WO2023119911A1 - 粘着剤組成物及びその製造方法、粘着剤層、並びに粘着シート - Google Patents
粘着剤組成物及びその製造方法、粘着剤層、並びに粘着シート Download PDFInfo
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- WO2023119911A1 WO2023119911A1 PCT/JP2022/041379 JP2022041379W WO2023119911A1 WO 2023119911 A1 WO2023119911 A1 WO 2023119911A1 JP 2022041379 W JP2022041379 W JP 2022041379W WO 2023119911 A1 WO2023119911 A1 WO 2023119911A1
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- mass
- sensitive adhesive
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- 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
- C09J133/18—Homopolymers or copolymers of nitriles
- C09J133/20—Homopolymers or copolymers of acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- 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
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
Definitions
- the present disclosure relates to an adhesive composition and its manufacturing method, an adhesive layer, and an adhesive sheet.
- Water-based pressure-sensitive adhesives are representative examples thereof.
- JP-A-2010-209170 describes a pressure-sensitive adhesive tape using a water-based pressure-sensitive adhesive containing acrylic copolymer emulsion particles and a cross-linking agent in an aqueous medium.
- a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer made of a water-dispersed acrylic pressure-sensitive adhesive composition, wherein the acrylic copolymer forming the acrylic copolymer emulsion particles has an alkyl group having 2 to 14 carbon atoms. (meth)acrylate, acrylic acid, methacrylic acid, and a nitrogen-containing vinyl monomer as monomer components, and the adhesive layer has a gel fraction of 20% to 38%.
- Japanese Patent Application Laid-Open No. 2009-57508 describes, as an adhesive instead of a solvent-based adhesive using an organic solvent as a solvent, an acid group-free monomer (a) of 87% by mass to 99.4% by mass and an acid 0.5% to 10% by mass of a group-containing monomer (b), 0.1% to 3% by mass of a hydroxyl group-containing (meth)acrylamide-based monomer (c), and a monomer (a) A copolymer consisting of 0.05 parts by mass to 10 parts by mass of a silane coupling agent (d) having a polymerizable double bond per 100 parts by mass of the total amount of the monomer (b) and the monomer (c) Aqueous emulsion adhesives containing coalescence are disclosed.
- Water-based pressure-sensitive adhesives are used for building materials from the viewpoint of preventing sick house syndrome, and are particularly frequently used for attaching wallpaper. On the other hand, water-based pressure-sensitive adhesives are considered unsuitable for use around water such as bathrooms, kitchens, washrooms, and toilets, and for application to top plates. In general, a pressure-sensitive adhesive layer formed from a water-based pressure-sensitive adhesive has poor water resistance and, for example, changes in appearance such as swelling and whitening may occur when immersed in water.
- water-based adhesives are required to be excellent in water resistance and capable of forming a pressure-sensitive adhesive layer that can withstand a load in the direction perpendicular to the sticking surface.
- water-based pressure-sensitive adhesives are also required to form a pressure-sensitive adhesive layer having high adhesive strength not only in a room temperature environment but also in a moist heat environment.
- the problem to be solved by one embodiment of the present disclosure is to provide a pressure-sensitive adhesive layer that has high adhesive strength even in a hot and humid environment, is excellent in water resistance, and can withstand a load in the direction perpendicular to the sticking surface.
- An object of the present invention is to provide a pressure-sensitive adhesive composition that can be formed.
- a problem to be solved by another embodiment of the present disclosure is to provide a method for producing the pressure-sensitive adhesive composition.
- the problem to be solved by another embodiment of the present disclosure is an adhesive that has high adhesive strength even in a moist and hot environment, is excellent in water resistance, and can withstand a load in the direction perpendicular to the adhesion surface.
- Another problem to be solved by another embodiment of the present disclosure is to provide a pressure-sensitive adhesive sheet including the pressure-sensitive adhesive layer.
- the content of the structural unit (D) is 0.2% by mass to 6.0% by mass based on all structural units [however, the structural unit (D) is excluded. ] 0.1 parts by mass to 1.0 parts by mass per 100 parts by mass of (meth)acrylic resin particles having an average particle diameter of 5 nm to 160 nm, and a pressure-sensitive adhesive composition containing water. . ⁇ 2> The pressure-sensitive adhesive composition according to ⁇ 1>, further comprising a cross-linking agent. ⁇ 3> The pressure-sensitive adhesive composition according to ⁇ 2>, wherein the cross-linking agent is at least one selected from carbodiimide-based cross-linking agents and oxazoline-based cross-linking agents.
- the (meth)acrylic resin particles do not contain structural units derived from (meth)acrylamide having a hydroxyl group, or the content of structural units derived from (meth)acrylamide having a hydroxyl group is the above ( All structural units of the meth)acrylic resin particles [excluding the structural unit (D). ]
- the pressure-sensitive adhesive composition according to any one of ⁇ 1> to ⁇ 4> which is in the range of more than 0% by mass and less than 0.1% by mass.
- the content of the structural unit (B) is equal to all the structural units [excluding the structural unit (D).
- a pressure-sensitive adhesive that has high adhesive strength even in a moist and hot environment, has excellent water resistance, and can form a pressure-sensitive adhesive layer that can withstand a load in the direction perpendicular to the sticking surface.
- a composition is provided.
- a method for producing the pressure-sensitive adhesive composition there is provided.
- a pressure-sensitive adhesive layer that has high adhesive strength even in a moist and hot environment, is excellent in water resistance, and can withstand a load in the direction perpendicular to the sticking surface is provided. be done.
- a pressure-sensitive adhesive sheet including the pressure-sensitive adhesive layer is provided.
- a numerical range indicated using “to” means a range including the numerical values described before and after “to” as lower and upper limits, respectively.
- upper or lower limits described in a certain numerical range may be replaced with upper or lower limits of other numerical ranges described step by step.
- upper or lower limits described in a certain numerical range may be replaced with values shown in Examples.
- the amount of each component in the adhesive composition is the above amount present in the adhesive composition unless otherwise specified. It means the total amount of multiple substances. The same applies to the amount of each component in the pressure-sensitive adhesive layer.
- (meth)acrylic monomer means a monomer having a (meth)acryloyl group.
- (meth)acrylic resin means that the content of structural units derived from a monomer having a (meth)acryloyl group is based on all structural units (that is, all structural units of the resin). It means a resin that is 50% by mass or more.
- “Monomer” in this disclosure does not include reactive surfactants.
- (meth)acrylic is a term that includes both “acrylic” and “methacrylic”
- (meth)acrylate is a term that includes both “acrylate” and “methacrylate”
- (Meth)acryloyl is a term that includes both “acryloyl” and “methacryloyl”.
- n- means normal, "i-” means iso, "s-" means secondary, and "t-" means tertiary.
- adheresive and “adhesive composition” are synonymous.
- the pressure-sensitive adhesive composition of the present disclosure includes a structural unit (A) derived from a (meth)acrylic acid alkyl ester monomer, a structural unit (B) derived from (meth)acrylonitrile, and a (meth)acrylic having a carboxy group. Containing a structural unit (C) derived from a monomer and a structural unit (D) derived from a reactive surfactant, the content of the structural unit (B) is the total structural unit [however, the structural unit (D )except for. ], and the content of the structural unit (C) is 10% by mass to 25% by mass based on all the structural units [however, the structural unit (D) is excluded.
- the content of the structural unit (D) is 0.2% by mass to 6.0% by mass based on all structural units [however, the structural unit (D) is excluded. ] 0.1 to 1.0 parts by mass per 100 parts by mass of (meth)acrylic resin particles having an average particle diameter of 5 nm to 160 nm, and water.
- the pressure-sensitive adhesive composition of the present disclosure it is possible to form a pressure-sensitive adhesive layer that has high adhesive strength even in a hot and humid environment, is excellent in water resistance, and can withstand a load in the direction perpendicular to the sticking surface.
- the present inventors speculate as follows. However, the following assumptions are not intended to limit the interpretation of the pressure-sensitive adhesive composition of the present disclosure, but are explained as an example.
- the pressure-sensitive adhesive composition of the present disclosure contains resin particles having a relatively small average particle size of 160 nm or less, they tend to be densely arranged during the drying step of the coating film of the pressure-sensitive adhesive composition. By densely arranging the resin particles, the pressure-sensitive adhesive layer to be formed has an increased surface smoothness, making it difficult for water to permeate. For this reason, it is believed that the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present disclosure has excellent water resistance, and appearance changes such as swelling and whitening are less likely to occur even in a humid environment.
- a reactive surfactant is present on the surface of an adhesive layer formed using an adhesive composition containing resin particles containing structural units derived from a reactive surfactant.
- the pressure-sensitive adhesive composition of the present disclosure since the amount of structural units derived from the reactive surfactant contained in the resin particles is small, the formed pressure-sensitive adhesive layer does not dissolve the reactive surfactant. It is thought that the resulting water permeation is suppressed and excellent water resistance is maintained.
- (meth)acrylonitrile exists in a polarized state due to its structure.
- the (meth)acrylonitrile is polarized, an electrostatic interaction occurs between the adhesive layer and the substrate and between the adhesive layer and the adherend, and the adhesive layer and the substrate and the adherend Increased adhesion with
- the resin particles contain a specific proportion or more of structural units derived from (meth)acrylonitrile, so it is believed that the above interaction occurs more effectively.
- the formed pressure-sensitive adhesive layer has high adhesive strength even in a hot and humid environment, and can withstand a load perpendicular to the sticking surface.
- (meth)acrylonitrile has a cyano group, which is a hydrophilic group. Therefore, if the resin particles contain an excessive amount of constitutional units derived from (meth)acrylonitrile, the water resistance of the formed pressure-sensitive adhesive layer is reduced. is vulnerable.
- the structural units derived from (meth)acrylonitrile contained in the resin particles are less than or equal to a specific ratio, so the cyano groups are not excessive.
- the resin particles contained in the pressure-sensitive adhesive composition of the present disclosure have an average particle diameter of 5 nm or more, and contain a specific proportion of structural units derived from a (meth)acrylic monomer having a carboxy group, Excellent dispersibility. Therefore, it is believed that the pressure-sensitive adhesive composition of the present disclosure can more effectively exhibit the above effects. From the above, it is presumed that the pressure-sensitive adhesive composition of the present disclosure has high adhesive strength even in a hot and humid environment, is excellent in water resistance, and can withstand a load in the direction perpendicular to the sticking surface.
- the “structural unit (A) derived from a (meth)acrylic acid alkyl ester monomer, the structural unit (B) derived from (meth)acrylonitrile, and a carboxy group-containing A structural unit (C) derived from a (meth)acrylic monomer and a structural unit (D) derived from a reactive surfactant are included, and the content of the structural unit (B) is the total structural unit [however, excluding the structural unit (D)], and the content of the structural unit (C) is 10% by mass to 25% by mass in all structural units [excluding the structural unit (D)] The content of the structural unit (D) is 0.2% by mass to 6.0% by mass relative to 100 parts by mass of all structural units (excluding the structural unit (D)).
- (Meth)acrylic resin particles of 1 part by mass to 1.0 part by mass and having an average particle diameter of 5 nm to 160 nm are also referred to as "specific (meth)acrylic resin particles”.
- the pressure-sensitive adhesive composition of the present disclosure includes a structural unit (A) derived from a (meth)acrylic acid alkyl ester monomer, a structural unit (B) derived from (meth)acrylonitrile, and a (meth)acrylic having a carboxy group. Containing a structural unit (C) derived from a monomer and a structural unit (D) derived from a reactive surfactant, the content of the structural unit (B) is the total structural unit [however, the structural unit (D )except for. ], and the content of the structural unit (C) is 10% by mass to 25% by mass based on all the structural units [however, the structural unit (D) is excluded.
- the content of the structural unit (D) is 0.2% by mass to 6.0% by mass based on all structural units [however, the structural unit (D) is excluded. ] 0.1 parts by mass to 1.0 parts by mass with respect to 100 parts by mass, and (meth)acrylic resin particles having an average particle diameter of 5 nm to 160 nm [that is, specific (meth)acrylic resin particles ⁇ including.
- the specific (meth)acrylic resin particles exist in a state of being dispersed in a medium containing water.
- the pressure-sensitive adhesive composition of the present disclosure may contain only one type of specific (meth)acrylic resin particles, or may contain two or more types.
- the specific (meth)acrylic resin particles contain structural units (A) derived from (meth)acrylic acid alkyl ester monomers.
- a structural unit derived from a (meth)acrylic acid alkyl ester monomer means a structural unit formed by addition polymerization of a (meth)acrylic acid alkyl ester monomer.
- the "(meth)acrylic acid alkyl ester monomer” in the present disclosure does not include a monomer corresponding to a (meth)acrylic monomer having a carboxy group, which will be described later.
- the type of (meth)acrylic acid alkyl ester monomer is not particularly limited.
- the (meth)acrylic acid alkyl ester monomer may be an acrylic acid alkyl ester monomer or a methacrylic acid alkyl ester monomer.
- the (meth)acrylic acid alkyl ester monomer may have an unsubstituted alkyl group or a substituted alkyl group. preferable.
- the alkyl group of the (meth)acrylic acid alkyl ester monomer may be linear, branched, or cyclic.
- the number of carbon atoms in the alkyl group of the (meth)acrylic acid alkyl ester monomer is not particularly limited, but for example, it is preferably 1 to 18, more preferably 2 to 14, and 2 to 8. is more preferred.
- (meth) acrylic acid alkyl ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylates, t-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, i-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, i-nonyl (meth)acrylate, n-decyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.
- the (meth)acrylic acid alkyl ester monomer is preferably at least one selected from the group consisting of n-butyl acrylate (n-BA), 2-ethylhexyl acrylate (2EHA), and methyl methacrylate (MMA), and n -Butyl acrylate (n-BA) is more preferred.
- the specific (meth)acrylic resin particles may contain only one type of structural unit (A), or may contain two or more types.
- the content of the structural unit (A) in the specific (meth)acrylic resin particles is not particularly limited. ], it is preferably 50% by mass to 89.8% by mass, more preferably 55% by mass to 89.8% by mass, and further preferably 60% by mass to 89.8% by mass. Preferably, 65% to 89.8% by weight is particularly preferred, and 69% to 85.2% by weight is most preferred.
- the content of the structural unit (A) in the specific (meth)acrylic resin particles is the total structural units of the specific (meth)acrylic resin particles [excluding the structural unit (D). ] means that the structural unit (A) is contained as a main component of the structural units constituting the specific (meth)acrylic resin particles.
- ⁇ Structural unit (B) derived from (meth)acrylonitrile> The specific (meth)acrylic resin particles contain a structural unit (B) derived from (meth)acrylonitrile.
- a structural unit derived from (meth)acrylonitrile means a structural unit formed by addition polymerization of (meth)acrylonitrile.
- the structural unit (B) may be a structural unit derived from methacrylonitrile or a structural unit derived from acrylonitrile.
- the specific (meth)acrylic resin particles contain at least one of a structural unit derived from methacrylonitrile and a structural unit derived from acrylonitrile as a structural unit (B), and a structural unit derived from methacrylonitrile or a structural unit derived from acrylonitrile It is preferable to contain any one of the structural units, and it is more preferable to contain a structural unit derived from methacrylonitrile.
- the content of the structural unit (B) in the specific (meth)acrylic resin particles is the total structural units of the specific (meth)acrylic resin particles [however, the structural unit (D) is excluded. ] is 10% by mass to 25% by mass.
- the content of the structural unit (B) in the specific (meth)acrylic resin particles is the total structural units of the specific (meth)acrylic resin particles [excluding the structural unit (D). ]
- the formed pressure-sensitive adhesive layer tends to be able to withstand a load in the direction perpendicular to the sticking surface. The reason may be as follows. It is presumed that (meth)acrylonitrile is polarized in the pressure-sensitive adhesive layer due to its structure.
- the content of the structural unit (B) in the specific (meth)acrylic resin particles is determined based on all the structural units of the specific (meth)acrylic resin particles [excluding the structural unit (D). ], preferably 15% by mass or more, more preferably 20% by mass or more.
- the content of the structural unit (B) in the specific (meth)acrylic resin particles is the total structural units of the specific (meth)acrylic resin particles [excluding the structural unit (D). ], the pressure-sensitive adhesive layer formed tends to be excellent in water resistance.
- the reason may be as follows. This is probably because the pressure-sensitive adhesive layer to be formed does not have an excessive amount of cyano groups, which are hydrophilic groups derived from (meth)acrylonitrile, so that the water resistance is less likely to be impaired and excellent water resistance is maintained.
- the content of the structural unit (B) in the specific (meth)acrylic resin particles is the total structural units of the specific (meth)acrylic resin particles [excluding the structural unit (D). ] may be 15% by mass to 25% by mass.
- the specific (meth)acrylic resin particles contain a structural unit (C) derived from a (meth)acrylic monomer having a carboxy group.
- a structural unit derived from a (meth)acrylic monomer having a carboxy group means a structural unit formed by addition polymerization of a (meth)acrylic monomer having a carboxy group. do.
- the type of (meth)acrylic monomer having a carboxy group is not particularly limited. Specific examples of (meth)acrylic monomers having a carboxy group include methacrylic acid, acrylic acid, ⁇ -carboxy-polycaprolactone monomethacrylate, and ⁇ -carboxy-polycaprolactone monoacrylate. Acrylic acid is preferable as the (meth)acrylic monomer having a carboxy group.
- the specific (meth)acrylic resin particles may contain only one type of structural unit (C), or may contain two or more types.
- the content of the structural unit (C) in the specific (meth)acrylic resin particles is determined from the viewpoint of the dispersion stability of the resin particles. except. ] is 0.2% by mass to 6.0% by mass, preferably 0.5% by mass to 6.0% by mass, and 1.0% by mass to 6.0% by mass. It is more preferably 2.0% by mass to 6.0% by mass, and particularly preferably 4.8% by mass to 6.0% by mass.
- the carboxy group derived from the structural unit (C) of the specific (meth)acrylic resin particles contributes to the cross-linking reaction with the cross-linking agent
- the specific The content of the structural unit (C) in the (meth)acrylic resin particles is the total structural units of the specific (meth)acrylic resin particles [excluding the structural unit (D). ] the cohesive force of the pressure-sensitive adhesive layer to be formed increases, and the load resistance in the vertical direction can be further improved.
- the specific (meth)acrylic resin particles contain a structural unit (D) derived from a reactive surfactant.
- reactive surfactant refers to surfactants with ethylenically unsaturated double bonds.
