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
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • 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
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

Definitions

• the present invention relates to an adhesive composition and an adhesive tape having an adhesive layer composed of the adhesive composition.
• Double-sided adhesive tape is used to attach the module to the housing.
• a portable electronic device for example, a mobile phone, a personal digital assistant, etc.
• an image display device or an input device for example, a mobile phone, a personal digital assistant, etc.
• a double-sided adhesive tape is used to bond a cover panel for protecting the surface of a portable electronic device to a touch panel module or a display panel module, or to bond a touch panel module to a display panel module. It is used.
• a double-sided adhesive tape is used, for example, by being punched into a shape such as a frame shape and arranged around a display screen (for example, Patent Documents 1 and 2).
• Double-sided adhesive tape is also used for fixing vehicle parts (for example, in-vehicle panels) to the vehicle body.
• a high-temperature heat treatment step with the adhesive tape attached to the adherend, and then peel off the adhesive tape.
• various high-temperature heat treatment processes are performed in a state where the semiconductor wafer is adhered to and reinforced by a double-sided adhesive tape to the support plate, and then the semiconductor wafer is attached from the support plate. Peeling is done.
• the adhesive tape is excessively adhered by the high-temperature heat treatment step, it may be difficult to peel the semiconductor wafer from the support plate, or adhesive may remain on the surface of the semiconductor wafer during peeling. ..
• a silicone compound is blended in the pressure-sensitive adhesive layer as a peeling aid. By blending the silicone compound, the increase in adhesion can be suppressed by the silicone compound bleeding out from the pressure-sensitive adhesive layer.
• the conventional silicone compound may be difficult for the conventional silicone compound to sufficiently suppress the adhesion enhancement depending on the type of the adherend. Since the conventional silicone compound has low polarity, it has a property of having low affinity with a highly polar substance, and when the adherend is a highly polar substance such as a semiconductor wafer, it bleeds out to the surface of the adhesive tape. The silicone compound cannot stay on the surface and diffuses from the interface with the adherend. Therefore, the silicone compound present at the interface between the adhesive tape and the adherend is reduced, and the enhancement of adhesion may not be sufficiently suppressed.
• the adhesive tape needs to suppress the increase in adhesion, it needs to have a high adhesive strength at the time of sticking (hereinafter, the adhesive strength at the time of sticking is referred to as the initial adhesive strength).
• the conventional silicone compound cannot suppress the adhesion enhancement unless it is used in a large amount, and there is also a problem that the initial adhesive strength is lowered when the silicone compound is used in a large amount.
• the present invention is a pressure-sensitive adhesive composition and a pressure-sensitive adhesive comprising the pressure-sensitive adhesive composition, which have high adhesive strength at the time of sticking and can suppress the increase in adhesion even when subjected to a high-temperature heat treatment step. It is an object of the present invention to provide an adhesive tape having a layer.
• the present invention is a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive component and a silicone-based graft copolymer having a crosslinkable functional group with the pressure-sensitive adhesive component.
• the present invention will be described in detail below.
• the pressure-sensitive adhesive composition according to one embodiment of the present invention contains a pressure-sensitive adhesive component.
• the above-mentioned pressure-sensitive adhesive component is not particularly limited, and may be a curable type pressure-sensitive adhesive component or a non-curable type pressure-sensitive adhesive component, but a curable type pressure-sensitive adhesive component is preferable.
• the pressure-sensitive adhesive composition according to one embodiment of the present invention is preferably a curable pressure-sensitive adhesive composition containing a polymerizable polymer as a main component as a curable pressure-sensitive adhesive component and containing a polymerization initiator.
• the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition can adhere well to the adherend before curing, so that high adhesive strength is exhibited at the time of sticking. it can. Furthermore, since the elastic modulus of the pressure-sensitive adhesive layer can be increased by curing the pressure-sensitive adhesive component, the pressure-sensitive adhesive component is cured before or during the heat treatment step to enhance adhesion at high temperatures. It can be suppressed. Further, by increasing the elastic modulus of the pressure-sensitive adhesive layer, it is possible to suppress the adhesive residue on the adherend.
• the curable pressure-sensitive adhesive composition examples include a photo-curable pressure-sensitive adhesive composition containing the above-mentioned polymerizable polymer and a photopolymerization initiator, and a heat-curable pressure-sensitive adhesive containing the above-mentioned polymerizable polymer and a thermopolymerization initiator.
• the composition is mentioned.
• a thermosetting pressure-sensitive adhesive composition is preferable because it can be cured by the heat of the heat treatment step and does not require a photocuring facility or a photocuring step.
• the curable pressure-sensitive adhesive composition is a thermosetting pressure-sensitive adhesive composition, the number of steps can be reduced because it is only necessary to go through a heating step and it is not necessary to separately provide a curing step.
