, 9.3 g (76.7 mmol) of 4-dimethylaminopyridine (DMAP), and 210 mL of dichloromethane were placed in a 1 L flask, and acetone was added. / 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC hydrochloride) (manufactured by Tokyo Chemical Industry Co., Ltd.) 84.9 g while maintaining an internal temperature of 5 ° C. or less under cooling in a mixed bath of ice (574 mmol) was added in portions and mixed and stirred to carry out the reaction. After completion of the reaction, the reaction solution was directly purified by silica gel chromatography (developing solvent: dichloromethane) twice. 0.004 g of hydroquinone monomethyl ether (MEHQ) is added to the fractionated liquid, and the solvent is distilled off under reduced pressure (30°C or less, 30 mmHg), then ice-cooled to precipitate, and dried under reduced pressure at 30°C to give a nitrobenzyl ester. 11.4 g of a monomer (2-nitro-1,3-bis(acryloyloxymethylene)benzene, pale yellow crystals) was obtained. Nitrobenzyl ester monomers correspond to compound (B).
（ニトロベンジルエステルモノマーの合成）
次に、１Ｌフラスコに上記モノマー前駆体２１．０ｇ（１１５ｍｍｏｌ）、アクリル酸３３．２ｇ（４６０ｍｍｏｌ）、４－ジメチルアミノピリジン（ＤＭＡＰ）９．３ｇ（７６．７ｍｍｏｌ）、およびジクロロメタン２１０ｍＬを入れ、アセトン／氷の混合バスで冷却下、内温５℃以下を維持しながら１－（３－ジメチルアミノプロピル）－３－エチルカルボジイミド塩酸塩（ＥＤＣ塩酸塩）（東京化成工業株式会社製）８４．９ｇ（５７４ｍｍｏｌ）を分割添加し、混合・撹拌して反応を行った。反応終了後、反応液をそのままシリカゲルクロマトグラフィー（展開溶媒：ジクロロメタン）を用いて計２回精製を行った。分取液にヒドロキノンモノメチルエーテル（ＭＥＨＱ）０．００４ｇを添加し、溶媒を減圧留去（３０℃以下、３０ｍｍＨｇ）し、その後氷冷して析出させ、３０℃で減圧乾燥することでニトロベンジルエステルモノマー（２－ニトロ－１，３－ビス（アクリロイルオキシメチレン）ベンゼン、淡黄色結晶）１１．４ｇを得た。ニトロベンジルエステルモノマーは化合物（Ｂ）に相当する。 Preparation example 2
(Synthesis of nitrobenzyl ester monomer)
Next, 21.0 g (115 mmol) of the above monomer precursor, 33.2 g (460 mmol) of acrylic acid, 9.3 g (76.7 mmol) of 4-dimethylaminopyridine (DMAP), and 210 mL of dichloromethane were placed in a 1 L flask, and acetone was added. / 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC hydrochloride) (manufactured by Tokyo Chemical Industry Co., Ltd.) 84.9 g while maintaining an internal temperature of 5 ° C. or less under cooling in a mixed bath of ice (574 mmol) was added in portions and mixed and stirred to carry out the reaction. After completion of the reaction, the reaction solution was directly purified by silica gel chromatography (developing solvent: dichloromethane) twice. 0.004 g of hydroquinone monomethyl ether (MEHQ) is added to the fractionated liquid, and the solvent is distilled off under reduced pressure (30°C or less, 30 mmHg), then ice-cooled to precipitate, and dried under reduced pressure at 30°C to give a nitrobenzyl ester. 11.4 g of a monomer (2-nitro-1,3-bis(acryloyloxymethylene)benzene, pale yellow crystals) was obtained. Nitrobenzyl ester monomers correspond to compound (B).
調製例３
（アクリル系ポリマーＰ１の合成）
撹拌機、温度計、還流冷却器、および窒素ガス導入管を備える反応容器内で、ｎ－ブチルアクリレート（ＢＡ）９５質量部、アクリル酸（ＡＡ）５質量部、重合開始剤としてのＡＩＢＮ０．２質量部、および溶媒としての酢酸エチル１２２質量部を含む混合物を、６０℃で７時間、窒素雰囲気下で撹拌し、重合反応を行った。これにより、アクリル系ポリマーＰ１を含有するポリマー溶液を得た。このポリマー溶液中のアクリル系ポリマーＰ１の重量平均分子量（Ｍｗ）は６０万であった。 Preparation example 3
(Synthesis of acrylic polymer P1)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 95 parts by mass of n-butyl acrylate (BA), 5 parts by mass of acrylic acid (AA), and 0.2 of AIBN as a polymerization initiator. A mixture containing parts by mass and 122 parts by mass of ethyl acetate as a solvent was stirred at 60° C. for 7 hours under a nitrogen atmosphere to carry out a polymerization reaction. As a result, a polymer solution containing the acrylic polymer P1 was obtained. The weight average molecular weight (Mw) of the acrylic polymer P1 in this polymer solution was 600,000.