- structural unit derived from a reactive surfactant means a structural unit formed by addition polymerization of a reactive surfactant.
- the type of reactive surfactant is not particularly limited.
- the reactive surfactant may be an anionic reactive surfactant, a nonionic reactive surfactant, or a cationic reactive surfactant.
- the reactive surfactant is preferably at least one selected from the group consisting of anionic reactive surfactants and nonionic reactive surfactants, and at least one selected from anionic reactive surfactants. and at least one selected from nonionic reactive surfactants.
- the reactive surfactant preferably has an oxyalkylene group and an ethylenically unsaturated double bond.
- oxyalkylene groups include oxyethylene, oxypropylene, and oxybutylene groups.
- the oxyalkylene group for example, an oxyethylene group is preferable from the viewpoint of high reactivity with the monomer.
- the average number of added moles of the oxyalkylene group is not particularly limited.
- the average added mole number of the oxyalkylene group is, for example, preferably from 5 to 50, more preferably from 5 to 40, more preferably from 10 to 30, from the viewpoint of dispersibility of the specific (meth)acrylic resin particles. It is even more preferable to have
- At least one reactive surfactant has an average addition mole number of 10 to 15 as an embodiment of the reactive surfactant. and at least one reactive surfactant is a nonionic reactive surfactant having an oxyethylene group with an average number of added moles of 20 to 30. Aspects are preferred.
- a reactive surfactant having an ethylenically unsaturated double bond is obtained by providing a surfactant with a group having an ethylenically unsaturated double bond.
- groups having ethylenically unsaturated double bonds include (meth)acryloyl groups, vinyl groups, allyl groups, isopropenyl groups, 1-propenyl groups, allyloxy groups, and styryl groups.
- the group having an ethylenically unsaturated double bond for example, a 1-propenyl group or an allyl group is preferable from the viewpoint of high reactivity with the monomer.
- a commercially available product can be used as the reactive surfactant.
- anionic reactive surfactants include "Aqualon KH-05” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. [active ingredient: polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate ester ammonium [Type of oxyalkylene group: oxyethylene group, average number of added moles: 5], active ingredient concentration: 99% by mass], “Aqualon KH-10” [active ingredient: polyoxyethylene-1-(allyloxymethyl)alkyl Ether sulfate ester ammonium [type of oxyalkylene group: oxyethylene group, average number of added moles: 10], active ingredient concentration: 99% by mass], "Aqualon AR-10" [active ingredient: polyoxyethylene styrenated propenylphenyl ether Ammonium sulfate [type of oxyalkylene group: oxyethylene group, average number of added moles: 10], active ingredient concentration: 99% by
- nonionic reactive surfactants examples include "Adekari Soap ER-10" manufactured by ADEKA Corporation [active ingredient: polyoxyethylene-1-(allyloxymethyl) alkyl ether [oxyalkylene group type: oxyethylene group, average number of added moles: 10], active ingredient concentration: 100% by mass], “Adekari Soap ER-30” [active ingredient: polyoxyethylene-1-(allyloxymethyl) alkyl ether [ Type of oxyalkylene group: oxyethylene group, average number of added moles: 30], active ingredient concentration: 65% by mass], and “Adekari Soap ER-40” [active ingredient: polyoxyethylene-1-(allyloxymethyl ) alkyl ether [kind of oxyalkylene group: oxyethylene group, average number of added moles: 40], active ingredient concentration: 60% by mass]. Both “Aqualon” and “Adekari Soap” are registered trademarks.
- the specific (meth)acrylic resin particles may contain only one type of structural unit (D), or may contain two or more types.
- the content of the structural unit (D) in the specific (meth)acrylic resin particles is the total structural units of the specific (meth)acrylic resin particles [however, the structural unit (D) is excluded. ] is 0.1 to 1.0 parts by mass with respect to 100 parts by mass.
- the content of the structural unit (D) in the specific (meth)acrylic resin particles is the total structural units of the specific (meth)acrylic resin particles [however, the structural unit (D) is excluded. ] When the content is 0.1 part by mass or more per 100 parts by mass, the specific (meth)acrylic resin particles can be produced by emulsion polymerization.
- the content of the structural unit (D) in the specific (meth)acrylic resin particles is the total structural units of the specific (meth)acrylic resin particles [however, the structural unit (D) is excluded. ] With respect to 100 parts by mass, the amount is preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more.
- the structural unit (D) can exist on the surface of the pressure-sensitive adhesive layer. Therefore, for example, when water adheres to the pressure-sensitive adhesive layer, a phenomenon may occur in which water permeates the pressure-sensitive adhesive layer by dissolving the reactive surfactant in water.
- the content of the structural unit (D) in the specific (meth)acrylic resin particles is the total structural units of the specific (meth)acrylic resin particles [however, the structural unit (D) is excluded. ] If the amount is 1.0 parts by mass or less with respect to 100 parts by mass, the permeation of water into the adhesive layer due to dissolution of the reactive surfactant is suppressed, so that the excellent water resistance of the adhesive layer is obtained. retained. From this point of view, the content of the structural unit (D) in the specific (meth)acrylic resin particles should be the total structural units of the specific (meth)acrylic resin particles [however, the structural unit (D) is excluded. ] With respect to 100 parts by mass, it is 1.0 parts by mass or less, preferably 0.9 parts by mass or less, more preferably 0.8 parts by mass or less, and 0.6 parts by mass or less is more preferred.
- the specific (meth)acrylic resin particles do not contain structural units derived from (meth)acrylamide having a hydroxyl group, or the content of structural units derived from (meth)acrylamide having a hydroxyl group is specified (meth)acrylic All constituent units of the resin particles (excluding the constituent unit (D)). ] It is preferably in the range of more than 0% by mass and less than 0.1% by mass, and does not contain a structural unit derived from (meth)acrylamide having a hydroxyl group, or (meth)acrylamide having a hydroxyl group All structural units of the specific (meth)acrylic resin particles [excluding the structural unit (D).
- a structural unit derived from (meth)acrylamide having a hydroxyl group means a structural unit formed by addition polymerization of (meth)acrylamide having a hydroxyl group.
- (Meth)acrylamide having a hydroxyl group has self-crosslinking properties and can self-crosslink by dehydration condensation.
- cross-linking between (meth)acrylamides having hydroxyl groups tends to shorten the distance between cross-links, and the pressure-sensitive adhesive layer tends to be hard and brittle.
- a (meth)acrylamide having a hydroxyl group is included, it tends to be weak against a load perpendicular to the sticking surface.
- the specific (meth)acrylic resin particles do not contain structural units derived from (meth)acrylamide having a hydroxyl group, or the content of structural units derived from (meth)acrylamide having a hydroxyl group is specified.
- the type of (meth)acrylamide having a hydroxyl group is not particularly limited.
- Specific examples of (meth)acrylamides having a hydroxyl group include N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-(2-hydroxyethyl)acrylamide, N-(2-hydroxyethyl)methacrylamide, 2,3 -dihydroxypropyl acrylamide, and 2,3-dihydroxypropyl methacrylamide.
- the specific (meth)acrylic resin particles contain structural units other than the above-described structural units (so-called other structural units), if necessary, as long as the effects of the pressure-sensitive adhesive composition of the present disclosure are not impaired. You can
- Examples of monomers constituting other structural units include (meth)acrylates having an aromatic ring represented by benzyl (meth)acrylate and phenoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate and ethoxyethyl Alkoxyalkyl (meth)acrylates typified by (meth)acrylates, aromatic monovinyls typified by styrene, ⁇ -methylstyrene, t-butylstyrene, p-chlorostyrene, chloromethylstyrene, and vinyltoluene, and formic acid Vinyl esters typified by vinyl, vinyl acetate, vinyl propionate, and vinyl versatate can be mentioned. In addition, various derivatives of these monomers can be mentioned as monomers constituting other structural units.
- the specific (meth)acrylic resin particles may contain other structural units, they may contain only one type of other structural units, or may contain two or more types.
- the content of the other structural units can be appropriately set according to the purpose within a range that does not impair the effects of the pressure-sensitive adhesive composition of the present disclosure.
- the shape of the specific (meth)acrylic resin particles is not particularly limited, but is preferably spherical.
- the term “spherical” as used in the present disclosure includes not only a true spherical shape but also a substantially spherical shape.
- the average particle size of the specific (meth)acrylic resin particles is 5 nm to 160 nm.
- the average particle size of the specific (meth)acrylic resin particles is 5 nm or more, preferably 10 nm or more, and more preferably 20 nm or more, from the viewpoint of production suitability of the specific (meth)acrylic resin particles. , 30 nm or more.
- the average particle size of the specific (meth)acrylic resin particles is 160 nm or less, there is a tendency that a pressure-sensitive adhesive layer having excellent water resistance can be formed. The reason may be as follows.
- the specific (meth)acrylic resin particles have a relatively small average particle size of 160 nm or less, they tend to be densely arranged during the drying step of the coating film of the pressure-sensitive adhesive composition. It is thought that the density of the specific (meth)acrylic resin particles arranged densely increases the surface smoothness of the pressure-sensitive adhesive layer to be formed, making it difficult for water to permeate. From such a viewpoint, the average particle size of the specific (meth)acrylic resin particles is 160 nm or less, preferably 150 nm or less, more preferably 130 nm or less, and even more preferably 110 nm or less. . In one embodiment, the specific (meth)acrylic resin particles may have an average particle size of 30 nm to 160 nm.
- the average particle size of the specific (meth)acrylic resin particles can be adjusted, for example, by changing the concentration of the reactive surfactant in the polymerization reaction solution when producing the specific (meth)acrylic resin particles.
- the particle diameter of the specific (meth)acrylic resin particles becomes small when the concentration of the reactive surfactant in the polymerization reaction solution is high in the initial stage of the production process, and the concentration of the reactive surfactant in the polymerization reaction solution is low and large early in the manufacturing process.
- initial stage of the production process means, for example, when the method [3] is employed as an emulsion polymerization method for producing the specific (meth)acrylic resin particles described later, the monomer components and It refers to the point in time when an emulsion of a mixture containing a reactive surfactant is prepared.
- particle size of the specific (meth)acrylic resin particles can also be adjusted, for example, by changing the dispersion conditions of the reaction field (eg, stirring speed) so that the components contained in the polymerization reaction solution are dispersed differently. can.
- the average particle size of the specific (meth)acrylic resin particles means the volume average particle size.
- the average particle size of the specific (meth)acrylic resin particles is a value measured by the following method using a laser diffraction particle size distribution analyzer. After diluting the specific (meth)acrylic resin particles with distilled water and sufficiently stirring and mixing, they were collected using a Pasteur pipette in a glass cell of 10 mm ⁇ 75 mm ⁇ 85 mm, and measured by laser diffraction particle size distribution. set in the device. After adjusting the concentration of the diluent of the specific (meth)acrylic resin particles so that the laser beam transmittance is 85%, the particle size distribution is measured at a measurement temperature of 25°C.
- the volume average particle size of the specific (meth)acrylic resin particles is obtained. Specifically, the particle diameter at 50% (volume basis) of the integrated value in the obtained particle diameter distribution is defined as the volume average particle diameter.
- the laser diffraction particle size distribution analyzer for example, "Laser Scattering Particle Size Distribution Analyzer LA-960" manufactured by Horiba, Ltd. can be suitably used. However, the laser diffraction particle size distribution measuring device is not limited to this.
- the glass transition temperature (hereinafter also referred to as “Tg”) of the specific (meth)acrylic resin particles is not particularly limited. It is more preferably -60°C to 20°C.
- Tg glass transition temperature of the specific (meth)acrylic resin particles
- the pressure-sensitive adhesive layer formed tends to exhibit moderate wettability to adherends.
- the glass transition temperature of the specific (meth)acrylic resin particles is 30° C. or lower, there is a tendency that zipping hardly occurs when the particles are peeled off from the adherend.
- the glass transition temperature of the specific (meth)acrylic resin particles is a value measured by the following method using a differential scanning calorimetry (DSC).
- DSC differential scanning calorimetry
- a release paper is coated with an aqueous dispersion of specific (meth)acrylic resin particles using a 4 mil (101.6 ⁇ m) applicator.
- the applied aqueous dispersion of the specific (meth)acrylic resin particles is dried (drying temperature: 105° C., drying time: 10 minutes) to obtain a dried product of the specific (meth)acrylic resin particles.
- the glass transition temperature is measured using a differential scanning calorimeter under the following measurement conditions.
- a differential scanning calorimeter for example, a differential scanning calorimeter (trade name: Discovery DSC 2500) manufactured by TA Instruments Japan Co., Ltd. can be used.
- the differential scanning calorimeter is not limited to this.
- Atmosphere Measurement temperature range -90°C to 100°C Heating rate: 10°C/min Reference material: Empty sample pan
- the gel fraction of the specific (meth)acrylic resin particles is not particularly limited. % to 65 mass %.
- the gel fraction of the specific (meth)acrylic resin particles is the ratio of solvent-insoluble matter measured using ethyl acetate as an extraction solvent. Specifically, the gel fraction of the specific (meth)acrylic resin particles is obtained according to the procedures [1] to [17] shown below. [1] After adjusting the pH to 8.5 (liquid temperature 25° C.) by adding aqueous ammonia to the aqueous dispersion of the specific (meth)acrylic resin particles, peeling of polyethylene terephthalate (PET) with a thickness of 100 ⁇ m It is applied on a film to form a coating film. Next, the formed coating film is dried at 105° C. for 2 minutes to obtain a resin film with a release film.
- PTT polyethylene terephthalate
- the obtained resin film with release film is cut into a size of 75 mm ⁇ 75 mm.
- the weight of the resin film included in the cut resin film with a release film is about 0.2 g.
- a 250-mesh (wire diameter: 0.03 mm, opening: 72 ⁇ m) stainless steel wire mesh is prepared, and this wire mesh is cut into a size of 100 mm ⁇ 100 mm. Note that fraying at the ends of the wire mesh causes measurement errors and should be removed in advance.
- the cut wire mesh is degreased with ethyl acetate and then dried. Store the dried wire mesh in a desiccator.
- the release film After attaching the resin film with a release film of [2] cut into a size of 75 mm ⁇ 75 mm to the center of the wire mesh, the release film is peeled off from the resin film to obtain a wire mesh with a resin film.
- the adhesion of the resin film to the wire mesh is performed so that the resin film is arranged in the plane after the wire mesh is folded in steps [7] to [9] described later.
- [7] Fold the wire mesh with resin film in half with the resin film on the inside. Specifically, the wire mesh with the resin film is folded so that the back side of the wire mesh with the resin film overlaps the front side.
- sample X1 After folding the front side (the side where two sides overlap) 1/3 of the metal mesh with a resin film folded in half to the back side, fold the back side 1/3 to the front side. At this point, the resin-coated wire mesh is folded vertically to 1/6 of its original size (100 mm), and is not folded horizontally. [9] After folding the left one-third of the wire mesh with the resin film folded in the above [8] to the right in the longitudinal direction, fold the right one-third to the left. This sample is designated as sample X1. The sample X1 is folded vertically to 1/6 of its original size (100 mm), and folded horizontally to 1/3 its size. [10] Accurately measure the mass of sample X1 using a precision balance. Let this mass be B (unit: g).
- sample X1 The folds of the sample X1 are stapled so that the folds do not open. This sample is designated as sample X2.
- Two samples X2 are produced for each sample.
- [12] Accurately measure the mass of sample X2 using a precision balance. Let this mass be C (unit: g).
- Sample X2 is placed in a glass bottle containing 80 g of ethyl acetate, and the bottle is capped.
- the glass bottle containing the sample X2 is left for 3 days in an atmosphere of 23° C. and 50% RH.
- the content of the specific (meth)acrylic resin particles in the pressure-sensitive adhesive composition of the present disclosure is not particularly limited, but is, for example, 80% by mass to 100% by mass relative to the total solid content in the pressure-sensitive adhesive composition. preferably 85% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.
- total solid content in the adhesive composition means the mass of the residue after removing the solvent from the adhesive composition.
- solvent means water and organic solvents.
- the adhesive composition of the present disclosure preferably further contains a cross-linking agent.
- the carboxy group derived from the structural unit (C) of the specific (meth)acrylic resin particles contributes to the cross-linking reaction with the cross-linking agent. Therefore, when the pressure-sensitive adhesive composition of the present disclosure contains a cross-linking agent, the cohesive force of the pressure-sensitive adhesive layer to be formed increases, and the load resistance in the vertical direction can be further improved.
- cross-linking agent is not particularly limited.
- cross-linking agents include carbodiimide-based cross-linking agents, oxazoline-based cross-linking agents, hydrazide-based cross-linking agents, epoxy-based cross-linking agents, and isocyanate-based cross-linking agents.
- carbodiimide-based cross-linking agent refers to a compound having two or more carbodiimide groups or cyanamide groups in a tautomeric relationship in one molecule
- oxazoline-based cross-linking agent refers to one molecule.
- hydrazide cross-linking agent refers to a compound having two or more hydrazide groups in one molecule
- epoxy cross-linking agent refers to a compound having two or more hydrazide groups in one molecule. It refers to a compound having two or more epoxy groups
- isocyanate-based cross-linking agent refers to a compound having two or more isocyanate groups in one molecule.
- the cross-linking agent is preferably at least one selected from carbodiimide-based cross-linking agents and oxazoline-based cross-linking agents, more preferably carbodiimide-based cross-linking agents.
- carbodiimide-based cross-linking agents include poly(4,4′-diphenylmethanecarbodiimide), poly(p-phenylenecarbodiimide), poly(m-phenylenecarbodiimide), poly(diisopropylphenylcarbodiimide), and poly(triisopropylphenylcarbodiimide).
- alicyclic polycarbodiimides such as poly(dicyclohexylmethanecarbodiimide)
- aliphatic polycarbodiimides such as poly(diisopropylcarbodiimide).
- carbodiimide-based cross-linking agents examples include "Carbodilite (registered trademark) V-02", “Carbodilite (registered trademark) V-02-L2” and “Carbodilite (registered trademark)” manufactured by Nisshinbo Chemical Co., Ltd. ) SV-02”, “Carbodilite (registered trademark) V-04”, “Carbodilite (registered trademark) V-10”, “Carbodilite (registered trademark) E-02”, and “Carbodilite (registered trademark) E-05” is mentioned.
- the oxazoline group possessed by the oxazoline-based cross-linking agent may be either a 2-oxazoline group, a 3-oxazoline group, or a 4-oxazoline group.