• the curable pressure-sensitive adhesive composition is not particularly limited, but is preferably an acrylic pressure-sensitive adhesive composition because it has excellent heat resistance and weather resistance and can be applied to a wide range of adherends.
• the structure of the pressure-sensitive adhesive component is not particularly limited, and may be a random copolymer, a block copolymer, or a graft copolymer.
• the crosslinkable functional group for exhibiting curability is not particularly limited, but a radically polymerizable unsaturated bond is preferable. That is, the pressure-sensitive adhesive component preferably has a radically polymerizable unsaturated bond in the molecule.
• the above-mentioned pressure-sensitive adhesive component has a radically polymerizable unsaturated bond in the molecule, that is, when the crosslinkable functional group of the curable pressure-sensitive adhesive component is a radically polymerizable unsaturated bond, another crosslinkable functional group is used.
• the polarity of the cross-linking point is lower than that of using a group, and the cross-linking density can be increased.
• the elastic modulus of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is further improved, and the enhancement of adhesion can be further suppressed. Further, by improving the elastic modulus, it is possible to suppress the adhesive residue.
• the radically polymerizable unsaturated bond can not only construct a crosslinked structure in the pressure-sensitive adhesive component, but is also a functional group capable of cross-linking with a silicone-based graft copolymer described later, and the pressure-sensitive adhesive component and the silicone-based component. It also contributes to cross-linking with the graft copolymer.
• the pressure-sensitive adhesive component has a functional group that can be crosslinked with a silicone-based graft copolymer other than the radically polymerizable unsaturated bond
• a functional group is not particularly limited, and for example, a carboxy group, a hydroxy group, etc. Examples thereof include an amide group, an isocyanate group and an epoxy group.
• These silicone-based graft copolymers and crosslinkable functional groups may be used alone or in combination of two or more.
• the radically polymerizable unsaturated bond can be introduced, for example, by using a monomer having a radically polymerizable unsaturated bond when synthesizing the above-mentioned polymerizable polymer.
• the radically polymerizable unsaturated bond can also be introduced by obtaining the above polymerizable polymer by the following method. That is, for the polymerizable polymer, for example, a (meth) acrylic polymer having a functional group in the molecule (hereinafter, referred to as a functional group-containing (meth) acrylic polymer) is synthesized in advance, and the functional group is contained in the molecule. It can be obtained by reacting with a compound having a functional group that reacts with and a radically polymerizable unsaturated bond (hereinafter, referred to as a functional group-containing unsaturated compound).
• the functional group-containing (meth) acrylic polymer includes an acrylic acid alkyl ester and / or a methacrylic acid alkyl ester in which the number of carbon atoms of the alkyl group is usually in the range of 2 to 18, a functional group-containing monomer, and if necessary. It is obtained by copolymerizing these with other modifying monomers that can be copolymerized by a conventional method such as radical polymerization. This is the same as in the case of a general (meth) acrylic polymer, which is a polymer having adhesiveness at room temperature.
• the weight average molecular weight of the functional group-containing (meth) acrylic polymer is usually about 200,000 to 2,000,000.
• the functional group-containing monomer is, for example, a carboxyl group-containing monomer such as acrylic acid or methacrylic acid; (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-4. -Hydroxybutyl and other hydroxyl group-containing monomers can be mentioned.
• an epoxy group-containing monomer such as glycidyl acrylate and glycidyl methacrylate
• an isocyanate group-containing monomer such as isocyanate ethyl acrylate and ethyl isocyanate ethyl
• aminoethyl acrylate and aminoethyl methacrylate Amino group-containing monomers and the like can also be mentioned.
• the functional groups of these functional group-containing monomers the unreacted functional groups that were not used in the reaction with the functional group-containing unsaturated compound were used as functional groups that could be crosslinked with the silicone-based graft copolymer.
• the other copolymerizable monomer for modification include various monomers used in general (meth) acrylic polymers such as vinyl acetate, acrylonitrile, styrene, and maleic anhydride.
• the polymerization method of the radical polymerization a conventionally known method is used, and examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, bulk polymerization and the like.
• the polymerization initiator used in the above radical polymerization is not particularly limited, and examples thereof include organic peroxides and azo compounds. Examples of the organic peroxide include 1,1-bis (t-hexyl peroxy) -3,3,5-trimethylcyclohexane, t-hexyl peroxypivalate, t-butylperoxypivalate, 2,5.
• the functional group-containing (meth) acrylic polymer may be obtained by living radical polymerization.
• Living radical polymerization is a polymerization in which a molecular chain grows without being hindered by a side reaction such as a termination reaction or a chain transfer reaction.
• a side reaction such as a termination reaction or a chain transfer reaction.
• a polymer having a more uniform molecular weight and composition as compared with, for example, free radical polymerization can be obtained, and the formation of low molecular weight components and the like can be suppressed, so that the obtained pressure-sensitive adhesive composition has a high temperature. While the enhancement of adhesion underneath can be suppressed, the pressure-sensitive adhesive composition can be made difficult to peel off to the extent that unintended peeling does not occur.