（アクリル系ポリマーＰ１の合成）
撹拌機、温度計、還流冷却器、および窒素ガス導入管を備える反応容器内で、ｎ－ブチルアクリレート（ＢＡ）９５質量部、アクリル酸（ＡＡ）５質量部、重合開始剤としてのＡＩＢＮ０．２質量部、および溶媒としての酢酸エチル１２２質量部を含む混合物を、６０℃で７時間、窒素雰囲気下で撹拌し、重合反応を行った。これにより、アクリル系ポリマーＰ１を含有するポリマー溶液を得た。このポリマー溶液中のアクリル系ポリマーＰ１の重量平均分子量（Ｍｗ）は６０万であった。 Preparation example 3
(Synthesis of acrylic polymer P1)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 95 parts by mass of n-butyl acrylate (BA), 5 parts by mass of acrylic acid (AA), and 0.2 of AIBN as a polymerization initiator. A mixture containing parts by mass and 122 parts by mass of ethyl acetate as a solvent was stirred at 60° C. for 7 hours under a nitrogen atmosphere to carry out a polymerization reaction. As a result, a polymer solution containing the acrylic polymer P1 was obtained. The weight average molecular weight (Mw) of the acrylic polymer P1 in this polymer solution was 600,000.
実施例１
（アクリル系ポリマーＰ２の合成）
撹拌機、温度計、還流冷却器、および窒素ガス導入管を備える反応容器内で、アクリル酸ブチル（ＢＡ）９５質量部、調製例２で作製したニトロベンジルエステルモノマー（化合物（Ｂ）に相当）５質量部、連鎖移動剤としての商品名「Ｃ１２ＴＣＳＳ」（日本テルペン化学株式会社製）２．８３質量部、重合開始剤としての２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ）０．２８質量部、および溶媒としての酢酸エチル３０１質量部を含む混合物を、６０℃で６時間、窒素雰囲気下で撹拌し、重合反応を行った。これにより、アクリロイル基を有するプレポリマーであるアクリル系ポリマーＰ２（ポリマー（Ａ）に相当）を含有するポリマー溶液を得た。 Example 1
(Synthesis of acrylic polymer P2)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 95 parts by mass of butyl acrylate (BA) and the nitrobenzyl ester monomer prepared in Preparation Example 2 (corresponding to compound (B)) 5 parts by mass, trade name "C12TCSS" (manufactured by Nippon Terpene Chemical Co., Ltd.) as a chain transfer agent 2.83 parts by mass, 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator 0.28 A mixture containing parts by mass and 301 parts by mass of ethyl acetate as a solvent was stirred at 60° C. for 6 hours under a nitrogen atmosphere to carry out a polymerization reaction. As a result, a polymer solution containing acrylic polymer P2 (corresponding to polymer (A)), which is a prepolymer having acryloyl groups, was obtained.
（アクリル系ポリマーＰ２の合成）
撹拌機、温度計、還流冷却器、および窒素ガス導入管を備える反応容器内で、アクリル酸ブチル（ＢＡ）９５質量部、調製例２で作製したニトロベンジルエステルモノマー（化合物（Ｂ）に相当）５質量部、連鎖移動剤としての商品名「Ｃ１２ＴＣＳＳ」（日本テルペン化学株式会社製）２．８３質量部、重合開始剤としての２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ）０．２８質量部、および溶媒としての酢酸エチル３０１質量部を含む混合物を、６０℃で６時間、窒素雰囲気下で撹拌し、重合反応を行った。これにより、アクリロイル基を有するプレポリマーであるアクリル系ポリマーＰ２（ポリマー（Ａ）に相当）を含有するポリマー溶液を得た。 Example 1
(Synthesis of acrylic polymer P2)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 95 parts by mass of butyl acrylate (BA) and the nitrobenzyl ester monomer prepared in Preparation Example 2 (corresponding to compound (B)) 5 parts by mass, trade name "C12TCSS" (manufactured by Nippon Terpene Chemical Co., Ltd.) as a chain transfer agent 2.83 parts by mass, 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator 0.28 A mixture containing parts by mass and 301 parts by mass of ethyl acetate as a solvent was stirred at 60° C. for 6 hours under a nitrogen atmosphere to carry out a polymerization reaction. As a result, a polymer solution containing acrylic polymer P2 (corresponding to polymer (A)), which is a prepolymer having acryloyl groups, was obtained.