- oxazoline cross-linking agents include 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 2-isopropenyl-2 -oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline, 4-acryloyl-oxymethyl-2,4-dimethyl-2-oxazoline, 4-methacryloyloxymethyl-2,4-dimethyl-2-oxazoline , 4-methacryloyloxymethyl-2,4-dimethyl-2-oxazoline , 4-methacryloyloxymethyl-2-phenyl-4-methyl-2-oxazoline, 2-(4-vinylphenyl)-4,4
- oxazoline cross-linking agents examples include "Epocross (registered trademark) WS-300”, “Epocross (registered trademark) WS-500” and “Epocross (registered trademark)” manufactured by Nippon Shokubai Co., Ltd. WS-700”.
- the pressure-sensitive adhesive composition of the present disclosure contains a cross-linking agent, it may contain only one cross-linking agent, or may contain two or more cross-linking agents.
- the content of the cross-linking agent is not particularly limited. It is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and particularly preferably 3 parts by mass or more.
- the content of the cross-linking agent in the pressure-sensitive adhesive composition of the present disclosure is 0.1 parts by mass or more with respect to 100 parts by mass of the acrylic resin, the cohesive force of the pressure-sensitive adhesive layer formed increases, and the load capacity in the vertical direction increases. performance can be improved.
- the content of the cross-linking agent is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and 5 parts by mass or less with respect to 100 parts by mass of the specific (meth)acrylic resin particles.
- the content of the cross-linking agent in the pressure-sensitive adhesive composition of the present disclosure is 10 parts by mass or less with respect to 100 parts by mass of the acrylic resin, the formed pressure-sensitive adhesive layer tends to have higher adhesive strength.
- the content of the cross-linking agent may be 1 part by mass to 5 parts by mass, or 3 parts by mass to 5 parts by mass with respect to 100 parts by mass of the specific (meth)acrylic resin particles. good.
- the adhesive composition of the present disclosure contains water.
- water is not particularly limited, for example, distilled water, ion-exchanged water, pure water, and the like are preferable from the viewpoint of containing few impurities.
- the content of water in the pressure-sensitive adhesive composition of the present disclosure is not particularly limited, but for example, it is preferably 40% by mass to 80% by mass, and 40% by mass to 70% by mass, based on the total mass of the pressure-sensitive adhesive composition. % by mass is more preferred.
- the pressure-sensitive adhesive composition of the present disclosure may optionally contain an aqueous medium other than water as long as the effect is not impaired.
- aqueous media other than water include water-miscible organic solvents.
- water-miscible organic solvents include monohydric alcohol compounds such as methanol, ethanol, propanol and isopropanol; polyhydric alcohol compounds such as glycerin, ethylene glycol, diethylene glycol and propylene glycol; ethylene glycol monomethyl ether and ethylene glycol monoethyl.
- Glycol derivatives such as ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether; and other organic solvents.
- the adhesive composition of the present disclosure contains an aqueous medium other than water, it may contain only one type of aqueous medium other than water, or may contain two or more types.
- the adhesive composition of the present disclosure contains an aqueous medium other than water
- the content of the aqueous medium other than water can be appropriately set according to the purpose within a range that does not impair the effects of the adhesive composition of the present disclosure.
- the pressure-sensitive adhesive composition of the present disclosure does not contain a water-immiscible organic solvent, or the content of the water-immiscible organic solvent exceeds 0% by mass relative to the total weight of the pressure-sensitive adhesive composition. It is preferably in the range of 5% by mass or less, and does not contain a water-immiscible organic solvent, or the content of the water-immiscible organic solvent is 0% by mass with respect to the total mass of the adhesive composition.
- the range is more preferably in the range of 3% by mass or less, and does not contain a water-immiscible organic solvent, or the content of the water-immiscible organic solvent is based on the total mass of the pressure-sensitive adhesive composition It is more preferable that the range is more than 0% by mass and 1% by mass or less, and does not contain a water-immiscible organic solvent, or the content of the water-immiscible organic solvent is the pressure-sensitive adhesive composition. It is particularly preferable to be in the range of more than 0% by mass and 0.5% by mass or less with respect to the total mass.
- water-immiscible organic solvents include aromatic hydrocarbon compounds such as benzene, toluene and xylene; ether compounds such as diethyl ether and diisopropyl ether; aliphatic hydrocarbon compounds such as hexane and heptane; ester compounds such as ethyl acetate and butyl acetate; alcohol compounds such as octanol; ketone compounds such as methyl isobutyl ketone; and other organic solvents.
- aromatic hydrocarbon compounds such as benzene, toluene and xylene
- ether compounds such as diethyl ether and diisopropyl ether
- aliphatic hydrocarbon compounds such as hexane and heptane
- ester compounds such as ethyl acetate and butyl acetate
- alcohol compounds such as octanol
- ketone compounds such as methyl isobutyl ketone
- the pressure-sensitive adhesive composition of the present disclosure may optionally contain components other than the components described above (so-called other components) as long as the effects are not impaired.
- Other components include resin particles other than specific (meth)acrylic resin particles, antioxidants, antistatic agents, conductivity imparting agents, pH adjusters, antifoaming agents, wetting agents, thickeners, fillers, Various additives such as pigments and plasticizers can be used.
- the content of the other components can be appropriately set according to the purpose within a range that does not impair the effects of the pressure-sensitive adhesive composition of the present disclosure.
- the pH of the pressure-sensitive adhesive composition of the present disclosure is preferably 2 to 10, for example, from the viewpoint of the dispersibility of the specific (meth)acrylic resin particles in the pressure-sensitive adhesive composition.
- a method for measuring the pH of the pressure-sensitive adhesive composition of the present disclosure is not particularly limited.
- the pH of the pressure-sensitive adhesive composition of the present disclosure adopts a value measured at a liquid temperature of 25°C by a method conforming to JIS Z 8802:2011 using a pH meter.
- a pH meter (trade name: F-51) manufactured by HORIBA, Ltd. can be used.
- the measuring device is not limited to this.
- the method for producing the pressure-sensitive adhesive composition of the present disclosure is not particularly limited as long as the above-described pressure-sensitive adhesive composition of the present disclosure can be manufactured.
- the pressure-sensitive adhesive composition of the present disclosure is preferably produced, for example, by a method including a step of producing specific (meth)acrylic resin particles by an emulsion polymerization method.
- Examples of emulsion polymerization methods for producing specific (meth)acrylic resin particles include methods [1] to [3] shown below.
- the monomers forming the constituent units of the specific (meth)acrylic resin particles [at least, the (meth)acrylic acid alkyl ester monomer, the (meth)acrylonitrile, and the (meth)acrylic monomer having a carboxy group monomer] is also referred to as a "monomer component".
- a reactor equipped with a thermometer, a stirrer, a raw material introduction pipe, a reflux condenser, a nitrogen introduction pipe, etc. is charged with a monomer component, a reactive surfactant, and water, and a nitrogen stream is introduced. After raising the temperature while stirring at the bottom, a polymerization initiator, a reducing agent, etc. are added as appropriate to allow the emulsion polymerization reaction to proceed (so-called batch charging method).
- At least a reactive surfactant and water are charged in a reactor equipped with a thermometer, a stirrer, a raw material introduction pipe, a reflux condenser, a nitrogen introduction pipe, etc., and the mixture is raised while being stirred under a nitrogen stream.
- a polymerization initiator, a reducing agent, etc. are added as appropriate to proceed with the emulsion polymerization reaction (so-called monomer dropwise method).
- a reactive surfactant were charged into a reactor equipped with a thermometer, a stirrer, a raw material introduction pipe, a reflux condenser, a nitrogen introduction pipe, etc., and the temperature was raised while stirring under a nitrogen stream. After that, a polymerization initiator, a reducing agent and the like are appropriately added.
- the monomer component is previously emulsified using at least a reactive surfactant and water to prepare an emulsified mixture containing the monomer component and the reactive surfactant.
- an emulsion of a mixture containing a monomer component and a reactive surfactant is added dropwise into the reactor, and a polymerization initiator, a reducing agent, etc. are added as appropriate to allow the emulsion polymerization reaction to proceed (so-called , emulsified monomer dropping method)
- the emulsion polymerization method for producing the specific (meth)acrylic resin particles for example, from the viewpoint of industrial productivity, the above [3] emulsified monomer dropping method is preferable.
- the method for producing a pressure-sensitive adhesive composition of the present disclosure comprises at least a (meth)acrylic acid alkyl ester monomer, (meth)acrylonitrile, a (meth)acrylic monomer having a carboxy group, and a reactive surfactant.
- a step of producing (meth)acrylic resin particles by emulsion polymerization using a chain transfer agent Polymerizability can be improved by emulsion polymerization of the monomer component and the reactive surfactant using a chain transfer agent.
- the emulsified monomer dropping method of [3] above is adopted as the emulsion polymerization method for producing the specific (meth)acrylic resin particles, the following operations are performed.
- a reactor equipped with a thermometer, stirrer, raw material introduction tube, reflux condenser, nitrogen introduction tube, etc., is charged with water and a reactive surfactant, and after being heated while being stirred under a nitrogen stream, the temperature is appropriately increased. , a polymerization initiator, a reducing agent, etc. are added.
- a monomer component is emulsified in advance using at least a reactive surfactant, a chain transfer agent, and water, and an emulsion of a mixture containing the monomer component and the reactive surfactant is obtained. to prepare.
- an emulsion of a mixture containing a monomer component and a reactive surfactant is dropped into the reactor, and a polymerization initiator, a reducing agent, etc. are added as appropriate to allow the emulsion polymerization reaction to proceed.
- the specific (meth)acrylic resin particles obtained by the above emulsion polymerization method are obtained in the form of a dispersion dispersed in a medium containing at least water.
- the details of the (meth)acrylic acid alkyl ester monomer are as described above.
- the amount of the (meth)acrylic acid alkyl ester monomer used is not particularly limited, but for example, it is preferably 50 parts by mass to 89.8 parts by mass with respect to the total of 100 parts by mass of the monomers. It is more preferably from 60 parts by mass to 89.8 parts by mass, and particularly preferably from 65 parts by mass to 89.8 parts by mass.
- the details of (meth)acrylonitrile are as described above.
- the amount of (meth)acrylonitrile used is 10 parts by mass to 25 parts by mass with respect to the total of 100 parts by mass of the monomers.
- the lower limit of the amount of (meth)acrylonitrile to be used is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, with respect to the total of 100 parts by mass of the monomers.
- the amount of the (meth)acrylic monomer having a carboxy group is 0.2 parts by mass to 6.0 parts by mass, and 0.5 parts by mass to 6 parts by mass with respect to the total 100 parts by mass of the monomers. 0 parts by mass, more preferably 1.0 to 6.0 parts by mass, even more preferably 2.0 to 6.0 parts by mass.
- the amount of the reactive surfactant to be used is 0.1 to 1.0 parts by mass with respect to 100 parts by mass of the total monomers.
- the lower limit of the amount of the reactive surfactant used is preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, with respect to the total 100 parts by mass of the monomers. 0.5 parts by mass or more is more preferable.
- the upper limit of the amount of reactive surfactant used is preferably 0.9 parts by mass or less, more preferably 0.8 parts by mass or less, with respect to a total of 100 parts by mass of the monomers. 0.6 parts by mass or less is more preferable.
- the chain transfer agent is not particularly limited as long as it can be used in normal emulsion polymerization.
- Examples of chain transfer agents include cyanoacetic acid, cyanoacetic acid alkyl ester compounds having 1 to 8 carbon atoms, bromoacetic acid, bromoacetic acid alkyl ester compounds having 1 to 8 carbon atoms, ⁇ -methylstyrene, anthracene, phenanthrene, and fluorene.
- aromatic compounds represented by 9-phenylfluorene aromatic nitro compounds represented by p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol, and p-nitrotoluene, benzoquinone and Benzoquinone derivatives typified by 2,3,5,6-tetramethyl-p-benzoquinone, borane derivatives typified by tributylborane, carbon tetrabromide, carbon tetrachloride, 1,1,2,2-tetrabromoethane Halogenated hydrocarbon compounds typified by , tribromoethylene, trichlorethylene, bromotrichloromethane, tribromomethane, and 3-chloro-1-propene; aldehyde compounds typified by chloral and furaldehyde; alkyls having 1 to 18 carbon atoms; Mercaptan compounds, aromatic mercaptan compounds represented by thiophenol
- chain transfer agent When using a chain transfer agent, only one type of chain transfer agent may be used, or two or more types may be used.
- a chain transfer agent is used in a conventional amount.
- the amount of the chain transfer agent to be used is preferably 0.01 to 0.05 parts by mass with respect to 100 parts by mass of the total monomers.
- the polymerization initiator is not particularly limited as long as it can be used for normal emulsion polymerization.
- Polymerization initiators include, for example, persulfates, organic peroxides and azo compounds.
- persulfates include ammonium persulfate, sodium persulfate, and potassium persulfate.
- organic peroxides include t-butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, di-i-propylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, and t-butyl Peroxypivalate can be mentioned.
- azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy-2,4 -dimethylvaleronitrile), 1,1′-azobis(cyclohexane-1-carbonitrile), and 2,2′-azobis(isobutyrate)dimethyl.
- polymerization initiator When using a polymerization initiator, only one polymerization initiator may be used, or two or more polymerization initiators may be used.
- a polymerization initiator is used in an amount usually used.
- the amount of the polymerization initiator to be used is preferably 0.2 to 5.0 parts by mass with respect to 100 parts by mass of the total monomers.
- the reducing agent is not particularly limited as long as it can be used in normal emulsion polymerization.
- reducing agents include sodium metabisulfite, sodium sulfite, sodium hydrogensulfite, sodium pyrosulfite (also referred to as "sodium disulfite"), sodium hydroxymethanesulfinate, sodium pyrophosphate, thioglycolic acid, and sodium thiosulfate. , thiourea dioxide, L-ascorbic acid, tartaric acid, citric acid, and glucose.
- reducing agent When using a reducing agent, only one type of reducing agent may be used, or two or more types may be used.
- the reducing agent is used in the amount normally used.
- the amount of the reducing agent used is preferably 0.2 parts by mass to 5.0 parts by mass with respect to 100 parts by mass of the monomers in total.
- the polymerization temperature is preferably, for example, 50°C to 90°C.
- the polymerization time is preferably, for example, 1 hour to 5 hours.
- the method for producing the pressure-sensitive adhesive composition of the present disclosure preferably includes a step of adjusting the pH of the dispersion containing the specific (meth)acrylic resin particles obtained above.
- the pH of the dispersion containing the specific (meth)acrylic resin particles is preferably adjusted to 2 to 10 from the viewpoint of the dispersibility of the specific (meth)acrylic resin particles in the pressure-sensitive adhesive composition.
- the method for adjusting the pH of the dispersion containing the specific (meth)acrylic resin particles is not particularly limited, and examples thereof include a method using a pH adjuster.
- a pH adjuster for example, aqueous ammonia can be preferably used.
- a value measured at a liquid temperature of 25°C using a pH meter in accordance with JIS Z 8802:2011 is adopted.
- a pH meter (trade name: F-51) manufactured by HORIBA, Ltd. can be used.
- the measuring device is not limited to this.
- the method for producing the pressure-sensitive adhesive composition of the present disclosure may optionally include steps other than the steps described above (so-called other steps).
- Other steps include, for example, a step of mixing a dispersion containing specific (meth)acrylic resin particles with a cross-linking agent and other additives that are optional components of the pressure-sensitive adhesive composition of the present disclosure. .
- the pressure-sensitive adhesive layer of the present disclosure is formed from the pressure-sensitive adhesive composition of the present disclosure as described above, and includes a structural unit (A) derived from a (meth)acrylic acid alkyl ester monomer and a structure derived from (meth)acrylonitrile A unit (B), a structural unit (C) derived from a (meth)acrylic monomer having a carboxy group, and a structural unit (D) derived from a reactive surfactant,
- the content of B) is in all structural units [excluding the above structural unit (D). ]
- the content of the structural unit (C) is 10% by mass to 25% by mass based on all the structural units [however, the structural unit (D) is excluded.
- the content of the structural unit (D) is 0.2% by mass to 6.0% by mass based on all structural units [however, the structural unit (D) is excluded. ] Contains 0.1 to 1.0 parts by mass of (meth)acrylic resin per 100 parts by mass.
- the "structural unit (A) derived from a (meth)acrylic acid alkyl ester monomer, a structural unit (B) derived from (meth)acrylonitrile, and a carboxyl group contained in the pressure-sensitive adhesive layer of the present disclosure Containing a structural unit (C) derived from a meth)acrylic monomer and a structural unit (D) derived from a reactive surfactant, the content of the structural unit (B) is the total structural unit [however, the above excluding the structural unit (D)], and the content of the structural unit (C) is 10% by mass to 25% by mass relative to all the structural units [excluding the structural unit (D)] is 0.2% by mass to 6.0% by mass, and the content of the structural unit (D) is 0.1 per 100 parts by mass of all structural units [excluding the structural unit (D)].
- a (meth)acrylic resin having a mass part to 1.0 part by mass is also referred to as a "specific (meth)acrylic resin".
- the pressure-sensitive adhesive layer of the present disclosure is a pressure-sensitive adhesive layer formed from the above-described pressure-sensitive adhesive composition of the present disclosure, and contains a specific (meth)acrylic resin, so that it has high adhesive strength even in a moist and heat environment. It has excellent water resistance and can withstand a load perpendicular to the adhered surface.
- the thickness of the adhesive layer of the present disclosure is not particularly limited.
- the thickness of the adhesive layer of the present disclosure is generally 1 ⁇ m to 300 ⁇ m, preferably 5 ⁇ m to 200 ⁇ m, more preferably 10 ⁇ m to 100 ⁇ m.
- the "thickness of the adhesive layer” in the present disclosure means the average thickness of the adhesive layer.
- the average thickness of the pressure-sensitive adhesive layer is a value obtained by the following method. The thickness of 10 randomly selected points in the thickness direction of the pressure-sensitive adhesive layer is measured using a film thickness meter. An arithmetic mean value of the measured values is obtained, and the obtained value is defined as the average thickness of the pressure-sensitive adhesive layer.
- the method for forming the pressure-sensitive adhesive layer of the present disclosure is not particularly limited.
- the pressure-sensitive adhesive layer of the present disclosure can be formed, for example, by the following method.
- the pressure-sensitive adhesive composition of the present disclosure is applied onto a support (eg, base material and release sheet) to form a coating film.
- the adhesive layer is formed by drying the formed coating film.
- the method of applying the pressure-sensitive adhesive composition is not particularly limited.