• the living radical polymerization is not particularly limited as long as it is generally used, and examples thereof include a TERP method, a RAFT method, and an NMP method.
• An organic tellurium compound is used in the TERP method, a RAFT agent is used in the RAFT method, and a nitroxide compound is used in the NMP method.
• the above-mentioned polymerization initiators such as organic peroxides and azo compounds are used in combination.
• the ATRP method can be used.
• a dispersion stabilizer may be used.
• the dispersion stabilizer include polyvinylpyrrolidone, polyvinyl alcohol, methyl cellulose, ethyl cellulose, poly (meth) acrylic acid, poly (meth) acrylic acid ester, polyethylene glycol and the like.
• the polymerization solvent is not particularly limited.
• the polymerization solvent include non-polar solvents such as hexane, cyclohexane, octane, toluene and xylene, water, methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, N, N-.
• a highly polar solvent such as dimethylformamide can be used.
• These polymerization solvents may be used alone or in combination of two or more.
• the polymerization temperature is preferably 0 to 110 ° C. from the viewpoint of the polymerization rate.
• the same one as the above-mentioned functional group-containing monomer is used depending on the functional group of the functional group-containing (meth) acrylic polymer. it can.
• the functional group of the functional group-containing (meth) acrylic polymer is a carboxyl group
• an epoxy group-containing monomer or an isocyanate group-containing monomer is used.
• the functional group is a hydroxyl group
• an isocyanate group-containing monomer is used.
• the functional group is an epoxy group
• a carboxyl group-containing monomer or an amide group-containing monomer such as acrylamide is used.
• an amino group an epoxy group-containing monomer is used.
• the pressure-sensitive adhesive composition according to one embodiment of the present invention may contain a polyfunctional oligomer or a monomer.
• the polyfunctional oligomer or monomer preferably has a molecular weight of 10,000 or less, and more preferably has a molecular weight of 5000 or less so that the pressure-sensitive adhesive layer can be efficiently reticulated by heating or irradiation with light.
• the number of radically polymerizable unsaturated bonds in the molecule is 2 to 20.
• Such more preferred polyfunctional oligomers or monomers include, for example, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate or. Examples thereof include the same methacrylates as described above.
• Examples of the polyfunctional oligomer or monomer include 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, commercially available oligoester acrylate, and the same methacrylates as described above. These polyfunctional oligomers or monomers may be used alone or in combination of two or more.
• the pressure-sensitive adhesive composition according to one embodiment of the present invention is preferably a curable pressure-sensitive adhesive composition containing a polymerizable polymer as a main component as a curable pressure-sensitive adhesive component and containing a polymerization initiator. ..
• the above-mentioned polymerization initiator is not particularly limited, and examples thereof include a photopolymerization initiator and a thermal polymerization initiator. Examples of the photopolymerization initiator include those that are activated by irradiating light having a wavelength of 250 to 800 nm.
• Such photopolymerization initiators include, for example, photoradical polymerization of acetophenone derivative compounds such as methoxyacetophenone; benzoin ether compounds such as benzoin propyl ether and benzoin isobutyl ether; and ketal derivative compounds such as benzyl dimethyl ketal and acetophenone diethyl ketal. Initiator is mentioned. Further, a photoradical polymerization initiator such as a phosphine oxide derivative compound and a bis ( ⁇ 5-cyclopentadienyl) titanocene derivative compound can also be mentioned.
• photoradical polymerization initiators such as benzophenone, Michler ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, ⁇ -hydroxycyclohexylphenylketone, and 2-hydroxymethylphenylpropane are also mentioned. These photopolymerization initiators may be used alone or in combination of two or more.
• thermal polymerization initiator examples include those that generate active radicals that are decomposed by heat and initiate polymerization curing. Specifically, for example, dicumyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoale, t-butylhydroperoxide, benzoyl peroxide, cumenehydroperoxide, diisopropylbenzenehydroperoxide, para. Mentan hydroperoxide, di-t-butyl peroxide and the like can be mentioned.
• the pressure-sensitive adhesive composition according to one embodiment of the present invention contains a silicone-based graft copolymer.
• the silicone-based graft copolymer refers to a copolymer in which the silicone moiety serves as a graft chain.
• the pressure-sensitive adhesive composition contains a silicone-based graft copolymer
• the pressure-sensitive adhesive layer and the adherend when the pressure-sensitive adhesive tape using the pressure-sensitive adhesive composition according to one embodiment of the present invention is subjected to a high-temperature heat treatment step. Since the silicone-based graft copolymer gathers at the interface with, it is possible to prevent the adhesion from being enhanced.