（粘接着剤組成物の合成）
調製例３で作製したアクリル系ポリマーＰ１を含有するポリマー溶液と、上記アクリル系ポリマーＰ２を含有するポリマー溶液とを、アクリル系ポリマーＰ１を１００質量部に対してアクリル系ポリマーＰ２が１００質量部となる割合で混合し、２０００ｒｐｍで５分間撹拌し、さらに２２００ｒｐｍで５分間撹拌および脱泡を行い、粘接着剤組成物を作製した。なお、本明細書において、「粘接着」は、粘着性および接着性の両方の性質を有することをいう。 (Synthesis of adhesive composition)
The polymer solution containing the acrylic polymer P1 prepared in Preparation Example 3 and the polymer solution containing the acrylic polymer P2 were mixed with 100 parts by mass of the acrylic polymer P2 per 100 parts by mass of the acrylic polymer P1. The mixture was mixed at the same ratio, stirred at 2000 rpm for 5 minutes, and further stirred and defoamed at 2200 rpm for 5 minutes to prepare a pressure-sensitive adhesive composition. In this specification, the term "adhesion" refers to having properties of both stickiness and adhesiveness.
調製例３で作製したアクリル系ポリマーＰ１を含有するポリマー溶液と、上記アクリル系ポリマーＰ２を含有するポリマー溶液とを、アクリル系ポリマーＰ１を１００質量部に対してアクリル系ポリマーＰ２が１００質量部となる割合で混合し、２０００ｒｐｍで５分間撹拌し、さらに２２００ｒｐｍで５分間撹拌および脱泡を行い、粘接着剤組成物を作製した。なお、本明細書において、「粘接着」は、粘着性および接着性の両方の性質を有することをいう。 (Synthesis of adhesive composition)
The polymer solution containing the acrylic polymer P1 prepared in Preparation Example 3 and the polymer solution containing the acrylic polymer P2 were mixed with 100 parts by mass of the acrylic polymer P2 per 100 parts by mass of the acrylic polymer P1. The mixture was mixed at the same ratio, stirred at 2000 rpm for 5 minutes, and further stirred and defoamed at 2200 rpm for 5 minutes to prepare a pressure-sensitive adhesive composition. In this specification, the term "adhesion" refers to having properties of both stickiness and adhesiveness.
（粘接着シートの形成）
上記粘接着剤組成物をシリコーン系剥離剤で剥離処理されたポリエチレンテレフタレートフィルム（商品名「ＭＲＦ３８」、三菱化学株式会社製）の剥離処理面に、乾燥後の粘接着剤層の厚さが２５μｍになるように塗布し、これを常温で５分間静置した後、１３０℃で３分間乾燥した。溶媒として含まれる酢酸エチルを充分に揮発・除去することで粘接着シートを得た。 (Formation of Adhesive Sheet)
The pressure-sensitive adhesive composition was applied to the release-treated surface of a polyethylene terephthalate film (trade name: "MRF38", manufactured by Mitsubishi Chemical Corporation) with a silicone-based release agent, and the thickness of the pressure-sensitive adhesive layer after drying was was applied so as to have a thickness of 25 μm, allowed to stand at room temperature for 5 minutes, and then dried at 130° C. for 3 minutes. A pressure-sensitive adhesive sheet was obtained by sufficiently volatilizing and removing ethyl acetate contained as a solvent.
上記粘接着剤組成物をシリコーン系剥離剤で剥離処理されたポリエチレンテレフタレートフィルム（商品名「ＭＲＦ３８」、三菱化学株式会社製）の剥離処理面に、乾燥後の粘接着剤層の厚さが２５μｍになるように塗布し、これを常温で５分間静置した後、１３０℃で３分間乾燥した。溶媒として含まれる酢酸エチルを充分に揮発・除去することで粘接着シートを得た。 (Formation of Adhesive Sheet)
The pressure-sensitive adhesive composition was applied to the release-treated surface of a polyethylene terephthalate film (trade name: "MRF38", manufactured by Mitsubishi Chemical Corporation) with a silicone-based release agent, and the thickness of the pressure-sensitive adhesive layer after drying was was applied so as to have a thickness of 25 μm, allowed to stand at room temperature for 5 minutes, and then dried at 130° C. for 3 minutes. A pressure-sensitive adhesive sheet was obtained by sufficiently volatilizing and removing ethyl acetate contained as a solvent.
比較例１
（アクリル系ポリマーＰ３の合成）
撹拌機、温度計、還流冷却器、および窒素ガス導入管を備える反応容器内で、アクリル酸ブチル（ＢＡ）９５質量部、１，６－ヘキサンジオールジアクリレート５質量部、連鎖移動剤としての商品名「Ｃ１２ＴＣＳＳ」（日本テルペン化学株式会社製）２．８３質量部、重合開始剤としての２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ）０．２８質量部、および溶媒としての酢酸エチル３０１質量部を含む混合物を、６０℃で６時間、窒素雰囲気下で撹拌し、重合反応を行った。これにより、アクリロイル基を有するプレポリマーであるアクリル系ポリマーＰ３を含有するポリマー溶液を得た。 Comparative example 1
(Synthesis of acrylic polymer P3)
95 parts by mass of butyl acrylate (BA), 5 parts by mass of 1,6-hexanediol diacrylate, and a commercial product as a chain transfer agent were placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube. Name "C12TCSS" (manufactured by Nippon Terpene Chemical Co., Ltd.) 2.83 parts by mass, 2,2'-azobisisobutyronitrile (AIBN) 0.28 parts by mass as a polymerization initiator, and ethyl acetate 301 as a solvent A mixture containing parts by mass was stirred at 60° C. for 6 hours under a nitrogen atmosphere to carry out a polymerization reaction. As a result, a polymer solution containing acrylic polymer P3, which is a prepolymer having acryloyl groups, was obtained.