- Examples of the method of applying the adhesive composition include known methods using a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, knife coater, spray coater, bar coater, applicator, and the like.
- the coating amount of the pressure-sensitive adhesive composition is not particularly limited, and is appropriately set, for example, according to the thickness of the pressure-sensitive adhesive layer to be formed.
- a method for drying the coating film is not particularly limited.
- Methods for drying the coating film include, for example, natural drying, heat drying, hot air drying, and vacuum drying.
- the drying temperature and drying time of the coating film are not particularly limited, and are appropriately set according to the thickness of the coating film, the amount of water contained in the coating film, and the like.
- An example of the drying conditions is a condition of drying at 70° C. to 120° C. for 30 seconds to 180 seconds using a hot air circulation dryer.
- the pressure-sensitive adhesive sheet of the present disclosure includes the pressure-sensitive adhesive layer of the present disclosure. Since the pressure-sensitive adhesive sheet of the present disclosure includes the pressure-sensitive adhesive layer of the present disclosure, it has high adhesive strength even in a moist and hot environment, has excellent water resistance, and can withstand a load in the direction perpendicular to the sticking surface. bearable. Therefore, the pressure-sensitive adhesive sheet of the present disclosure is suitable for use around water such as bathrooms, washrooms, kitchens, and toilets. It is suitable as a pressure-sensitive adhesive sheet.
- the pressure-sensitive adhesive sheet of the present disclosure may be a substrate-free pressure-sensitive adhesive sheet having no substrate, or a substrate-containing pressure-sensitive adhesive sheet having an adhesive layer on one or both sides of a substrate. If the pressure-sensitive adhesive sheet of the present disclosure is a substrate-free type pressure-sensitive adhesive sheet that does not have a substrate, or if it is a substrate-containing pressure-sensitive adhesive sheet that includes an adhesive layer on one side of the substrate, the pressure-sensitive adhesive of the present disclosure In the sheet, the exposed surface of the pressure-sensitive adhesive layer may be protected with a release sheet.
- the release sheet is not particularly limited as long as it can be easily peeled off from the pressure-sensitive adhesive layer.
- the release sheet includes, for example, a resin film, paper, synthetic paper, and a composite sheet in which two or more of these are laminated, having one or both sides surface-treated with a release agent (so-called easy-release treatment).
- a release sheet in which one side or both sides of a resin film are surface-treated with a release agent (so-called easy release treatment) is also referred to as a "release film".
- release agents include silicone-based release agents (eg, silicone), wax-based release agents (eg, paraffin wax), and fluorine-based release agents (eg, fluorine-based resins).
- resin films examples include polyester films typified by polyethylene terephthalate (PET) films.
- Paper includes, for example, woodfree paper and coated paper.
- the film thickness of the release sheet is not particularly limited, and is generally 20 ⁇ m to 180 ⁇ m. The release sheet protects the surface of the adhesive layer until the adhesive tape is put to practical use, and is peeled off during use.
- the base material is not particularly limited as long as the pressure-sensitive adhesive layer can be formed on the base material.
- base materials include polyolefin resins [e.g., polyethylene (PE) and polypropylene (PP)], polyester resins [e.g., polyethylene terephthalate (PET)], acetate resins (e.g., triacetyl cellulose resin), poly Ethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyurethane resins, acrylic resins, vinyl chloride resins, ABS (Acrylonitrile Butadiene Styrene) resins, films and paper containing resins such as fluorine resins (for example, woodfree paper and coated paper), synthetic paper, and composite sheets obtained by laminating two or more of these.
- PE polyethylene
- PP polypropylene
- PET polyethylene terephthalate
- acetate resins e.g., triacetyl cellulose resin
- the surface of the substrate on which the adhesive layer is provided is subjected to surface treatment such as corona discharge treatment or plasma discharge treatment (so-called easy-adhesion treatment). may be applied.
- the substrate may contain various additives such as plasticizers, colorants (eg, dyes and pigments), heat stabilizers, light stabilizers, antistatic agents, flame retardants, antioxidants, and the like.
- the substrate may be partially or wholly patterned.
- the thickness of the substrate is not particularly limited, it is generally 10 ⁇ m to 500 ⁇ m, preferably 10 ⁇ m to 300 ⁇ m, more preferably 10 ⁇ m to 200 ⁇ m, and even more preferably 10 ⁇ m to 100 ⁇ m.
- Substrate thickness in the present disclosure means the average thickness of the substrate.
- the average thickness of the substrate is a value obtained by the following method. The thickness of 10 randomly selected points in the thickness direction of the substrate is measured using a film thickness meter. An arithmetic average value of the measured values is obtained, and the obtained value is defined as the average thickness of the substrate.
- the method for producing the pressure-sensitive adhesive sheet of the present disclosure is not particularly limited.
- the pressure-sensitive adhesive sheet of the present disclosure can be produced by a known method. Examples of methods for producing the pressure-sensitive adhesive sheet of the present disclosure include the following methods.
- the pressure-sensitive adhesive sheet of the present disclosure is a non-substrate type pressure-sensitive adhesive sheet
- the pressure-sensitive adhesive composition of the present disclosure is applied to the easily peelable surface of the release sheet to form a coating film on the release sheet.
- a pressure-sensitive adhesive layer is formed on the release sheet.
- the exposed surface of the formed pressure-sensitive adhesive layer is overlaid on the easy-releasing treatment surface of a separately prepared release sheet, thereby obtaining a substrate-free structure having a laminate structure of release sheet/adhesive layer/release sheet. You can make a type of adhesive sheet.
- the pressure-sensitive adhesive sheet of the present disclosure is a substrate-containing pressure-sensitive adhesive sheet
- a coating film is formed on the substrate by applying the pressure-sensitive adhesive composition of the present disclosure to the easy-adhesion-treated surface of the substrate.
- a pressure-sensitive adhesive layer is formed on the substrate.
- the exposed surface of the formed pressure-sensitive adhesive layer is superimposed on the easy-release treated surface of the release sheet and adhered, thereby forming a substrate-based pressure-sensitive adhesive sheet having a laminate structure of release sheet/adhesive layer/substrate. can be made.
- another method includes, for example, the following method.
- a coating film is formed on the release sheet by applying the pressure-sensitive adhesive composition of the present disclosure to the easy-release-treated surface of the release sheet.
- a pressure-sensitive adhesive layer is formed on the release sheet.
- the exposed surface of the formed pressure-sensitive adhesive layer is superimposed on the easy-adhesion-treated surface of the base material and adhered to the base material type pressure-sensitive adhesive sheet having a laminated structure of base material/adhesive layer/release sheet. can be made.
- the method and amount of application of the pressure-sensitive adhesive composition, and the drying method, drying temperature, and drying time of the coating film are as described above, so the description is omitted here.
- the adhesive composition of the present disclosure the method for producing the same, and the adhesive layer will be more specifically described with reference to examples.
- the present disclosure is not limited to the following examples as long as the gist thereof is not exceeded.
- n-butyl acrylate (n-BA) [acrylic acid alkyl ester monomer] 85.2 parts by mass (340.8 g), acrylonitrile (AN) 10.0 parts by mass (40.0 g) and acrylic acid (AA) [ Acrylic monomer having a carboxyl group] 4.8 parts by mass (19.2 g) were mixed to prepare a monomer mixture.
- an anionic reactive surfactant Aqualon (registered trademark) AR-10 [trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] 0.16 parts by mass [active ingredient conversion value] ( 0.63 g), Adekari Soap (registered trademark) ER-30 (trade name, manufactured by ADEKA), which is an anionic reactive surfactant, 0.25 parts by mass [effective ingredient conversion value] (1.5 g), N - Dodecyl mercaptan [chain transfer agent] 0.025 parts by mass (0.10 g) and ion-exchanged water 77.8 parts by mass (311.7 g) are added and stirred to obtain a monomer component and a reactive surfactant.
- Aqualon (registered trademark) AR-10 trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
- Adekari Soap registered trademark
- ER-30 trade name, manufactured by ADEKA
- An emulsion X of a mixture containing was prepared. Next, 33.1 parts by mass (132.7 g) of ion-exchanged water and an anionic reactive surfactant were added to a reactor equipped with a thermometer, a stirrer, a sequential dropping device, a reflux condenser, and a nitrogen inlet tube. A certain Aqualon (registered trademark) AR-10 [trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] 0.09 parts by mass [active ingredient conversion value] (0.36 g) was charged, nitrogen was sealed, and the internal temperature was increased. The temperature was raised to 80°C.
- aqueous dispersion of (meth)acrylic resin particles A-1 After adjusting the pH, ion-exchanged water was added to adjust the concentration to obtain an aqueous dispersion of (meth)acrylic resin particles A-1.
- the resulting aqueous dispersion of (meth)acrylic resin particles A-1 had a solid content concentration of 40.6% by mass and a pH of 3.8.
- the "solid content concentration” as used herein means the mass ratio of the (meth)acrylic resin particles A-1 in the aqueous dispersion of the (meth)acrylic resin particles A-1. The same applies to each aqueous dispersion of (meth)acrylic resin particles A-2 to A-22 produced below.
- Production Examples A-2 to A-9 and A-15 to A-18 In Production Examples A-2 to A-9 and A-15 to A-18, the same operation as in Production Example A-1 except that the composition of the (meth)acrylic resin particles was changed to the composition shown in Table 1. to obtain aqueous dispersions of (meth)acrylic resin particles A-2 to A-9 and A-15 to A-18.
- Production Example A-21 In Production Example A-21, the same operation as in Production Example A-1 was performed, except that the composition of the (meth)acrylic resin particles was changed to the composition shown in Table 1, and (meth)acrylic resin particles A- An attempt was made to produce No. 21, but the monomer component and reactive surfactant could not be polymerized.
- the pH of each aqueous dispersion of the (meth)acrylic resin particles A-2 to A-20 and A-22 obtained above is shown below.
- the pH of each aqueous dispersion of (meth)acrylic resin particles A-1 to A-20 and A-22 was measured using a pH meter (trade name: F-51) manufactured by Horiba, Ltd., using JIS Z 8802. : 2011 at a liquid temperature of 25°C.
- composition of (meth)acrylic resin particles A-1 to A-22 (unit: parts by mass), glass transition temperature of (meth)acrylic resin particles A-1 to A-20 and A-22 (Tg, unit: ° C.), the average particle diameter (unit: nm) of the (meth)acrylic resin particles A-1 to A-20 and A-22, and the (meth)acrylic resin particles A-1 to A-20 and A-22
- Table 1 shows the gel fraction (unit: mass %).
- the glass transition temperatures of the (meth)acrylic resin particles A-1 to A-20 and A-22 were measured by the same method as the method for measuring the glass transition temperature of the specific (meth)acrylic resin particles described above.
- Discovery DSC 2500 (trade name) manufactured by TA Instruments Japan Co., Ltd. was used as a measuring device.
- the average particle size of the (meth)acrylic resin particles A-1 to A-20 and A-22 was measured by the same method as the method for measuring the average particle size of the specific (meth)acrylic resin particles described above.
- Laser Scattering Particle Size Distribution Analyzer LA-960 (trade name), which is a laser diffraction particle size distribution measurement device manufactured by Horiba, Ltd., was used.
- the gel fractions of the (meth)acrylic resin particles A-1 to A-20 and A-22 were measured by the same method as the method for measuring the gel fraction of the specific (meth)acrylic resin particles described above.
- the (meth)acrylic resin particles A-1 to A-20 and A-22 obtained above are It corresponds to specific (meth)acrylic resin particles.
- the amount of reactive surfactant shown in Table 1 is the active ingredient conversion value.
- AR-10 [trade name: Aqualon (registered trademark) AR-10, active ingredient: polyoxyethylene styrenated propenylphenyl ether sulfate ester ammonium [type of oxyalkylene group: oxyethylene group, average number of added moles: 10] , Active ingredient concentration: 99% by mass]
- AR-20 [trade name: Aqualon (registered trademark) AR-20, active ingredient: polyoxyethylene styrenated propenylphenyl ether sulfate ester ammonium [type of oxyalkylene group: oxyethylene group, average number of added moles: 20] , Active ingredient concentration: 99% by mass]
- ER-30 [trade name: Adekari Soap (registered trademark) ER-30, active ingredient: polyoxyethylene-1-(allyloxymethyl) alkyl ether [type of oxyalkylene group: oxyethylene group, average addition mole number: 30], active ingredient concentration: 65% by mass
- Example 1 100 parts by mass (solid content conversion value) of the aqueous dispersion of the (meth)acrylic resin particles A-1 obtained above, 0.32 parts by mass of ammonia water, and CP-101 [trade name] as an antifoaming agent.
- Examples 2 to 19 In Examples 2 to 19, the same operation as in Example 1 was performed except that the composition of the adhesive composition was as shown in Table 2, and each adhesive composition of Examples 2 to 19 was prepared. .
- Comparative Examples 1 to 6 In Comparative Examples 1 to 6, the same operation as in Example 1 was performed except that the composition of the adhesive composition was as shown in Table 3, and each adhesive composition of Comparative Examples 1 to 6 was prepared. .
- Example 2 59.8% by mass
- Example 3 59.8% by mass
- Example 4 59.8% by mass
- Example 5 59.8% by mass
- Example 6 59.8% by mass
- Example 7 59.8% by mass
- Example 8 59.8% by mass
- Example 9 59.8% by mass
- Example 10 75.3% by mass
- Example 11 59.8% by mass
- Example 12 59.8% by mass
- Example 13 59.8% by mass
- Example 14 64.8% by mass
- Example 16 59.8% by mass
- Example 17 59.8% by mass
- Example 18 50.5% by mass
- Example 19 59.8% by mass
- the pressure-sensitive adhesive composition prepared above was applied to a release sheet [trade name: Film Biner (registered trademark) 100E-0010 No. 23, manufactured by Fujimori Kogyo Co., Ltd.] using an applicator so that the coating amount after drying was 25 g/m 2 to form a coating film. Then, the formed coating film was dried using a hot air circulating dryer under conditions of a drying temperature of 105° C. and a drying time of 90 seconds to form an adhesive layer on the surface of the release sheet.
- a release sheet trade name: Film Biner (registered trademark) 100E-0010 No. 23, manufactured by Fujimori Kogyo Co., Ltd.
- PET polyethylene terephthalate
- Teijin registered trademark
- Tetoron registered trademark
- the produced adhesive tape for evaluation has a laminated structure of release sheet/adhesive layer/base material (PET).
- Adhesive Strength (1) Initial Adhesive Strength The adhesive sheet for evaluation prepared above was cut into a size of 25 mm ⁇ 100 mm to prepare an adhesive sheet piece for evaluation. The release sheet was peeled off from the prepared adhesive sheet piece for evaluation (constitution: base material / adhesive layer / release sheet), and the surface of the adhesive layer exposed by peeling was subjected to JIS Z 0237: according to the method in accordance with 2009. A surface of SUS304 (stainless steel plate; hereinafter simply referred to as "SUS”) polished with #360 waterproof abrasive paper specified in R 6253:2006 was overlaid and crimped to prepare a test piece.
- SUS304 stainless steel plate; hereinafter simply referred to as "SUS”
- the prepared test piece was allowed to stand for 30 minutes in an environment with an ambient temperature of 23° C. and 50% RH.
- the adhesive force (unit: N / 25 mm) when the adhesive sheet piece for evaluation (configuration: base material / adhesive layer) was peeled off 180 ° in the long side (100 mm) direction from SUS, Using a single-column material testing machine (model number: STA-1225) manufactured by A&D Co., Ltd. as a measuring device, under the conditions of an atmosphere temperature of 23 ° C. and 50% RH, a peeling speed of 300 mm / min. bottom. If the measured value was 10 N/25 mm or more, it was determined that the adhesive layer had high initial adhesive strength. The measured values are shown in Tables 2 and 3.
- the prepared test piece was allowed to stand for 30 minutes in an environment with an ambient temperature of 23° C. and 50% RH, and then allowed to stand in an environment with an ambient temperature of 40° C. and 90% RH for 7 days. After standing still, the test piece was taken out in an environment with an ambient temperature of 23°C and 50% RH.
- the adhesive force (unit: N / 25 mm) when the evaluation adhesive sheet piece (configuration: base material / adhesive layer) was peeled off from SUS at 180 ° in the long side (100 mm) direction was measured.
- a single-column material testing machine (model number: STA-1225) manufactured by A&D Co., Ltd.
- the pressure-sensitive adhesive sheet for evaluation prepared above was cut into a size of 25 mm ⁇ 100 mm to prepare a pressure-sensitive adhesive sheet piece for evaluation.
- the release sheet was peeled off from the prepared adhesive sheet piece for evaluation (constitution: base material / adhesive layer / release sheet), and the surface of the adhesive layer exposed by peeling was subjected to JIS Z 0237: according to the method in accordance with 2009.
- a surface of SUS304 (stainless steel plate) polished with water-resistant abrasive paper of #360 specified in R 6253:2006 was overlaid and pressed to prepare a test piece.
- test piece After the prepared test piece was immersed in deionized water for 72 hours, it was taken out from the deionized water and allowed to stand in an environment with an ambient temperature of 23° C. and 50% RH for 1 hour. After standing still, the test piece was visually observed and evaluated according to the following evaluation criteria. Evaluation results are shown in Tables 2 and 3. In the following evaluation criteria, "A” and "B” are practically acceptable levels, and "A” is most preferred.
- the pressure-sensitive adhesive sheet for evaluation produced above was cut into a size of 25 mm ⁇ 100 mm to prepare a pressure-sensitive adhesive sheet piece for evaluation. A part of the release sheet was peeled off from the prepared adhesive sheet piece for evaluation (constitution: substrate/adhesive layer/release sheet) so that the exposed portion of the adhesive layer had a size of 25 mm ⁇ 80 mm.
- the surface of the pressure-sensitive adhesive layer exposed by peeling was subjected to #360 water-resistant abrasive paper specified in JIS R 6253:2006 in an environment of an ambient temperature of 23 ° C. and 50% RH according to a method in accordance with JIS Z 0237:2009.
- SUS304 stainless steel plate; hereinafter simply referred to as "SUS"
- a 2-kg roller was reciprocated once to make a test piece.
- the size of the portion where the SUS and the pressure-sensitive adhesive layer were bonded together was 25 mm ⁇ 80 mm.
- the prepared test piece was allowed to stand in an environment with an ambient temperature of 23° C. and 50% RH for 1 hour, and then in an environment with an atmospheric temperature of 40° C. and 90% RH for 1 hour. Next, in an environment with an ambient temperature of 40 ° C.