• the conventional silicone compound has a structure having a functional group at the end of the silicone compound, and most of the molecules are silicone sites. Therefore, when the silicone compound is used to the extent that the adhesion enhancement can be reduced, it may cause a decrease in the initial adhesive strength.
• the silicone compound is a silicone-based graft copolymer
• the polarity of the surface of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is appropriately ranged depending on the parts other than the silicone parts. It is possible to suppress a decrease in the initial adhesive strength.
• the silicone site is a graft chain instead of the main chain, the number of silicone sites can be easily increased, so that high adhesion enhancement suppressing performance can be exhibited.
• the silicone-based graft copolymer is not particularly limited as long as it has the adhesive component described later, a crosslinkable functional group, and a graft chain containing a silicone group.
• a monomer having a functional group crosslinkable with the pressure-sensitive adhesive component, a silicone macromonomer, and if necessary, other components is preferably a copolymer of a raw material monomer mixture containing a monomer.
• silicone macromonomer examples include acrylic silicone macromonomers and styrene silicone macromonomers. Among them, acrylic silicone macromonomers are preferable because they are excellent in heat resistance and weather resistance, and acrylic silicone macromonomers as shown in the following structural formulas (1) and (2) are more preferable.
• R represents a (meth) acryloyl group-containing functional group, for example, a (meth) acryloyl group
• X and Y each independently represent an integer of 0 or more.
• the upper limit of X and Y is not particularly limited, but is, for example, 500 or less, particularly 200 or less.
• the content of the silicone macromonomer in the raw material monomer mixture is preferably 1% by weight or more and 90% by weight or less.
• the adhesion enhancement at a high temperature can be suppressed and the obtained pressure-sensitive adhesive composition can exhibit a high initial adhesive strength.
• the more preferable lower limit of the content of the silicone macromonomer in the raw material monomer mixture is 5% by weight, the more preferable lower limit is 10% by weight, and the more preferable upper limit is 80.
• a more preferred upper limit is 60% by weight.
• the content of the structural unit derived from the silicone macromonomer in the silicone-based graft copolymer is preferably 1% by weight or more and 90% by weight or less.
• a more preferable lower limit of the content of the structural unit derived from the silicone macromonomer is 5% by weight, a further preferable lower limit is 10% by weight, a more preferable upper limit is 80% by weight, and a further preferable upper limit is 60% by weight.
• the silicone-based graft copolymer has a functional group that can be crosslinked with the pressure-sensitive adhesive component. Since the silicone-based graft copolymer has a functional group capable of cross-linking with the pressure-sensitive adhesive component, the silicone-based graft copolymer gathered at the interface with the adherend is cross-linked and fixed with the pressure-sensitive adhesive component, and thus adheres. The effect of suppressing the enhancement can be enhanced. Further, by fixing the silicone-based graft copolymer to the pressure-sensitive adhesive component, contamination of the adherend by the silicone-based graft copolymer can be suppressed.
• the functional group that can be crosslinked with the pressure-sensitive adhesive component is appropriately selected depending on the functional group of the pressure-sensitive adhesive component.
• the group etc. can be mentioned.
• the monomer having a functional group crosslinkable with the pressure-sensitive adhesive component include a monomer having a carboxy group such as (meth) acrylic acid, a monomer having an isocyanate group such as 2- (meth) acryloyloxyethyl isocyanate, and the like. Be done.
• Examples of the monomer having a functional group that can be crosslinked with the pressure-sensitive adhesive component include a monomer having a hydroxy group such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, and (meth) acrylamide. Examples thereof include a monomer having an amide group and a monomer having an epoxy group such as glycidyl (meth) acrylate.
• the functional groups capable of cross-linking with the pressure-sensitive adhesive component are radically polymerized. It is preferably a sex unsaturated bond.
• the functional groups that can be crosslinked with these pressure-sensitive adhesive components may be used alone or in combination of two or more.
• the functional group crosslinkable with the pressure-sensitive adhesive component can be introduced, for example, by using a monomer having a functional group crosslinkable with the pressure-sensitive adhesive component in the raw material monomer mixture.
• the functional group that can be crosslinked with the pressure-sensitive adhesive component is a radically polymerizable unsaturated bond
• the raw material monomer mixture containing the (meth) acrylic monomer having a functional group is radically polymerized, and then the radical is subjected to radical polymerization. It can be introduced by reacting a monomer having a polymerizable unsaturated bond and a functional group that reacts with the above functional group.
• the content of the monomer having a functional group crosslinkable with the pressure-sensitive adhesive component in the raw material monomer mixture is preferably 0.1% by weight or more and 10% by weight or less.
• the blending amount of the monomer having a crosslinkable functional group with the pressure-sensitive adhesive component is within the above range, the pressure-sensitive adhesive component and the silicone-based graft copolymer are sufficiently crosslinked, but also within the pressure-sensitive adhesive component. Since a crosslinked structure can be constructed, it is possible to further suppress the increase in adhesion at high temperatures.