（アクリル系ポリマーＰ３の合成）
撹拌機、温度計、還流冷却器、および窒素ガス導入管を備える反応容器内で、アクリル酸ブチル（ＢＡ）９５質量部、１，６－ヘキサンジオールジアクリレート５質量部、連鎖移動剤としての商品名「Ｃ１２ＴＣＳＳ」（日本テルペン化学株式会社製）２．８３質量部、重合開始剤としての２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ）０．２８質量部、および溶媒としての酢酸エチル３０１質量部を含む混合物を、６０℃で６時間、窒素雰囲気下で撹拌し、重合反応を行った。これにより、アクリロイル基を有するプレポリマーであるアクリル系ポリマーＰ３を含有するポリマー溶液を得た。 Comparative example 1
(Synthesis of acrylic polymer P3)
95 parts by mass of butyl acrylate (BA), 5 parts by mass of 1,6-hexanediol diacrylate, and a commercial product as a chain transfer agent were placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube. Name "C12TCSS" (manufactured by Nippon Terpene Chemical Co., Ltd.) 2.83 parts by mass, 2,2'-azobisisobutyronitrile (AIBN) 0.28 parts by mass as a polymerization initiator, and ethyl acetate 301 as a solvent A mixture containing parts by mass was stirred at 60° C. for 6 hours under a nitrogen atmosphere to carry out a polymerization reaction. As a result, a polymer solution containing acrylic polymer P3, which is a prepolymer having acryloyl groups, was obtained.
（粘接着剤組成物の合成）
調製例３で作製したアクリル系ポリマーＰ１を含有するポリマー溶液と、上記アクリル系ポリマーＰ３を含有するポリマー溶液とを、アクリル系ポリマーＰ１を１００質量部に対してアクリル系ポリマーＰ３が１００質量部となる割合で混合し、２０００ｒｐｍで５分間撹拌し、さらに２２００ｒｐｍで５分間撹拌および脱泡を行い、粘接着剤組成物を作製した。 (Synthesis of adhesive composition)
The polymer solution containing the acrylic polymer P1 prepared in Preparation Example 3 and the polymer solution containing the acrylic polymer P3 were mixed with 100 parts by mass of the acrylic polymer P3 per 100 parts by mass of the acrylic polymer P1. The mixture was mixed at the same ratio, stirred at 2000 rpm for 5 minutes, and further stirred and defoamed at 2200 rpm for 5 minutes to prepare a pressure-sensitive adhesive composition.
調製例３で作製したアクリル系ポリマーＰ１を含有するポリマー溶液と、上記アクリル系ポリマーＰ３を含有するポリマー溶液とを、アクリル系ポリマーＰ１を１００質量部に対してアクリル系ポリマーＰ３が１００質量部となる割合で混合し、２０００ｒｐｍで５分間撹拌し、さらに２２００ｒｐｍで５分間撹拌および脱泡を行い、粘接着剤組成物を作製した。 (Synthesis of adhesive composition)
The polymer solution containing the acrylic polymer P1 prepared in Preparation Example 3 and the polymer solution containing the acrylic polymer P3 were mixed with 100 parts by mass of the acrylic polymer P3 per 100 parts by mass of the acrylic polymer P1. The mixture was mixed at the same ratio, stirred at 2000 rpm for 5 minutes, and further stirred and defoamed at 2200 rpm for 5 minutes to prepare a pressure-sensitive adhesive composition.
（粘接着シートの形成）
上記で作製した粘接着剤組成物を使用したこと以外は実施例１と同様にして粘接着シートを作製した。 (Formation of Adhesive Sheet)
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1, except that the pressure-sensitive adhesive composition prepared above was used.
上記で作製した粘接着剤組成物を使用したこと以外は実施例１と同様にして粘接着シートを作製した。 (Formation of Adhesive Sheet)
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1, except that the pressure-sensitive adhesive composition prepared above was used.