- the SUS plate is kept horizontal so that the surface to which the adhesive sheet piece for evaluation is attached faces downward, and the adhesive layer is not attached to the SUS.
- a weight of 200 g was hung from the end of the adhesive sheet piece for evaluation, and left for 3 hours. After standing, the length of the adhesive layer peeled off from the SUS was measured and evaluated according to the following evaluation criteria. Tables 2 and 3 show the measured values and evaluation results. In the following evaluation criteria, "A", "B” and “C” are practically acceptable levels, and "A" is most preferred.
- cross-linking agents listed in Table 2 and/or Table 3 are as follows.
- ⁇ Crosslinking agent> “V-04” [trade name: Carbodilite (registered trademark) V-04, carbodiimide-based cross-linking agent, manufactured by Nisshinbo Chemical Inc.]
- WS-300 [trade name: Epocross (registered trademark) WS-300, oxazoline-based cross-linking agent, manufactured by Nippon Shokubai Co., Ltd.]
- the pressure-sensitive adhesive layers formed from the pressure-sensitive adhesive compositions of Examples have both high initial adhesive strength and high adhesive strength in a moist and heat environment, excellent water resistance, and have excellent water resistance. It was confirmed that the pressure-sensitive adhesive layer can withstand a load in the vertical direction.
- the pressure-sensitive adhesive layer formed by the pressure-sensitive adhesive composition of the comparative example has high initial adhesive strength and high adhesive strength in a wet and heat environment, but has poor water resistance or vertical load resistance. It was confirmed that either was inferior to the pressure-sensitive adhesive layers formed from the pressure-sensitive adhesive compositions of Examples.
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Abstract
Description
一般に、水系粘着剤により形成された粘着剤層は、耐水性が悪く、例えば、水に浸漬した場合に、膨潤、白化等の外観変化が起こり得る。また、水系粘着剤により形成された粘着剤は、せん断方向(所謂、粘着剤層と平行な方向)の応力に耐え得る凝集力を有していても、貼着面に対して垂直方向の応力に弱く、剥がれが発生しやすい。
このため、水系粘着剤には、耐水性に優れ、かつ、貼着面に対して垂直方向の荷重にも耐え得る粘着剤層を形成できることが求められる。加えて、水系粘着剤には、室温環境下のみならず、湿熱環境下においても高い粘着力を有する粘着剤層を形成できることも求められる。
本開示の他の実施形態が解決しようとする課題は、上記粘着剤組成物の製造方法を提供することにある。
また、本開示の他の実施形態が解決しようとする課題は、湿熱環境下でも高い粘着力を有し、耐水性に優れ、かつ、貼着面に対して垂直方向の荷重にも耐え得る粘着剤層を提供することにある。
また、本開示の他の実施形態が解決しようとする課題は、上記粘着剤層を備える粘着シートを提供することにある。
<1> (メタ)アクリル酸アルキルエステル単量体に由来する構成単位(A)、(メタ)アクリロニトリルに由来する構成単位(B)、カルボキシ基を有する(メタ)アクリル系単量体に由来する構成単位(C)、及び反応性界面活性剤に由来する構成単位(D)を含み、上記構成単位(B)の含有率が全構成単位〔但し、上記構成単位(D)を除く。〕に対して10質量%~25質量%であり、上記構成単位(C)の含有率が全構成単位〔但し、上記構成単位(D)を除く。〕に対して0.2質量%~6.0質量%であり、上記構成単位(D)の含有量が全構成単位〔但し、上記構成単位(D)を除く。〕100質量部に対して0.1質量部~1.0質量部であり、かつ、平均粒子径が5nm~160nmである(メタ)アクリル系樹脂粒子と、水と、を含む粘着剤組成物。
<2> さらに、架橋剤を含む<1>に記載の粘着剤組成物。
<3> 上記架橋剤が、カルボジイミド系架橋剤及びオキサゾリン系架橋剤から選ばれる少なくとも1種である<2>に記載の粘着剤組成物。
<4> 上記反応性界面活性剤が、アニオン型反応性界面活性剤及びノニオン型反応性界面活性剤からなる群より選ばれる少なくとも1種である<1>~<3>のいずれか1つに記載の粘着剤組成物。
<5> 上記(メタ)アクリル系樹脂粒子は、水酸基を有する(メタ)アクリルアミドに由来する構成単位を含まないか、又は、水酸基を有する(メタ)アクリルアミドに由来する構成単位の含有率が上記(メタ)アクリル系樹脂粒子の全構成単位〔但し、前記構成単位(D)を除く。〕に対して0質量%を超えて0.1質量%未満の範囲である<1>~<4>のいずれか1つに記載の粘着剤組成物。
<6> 上記(メタ)アクリル系樹脂粒子のガラス転移温度が、-70℃~30℃である<1>~<5>のいずれか1つに記載の粘着剤組成物。
<7> <1>~<6>のいずれか1つに記載の粘着剤組成物により形成され、(メタ)アクリル酸アルキルエステル単量体に由来する構成単位(A)と、(メタ)アクリロニトリルに由来する構成単位(B)と、カルボキシ基を有する(メタ)アクリル系単量体に由来する構成単位(C)と、反応性界面活性剤に由来する構成単位(D)と、を含み、上記構成単位(B)の含有率が全構成単位〔但し、上記構成単位(D)を除く。〕に対して10質量%~25質量%であり、上記構成単位(C)の含有率が全構成単位〔但し、上記構成単位(D)を除く。〕に対して0.2質量%~6.0質量%であり、上記構成単位(D)の含有量が全構成単位〔但し、上記構成単位(D)を除く。〕100質量部に対して0.1質量部~1.0質量部である(メタ)アクリル系樹脂を含む粘着剤層。
<8> <7>に記載の粘着剤層を備える粘着シート。
<9> <1>~<6>のいずれか1つに記載の粘着剤組成物の製造方法であり、
少なくとも、(メタ)アクリル酸アルキルエステル単量体、(メタ)アクリロニトリル、カルボキシ基を有する(メタ)アクリル系単量体、及び反応性界面活性剤を、連鎖移動剤を用いて乳化重合させることにより、(メタ)アクリル系樹脂粒子を製造する工程を含む粘着剤組成物の製造方法。
本開示の他の実施形態によれば、上記粘着剤組成物の製造方法が提供される。
また、本開示の他の実施形態によれば、湿熱環境下でも高い粘着力を有し、耐水性に優れ、かつ、貼着面に対して垂直方向の荷重にも耐え得る粘着剤層が提供される。
また、本開示の他の実施形態によれば、上記粘着剤層を備える粘着シートが提供される。
本開示に段階的に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本開示において、「(メタ)アクリル系樹脂」とは、(メタ)アクリロイル基を有する単量体に由来する構成単位の含有率が、全構成単位(即ち、樹脂の全構成単位)に対して50質量%以上である樹脂を意味する。
本開示における「単量体」には、反応性界面活性剤は含まれない。
本開示の粘着剤組成物は、(メタ)アクリル酸アルキルエステル単量体に由来する構成単位(A)、(メタ)アクリロニトリルに由来する構成単位(B)、カルボキシ基を有する(メタ)アクリル系単量体に由来する構成単位(C)、及び反応性界面活性剤に由来する構成単位(D)を含み、上記構成単位(B)の含有率が全構成単位〔但し、上記構成単位(D)を除く。〕に対して10質量%~25質量%であり、上記構成単位(C)の含有率が全構成単位〔但し、上記構成単位(D)を除く。〕に対して0.2質量%~6.0質量%であり、上記構成単位(D)の含有量が全構成単位〔但し、上記構成単位(D)を除く。〕100質量部に対して0.1質量部~1.0質量部であり、かつ、平均粒子径が5nm~160nmである(メタ)アクリル系樹脂粒子と、水と、を含む。
本開示の粘着剤組成物によれば、湿熱環境下でも高い粘着力を有し、耐水性に優れ、かつ、貼着面に対して垂直方向の荷重にも耐え得る粘着剤層を形成できる。
本開示の粘着剤組成物がこのような効果を奏し得る理由については明らかでないが、本発明者らは以下のように推測している。但し、以下の推測は、本開示の粘着剤組成物を限定的に解釈するものではなく、一例として説明するものである。
反応性界面活性剤に由来する構成単位を含む樹脂粒子を含有する粘着剤組成物を用いて形成された粘着剤層の表面には、反応性界面活性剤が存在する。このため、粘着剤層の表面が平滑性を有していても、粘着剤層に水が付着すると、反応性界面活性剤が水に溶解することで、粘着剤層に水が浸透する現象が生じ得る。これに対し、本開示の粘着剤組成物は、樹脂粒子に含まれる反応性界面活性剤に由来する構成単位の量が少ないため、形成される粘着剤層では、反応性界面活性剤の溶解に起因する水の浸透が抑制され、優れた耐水性が保持されると考えられる。
(メタ)アクリロニトリルに由来する構成単位を含む樹脂粒子を含有する粘着剤組成物を用いて形成された粘着剤層では、(メタ)アクリロニトリルがその構造に起因し、分極して存在する。(メタ)アクリロニトリルが分極すると、粘着剤層と基材との間、及び、粘着剤層と被着体との間に静電的な相互作用が生じ、粘着剤層と基材及び被着体との密着性が高まる。本開示の粘着剤組成物は、樹脂粒子が(メタ)アクリロニトリルに由来する構成単位を特定割合以上含むため、上記の相互作用がより効果的に生じると考えられる。このため、形成される粘着剤層は、湿熱環境下でも高い粘着力を有し、かつ、貼着面に対して垂直方向の荷重にも耐え得る。一方で、(メタ)アクリロニトリルは、親水性基であるシアノ基を有しているため、樹脂粒子が(メタ)アクリロニトリルに由来する構成単位を過剰に含むと、形成される粘着剤層の耐水性が損なわれやすい。これに対し、本開示の粘着剤組成物は、樹脂粒子に含まれる(メタ)アクリロニトリルに由来する構成単位が特定割合以下であるため、シアノ基が過多にならない。このため、形成される粘着剤層では、耐水性が損なわれ難く、優れた耐水性が保持されると考えられる。
本開示の粘着剤組成物に含まれる樹脂粒子は、平均粒子径が5nm以上であり、かつ、カルボキシ基を有する(メタ)アクリル系単量体に由来する構成単位を特定割合で含むことで、分散性に優れる。このため、本開示の粘着剤組成物は、上述の効果をより効果的に奏し得ると考えられる。
以上より、本開示の粘着剤組成物は、湿熱環境下でも高い粘着力を有し、耐水性に優れ、かつ、貼着面に対して垂直方向の荷重にも耐え得ると推測される。
本開示の粘着剤組成物は、(メタ)アクリル酸アルキルエステル単量体に由来する構成単位(A)、(メタ)アクリロニトリルに由来する構成単位(B)、カルボキシ基を有する(メタ)アクリル系単量体に由来する構成単位(C)、及び反応性界面活性剤に由来する構成単位(D)を含み、上記構成単位(B)の含有率が全構成単位〔但し、上記構成単位(D)を除く。〕に対して10質量%~25質量%であり、上記構成単位(C)の含有率が全構成単位〔但し、上記構成単位(D)を除く。〕に対して0.2質量%~6.0質量%であり、上記構成単位(D)の含有量が全構成単位〔但し、上記構成単位(D)を除く。〕100質量部に対して0.1質量部~1.0質量部であり、かつ、平均粒子径が5nm~160nmである(メタ)アクリル系樹脂粒子〔即ち、特定(メタ)アクリル系樹脂粒子〕を含む。本開示の粘着剤組成物において、特定(メタ)アクリル系樹脂粒子は、水を含む媒体中に分散している状態で存在している。
本開示の粘着剤組成物は、特定(メタ)アクリル系樹脂粒子を1種のみ含んでいてもよく、2種以上含んでいてもよい。
特定(メタ)アクリル系樹脂粒子は、(メタ)アクリル酸アルキルエステル単量体に由来する構成単位(A)を含む。
本開示において、「(メタ)アクリル酸アルキルエステル単量体に由来する構成単位」とは、(メタ)アクリル酸アルキルエステル単量体が付加重合して形成される構成単位を意味する。本開示における「(メタ)アクリル酸アルキルエステル単量体」には、後述するカルボキシ基を有する(メタ)アクリル系単量体に該当する単量体は、包含されない。
(メタ)アクリル酸アルキルエステル単量体は、アクリル酸アルキルエステル単量体であってもよく、メタクリル酸アルキルエステル単量体であってもよい。
(メタ)アクリル酸アルキルエステル単量体は、アルキル基が無置換であっても、置換されていてもよいが、アルキル基が無置換の(メタ)アクリル酸アルキルエステル単量体であることが好ましい。
(メタ)アクリル酸アルキルエステル単量体が有するアルキル基は、直鎖状、分岐鎖状、又は環状のいずれであってもよい。
(メタ)アクリル酸アルキルエステル単量体が有するアルキル基の炭素数は、特に限定されないが、例えば、1~18であることが好ましく、2~14であることがより好ましく、2~8あることが更に好ましい。
(メタ)アクリル酸アルキルエステル単量体としては、n-ブチルアクリレート(n-BA)、2-エチルヘキシルアクリレート(2EHA)、及びメチルメタクリレート(MMA)からなる群より選ばれる少なくとも1種が好ましく、n-ブチルアクリレート(n-BA)がより好ましい。
ここで、特定(メタ)アクリル系樹脂粒子における構成単位(A)の含有率が、特定(メタ)アクリル系樹脂粒子の全構成単位〔但し、構成単位(D)を除く。〕に対して50質量%以上であることは、構成単位(A)が、特定(メタ)アクリル系樹脂粒子を構成する構成単位の主成分として含まれていることを意味する。
特定(メタ)アクリル系樹脂粒子は、(メタ)アクリロニトリルに由来する構成単位(B)を含む。本開示において、「(メタ)アクリロニトリルに由来する構成単位」とは、(メタ)アクリロニトリルが付加重合して形成される構成単位を意味する。
特定(メタ)アクリル系樹脂粒子における構成単位(B)の含有率が、特定(メタ)アクリル系樹脂粒子の全構成単位〔但し、構成単位(D)を除く。〕に対して10質量%以上であると、形成される粘着剤層は、貼着面に対して垂直方向の荷重にも耐え得る傾向がある。理由としては、以下のことが考えられる。粘着剤層において(メタ)アクリロニトリルは、その構造に起因して、分極して存在すると推測される。(メタ)アクリロニトリルが分極することで、粘着剤層と基材との間、及び、粘着剤層と被着体との間に静電的な相互作用が生じ、粘着剤層と基材及び被着体との密着性が十分に高まるためと考えられる。このような観点から、特定(メタ)アクリル系樹脂粒子における構成単位(B)の含有率は、特定(メタ)アクリル系樹脂粒子の全構成単位〔但し、構成単位(D)を除く。〕に対して10質量%以上であり、15質量%以上であることが好ましく、20質量%以上であることがより好ましい。
特定(メタ)アクリル系樹脂粒子における構成単位(B)の含有率が、特定(メタ)アクリル系樹脂粒子の全構成単位〔但し、構成単位(D)を除く。〕に対して25質量%以下であると、形成される粘着剤層は、耐水性に優れる傾向がある。理由としては、以下のことが考えられる。形成される粘着剤層では、(メタ)アクリロニトリルに由来する親水性基であるシアノ基が過多にならないことで、耐水性が損なわれ難くなり、優れた耐水性が保持されるためと考えられる。
ある態様では、特定(メタ)アクリル系樹脂粒子における構成単位(B)の含有率は、特定(メタ)アクリル系樹脂粒子の全構成単位〔但し、構成単位(D)を除く。〕に対して15質量%~25質量%であってもよい。
特定(メタ)アクリル系樹脂粒子は、カルボキシ基を有する(メタ)アクリル系単量体に由来する構成単位(C)を含む。本開示において、「カルボキシ基を有する(メタ)アクリル系単量体に由来する構成単位」とは、カルボキシ基を有する(メタ)アクリル系単量体が付加重合して形成される構成単位を意味する。
カルボキシ基を有する(メタ)アクリル系単量体の具体例としては、メタクリル酸、アクリル酸、ω-カルボキシ-ポリカプロラクトンモノメタクリレート、及びω-カルボキシ-ポリカプロラクトンモノアクリレートが挙げられる。
カルボキシ基を有する(メタ)アクリル系単量体としては、アクリル酸が好ましい。
また、特定(メタ)アクリル系樹脂粒子の構成単位(C)に由来するカルボキシ基は、架橋剤との架橋反応に寄与するため、本開示の粘着剤組成物が架橋剤を含む場合に、特定(メタ)アクリル系樹脂粒子における構成単位(C)の含有率が、特定(メタ)アクリル系樹脂粒子の全構成単位〔但し、構成単位(D)を除く。〕に対して0.2質量%以上であると、形成される粘着剤層の凝集力が高まり、垂直方向の耐荷重性がより向上し得る。