• the blending amount of the monomer having a crosslinkable functional group with the pressure-sensitive adhesive component is more preferably 0.5% by weight or more, and more preferably 2% by weight or more. It is more preferably 8% by weight or less, and even more preferably 5% by weight or less. That is, the content of the structural unit derived from the monomer having a functional group crosslinkable with the pressure-sensitive adhesive component in the silicone-based graft copolymer is preferably 0.1% by weight or more and 10% by weight or less.
• the content of the structural unit derived from the monomer having a crosslinkable functional group with the pressure-sensitive adhesive component is more preferably 0.5% by weight or more, further preferably 2% by weight or more, and 8% by weight or less. Is more preferable, and 5% by weight or less is further preferable.
• the functional group crosslinkable with the pressure-sensitive adhesive component has a radically polymerizable unsaturated bond
• the amount of the monomer having the radically polymerizable unsaturated bond to be reacted with 100% by weight of the raw material monomer mixture is blended. Is preferably 0.5% by weight or more, more preferably 1% by weight or more, and further preferably 2% by weight or more.
• the blending amount of the monomer having a radically polymerizable unsaturated bond is preferably 10% by weight or less, more preferably 8% by weight or less, and further preferably 5% by weight or less.
• the functional group that can be crosslinked with the pressure-sensitive adhesive component is preferably a functional group that reacts with the pressure-sensitive adhesive component by heating.
• the crosslinking reaction can be carried out by the heat of the high temperature treatment step, so that the number of steps for crosslinking such as the photocuring step can be reduced, and production The sex can be improved.
• the functional group that can be crosslinked with the pressure-sensitive adhesive component that reacts with the pressure-sensitive adhesive component by heating include a radical-polymerizable unsaturated bond and a transesterification-reactive hydroxyl group.
• the silicone-based graft copolymer preferably has a polar functional group.
• the polar functional group referred to here includes both a polar functional group as a functional group that can be crosslinked with the pressure-sensitive adhesive component and a polar functional group that does not crosslink with the pressure-sensitive adhesive component.
• the initial adhesive strength of the obtained pressure-sensitive adhesive composition can be improved.
• the polar functional group include a hydroxyl group and a carboxy group.
• the polar functional group can be introduced by using a monomer having the polar functional group in the raw material monomer mixture.
• Examples of the monomer having a hydroxyl group include 4-hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate.
• Examples of the monomer having a carboxy group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl-phthalic acid, and 2- (meth) acryloyloxyethyl hexahydro. Examples thereof include phthalic acid and ⁇ -carboxyethyl (meth) acrylate.
• the content of the monomer having the polar functional group in the raw material monomer mixture is preferably 0.1% by weight or more and 50% by weight or less.
• the initial adhesive strength of the obtained pressure-sensitive adhesive composition can be further improved, and the silicone-based graft copolymer is interfaced with the adherend. It can be made easier to gather in.
• the content of the monomer having the polar functional group is more preferably 0.5% by weight or more. It is preferably 1% by weight or more, and even more preferably 2% by weight or more.
• the content of the monomer having a polar functional group is more preferably 40% by weight or less, further preferably 30% by weight or less, further preferably 10% by weight or less, and 8% by weight or less. It is even more preferable that the content is 5% by weight or less. That is, the content of the structural unit derived from the monomer having the polar functional group in the silicone-based graft copolymer is preferably 0.1% by weight or more and 50% by weight or less. The content of the structural unit derived from the monomer having a polar functional group is more preferably 0.5% by weight or more, further preferably 1% by weight or more, still more preferably 2% by weight or more. preferable.
• the content of the structural unit derived from the monomer having a polar functional group is more preferably 40% by weight or less, further preferably 30% by weight or less, still more preferably 10% by weight or less. It is even more preferably 8% by weight or less, and particularly preferably 5% by weight or less.
• Examples of the other monomer include (meth) acrylic acid alkyl ester.
• Examples of the (meth) acrylic acid alkyl ester include 2-ethylhexyl acrylate, butyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and tert.
• Examples of the other monomers include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, and glycidyl (meth).
• Acrylate, tetrahydrofurfuryl (meth) acrylate, polypropylene glycol mono (meth) acrylate and the like can also be mentioned.
• 2-ethylhexyl acrylate is preferable because it can impart an appropriate adhesive strength.
• the silicone-based graft copolymer preferably has a structure represented by the following structural formula (3). Since the silicone site of the silicone-based graft copolymer having a structure as shown in the following structural formula (3) is a graft chain, the number of silicone sites can be easily adjusted, and the adhesion enhancement is suppressed as compared with the conventional silicone compound. Can be done. Further, since the silicone-based graft copolymer having a structure as shown in the following structural formula (3) has a radically polymerizable unsaturated bond as a functional group crosslinkable with the pressure-sensitive adhesive component, it can be combined with the pressure-sensitive adhesive component.