比較例２
（アクリル系ポリマーＰ４の合成）
撹拌機、温度計、還流冷却器、および窒素ガス導入管を備える反応容器内で、アクリル酸ブチル（ＢＡ）１００質量部、連鎖移動剤としての商品名「Ｃ１２ＴＣＳＳ」（日本テルペン化学株式会社製）２．８３質量部、重合開始剤としての２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ）０．２８質量部、および溶媒としての酢酸エチル３０１質量部を含む混合物を、６０℃で６時間、窒素雰囲気下で撹拌し、重合反応を行った。これにより、アクリロイル基を有するプレポリマーであるアクリル系ポリマーＰ４を含有するポリマー溶液を得た。 Comparative example 2
(Synthesis of acrylic polymer P4)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, 100 parts by mass of butyl acrylate (BA) and the trade name "C12TCSS" (manufactured by Nippon Terpene Chemical Co., Ltd.) as a chain transfer agent. A mixture containing 2.83 parts by mass, 0.28 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator, and 301 parts by mass of ethyl acetate as a solvent was heated at 60°C for 6 hours. , and stirred under a nitrogen atmosphere to carry out a polymerization reaction. As a result, a polymer solution containing acrylic polymer P4, which is a prepolymer having acryloyl groups, was obtained.
（アクリル系ポリマーＰ４の合成）
撹拌機、温度計、還流冷却器、および窒素ガス導入管を備える反応容器内で、アクリル酸ブチル（ＢＡ）１００質量部、連鎖移動剤としての商品名「Ｃ１２ＴＣＳＳ」（日本テルペン化学株式会社製）２．８３質量部、重合開始剤としての２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ）０．２８質量部、および溶媒としての酢酸エチル３０１質量部を含む混合物を、６０℃で６時間、窒素雰囲気下で撹拌し、重合反応を行った。これにより、アクリロイル基を有するプレポリマーであるアクリル系ポリマーＰ４を含有するポリマー溶液を得た。 Comparative example 2
(Synthesis of acrylic polymer P4)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, 100 parts by mass of butyl acrylate (BA) and the trade name "C12TCSS" (manufactured by Nippon Terpene Chemical Co., Ltd.) as a chain transfer agent. A mixture containing 2.83 parts by mass, 0.28 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator, and 301 parts by mass of ethyl acetate as a solvent was heated at 60°C for 6 hours. , and stirred under a nitrogen atmosphere to carry out a polymerization reaction. As a result, a polymer solution containing acrylic polymer P4, which is a prepolymer having acryloyl groups, was obtained.
（粘接着剤組成物の合成）
調製例３で作製したアクリル系ポリマーＰ１を含有するポリマー溶液と、上記アクリル系ポリマーＰ４を含有するポリマー溶液とを、アクリル系ポリマーＰ１を１００質量部に対してアクリル系ポリマーＰ４が１００質量部となる割合で混合し、２０００ｒｐｍで５分間撹拌し、さらに２２００ｒｐｍで５分間撹拌および脱泡を行い、粘接着剤組成物を作製した。 (Synthesis of adhesive composition)
The polymer solution containing the acrylic polymer P1 prepared in Preparation Example 3 and the polymer solution containing the acrylic polymer P4 were mixed with 100 parts by mass of the acrylic polymer P4 per 100 parts by mass of the acrylic polymer P1. The mixture was mixed at the same ratio, stirred at 2000 rpm for 5 minutes, and further stirred and defoamed at 2200 rpm for 5 minutes to prepare a pressure-sensitive adhesive composition.
調製例３で作製したアクリル系ポリマーＰ１を含有するポリマー溶液と、上記アクリル系ポリマーＰ４を含有するポリマー溶液とを、アクリル系ポリマーＰ１を１００質量部に対してアクリル系ポリマーＰ４が１００質量部となる割合で混合し、２０００ｒｐｍで５分間撹拌し、さらに２２００ｒｐｍで５分間撹拌および脱泡を行い、粘接着剤組成物を作製した。 (Synthesis of adhesive composition)
The polymer solution containing the acrylic polymer P1 prepared in Preparation Example 3 and the polymer solution containing the acrylic polymer P4 were mixed with 100 parts by mass of the acrylic polymer P4 per 100 parts by mass of the acrylic polymer P1. The mixture was mixed at the same ratio, stirred at 2000 rpm for 5 minutes, and further stirred and defoamed at 2200 rpm for 5 minutes to prepare a pressure-sensitive adhesive composition.
（粘接着シートの形成）
上記で作製した粘接着剤組成物を使用したこと以外は実施例１と同様にして粘接着シートを作製した。 (Formation of Adhesive Sheet)
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1, except that the pressure-sensitive adhesive composition prepared above was used.
上記で作製した粘接着剤組成物を使用したこと以外は実施例１と同様にして粘接着シートを作製した。 (Formation of Adhesive Sheet)
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1, except that the pressure-sensitive adhesive composition prepared above was used.