特定(メタ)アクリル系樹脂粒子は、反応性界面活性剤に由来する構成単位(D)を含む。本開示において、「反応性界面活性剤」とは、エチレン性不飽和二重結合を有する界面活性剤を指す。また、本開示において、「反応性界面活性剤に由来する構成単位」とは、反応性界面活性剤が付加重合して形成される構成単位を意味する。
反応性界面活性剤は、アニオン型反応性界面活性剤であってもよく、ノニオン型反応性界面活性剤であってもよく、カチオン型反応性界面活性剤であってもよい。
反応性界面活性剤は、アニオン型反応性界面活性剤及びノニオン型反応性界面活性剤からなる群より選ばれる少なくとも1種であることが好ましく、アニオン型反応性界面活性剤から選ばれる少なくとも1種とノニオン型反応性界面活性剤から選ばれる少なくとも1種との組み合わせであることがより好ましい。
オキシアルキレン基の具体例としては、オキシエチレン基、オキシプロピレン基、及びオキシブチレン基が挙げられる。
オキシアルキレン基としては、例えば、単量体との反応性が高いとの観点から、オキシエチレン基が好ましい。
オキシアルキレン基の平均付加モル数は、例えば、特定(メタ)アクリル系樹脂粒子の分散性の観点から、5~50であることが好ましく、5~40であることがより好ましく、10~30であることが更に好ましい。
エチレン性不飽和二重結合を有する基の具体例としては、(メタ)アクリロイル基、ビニル基、アリル基、イソプロペニル基、1-プロペニル基、アリルオキシ基、及びスチリル基が挙げられる。
エチレン性不飽和二重結合を有する基としては、例えば、単量体との反応性が高いとの観点から、1-プロペニル基又はアリル基が好ましい。
アニオン型反応性界面活性剤の市販品の例としては、第一工業製薬(株)製の「アクアロン KH-05」[有効成分:ポリオキシエチレン-1-(アリルオキシメチル)アルキルエーテル硫酸エステルアンモニウム〔オキシアルキレン基の種類:オキシエチレン基、平均付加モル数:5〕、有効成分濃度:99質量%]、「アクアロン KH-10」[有効成分:ポリオキシエチレン-1-(アリルオキシメチル)アルキルエーテル硫酸エステルアンモニウム〔オキシアルキレン基の種類:オキシエチレン基、平均付加モル数:10〕、有効成分濃度:99質量%]、「アクアロン AR-10」[有効成分:ポリオキシエチレンスチレン化プロペニルフェニルエーテル硫酸エステルアンモニウム〔オキシアルキレン基の種類:オキシエチレン基、平均付加モル数:10〕、有効成分濃度:99質量%]、「アクアロン HS-10」[有効成分:ポリオキシエチレンノニルプロペニルフェニルエーテル硫酸エステルアンモニウム〔オキシアルキレン基の種類:オキシエチレン基、平均付加モル数:10〕、有効成分濃度:99質量%]、「アクアロン BC-10」[有効成分:ポリオキシエチレンノニルプロペニルフェニルエーテル硫酸エステルアンモニウム〔オキシアルキレン基の種類:オキシエチレン基、平均付加モル数:10〕、有効成分濃度:99質量%]、「アクアロン AR-20」[有効成分:ポリオキシエチレンスチレン化プロペニルフェニルエーテル硫酸エステルアンモニウム〔オキシアルキレン基の種類:オキシエチレン基、平均付加モル数:20〕、有効成分濃度:99質量%]、及び「アクアロン BC-20」[有効成分:ポリオキシエチレンノニルプロペニルフェニルエーテル硫酸エステルアンモニウム〔オキシアルキレン基の種類:オキシエチレン基、平均付加モル数:20〕、有効成分濃度:99質量%]、並びに、(株)ADEKA製の「アデカリアソープ SR-10」[有効成分:ポリオキシエチレン-1-(アリルオキシメチル)アルキルエーテル硫酸エステルアンモニウム〔オキシアルキレン基の種類:オキシエチレン基、平均付加モル数:10〕、有効成分濃度:100質量%]、「アデカリアソープ SR-20」[有効成分:ポリオキシエチレン-1-(アリルオキシメチル)アルキルエーテル硫酸エステルアンモニウム〔オキシアルキレン基の種類:オキシエチレン基、平均付加モル数:20〕、有効成分濃度:100質量%]、及び「アデカリアソープ SR-3025」[有効成分:ポリオキシエチレン-1-(アリルオキシメチル)アルキルエーテル硫酸エステルアンモニウム〔オキシアルキレン基の種類:オキシエチレン基、平均付加モル数:30〕、有効成分濃度:25質量%]が挙げられる。
上記「アクアロン」及び「アデカリアソープ」は、いずれも登録商標である。
特定(メタ)アクリル系樹脂粒子における構成単位(D)の含有量が、特定(メタ)アクリル系樹脂粒子の全構成単位〔但し、構成単位(D)を除く。〕100質量部に対して0.1質量部以上であると、乳化重合により特定(メタ)アクリル系樹脂粒子を製造できる。特定(メタ)アクリル系樹脂粒子における構成単位(D)の含有量は、特定(メタ)アクリル系樹脂粒子の全構成単位〔但し、構成単位(D)を除く。〕100質量部に対して、0.2質量部以上であることが好ましく、0.3質量部以上であることがより好ましく、0.5質量部以上であることが更に好ましい。
本開示の粘着剤組成物により粘着剤層を形成すると、構成単位(D)は、粘着剤層の表面に存在し得る。このため、例えば、粘着剤層に水が付着すると、反応性界面活性剤が水に溶解することで、粘着剤層に水が浸透する現象が生じ得る。これに対し、特定(メタ)アクリル系樹脂粒子における構成単位(D)の含有量が、特定(メタ)アクリル系樹脂粒子の全構成単位〔但し、構成単位(D)を除く。〕100質量部に対して1.0質量部以下であると、反応性界面活性剤の溶解に起因する粘着剤層への水の浸透が抑制されるため、粘着剤層の優れた耐水性が保持される。このような観点から、特定(メタ)アクリル系樹脂粒子における構成単位(D)の含有量は、特定(メタ)アクリル系樹脂粒子の全構成単位〔但し、構成単位(D)を除く。〕100質量部に対して、1.0質量部以下であり、0.9質量部以下であることが好ましく、0.8質量部以下であることがより好ましく、0.6質量部以下であることが更に好ましい。
特定(メタ)アクリル系樹脂粒子は、水酸基を有する(メタ)アクリルアミドに由来する構成単位を含まないか、又は、水酸基を有する(メタ)アクリルアミドに由来する構成単位の含有率が特定(メタ)アクリル系樹脂粒子の全構成単位〔但し、構成単位(D)を除く。〕に対して0質量%を超えて0.1質量%未満の範囲であることが好ましく、水酸基を有する(メタ)アクリルアミドに由来する構成単位を含まないか、又は、水酸基を有する(メタ)アクリルアミドに由来する構成単位の含有率が特定(メタ)アクリル系樹脂粒子の全構成単位〔但し、構成単位(D)を除く。〕に対して0質量%を超えて0.05質量%以下の範囲であることがより好ましく、水酸基を有する(メタ)アクリルアミドに由来する構成単位を含まないことが更に好ましい。本開示において、「水酸基を有する(メタ)アクリルアミドに由来する構成単位」とは、水酸基を有する(メタ)アクリルアミドが付加重合して形成される構成単位を意味する。
水酸基を有する(メタ)アクリルアミドの具体例としては、N-ヒドロキシメチルアクリルアミド、N-ヒドロキシメチルメタクリルアミド、N-(2-ヒドロキシエチル)アクリルアミド、N-(2-ヒドロキシエチル)メタクリルアミド、2,3-ジヒドロキシプロピルアクリルアミド、及び2,3-ジヒドロキシプロピルメタクリルアミドが挙げられる。
特定(メタ)アクリル系樹脂粒子は、本開示の粘着剤組成物の効果を損なわない範囲において、必要に応じて、既述の構成単位以外の構成単位(所謂、その他の構成単位)を含んでいてもよい。
特定(メタ)アクリル系樹脂粒子の形状は、特に限定されないが、球状であることが好ましい。本開示でいう「球状」には、真球状のみならず、略球状も包含される。
特定(メタ)アクリル系樹脂粒子の平均粒子径は、5nm~160nmである。
特定(メタ)アクリル系樹脂粒子の平均粒子径は、特定(メタ)アクリル系樹脂粒子の製造適性の観点から、5nm以上であり、10nm以上であることが好ましく、20nm以上であることがより好ましく、30nm以上であることが更に好ましい。
特定(メタ)アクリル系樹脂粒子の平均粒子径が160nm以下であると、耐水性に優れる粘着剤層を形成できる傾向がある。理由としては、以下のことが考えられる。特定(メタ)アクリル系樹脂粒子は、平均粒子径が160nm以下と比較的小粒子径であるため、粘着剤組成物の塗布膜の乾燥工程中に、密に並ぶ傾向がある。特定(メタ)アクリル系樹脂粒子が密に並ぶことで、形成される粘着剤層は、表面の平滑性が高まり、水が浸透し難くなると考えられる。このような観点から、特定(メタ)アクリル系樹脂粒子の平均粒子径は、160nm以下であり、150nm以下であることが好ましく、130nm以下であることがより好ましく、110nm以下であることが更に好ましい。
ある態様では、特定(メタ)アクリル系樹脂粒子の平均粒子径は、30nm~160nmであってもよい。
また、特定(メタ)アクリル系樹脂粒子の粒子径は、例えば、重合反応溶液中に含まれる成分の分散状態が異なるように反応場の分散条件(例:撹拌速度)を変更することによっても調整できる。
特定(メタ)アクリル系樹脂粒子の平均粒子径は、レーザ回折式粒子径分布測定装置を用い、下記の方法により測定される値である。
特定(メタ)アクリル系樹脂粒子を蒸留水で希釈し、十分に撹拌混合した後、10mm×75mm×85mmのガラスセル中にパスツールピペットを用いて採取し、これをレーザ回折式粒子径分布測定装置にセットする。レーザ光の透過率が85%となるように特定(メタ)アクリル系樹脂粒子の希釈液の濃度を調整した後、測定温度25℃の条件で粒子径分布を測定する。測定結果をコンピュータ処理することにより、特定(メタ)アクリル系樹脂粒子の体積平均粒子径を求める。具体的には、得られた粒子径分布における積算値50%(体積基準)での粒子径を体積平均粒子径とする。
レーザ回折式粒子径分布測定装置としては、例えば、(株)堀場製作所製の「Laser Scattering Particle Size Distribution Analyzer LA-960」を好適に使用できる。但し、レーザ回折式粒子径分布測定装置は、これに限定されない。
特定(メタ)アクリル系樹脂粒子のガラス転移温度(以下、「Tg」ともいう。)は、特に限定されないが、例えば、-70℃~30℃であることが好ましく、-65℃~25℃であることがより好ましく、-60℃~20℃であることが更に好ましい。
特定(メタ)アクリル系樹脂粒子のガラス転移温度が-70℃以上であると、形成される粘着剤層が被着体に対して適度な濡れ性を示す傾向がある。
特定(メタ)アクリル系樹脂粒子のガラス転移温度が30℃以下であると、被着体から剥離した際のジッピングが起こり難い傾向がある。
剥離紙上に、特定(メタ)アクリル系樹脂粒子の水分散液を、4ミル(101.6μm)のアプリケーターを用いて塗布する。次いで、塗布した特定(メタ)アクリル系樹脂粒子の水分散液を乾燥(乾燥温度:105℃、乾燥時間:10分間)させ、特定(メタ)アクリル系樹脂粒子の乾燥物を得る。この乾燥物10mgをアルミ製のサンプルパン〔例えば、TA Instrument(株)製のTzero Pan(商品名)〕に詰め、アルミ製の蓋〔例えば、TA Instrument(株)製のTzero Hermetic Lid(商品名)〕で封をした後、示差走査熱量計を用いて、以下の測定条件により、ガラス転移温度を測定する。なお、本測定では、得られたDSCカーブにおける、低温側のベースラインを高温側に延長した直線と、ガラス転移の階段状変化部分の曲線の勾配が最大になるような点で引いた接線と、の交点の温度をカラス転移温度とする。
示差走査熱量計としては、例えば、ティー・エイ・インスツルメント・ジャパン(株)製の示差走査熱量計(商品名:Discovery DSC 2500)を用いることができる。但し、示差走査熱量計は、これに限定されない。
雰囲気条件:大気下
測定温度範囲:-90℃~100℃
昇温速度:10℃/分
標準物質:空のサンプルパン
特定(メタ)アクリル系樹脂粒子のゲル分率は、特に限定されないが、例えば、10質量%~70質量%であることが好ましく、12質量%~68質量%であることがより好ましく、15質量%~65質量%であることが更に好ましい。
[1]特定(メタ)アクリル系樹脂粒子の水分散液にアンモニア水を添加してpHを8.5(液温25℃)に調整した後、厚さ100μmのポリエチレンテレフタレート(PET)製の剥離フィルム上に塗布し、塗布膜を形成する。次いで、形成した塗布膜を105℃で2分間乾燥させることにより、剥離フィルム付き樹脂膜を得る。
[2]得られた剥離フィルム付き樹脂膜を75mm×75mmの大きさに切り出す。切り出した剥離フィルム付き樹脂膜が備える樹脂膜の重さは、0.2g程度となる。
[3]250メッシュ(線径:0.03mm、目開き:72μm)のステンレス製の金網を準備し、この金網を100mm×100mmの大きさに切り出す。なお、金網の端部の解れは、測定誤差の原因となるため、予め取り除く。
[4]切り出した金網を、酢酸エチルを用いて脱脂した後、乾燥させる。乾燥後の金網は、デシケーター内に保管する。
[5]金網の質量を正確に測定する。測定した金網の質量をA(単位:g)とする。
[6]金網の中央に、75mm×75mmの大きさに切り出した上記[2]の剥離フィルム付き樹脂膜を貼り付けた後、樹脂膜から剥離フィルムを剥がし取り、樹脂膜付き金網を得る。なお、樹脂膜の金網への貼り付けは、後述の[7]~[9]の工程により金網を折り畳んだ後の面内に、樹脂膜が配置されるように行う。
[7]樹脂膜付き金網を、樹脂膜を内側にして半分に折り畳む。具体的には、樹脂膜付き金網の奥側の辺が手前側の辺に重なるように、樹脂膜付き金網を折り畳む。
[8]半分に折った樹脂膜付き金網の手前側(2辺が重なっている側)3分の1を奥側に折り畳んだ後、奥側3分の1を手前側に折り畳む。この時点で、樹脂膜付き金網は、当初の大きさ(100mm)から、縦方向に6分の1の大きさに折り畳まれており、横方向には折り畳まれていない状態となっている。
[9]上記[8]で折り畳まれた樹脂膜付き金網の長手方向の左側3分の1を右側に折り畳んだ後、右側3分の1を左側に折り畳む。これを試料X1とする。試料X1は、当初の大きさ(100mm)から、縦方向に6分の1の大きさに折り畳まれており、横方向に3分の1の大きさに折り畳まれている。
[10]試料X1の質量を、精密天秤を用いて正確に測定する。この質量をB(単位:g)とする。
[11]試料X1の折り目が開かないように、折り目をホッチキスで留める。これを試料X2とする。試料X2は、1サンプルあたり2個作製する。
[12]試料X2の質量を、精密天秤を用いて正確に測定する。この質量をC(単位:g)とする。
[13]試料X2を、酢酸エチル80gを入れたガラス瓶に入れ、蓋をする。
[14]試料X2を入れたガラス瓶を雰囲気温度23℃、50%RHの環境下に3日間放置する。
[15]試料X2をガラス瓶から取り出し、少量の酢酸エチルを用いて洗浄する。
[16]試料X2を、乾燥温度100℃、乾燥時間24時間の条件で乾燥させる。この乾燥後の試料X2の質量を、精密天秤を用いて正確に測定する。この質量をD(単位:g)とする。
[17]下記式によりゲル分率を計算し、得られた値を算術平均する。
ゲル分率[質量%]=(D-(A+(C-B)))/(B-A)×100
本開示の粘着剤組成物における特定(メタ)アクリル系樹脂粒子の含有率は、特に限定されないが、例えば、粘着剤組成物中の全固形分量に対して、80質量%~100質量%であることが好ましく、85質量%~100質量%であることがより好ましく、90質量%~100質量%であることが更に好ましい。
本開示の粘着剤組成物は、さらに、架橋剤を含むことが好ましい。
特定(メタ)アクリル系樹脂粒子の構成単位(C)に由来するカルボキシ基は、架橋剤との架橋反応に寄与する。このため、本開示の粘着剤組成物が架橋剤を含むと、形成される粘着剤層の凝集力が高まり、垂直方向の耐荷重性がより向上し得る。
架橋剤としては、例えば、カルボジイミド系架橋剤、オキサゾリン系架橋剤、ヒドラジド系架橋剤、エポキシ系架橋剤、及びイソシアネート系架橋剤が挙げられる。
また、カルボジイミド系架橋剤の市販品の例としては、日清紡ケミカル(株)製の「カルボジライト(登録商標) V-02」、「カルボジライト(登録商標) V-02-L2」、「カルボジライト(登録商標) SV-02」、「カルボジライト(登録商標) V-04」、「カルボジライト(登録商標) V-10」、「カルボジライト(登録商標) E-02」、及び「カルボジライト(登録商標) E-05」が挙げられる。
オキサゾリン系架橋剤の具体例としては、2-ビニル-2-オキサゾリン、5-メチル-2-ビニル-2-オキサゾリン、4,4-ジメチル-2-ビニル-2-オキサゾリン、2-イソプロペニル-2-オキサゾリン、4,4-ジメチル-2-イソプロペニル-2-オキサゾリン、4-アクリロイル-オキシメチル-2,4-ジメチル-2-オキサゾリン、4-メタクリロイルオキシメチル-2,4-ジメチル-2-オキサゾリン、4-メタクリロイルオキシメチル-2-フェニル-4-メチル-2-オキサゾリン、2-(4-ビニルフェニル)-4,4-ジメチル-2-オキサゾリン、4-エチル-4-ヒドロキシメチル-2-イソプロペニル-2-オキサゾリン、及び4-エチル-4-カルボエトキシメチル-2-イソプロペニル-2-オキサゾリン、並びに、これらの化合物に由来する構成単位を含むポリマー組成物が挙げられる。
また、オキサゾリン系架橋剤の市販品の例としては、(株)日本触媒製の「エポクロス(登録商標) WS-300」、「エポクロス(登録商標) WS-500」、及び「エポクロス(登録商標) WS-700」が挙げられる。
また、架橋剤の含有量は、特定(メタ)アクリル系樹脂粒子100質量部に対して、10質量部以下であることが好ましく、8質量部以下であることがより好ましく、5質量部以下であることが更に好ましい。本開示の粘着剤組成物における架橋剤の含有量が、アクリル樹脂100質量部に対して10質量部以下であると、形成される粘着剤層がより高い粘着力を有する傾向がある。
ある態様では、架橋剤の含有量は、特定(メタ)アクリル系樹脂粒子100質量部に対して、1質量部~5質量部であってもよく、3質量部~5質量部であってもよい。
本開示の粘着剤組成物は、水を含む。
水は、特に限定されないが、例えば、不純物が少ないとの観点から、蒸留水、イオン交換水、純水等が好ましい。
本開示の粘着剤組成物は、その効果を損なわない範囲において、必要に応じて、水以外の水性媒体を含んでいてもよい。
水以外の水性媒体としては、例えば、水混和性の有機溶剤が挙げられる。
水混和性の有機溶剤としては、例えば、メタノール、エタノール、プロパノール、イソプロパノール等の一価アルコール化合物;グリセリン、エチレングリコール、ジエチレングリコール、プロピレングリコール等の多価アルコール化合物;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル等のグリコール誘導体;などの有機溶剤が挙げられる。