• the crosslink density of the polymer can be improved, the adhesion enhancement can be further suppressed, and the contamination of the adherend can be reduced. Further, since the silicone-based graft copolymer having a structure as shown in the following structural formula (3) has a polar functional group, the initial adhesive strength is improved, and even when the number of silicone sites is increased, the initial adhesive strength is improved. It is possible to suppress a decrease in adhesive strength.
• R 1 , R 2 , R 3 , and R 4 independently represent a methyl group or a hydrogen atom
• R 5 , R 6 , and R 7 are independently linear or branched, respectively.
• R 8 represents a (meth) acryloyl group-containing functional group
• R 9 represents a polar functional group-containing group.
• L, M, N, O and P each independently represent an integer of 0 or more.
• the carbon number of the saturated hydrocarbon group having 1 to 18 carbon atoms having a linear or branched carbon chain in the structural formula (3) is preferably from the viewpoint of optimizing the polarity of the adherend interface. It is 3 or more, more preferably 6 or more, preferably 15 or less, and more preferably 12 or less.
• the (meth) acryloyl group-containing functional group in the structural formula (3) has, for example, 1 to 18 carbon atoms (preferably 2 to 15 carbon atoms, more preferably 3 to 12 carbon atoms) ( Meta) Acryloyl group-containing functional groups can be mentioned.
• Examples of the polar functional group-containing group in the structural formula (3) include saturated hydrocarbon groups and unsaturated hydrocarbon groups containing polar functional groups, and from the viewpoint of controlling adhesive strength, polar functional groups are preferable. It is a saturated hydrocarbon group containing a group, more preferably a saturated hydrocarbon group having 1 to 18 carbon atoms (more preferably 3 to 15 carbon atoms) having a polar functional group.
• Examples of the polar functional group contained in the polar functional group-containing group include a carboxy group and a hydroxy group. From the viewpoint of suppressing the enhancement of adhesion, the polar functional group is preferably a hydroxy group.
• the above L, M, N, O and P in the above structural formula (3) are independently 0 or more, and are likely to gather at the interface with the adherend, which is preferable from the viewpoint of effectively suppressing the enhancement of adhesion.
• the silicone-based graft copolymer preferably has a weight average molecular weight of 400,000 or less.
• the silicone-based graft copolymer can easily move in the pressure-sensitive adhesive layer and can be collected at the interface with the adherend, so that the adhesion enhancement is further suppressed. be able to.
• the weight average molecular weight is more preferably 200,000 or less, and further preferably 100,000 or less.
• the upper limit of the weight average molecular weight is not particularly limited, but is preferably 5000 or more from the viewpoint of suppressing contamination of the adherend.
• the weight average molecular weight can be determined by, for example, the GPC method using a polystyrene standard. Specifically, for example, "2690 Separations Module” manufactured by Water Co., Ltd., "GPC KF-806L” manufactured by Showa Denko Co., Ltd. as a column, and ethyl acetate as a solvent are used as a measuring device, a sample flow rate of 1 mL / min, and a column temperature of 40 ° C. It can be measured under conditions.
• the method for producing the silicone-based graft copolymer is not particularly limited, and the silicone-based graft copolymer can be obtained by radical polymerization of the raw material monomer mixture in a solvent.
• the polymerization method of the radical polymerization the same method as the pressure-sensitive adhesive component can be used.
• the content of the silicone-based graft copolymer in the pressure-sensitive adhesive composition according to one embodiment of the present invention is preferably 0.1% by weight or more and 20% by weight or less.
• the content of the silicone-based graft copolymer in the pressure-sensitive adhesive composition is 0.1% by weight or more, the enhancement of adhesion at high temperature can be further suppressed.
• the content of the silicone-based graft copolymer is 20% by weight or less, the initial adhesive strength of the pressure-sensitive adhesive composition can be enhanced, and the white turbidity of the pressure-sensitive adhesive composition can be suppressed.
• a process using light such as alignment can be performed through the composition.
• the silicone-based graft copolymer tends to collect at the interface of the adherend, the adhesion enhancement can be suppressed with a smaller amount than that of the conventional silicone compound.
• the content of the silicone-based graft copolymer in the pressure-sensitive adhesive composition is more preferably 1.5% by weight or more, and more preferably 3% by weight or more. Is more preferable.
• the content of the silicone-based graft copolymer is more preferably 15% by weight or less, further preferably 10% by weight or less, further preferably 8% by weight or less, and 5% by weight or less. It is particularly preferable to have.
• the pressure-sensitive adhesive composition according to one embodiment of the present invention preferably contains a cross-linking agent.
• the cross-linking agent can sufficiently cross-link the pressure-sensitive adhesive component and the silicone-based graft copolymer. Further, by containing the cross-linking agent, the cohesive force of the pressure-sensitive adhesive composition is increased, so that the initial adhesive force can be improved.