＜評価＞
実施例および比較例で作製した粘接着シートについて、ＵＶ照射前後においてそれぞれ以下の評価を行った。結果を表に示す。なお、ＵＶ照射は以下の方法で行った。 <Evaluation>
The adhesive sheets prepared in Examples and Comparative Examples were evaluated as follows before and after UV irradiation. The results are shown in the table. In addition, UV irradiation was performed by the following method.
実施例および比較例で作製した粘接着シートについて、ＵＶ照射前後においてそれぞれ以下の評価を行った。結果を表に示す。なお、ＵＶ照射は以下の方法で行った。 <Evaluation>
The adhesive sheets prepared in Examples and Comparative Examples were evaluated as follows before and after UV irradiation. The results are shown in the table. In addition, UV irradiation was performed by the following method.
（ＵＶ照射）
実施例および比較例で得られた粘接着シートについて、露出した粘着面にさらにはく離ライナーを貼り合わせた状態で、クォークテクノロジー社製のＵＶ－ＬＥＤ照射装置（型番「ＱＥＬ－３５０－ＲＵ６Ｗ－ＣＷ－ＭＹ」）を用い、波長３６５ｎｍのＵＶ－ＬＥＤランプを光源として使用し、波長３２０～３９０ｎｍの範囲での照射積算光量を８０００ｍＪ／ｃｍ2として紫外線照射を行った。 (UV irradiation)
For the adhesive sheets obtained in Examples and Comparative Examples, a release liner was further attached to the exposed adhesive surface, and a UV-LED irradiation device manufactured by Quark Technology Co., Ltd. (model number "QEL-350-RU6W-CW -MY”), a UV-LED lamp with a wavelength of 365 nm was used as a light source, and ultraviolet irradiation was performed with an integrated irradiation light amount of 8000 mJ/cm 2 in the wavelength range of 320 to 390 nm.
実施例および比較例で得られた粘接着シートについて、露出した粘着面にさらにはく離ライナーを貼り合わせた状態で、クォークテクノロジー社製のＵＶ－ＬＥＤ照射装置（型番「ＱＥＬ－３５０－ＲＵ６Ｗ－ＣＷ－ＭＹ」）を用い、波長３６５ｎｍのＵＶ－ＬＥＤランプを光源として使用し、波長３２０～３９０ｎｍの範囲での照射積算光量を８０００ｍＪ／ｃｍ2として紫外線照射を行った。 (UV irradiation)
For the adhesive sheets obtained in Examples and Comparative Examples, a release liner was further attached to the exposed adhesive surface, and a UV-LED irradiation device manufactured by Quark Technology Co., Ltd. (model number "QEL-350-RU6W-CW -MY”), a UV-LED lamp with a wavelength of 365 nm was used as a light source, and ultraviolet irradiation was performed with an integrated irradiation light amount of 8000 mJ/cm 2 in the wavelength range of 320 to 390 nm.
（１）せん断貯蔵弾性率
粘接着シートを積層して、厚さ約１．０ｍｍの測定用試料を作製し、Ｒｈｅｏｍｅｔｒｉｃ Ｓｃｉｅｎｔｉｆｉｃ社製「Ａｄｖａｎｃｅｄ Ｒｈｅｏｍｅｔｒｉｃ Ｅｘｐａｎｓｉｏｎ Ｓｙｓｔｅｍ（ＡＲＥＳ）」を用いて、以下の条件により、動的粘弾性測定を行った。そして、２５℃、５０℃、および８０℃におけるせん断貯蔵弾性率を算出した。
（測定条件）
変形モード：ねじり
測定周波数：１Ｈｚ
昇温速度：５℃／分
測定温度：－５０～１５０℃
形状：パラレルプレート ８．０ｍｍφ (1) Shear storage modulus Adhesive sheets were laminated to prepare a sample for measurement with a thickness of about 1.0 mm, and subjected to the following conditions using "Advanced Rheometric Expansion System (ARES)" manufactured by Rheometric Scientific. A dynamic viscoelasticity measurement was performed by Then, the shear storage elastic moduli at 25°C, 50°C and 80°C were calculated.
(Measurement condition)
Deformation mode: Torsion Measurement frequency: 1Hz
Heating rate: 5°C/min Measurement temperature: -50 to 150°C
Shape: Parallel plate 8.0mmφ
粘接着シートを積層して、厚さ約１．０ｍｍの測定用試料を作製し、Ｒｈｅｏｍｅｔｒｉｃ Ｓｃｉｅｎｔｉｆｉｃ社製「Ａｄｖａｎｃｅｄ Ｒｈｅｏｍｅｔｒｉｃ Ｅｘｐａｎｓｉｏｎ Ｓｙｓｔｅｍ（ＡＲＥＳ）」を用いて、以下の条件により、動的粘弾性測定を行った。そして、２５℃、５０℃、および８０℃におけるせん断貯蔵弾性率を算出した。
（測定条件）
変形モード：ねじり
測定周波数：１Ｈｚ
昇温速度：５℃／分
測定温度：－５０～１５０℃
形状：パラレルプレート ８．０ｍｍφ (1) Shear storage modulus Adhesive sheets were laminated to prepare a sample for measurement with a thickness of about 1.0 mm, and subjected to the following conditions using "Advanced Rheometric Expansion System (ARES)" manufactured by Rheometric Scientific. A dynamic viscoelasticity measurement was performed by Then, the shear storage elastic moduli at 25°C, 50°C and 80°C were calculated.