本開示の粘着剤組成物は、水非混和性の有機溶剤を含まないか、又は、水非混和性の有機溶剤の含有率が粘着剤組成物の全質量に対して0質量%を超えて5質量%以下の範囲であることが好ましく、水非混和性の有機溶剤を含まないか、又は、水非混和性の有機溶剤の含有率が粘着剤組成物の全質量に対して0質量%を超えて3質量%以下の範囲であることがより好ましく、水非混和性の有機溶剤を含まないか、又は、水非混和性の有機溶剤の含有率が粘着剤組成物の全質量に対して0質量%を超えて1質量%以下の範囲であることが更に好ましく、水非混和性の有機溶剤を含まないか、又は、水非混和性の有機溶剤の含有率が粘着剤組成物の全質量に対して0質量%を超えて0.5質量%以下の範囲であることが特に好ましい。
本開示の粘着剤組成物は、その効果を損なわない範囲において、必要に応じて、既述した成分以外の成分(所謂、その他の成分)を含んでいてもよい。
その他の成分としては、特定(メタ)アクリル系樹脂粒子以外の樹脂粒子、酸化防止剤、帯電防止剤、導電性付与剤、pH調整剤、消泡剤、湿潤剤、増粘剤、充填剤、顔料、可塑剤等の各種添加剤が挙げられる。
本開示の粘着剤組成物のpHは、例えば、粘着剤組成物中における特定(メタ)アクリル系樹脂粒子の分散性の観点から、2~10であることが好ましい。
本開示の粘着剤組成物のpHの測定方法は、特に限定されない。
本開示の粘着剤組成物のpHは、pHメータを用い、JIS Z 8802:2011に準拠した方法により、液温25℃の条件にて測定した値を採用する。測定装置としては、例えば、(株)堀場製作所製のpHメータ(商品名:F-51)を用いることができる。但し、測定装置は、これに限定されない。
本開示の粘着剤組成物の製造方法は、既述の本開示の粘着剤組成物を製造できれば、特に限定されない。本開示の粘着剤組成物は、例えば、特定(メタ)アクリル系樹脂粒子を乳化重合法により製造する工程を含む方法により製造することが好ましい。
[2]温度計、撹拌機、原料導入管、還流冷却器、窒素導入管等を備えた反応器内に、少なくとも、反応性界面活性剤と水とを仕込み、窒素気流下で撹拌しながら昇温させた後、単量体成分を滴下し、適宜、重合開始剤、還元剤等を加えて、乳化重合反応を進行させる方法(所謂、モノマー滴下法)
[3]温度計、撹拌機、原料導入管、還流冷却器、窒素導入管等を備えた反応器内に、水及び反応性界面活性剤を仕込み、窒素気流下で撹拌しながら昇温させた後、適宜、重合開始剤、還元剤等を加える。一方、別の容器において、単量体成分を予め、少なくとも、反応性界面活性剤と水とを用いて乳化させ、単量体成分及び反応性界面活性剤を含む混合物の乳化物を調製する。次いで、単量体成分及び反応性界面活性剤を含む混合物の乳化物を、上記反応器内に滴下し、適宜、重合開始剤、還元剤等を加えて、乳化重合反応を進行させる方法(所謂、乳化モノマー滴下法)
これらの中でも、特定(メタ)アクリル系樹脂粒子を製造するための乳化重合法としては、例えば、工業的生産性の観点から、上記[3]の乳化モノマー滴下法が好ましい。
例えば、特定(メタ)アクリル系樹脂粒子を製造するための乳化重合法として、上記[3]の乳化モノマー滴下法を採用した場合には、以下の操作を行う。
温度計、撹拌機、原料導入管、還流冷却器、窒素導入管等を備えた反応器内に、水及び反応性界面活性剤を仕込み、窒素気流下で撹拌しながら昇温させた後、適宜、重合開始剤、還元剤等を加える。一方、別の容器において、単量体成分を予め、少なくとも、反応性界面活性剤と連鎖移動剤と水とを用いて乳化させ、単量体成分及び反応性界面活性剤を含む混合物の乳化物を調製する。次いで、単量体成分及び反応性界面活性剤を含む混合物の乳化物を、上記反応器内に滴下し、適宜、重合開始剤、還元剤等を加えて、乳化重合反応を進行させる
(メタ)アクリル酸アルキルエステル単量体の使用量は、特に限定されないが、例えば、単量体の合計100質量部に対して、50質量部~89.8質量部であることが好ましく、55質量部~89.8質量部であることがより好ましく、60質量部~89.8質量部であることが更に好ましく、65質量部~89.8質量部であることが特に好ましい。
(メタ)アクリロニトリルの使用量は、単量体の合計100質量部に対して10質量部~25質量部である。(メタ)アクリロニトリルの使用量の下限は、単量体の合計100質量部に対して、15質量部以上であることが好ましく、20質量部以上であることがより好ましい。
カルボキシ基を有する(メタ)アクリル系単量体の使用量は、単量体の合計100質量部に対して、0.2質量部~6.0質量部であり、0.5質量部~6.0質量部であることが好ましく、1.0質量部~6.0質量部であることがより好ましく、2.0質量部~6.0質量部であることが更に好ましい。
反応性界面活性剤の使用量は、単量体の合計100質量部に対して0.1質量部~1.0質量部である。反応性界面活性剤の使用量の下限は、単量体の合計100質量部に対して、0.2質量部以上であることが好ましく、0.3質量部以上であることがより好ましく、0.5質量部以上であることが更に好ましい。反応性界面活性剤の使用量の上限は、単量体の合計100質量部に対して、0.9質量部以下であることが好ましく、0.8質量部以下であることがより好ましく、0.6質量部以下であることが更に好ましい。
連鎖移動剤としては、例えば、シアノ酢酸、シアノ酢酸の炭素数1~8のアルキルエステル化合物、ブロモ酢酸、ブロモ酢酸の炭素数1~8のアルキルエステル化合物、α-メチルスチレン、アントラセン、フェナントレン、フルオレン、及び9-フェニルフルオレンに代表される芳香族化合物、p-ニトロアニリン、ニトロベンゼン、ジニトロベンゼン、p-ニトロ安息香酸、p-ニトロフェノール、及びp-ニトロトルエンに代表される芳香族ニトロ化合物、ベンゾキノン及び2,3,5,6-テトラメチル-p-ベンゾキノンに代表されるベンゾキノン誘導体、トリブチルボランに代表されるボラン誘導体、四臭化炭素、四塩化炭素、1,1,2,2-テトラブロモエタン、トリブロモエチレン、トリクロロエチレン、ブロモトリクロロメタン、トリブロモメタン、及び3-クロロ-1-プロペンに代表されるハロゲン化炭化水素化合物、クロラール及びフラルデヒドに代表されるアルデヒド化合物、炭素数1~18のアルキルメルカプタン化合物、チオフェノール及びトルエンメルカプタンに代表される芳香族メルカプタン化合物、メルカプト酢酸、メルカプト酢酸の炭素数1~10のアルキルエステル化合物、炭素数1~12のヒドロキシアルキルメルカプタン化合物、並びに、ピネン及びターピノレンに代表されるテルペン化合物が挙げられる。
連鎖移動剤の使用量は、例えば、単量体の合計100質量部に対して0.01質量部~0.05質量部であることが好ましい。
重合開始剤としては、例えば、過硫酸塩、有機過酸化物及びアゾ化合物が挙げられる。
過硫酸塩の具体例としては、過硫酸アンモニウム、過硫酸ナトリウム、及び過硫酸カリウムが挙げられる。
有機過酸化物の具体例としては、t-ブチルヒドロペルオキシド、ベンゾイルペルオキシド、ラウロイルペルオキシド、カプロイルペルオキシド、ジ-i-プロピルペルオキシジカルボナート、ジ-2-エチルヘキシルペルオキシジカルボナート、及びt-ブチルペルオキシピバレートが挙げられる。
アゾ化合物の具体例としては、2,2’-アゾビスイソブチロニトリル、2,2’-アゾビス(2,4-ジメチルバレロニトリル)、2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)、1,1’-アゾビス(シクロヘキサン-1-カルボニトリル)、及び2,2’-アゾビス(イソ酪酸)ジメチルが挙げられる。
重合開始剤の使用量は、例えば、単量体の合計100質量部に対して0.2質量部~5.0質量部であることが好ましい。
還元剤としては、例えば、メタ重亜硫酸ナトリウム、亜硫酸ナトリウム、亜硫酸水素ナトリウム、ピロ亜硫酸ナトリウム(「二亜硫酸ナトリウム」ともいう。)、ヒドロキシメタンスルフィン酸ナトリウム、ピロリン酸ナトリウム、チオグリコール酸、チオ硫酸ナトリウム、二酸化チオ尿素、L-アスコルビン酸、酒石酸、クエン酸、及びブドウ糖が挙げられる。
還元剤の使用量は、例えば、単量体の合計100質量部に対して0.2質量部~5.0質量部であることが好ましい。
重合時間は、例えば、1時間~5時間であることが好ましい。
特定(メタ)アクリル系樹脂粒子を含む分散液のpHは、粘着剤組成物中における特定(メタ)アクリル系樹脂粒子の分散性の観点から、2~10に調整することが好ましい。
特定(メタ)アクリル系樹脂粒子を含む分散液のpHを調整する方法は、特に限定されず、例えば、pH調整剤を用いる方法が挙げられる。
pH調整剤としては、例えば、アンモニア水を好適に使用できる。
他の工程としては、例えば、特定(メタ)アクリル系樹脂粒子を含む分散液と、本開示の粘着剤組成物の任意成分である架橋剤及びその他の添加剤と、を混合する工程が挙げられる。
本開示の粘着剤層は、既述の本開示の粘着剤組成物により形成され、(メタ)アクリル酸アルキルエステル単量体に由来する構成単位(A)と、(メタ)アクリロニトリルに由来する構成単位(B)と、カルボキシ基を有する(メタ)アクリル系単量体に由来する構成単位(C)と、反応性界面活性剤に由来する構成単位(D)と、を含み、上記構成単位(B)の含有率が全構成単位〔但し、上記構成単位(D)を除く。〕に対して10質量%~25質量%であり、上記構成単位(C)の含有率が全構成単位〔但し、上記構成単位(D)を除く。〕に対して0.2質量%~6.0質量%であり、上記構成単位(D)の含有量が全構成単位〔但し、上記構成単位(D)を除く。〕100質量部に対して0.1質量部~1.0質量部である(メタ)アクリル系樹脂を含む。
本開示の粘着剤層の厚さは、一般には1μm~300μmであり、5μm~200μmであることが好ましく、10μm~100μmであることがより好ましい。
粘着剤層の平均厚さは、以下の方法により求められる値である。
粘着剤層の厚み方向において無作為に選択した10箇所の厚さを、膜厚計を用いて測定する。測定値の算術平均値を求め、得られた値を粘着剤層の平均厚さとする。
本開示の粘着剤層の形成方法は、特に限定されない。
本開示の粘着剤層は、例えば、以下の方法により形成できる。
支持体(例えば、基材及び剥離シート)上に、本開示の粘着剤組成物を塗布し、塗布膜を形成する。次いで、形成した塗布膜を乾燥させることにより、粘着剤層を形成する。
粘着剤組成物の塗布方法としては、例えば、グラビアロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、ナイフコーター、スプレーコーター、バーコーター、アプリケーター等を用いる公知の方法が挙げられる。
粘着剤組成物の塗布量は、特に限定されず、例えば、形成する粘着剤層の厚さに応じて、適宜設定される。
塗布膜の乾燥方法としては、例えば、自然乾燥、加熱乾燥、熱風乾燥、真空乾燥等の方法が挙げられる。
塗布膜の乾燥温度及び乾燥時間は、特に限定されず、塗布膜の厚さ、塗布膜中に含まれる水の量等に応じて、適宜設定される。
乾燥条件の一例としては、熱風循環乾燥機を用いて、70℃~120℃で30秒間~180秒間乾燥させる条件が挙げられる。
本開示の粘着シートは、本開示の粘着剤層を備える。
本開示の粘着シートは、既述の本開示の粘着剤層を備えるため、湿熱環境下でも高い粘着力を有し、耐水性に優れ、かつ、貼着面に対して垂直方向の荷重にも耐え得る。このため、本開示の粘着シートは、浴室、洗面所、台所、トイレ等の水回りでの使用に好適であり、特に、これらの水回りに設置された家具の天板、天井等に貼付される粘着シートとして好適である。
本開示の粘着シートが、基材を有しない無基材タイプの粘着シートである場合、又は、基材の片面に粘着剤層を備える有基材タイプの粘着シートである場合、本開示の粘着シートにおいて、露出した粘着剤層の面は、剥離シートによって保護されていてもよい。
剥離シートとしては、例えば、片面又は両面に剥離処理剤による表面処理(所謂、易剥離処理)が施された樹脂フィルム、紙、合成紙、及びこれらの2種以上を積層した複合シートが挙げられる。本開示では、樹脂フィルムの片面又は両面に剥離処理剤による表面処理(所謂、易剥離処理)が施された態様の剥離シートを「剥離フィルム」ともいう。
剥離処理剤としては、例えば、シリコーン系剥離処理剤(例:シリコーン)、ワックス系剥離処理剤(例:パラフィンワックス)、及びフッ素系剥離処理剤(例:フッ素系樹脂)が挙げられる。
樹脂フィルムとしては、例えば、ポリエチレンテレフタレート(PET)フィルムに代表されるポリエステルフィルムが挙げられる。
紙としては、例えば、上質紙及びコート紙が挙げられる。
剥離シートの膜厚は、特に限定されず、一般的には、20μm~180μmである。
剥離シートは、粘着テープを実用に供するまでの間、粘着剤層の表面を保護し、使用時に剥離される。
基材としては、例えば、ポリオレフィン系樹脂〔例えば、ポリエチレン(PE)及びポリプロピレン(PP)〕、ポリエステル系樹脂〔例えば、ポリエチレンテレフタレート(PET)〕、アセテート系樹脂(例えば、トリアセチルセルロース樹脂)、ポリエーテルサルホン系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリウレタン系樹脂、アクリル系樹脂、塩化ビニル系樹脂、ABS(Acrylonitrile Butadiene Styrene)樹脂、フッ素系樹脂等の樹脂を含むフィルム、紙(例えば、上質紙及びコート紙)、合成紙、及びこれらの2種以上を積層した複合シートが挙げられる。
基材は、一部又は全体に、模様が施されていてもよい。
基材の平均厚さは、以下の方法により求められる値である。
基材の厚み方向において無作為に選択した10箇所の厚さを、膜厚計を用いて測定する。測定値の算術平均値を求め、得られた値を基材の平均厚さとする。
本開示の粘着シートの作製方法は、特に限定されない。
本開示の粘着シートは、公知の方法により作製できる。
本開示の粘着シートを作製する方法としては、例えば、以下の方法が挙げられる。
本開示の粘着剤組成物を剥離シートの易剥離処理面に塗布することにより、剥離シート上に塗布膜を形成する。次いで、形成した塗布膜を乾燥させることにより、剥離シート上に粘着剤層を形成する。次いで、形成した粘着剤層の露出した面を、基材の易接着処理面に重ねて貼り合わせることにより、基材/粘着剤層/剥離シートの積層構造を有する、有基材タイプの粘着シートを作製できる。
〔製造例A-1〕
n-ブチルアクリレート(n-BA)〔アクリル酸アルキルエステル単量体〕85.2質量部(340.8g)、アクリロニトリル(AN)10.0質量部(40.0g)及びアクリル酸(AA)〔カルボキシ基を有するアクリル系単量体〕4.8質量部(19.2g)を混合し、単量体混合物を調製した。調製した単量体混合物に、アニオン型反応性界面活性剤であるアクアロン(登録商標)AR-10〔商品名、第一工業製薬(株)製〕0.16質量部[有効成分換算値](0.63g)、アニオン型反応性界面活性剤であるアデカリアソープ(登録商標)ER-30〔商品名、ADEKA社製〕0.25質量部[有効成分換算値](1.5g)、N-ドデシルメルカプタン〔連鎖移動剤〕0.025質量部(0.10g)及びイオン交換水77.8質量部(311.7g)を加えて撹拌することにより、単量体成分及び反応性界面活性剤を含む混合物の乳化物Xを調製した。
次に、温度計、撹拌機、逐次滴下装置、還流冷却管及び窒素導入管を備えた反応器に、イオン交換水33.1質量部(132.7g)、及びアニオン型反応性界面活性剤であるアクアロン(登録商標)AR-10〔商品名、第一工業製薬(株)製〕0.09質量部[有効成分換算値](0.36g)を仕込み、窒素を封入した後、内温を80℃まで昇温させた。反応器の内温を80℃に保ちながら、4質量%濃度の過硫酸アンモニウム水溶液〔重合開始剤〕0.10質量部[固形分換算値](10.1g)、及び4質量%濃度のピロ亜硫酸ナトリウム水溶液〔還元剤〕0.10質量部[固形分換算値](10.1g)を添加し、直ちに、先に調製した乳化物Xを、連続的に3時間滴下して乳化重合させた。また、この操作と並行して、反応器内に、4質量%濃度の過硫酸アンモニウム水溶液〔重合開始剤〕0.56質量部[固形分換算値](56.9g)及び4質量%濃度のピロ亜硫酸ナトリウム水溶液〔還元剤〕0.56質量部[固形分換算値](56.9g)を滴下した。滴下終了後、得られた乳化重合物に、6.9質量%濃度のt-ブチルヒドロペルオキシド水溶液〔重合開始剤〕0.07質量部[有効成分換算値](4.1g)、及び6.9質量%濃度のテックライト〔商品名、有効成分:二酸化チオ尿素、有効成分濃度:100質量%、(株)ADEKA製、還元剤〕0.07質量部[有効成分換算値](4.1g)を添加し、80℃で2時間熟成させてから室温まで冷却した。冷却後、アンモニア水を添加してpHが2~5の範囲になるように調整を行った。pH調整後、イオン交換水を添加して濃度を調整し、(メタ)アクリル系樹脂粒子A-1の水分散液を得た。
得られた(メタ)アクリル系樹脂粒子A-1の水分散液は、固形分濃度が40.6質量%であり、pHが3.8であった。
製造例A-2~A-9及びA-15~A-18では、(メタ)アクリル系樹脂粒子の組成を表1に示す組成に変更したこと以外は、製造例A-1と同様の操作を行い、(メタ)アクリル系樹脂粒子A-2~A-9及びA-15~A-18の各水分散液を得た。
製造例A-10~A-14、A-19、A-20及びA-22では、(メタ)アクリル系樹脂粒子の組成を表1に示す組成に変更したこと、及び、乳化物Xの調製に使用する反応性界面活性剤の量と反応器に仕込む反応性界面活性剤の量との割合、撹拌速度等を適宜変更したこと以外は、製造例A-1と同様の操作を行い、(メタ)アクリル系樹脂粒子A-10~A-14、A-19、A-20及びA-22の各水分散液を得た。
製造例A-21では、(メタ)アクリル系樹脂粒子の組成を表1に示す組成に変更したこと以外は、製造例A-1と同様の操作を行い、(メタ)アクリル系樹脂粒子A-21の製造を試みたが、単量体成分及び反応性界面活性剤を重合することができなかった。
A-2:40.6質量%、A-3:40.6質量%、A-4:40.6質量%、A-5:40.6質量%、A-6:40.6質量%、A-7:40.6質量%、A-8:40.6質量%、A-9:40.6質量%、A-10:25.0質量%、A-11:40.6質量%、A-12:40.6質量%、A-13:40.6質量%、A-14:40.6質量%、A-15:40.6質量%、A-16:40.6質量%、A-17:40.6質量%、A-18:40.6質量%、A-19:40.6質量%、A-20:50.0質量%、A-22:40.6質量%