• the above-mentioned cross-linking agent is not particularly limited, and examples thereof include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, aziridine-based cross-linking agents, and metal chelate-based cross-linking agents. Of these, an epoxy-based cross-linking agent is preferable because the cohesive force of the pressure-sensitive adhesive component is further increased.
• the content of the cross-linking agent in the pressure-sensitive adhesive composition according to one embodiment of the present invention is preferably 0.01 to 20% by weight.
• the cross-linking agent in the above range, the pressure-sensitive adhesive component and the silicone-based graft copolymer are sufficiently cross-linked, and the cohesive force of the pressure-sensitive adhesive component is enhanced to further improve the initial adhesive force. Can be done.
• the more preferable lower limit of the content of the cross-linking agent is 0.05% by weight
• the more preferable lower limit is 0.1% by weight
• the more preferable upper limit is 10% by weight
• the further preferable upper limit is 5.
• the pressure-sensitive adhesive composition according to an embodiment of the present invention includes a gas generator that generates a gas by stimulation, an inorganic filler, a heat stabilizer, an antioxidant, an antistatic agent, a plasticizer, and a resin, if necessary. , Surfactants, waxes and other known additives may be contained.
• the method for producing the pressure-sensitive adhesive composition according to one embodiment of the present invention is not particularly limited.
• the above-mentioned silicone-based graft copolymer produced by the above method and, if necessary, the solution of the pressure-sensitive adhesive component produced by the above method are used. It can be obtained by adding other additives and mixing.
• the use of the pressure-sensitive adhesive composition according to one embodiment of the present invention is not particularly limited, but it can be suitably used as a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer of a pressure-sensitive adhesive tape.
• a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer of a pressure-sensitive adhesive tape.
• Such an adhesive tape having a base material and a pressure-sensitive adhesive layer laminated on at least one surface of the base material, wherein the pressure-sensitive adhesive layer comprises a pressure-sensitive adhesive composition according to an embodiment of the present invention.
• Tape is also one of the present inventions.
• the adhesive tape according to one embodiment of the present invention has a base material.
• the material constituting the base material is preferably a material having heat resistance.
• the heat-resistant material include polyethylene terephthalate, polyethylene naphthalate, polyacetal, polyamide, polycarbonate, polyphenylene ether, polybutylene terephthalate, ultrahigh molecular weight polyethylene, syndiotactic polystyrene, polyarylate, polysulfone, and polyethersulfon. , Polyphenylene sulfide, polyetheretherketone, polyimide, polyetherimide, fluororesin, liquid crystal polymer and the like. Of these, polyimide is preferable because it has excellent heat resistance.
• the thickness of the base material is not particularly limited, but a preferable lower limit is 25 ⁇ m, a more preferable lower limit is 50 ⁇ m, a preferable upper limit is 250 ⁇ m, and a more preferable upper limit is 125 ⁇ m. When the base material is in this range, an adhesive tape having excellent handleability can be obtained.
• the adhesive tape according to one embodiment of the present invention has an adhesive layer laminated on at least one surface of the base material.
• the pressure-sensitive adhesive layer comprises a pressure-sensitive adhesive composition according to an embodiment of the present invention.
• the gel fraction of the pressure-sensitive adhesive layer is not particularly limited, but is preferably less than 90% by weight. When the gel fraction is less than 90% by weight, higher adhesive strength can be exhibited at the time of sticking. From the viewpoint of further increasing the initial adhesive strength, the gel fraction of the pressure-sensitive adhesive layer is more preferably 80% by weight or less, and further preferably 70% by weight or less. The lower limit of the gel fraction of the pressure-sensitive adhesive layer is not particularly limited, but it is preferably 20% by weight or more from the viewpoint of handleability.
• the gel fraction of the pressure-sensitive adhesive layer can be adjusted by the type of the pressure-sensitive adhesive component, the type and amount of the cross-linking agent, and the like. When the pressure-sensitive adhesive layer is a curable pressure-sensitive adhesive layer, the gel fraction of the pressure-sensitive adhesive layer is the gel fraction (initial gel fraction) before curing by irradiation with light such as ultraviolet rays or heating. means.
• the thickness of the pressure-sensitive adhesive layer is not particularly limited, but the lower limit is preferably 3 ⁇ m and the upper limit is preferably 100 ⁇ m. When the thickness of the pressure-sensitive adhesive layer is within the above range, it can be adhered to the support with sufficient adhesive strength. From the same viewpoint, the more preferable lower limit of the thickness of the pressure-sensitive adhesive layer is 5 ⁇ m, and the more preferable upper limit is 50 ⁇ m.
• the method for producing the adhesive tape according to the embodiment of the present invention is not particularly limited, and a conventionally known method can be used.