(Measurement condition)
Deformation mode: Torsion Measurement frequency: 1Hz
Heating rate: 5°C/min Measurement temperature: -50 to 150°C
Shape: Parallel plate 8.0mmφ
（２）引張試験
積層して得られた５０μｍ厚の粘接着シートを１０ｍｍ×３０ｍｍに切り出し、はく離ライナーを除いた状態で、長さ３０ｍｍの短冊状サンプルを作製した。この上下１０ｍｍ部分を引張圧縮試験機（商品名「オートグラフＡＧＳ－５０ＮＸ」、株式会社島津製作所製）のチャックジグで固定し、チャック間距離１０ｍｍ、引張速度３００ｍｍ／ｍｉｎの条件で引張試験を行った。 (2) Tensile test A 10 mm x 30 mm piece was cut from the 50 µm thick adhesive/adhesive sheet obtained by lamination, and a strip-shaped sample with a length of 30 mm was produced in a state in which the release liner was removed. The upper and lower 10 mm portions were fixed with a chuck jig of a tensile compression tester (trade name “Autograph AGS-50NX” manufactured by Shimadzu Corporation), and a tensile test was performed under the conditions of a distance between chucks of 10 mm and a tensile speed of 300 mm/min. rice field.
積層して得られた５０μｍ厚の粘接着シートを１０ｍｍ×３０ｍｍに切り出し、はく離ライナーを除いた状態で、長さ３０ｍｍの短冊状サンプルを作製した。この上下１０ｍｍ部分を引張圧縮試験機（商品名「オートグラフＡＧＳ－５０ＮＸ」、株式会社島津製作所製）のチャックジグで固定し、チャック間距離１０ｍｍ、引張速度３００ｍｍ／ｍｉｎの条件で引張試験を行った。 (2) Tensile test A 10 mm x 30 mm piece was cut from the 50 µm thick adhesive/adhesive sheet obtained by lamination, and a strip-shaped sample with a length of 30 mm was produced in a state in which the release liner was removed. The upper and lower 10 mm portions were fixed with a chuck jig of a tensile compression tester (trade name “Autograph AGS-50NX” manufactured by Shimadzu Corporation), and a tensile test was performed under the conditions of a distance between chucks of 10 mm and a tensile speed of 300 mm/min. rice field.
（３）ヤング率Ｅ
上記引張試験において得られたスペクトルから、弾性変形領域での歪みεに対する応力σの変化量（Ｅ＝Δσ／Δε）から算出した。 (3) Young's modulus E
It was calculated from the amount of change in stress σ with respect to strain ε in the elastic deformation region (E=Δσ/Δε) from the spectrum obtained in the tensile test.
上記引張試験において得られたスペクトルから、弾性変形領域での歪みεに対する応力σの変化量（Ｅ＝Δσ／Δε）から算出した。 (3) Young's modulus E
It was calculated from the amount of change in stress σ with respect to strain ε in the elastic deformation region (E=Δσ/Δε) from the spectrum obtained in the tensile test.
（４）応力ピーク強度
上記引張試験において得られたスペクトルについて、上に凸形状のピークの値を応力ピーク強度とした。 (4) Stress Peak Strength Regarding the spectrum obtained in the above tensile test, the value of the upwardly convex peak was taken as the stress peak strength.
上記引張試験において得られたスペクトルについて、上に凸形状のピークの値を応力ピーク強度とした。 (4) Stress Peak Strength Regarding the spectrum obtained in the above tensile test, the value of the upwardly convex peak was taken as the stress peak strength.
（５）歪み応力
上記引張試験において得られたスペクトルについて、各歪み（％）における応力を歪み応力とした。 (5) Strain stress For the spectrum obtained in the above tensile test, the stress at each strain (%) was taken as the strain stress.
上記引張試験において得られたスペクトルについて、各歪み（％）における応力を歪み応力とした。 (5) Strain stress For the spectrum obtained in the above tensile test, the stress at each strain (%) was taken as the strain stress.
１ 粘着剤層または接着剤層
２ はく離ライナー
１０ はく離ライナー付き粘着シートまたは接着シート 1 adhesive layer oradhesive layer 2 release liner 10 adhesive sheet or adhesive sheet with release liner
２ はく離ライナー
１０ はく離ライナー付き粘着シートまたは接着シート 1 adhesive layer or
Claims (5)
- 外部刺激により結合が開裂しその後再結合しない非可逆分解性結合を分子内に有するポリマー、および／または、前記非可逆分解性結合をポリマーに導入可能な化合物を含有する、粘着剤および／または接着剤。 A pressure-sensitive adhesive and/or adhesive containing a polymer having an irreversible degradable bond in its molecule which is cleaved by an external stimulus and not rebonded thereafter, and/or a compound capable of introducing the irreversible degradable bond into the polymer. agent.