A-2:3.8、A-3:3.8、A-4:3.8、A-5:3.8、A-6:3.8、A-7:3.8、A-8:3.8、A-9:3.8、A-10:2.5、A-11:3.8、A-12:3.8、A-13:3.8、A-14:3.8、A-15:3.8、A-16:3.8、A-17:3.8、A-18:3.8、A-19:3.8、A-20:3.9、A-22:3.5
「n-BA」:n-ブチルアクリレート
「2EHA」:2-エチルヘキシルアクリレート
「MMA」:メチルメタクリレート
<(メタ)アクリロニトリル>
「AN」:アクリロニトリル
「MAN」:メタクリロニトリル
<カルボキシ基を有する(メタ)アクリル系単量体>
「AA」:アクリル酸
<水酸基を有する(メタ)アクリルアミド>
「HEAA」:N-(2-ヒドロキシエチル)アクリルアミド
「AR-10」[商品名:アクアロン(登録商標) AR-10、有効成分:ポリオキシエチレンスチレン化プロペニルフェニルエーテル硫酸エステルアンモニウム〔オキシアルキレン基の種類:オキシエチレン基、平均付加モル数:10〕、有効成分濃度:99質量%]
「AR-20」[商品名:アクアロン(登録商標) AR-20、有効成分:ポリオキシエチレンスチレン化プロペニルフェニルエーテル硫酸エステルアンモニウム〔オキシアルキレン基の種類:オキシエチレン基、平均付加モル数:20〕、有効成分濃度:99質量%]
「ER-30」[商品名:アデカリアソープ(登録商標) ER-30、有効成分:ポリオキシエチレン-1-(アリルオキシメチル)アルキルエーテル〔オキシアルキレン基の種類:オキシエチレン基、平均付加モル数:30〕、有効成分濃度:65質量%]
〔実施例1〕
上記にて得られた(メタ)アクリル系樹脂粒子A-1の水分散液100質量部(固形分換算値)と、アンモニア水0.32質量部と、消泡剤としてCP-101〔商品名、サンノプコ(株)製〕0.4質量部(固形分換算値)と、消泡剤としてSN デフォーマー 470〔商品名、サンノプコ(株)製〕0.2質量部(固形分換算値)と、防腐剤としてACTICIDE(登録商標) BW-20〔商品名、THOR JAPAN社製〕0.04質量部(固形分換算値)と、湿潤剤としてサーフィノール(登録商標) 440〔商品名、日信化学工業(株)製〕0.8質量部(固形分換算値)と、増粘剤としてニカゾール(登録商標) VT-253A〔商品名、日本カーバイド工業(株)製〕0.4質量部(固形分換算値)と、を混合した後、架橋剤としてカルボジライト(登録商標) V-04〔商品名、カルボジイミド系架橋剤、日清紡ケミカル(株)製〕1質量部(固形分換算値)を添加し、十分に混合して、実施例1の粘着剤組成物を調製した。
得られた実施例1の粘着剤組成物における水の含有率は、粘着剤組成物の全質量に対して59.8質量%である。
実施例2~19では、粘着剤組成物の組成を表2に記載のとおりにしたこと以外は、実施例1と同様の操作を行い、実施例2~19の各粘着剤組成物を調製した。
比較例1~6では、粘着剤組成物の組成を表3に記載のとおりにしたこと以外は、実施例1と同様の操作を行い、比較例1~6の各粘着剤組成物を調製した。
実施例2:59.8質量%、実施例3:59.8質量%、実施例4:59.8質量%、実施例5:59.8質量%、実施例6:59.8質量%、実施例7:59.8質量%、実施例8:59.8質量%、実施例9:59.8質量%、実施例10:75.3質量%、実施例11:59.8質量%、実施例12:59.8質量%、実施例13:59.8質量%、実施例14:64.8質量%、実施例15:59.8質量%、実施例16:59.8質量%、実施例17:59.8質量%、実施例18:50.5質量%、実施例19:59.8質量%
上記にて調製した粘着剤組成物を、剥離シート〔商品名:フィルムバイナ(登録商標)100E-0010 No.23、藤森工業(株)製〕の上に、乾燥後の塗布量が25g/m2となるようにアプリケーターを用いて塗布し、塗布膜を形成した。次いで、形成した塗布膜を、熱風循環式乾燥機を用いて、乾燥温度105℃、乾燥時間90秒間の条件で乾燥させ、剥離シートの面上に粘着剤層を形成した。次いで、剥離シートの面上に形成された粘着剤層の露出した面上に、基材としてのポリエチレンテレフタレート(PET)フィルム〔商品名:テイジン(登録商標)テトロン(登録商標)フィルム HPE、厚さ:50μm、東洋紡フィルムソリューション(株)製〕(以下、単に「PET」という。)の一方の面に重ねて貼り合わせることにより、評価用粘着シートを作製した。作製した評価用粘着テープは、剥離シート/粘着剤層/基材(PET)の積層構造を有する。
1.粘着力
(1)初期粘着力
上記にて作製した評価用粘着シートを25mm×100mmの大きさに切断し、評価用粘着シート片を準備した。準備した評価用粘着シート片(構成:基材/粘着剤層/剥離シート)から剥離シートを剥離し、剥離により露出した粘着剤層の面を、JIS Z 0237:2009に準拠した方法に従い、JIS R 6253:2006に規定の#360の耐水研磨紙を用いて磨いたSUS304(ステンレス鋼板;以下、単に「SUS」という。)の面に重ねて圧着し、試験片を作製した。作製した試験片を、雰囲気温度23℃、50%RHの環境下に30分間静置した。静置後の試験片について、SUSから評価用粘着シート片(構成:基材/粘着剤層)を長辺(100mm)方向に180°剥離したときの粘着力(単位:N/25mm)を、測定装置として(株)エー・アンド・デイ製のシングルコラム型材料試験機(型番:STA-1225)を用い、雰囲気温度23℃、50%RHの環境下、剥離速度300mm/分の条件で測定した。
測定値が10N/25mm以上であれば、初期粘着力が高い粘着剤層であると判断した。測定値を表2及び表3に示す。
上記にて作製した評価用粘着シートを25mm×100mmの大きさに切断し、評価用粘着シート片を準備した。準備した評価用粘着シート片(構成:基材/粘着剤層/剥離シート)から剥離シートを剥離し、剥離により露出した粘着剤層の面を、JIS Z 0237:2009に準拠した方法に従い、JIS R 6253:2006に規定の#360の耐水研磨紙を用いて磨いたSUS304(ステンレス鋼板;以下、単に「SUS」という。)の面に重ねて圧着し、試験片を作製した。作製した試験片を、雰囲気温度23℃、50%RHの環境下に30分間静置した後、雰囲気温度40℃、90%RHの環境下に7日間静置した。静置後、試験片を雰囲気温度23℃、50%RHの環境下に取り出した。取り出し直後の試験片について、SUSから評価用粘着シート片(構成:基材/粘着剤層)を長辺(100mm)方向に180°剥離したときの粘着力(単位:N/25mm)を、測定装置として(株)エー・アンド・デイ製のシングルコラム型材料試験機(型番:STA-1225)を用い、雰囲気温度23℃、50%RHの環境下、剥離速度300mm/分の条件で測定した。
測定値が15N/25mm以上であれば、湿熱環境下において高い粘着力を有する粘着剤層であると判断した。測定値を表2及び表3に示す。
上記にて作製した評価用粘着シートを25mm×100mmの大きさに切断し、評価用粘着シート片を準備した。準備した評価用粘着シート片(構成:基材/粘着剤層/剥離シート)から剥離シートを剥離し、剥離により露出した粘着剤層の面を、JIS Z 0237:2009に準拠した方法に従い、JIS R 6253:2006に規定の#360の耐水研磨紙を用いて磨いたSUS304(ステンレス鋼板)の面に重ねて圧着し、試験片を作製した。作製した試験片を、脱イオン水に72時間浸漬した後、脱イオン水から取り出し、雰囲気温度23℃、50%RHの環境下に1時間静置した。静置後の試験片を目視により観察し、下記の評価基準に従って、評価を行った。評価結果を表2及び表3に示す。
下記の評価基準において、「A」及び「B」は、実用上問題ないレベルであり、「A」であることが最も好ましい。
A:粘着剤層の膨潤及び白化が確認されなかった。
B:粘着剤層の端から5mm以内の範囲にのみ、膨潤及び/又は白化が確認された。
C:粘着剤層の端から5mmを超える広範囲に膨潤及び/又は白化が確認された。
上記にて作製した評価用粘着シートを25mm×100mmの大きさに切断し、評価用粘着シート片を準備した。準備した評価用粘着シート片(構成:基材/粘着剤層/剥離シート)から剥離シートの一部を、粘着剤層の露出部の大きさが25mm×80mmになるように剥離した。剥離により露出した粘着剤層の面を、雰囲気温度23℃、50%RHの環境下で、JIS Z 0237:2009に準拠した方法に従い、JIS R 6253:2006に規定の#360の耐水研磨紙を用いて磨いたSUS304(ステンレス鋼板;以下、単に「SUS」という。)の面に貼着した後、2kgのローラーを1往復させて圧着し、試験片を作製した。作製した試験片では、SUSと粘着剤層とを貼り合わせた部分の大きさが25mm×80mmとなっている。作製した試験片を、雰囲気温度23℃、50%RHの環境下に1時間静置した後、雰囲気温度40℃、90%RHの環境下に1時間静置した。次いで、雰囲気温度40℃、90%RHの環境下で、評価用粘着シート片を貼り付けた面が下側になるようにSUS板を水平に保ち、粘着剤層がSUSに貼り付けられていない評価用粘着シート片の端部に、重さ200gの錘を吊り下げ、3時間放置した。放置後、SUSから剥がれた粘着剤層の長さを計測し、下記の評価基準に従って、評価を行った。測定値及び評価結果を表2及び表3に示す。
下記の評価基準において、「A」、「B」及び「C」は、実用上問題ないレベルであり、「A」であることが最も好ましい。
A:評価用粘着シート片の剥がれが確認されなかった。
B:評価用粘着シート片の剥がれが確認されたが、35mm以内の剥がれであった。
C:評価用粘着シート片の剥がれが確認されたが、35mmを超えて55mm以内の剥がれであった。
D:評価用粘着シート片が55mmを超えて剥がれた、或いは、評価用粘着シート片が落下した。
<架橋剤>
「V-04」[商品名:カルボジライト(登録商標) V-04、カルボジイミド系架橋剤、日清紡ケミカル(株)製]
「WS-300」[商品名:エポクロス(登録商標) WS-300、オキサゾリン系架橋剤、(株)日本触媒製]
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的に、かつ、個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (9)
- (メタ)アクリル酸アルキルエステル単量体に由来する構成単位(A)、(メタ)アクリロニトリルに由来する構成単位(B)、カルボキシ基を有する(メタ)アクリル系単量体に由来する構成単位(C)、及び反応性界面活性剤に由来する構成単位(D)を含み、前記構成単位(B)の含有率が全構成単位〔但し、前記構成単位(D)を除く。〕に対して10質量%~25質量%であり、前記構成単位(C)の含有率が全構成単位〔但し、前記構成単位(D)を除く。〕に対して0.2質量%~6.0質量%であり、前記構成単位(D)の含有量が全構成単位〔但し、前記構成単位(D)を除く。〕100質量部に対して0.1質量部~1.0質量部であり、かつ、平均粒子径が5nm~160nmである(メタ)アクリル系樹脂粒子と、水と、を含む粘着剤組成物。
- さらに、架橋剤を含む請求項1に記載の粘着剤組成物。
- 前記架橋剤が、カルボジイミド系架橋剤及びオキサゾリン系架橋剤から選ばれる少なくとも1種である請求項2に記載の粘着剤組成物。
- 前記反応性界面活性剤が、アニオン型反応性界面活性剤及びノニオン型反応性界面活性剤からなる群より選ばれる少なくとも1種である請求項1に記載の粘着剤組成物。
- 前記(メタ)アクリル系樹脂粒子は、水酸基を有する(メタ)アクリルアミドに由来する構成単位を含まないか、又は、水酸基を有する(メタ)アクリルアミドに由来する構成単位の含有率が前記(メタ)アクリル系樹脂粒子の全構成単位〔但し、前記構成単位(D)を除く。〕に対して0質量%を超えて0.1質量%未満の範囲である請求項1に記載の粘着剤組成物。
- 前記(メタ)アクリル系樹脂粒子のガラス転移温度が、-70℃~30℃である請求項1に記載の粘着剤組成物。
- 請求項1~請求項6のいずれか1項に記載の粘着剤組成物により形成され、(メタ)アクリル酸アルキルエステル単量体に由来する構成単位(A)と、(メタ)アクリロニトリルに由来する構成単位(B)と、カルボキシ基を有する(メタ)アクリル系単量体に由来する構成単位(C)と、反応性界面活性剤に由来する構成単位(D)と、を含み、前記構成単位(B)の含有率が全構成単位〔但し、前記構成単位(D)を除く。〕に対して10質量%~25質量%であり、前記構成単位(C)の含有率が全構成単位〔但し、前記構成単位(D)を除く。〕に対して0.2質量%~6.0質量%であり、前記構成単位(D)の含有量が全構成単位〔但し、前記構成単位(D)を除く。〕100質量部に対して0.1質量部~1.0質量部である(メタ)アクリル系樹脂を含む粘着剤層。
- 請求項7に記載の粘着剤層を備える粘着シート。
- 請求項1~請求項6のいずれか1項に記載の粘着剤組成物の製造方法であり、
少なくとも、(メタ)アクリル酸アルキルエステル単量体、(メタ)アクリロニトリル、カルボキシ基を有する(メタ)アクリル系単量体、及び反応性界面活性剤を、連鎖移動剤を用いて乳化重合させることにより、(メタ)アクリル系樹脂粒子を製造する工程を含む粘着剤組成物の製造方法。
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EP22910631.5A EP4455245A1 (en) | 2021-12-20 | 2022-11-07 | Pressure-sensitive adhesive composition, production method therefor, pressure-sensitive adhesive layer, and pressure-sensitive adhesive sheet |
KR1020247021055A KR20240124930A (ko) | 2021-12-20 | 2022-11-07 | 점착제 조성물 및 그 제조 방법, 점착제층, 그리고 점착 시트 |
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JPS6386777A (ja) * | 1986-09-30 | 1988-04-18 | Japan Synthetic Rubber Co Ltd | 水系感圧接着剤 |
JPH0726229A (ja) * | 1993-07-07 | 1995-01-27 | Nippon Carbide Ind Co Inc | 水分散型アクリル系感圧接着剤組成物 |
JP2000109784A (ja) * | 1998-08-04 | 2000-04-18 | Toagosei Co Ltd | エマルジョン型粘着剤又は接着剤組成物及び粘着シ―ト |
JP2002080809A (ja) * | 2000-09-05 | 2002-03-22 | Showa Highpolymer Co Ltd | 水性エマルジョン型感圧接着剤 |
JP2009057508A (ja) | 2007-09-03 | 2009-03-19 | Saiden Chemical Industry Co Ltd | 水性エマルション接着剤 |
JP2010209170A (ja) | 2009-03-09 | 2010-09-24 | Dic Corp | 粘着テープ |
JP2011012216A (ja) * | 2009-07-03 | 2011-01-20 | Toagosei Co Ltd | エマルション組成物 |
JP2013049742A (ja) * | 2011-08-30 | 2013-03-14 | Emulsion Technology Co Ltd | 水系粘着剤組成物 |
JP2022076759A (ja) | 2020-11-10 | 2022-05-20 | 本田技研工業株式会社 | 車体下部構造 |
-
2022
- 2022-11-07 EP EP22910631.5A patent/EP4455245A1/en active Pending
- 2022-11-07 WO PCT/JP2022/041379 patent/WO2023119911A1/ja active Application Filing
- 2022-11-07 KR KR1020247021055A patent/KR20240124930A/ko unknown
- 2022-11-16 TW TW111143733A patent/TW202330844A/zh unknown
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS6386777A (ja) * | 1986-09-30 | 1988-04-18 | Japan Synthetic Rubber Co Ltd | 水系感圧接着剤 |
JPH0726229A (ja) * | 1993-07-07 | 1995-01-27 | Nippon Carbide Ind Co Inc | 水分散型アクリル系感圧接着剤組成物 |
JP2000109784A (ja) * | 1998-08-04 | 2000-04-18 | Toagosei Co Ltd | エマルジョン型粘着剤又は接着剤組成物及び粘着シ―ト |
JP2002080809A (ja) * | 2000-09-05 | 2002-03-22 | Showa Highpolymer Co Ltd | 水性エマルジョン型感圧接着剤 |
JP2009057508A (ja) | 2007-09-03 | 2009-03-19 | Saiden Chemical Industry Co Ltd | 水性エマルション接着剤 |
JP2010209170A (ja) | 2009-03-09 | 2010-09-24 | Dic Corp | 粘着テープ |
JP2011012216A (ja) * | 2009-07-03 | 2011-01-20 | Toagosei Co Ltd | エマルション組成物 |
JP2013049742A (ja) * | 2011-08-30 | 2013-03-14 | Emulsion Technology Co Ltd | 水系粘着剤組成物 |
JP2022076759A (ja) | 2020-11-10 | 2022-05-20 | 本田技研工業株式会社 | 車体下部構造 |
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