• it can be produced by applying a solution of the pressure-sensitive adhesive composition according to one embodiment of the present invention on a film that has been subjected to a mold release treatment, drying it to form a pressure-sensitive adhesive layer, and bonding it to a base material. it can.
• the use of the adhesive tape according to one embodiment of the present invention is not particularly limited, but since adhesion enhancement is unlikely to occur even at a high temperature, in the production of a product having a heat treatment step exceeding 200 ° C. such as the production of a semiconductor device. It can be suitably used as an adhesive tape for protecting a member.
• the present invention has a pressure-sensitive adhesive composition and a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition, which have high adhesive strength at the time of sticking and can suppress the increase in adhesion even when subjected to a high-temperature heat treatment step.
• Adhesive tape can be provided.
• Example 1 Preparation of adhesive component A
• a reactor equipped with a thermometer, a stirrer, and a cooling tube is prepared, and 79 parts by weight of 2-ethylhexyl acrylate (2EHA), 1 part by weight of acrylic acid (AAc), and 4-hydroxybutyl acrylate (4HBA) are contained in the reactor.
• EHA 2-ethylhexyl acrylate
• AAc acrylic acid
• 4HBA 4-hydroxybutyl acrylate
• the obtained pressure-sensitive adhesive component A-containing solution was diluted 50-fold with tetrahydrofuran (THF), and the obtained diluted solution was filtered through a polytetrafluoroethylene filter having a pore diameter of 0.2 ⁇ m. Then, the obtained filtrate was supplied to a gel permeation chromatograph and GPC measurement was performed. The polystyrene-equivalent molecular weight of the pressure-sensitive adhesive component was measured to determine the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn). As a result, Mw: 570,000 and Mw / Mn: 6.4.
• the measuring equipment and measuring conditions are as follows.
• silicone-based graft copolymer A 8 hours after the start of the polymerization, an ethyl acetate solution of the silicone-based graft copolymer A was obtained.
• Mw and Mw / Mn were measured in the same manner as in the preparation of the pressure-sensitive adhesive component A.
• the following silicone macromonomers were used. Silicone macromonomer: KF-2012, one-ended methacryloyl-modified PDMS, manufactured by Shin-Etsu Chemical Co., Ltd.
• Example 1 With respect to 100 parts by weight of the solid content of the obtained pressure-sensitive adhesive component A-containing solution, 5.0 parts by weight of the silicone-based graft copolymer A, 1.0 part by weight of the thermal polymerization initiator, and 0. 1 part by weight was added to obtain a pressure-sensitive adhesive composition solution. Next, the pressure-sensitive adhesive composition solution was applied on the release-treated surface of the polyethylene terephthalate film whose surface was subjected to the release treatment with a doctor knife so that the thickness of the dry film was 40 ⁇ m, and heated at 110 ° C. for 5 minutes. It was dried to obtain an adhesive layer.
• thermal polymerization initiator Perbutyl O
• NOF Epoxy cross-linking agent Tetrad C, manufactured by Mitsubishi Gas Chemical Company
• Examples 2 to 16, Comparative Examples 1 to 5 An adhesive tape was obtained in the same manner as in Example 1 except that the types and amounts of the pressure-sensitive adhesive component, the peeling aid, the polymerization initiator and the cross-linking agent used were as shown in Tables 2 and 3. The following substances were used as the peeling aid, the polymerization initiator and the cross-linking agent.
• Silicone diacrylate EBECRYL350, Silicone oil manufactured by Daicel Ornex: KF-96-10cs, Photopolymerization initiator manufactured by Shin-Etsu Chemical Co., Ltd .: Esacure One, Isocyanate-based cross-linking agent manufactured by Nihon Shibel Hegner Co., Ltd.
• the adhesive tape was cut into a width of 25 mm to obtain a test piece.
• the adhesive layer of the obtained test piece was placed on a glass plate (large slide glass white edge polishing No. 2 manufactured by Matsunami Glass Industry Co., Ltd.).
• the test piece and the glass plate were bonded together by reciprocating a 2 kg rubber roller once on the test piece at a speed of 300 mm / min.
• the test sample was prepared by letting it stand at 23 degreeC for 1 hour.
• the test sample after standing was subjected to a tensile test in the 180 ° direction at a peeling speed of 300 mm / min according to JIS Z0237, and the initial adhesive strength was measured.
• the measurement sample prepared by the same method as described above was heat-treated at 220 ° C. for 2 hours. After allowing to cool, a tensile test in the 180 ° direction was performed in the same manner as described above, and the adhesive strength after heating was measured. The adhesive strength of Comparative Examples 2 to 4 after heating could not be measured because the adhesive remained on the entire surface of the glass plate.
• the present invention has a pressure-sensitive adhesive composition and a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition, which have high adhesive strength at the time of sticking and can suppress the increase in adhesion even when subjected to a high-temperature heat treatment step.
• Adhesive tape can be provided.

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