- 前記非可逆分解性結合はニトロベンジル基を含む結合である請求項１に記載の粘着剤および／または接着剤。 The pressure-sensitive adhesive and/or adhesive according to claim 1, wherein the irreversibly degradable bond is a bond containing a nitrobenzyl group.
- 前記ポリマーは熱可塑性樹脂および／または熱硬化型樹脂である請求項１または２に記載の粘着剤および／または接着剤。 The pressure-sensitive adhesive and/or adhesive according to claim 1 or 2, wherein the polymer is a thermoplastic resin and/or a thermosetting resin.
- 前記ポリマーは結合または分子同士の絡み合いによりネットワーク構造を形成されたポリマーまたは前記ネットワーク構造を形成し得るポリマーである請求項１～３のいずれか１項に記載の粘着剤および／または接着剤。 The pressure-sensitive adhesive and/or adhesive according to any one of claims 1 to 3, wherein the polymer is a polymer in which a network structure is formed by bonding or entanglement between molecules or a polymer capable of forming the network structure.
- 光学用途に使用される請求項１～４のいずれか１項に記載の粘着剤および／または接着剤。 The pressure-sensitive adhesive and/or adhesive according to any one of claims 1 to 4, which is used for optical purposes.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202280079020.5A CN118318020A (en) | 2021-11-30 | 2022-11-29 | Adhesive and/or cohesive agent |
| KR1020247021554A KR20240118801A (en) | 2021-11-30 | 2022-11-29 | Adhesives and/or adhesives |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-194635 | 2021-11-30 | ||
| JP2021194635A JP2023081003A (en) | 2021-11-30 | 2021-11-30 | Adhesive and/or binder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2023100862A1 true WO2023100862A1 (en) | 2023-06-08 |
Family
ID=86612316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2022/043958 WO2023100862A1 (en) | 2021-11-30 | 2022-11-29 | Pressure-sensitive adhesive and/or adhesive |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2023081003A (en) |
| KR (1) | KR20240118801A (en) |
| CN (1) | CN118318020A (en) |
| TW (1) | TW202338056A (en) |
| WO (1) | WO2023100862A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007131710A (en) * | 2005-11-09 | 2007-05-31 | Lintec Corp | Method for producing photodegradable polymeric compound |
| WO2017191827A1 (en) * | 2016-05-02 | 2017-11-09 | 国立大学法人 東京医科歯科大学 | Internally degradable polyrotaxane and synthesis method therefor |
| CN109735280A (en) * | 2019-01-04 | 2019-05-10 | 中国科学技术大学 | Ultraviolet light response polymer adhesive and its preparation method and application |
| US20200332161A1 (en) * | 2019-04-17 | 2020-10-22 | The Florida State University Research Foundation, Inc. | Zwitterionic crosslinked polymer-based adhesives |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012159463A (en) | 2011-02-02 | 2012-08-23 | Canon Chemicals Inc | Pressure-sensitive sensor body |
| JP7069234B2 (en) | 2020-02-28 | 2022-05-17 | リンテック株式会社 | Adhesive sheet for flexible display, flexible laminated member and flexible display |
-
2021
- 2021-11-30 JP JP2021194635A patent/JP2023081003A/en active Pending
-
2022
- 2022-11-29 KR KR1020247021554A patent/KR20240118801A/en unknown
- 2022-11-29 WO PCT/JP2022/043958 patent/WO2023100862A1/en active Application Filing
- 2022-11-29 CN CN202280079020.5A patent/CN118318020A/en active Pending
- 2022-11-30 TW TW111145922A patent/TW202338056A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007131710A (en) * | 2005-11-09 | 2007-05-31 | Lintec Corp | Method for producing photodegradable polymeric compound |
| WO2017191827A1 (en) * | 2016-05-02 | 2017-11-09 | 国立大学法人 東京医科歯科大学 | Internally degradable polyrotaxane and synthesis method therefor |
| CN109735280A (en) * | 2019-01-04 | 2019-05-10 | 中国科学技术大学 | Ultraviolet light response polymer adhesive and its preparation method and application |
| US20200332161A1 (en) * | 2019-04-17 | 2020-10-22 | The Florida State University Research Foundation, Inc. | Zwitterionic crosslinked polymer-based adhesives |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20240118801A (en) | 2024-08-05 |
| JP2023081003A (en) | 2023-06-09 |
| TW202338056A (en) | 2023-10-01 |
| CN118318020A (en) | 2024-07-09 |
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