WO2011043269A1 - Process for production of pressure-sensitive adhesive composition, process for production of pressure-sensitive adhesive film, raw material composition for pressure-sensitive adhesive, and pressure-sensitive adhesive film - Google Patents
Process for production of pressure-sensitive adhesive composition, process for production of pressure-sensitive adhesive film, raw material composition for pressure-sensitive adhesive, and pressure-sensitive adhesive film Download PDFInfo
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- WO2011043269A1 WO2011043269A1 PCT/JP2010/067275 JP2010067275W WO2011043269A1 WO 2011043269 A1 WO2011043269 A1 WO 2011043269A1 JP 2010067275 W JP2010067275 W JP 2010067275W WO 2011043269 A1 WO2011043269 A1 WO 2011043269A1
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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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
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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]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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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
- 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
Definitions
- a shock absorbing protective plate is attached to the front surface of the liquid crystal panel via an air layer to prevent the liquid crystal panel from cracking.
- a thin protective plate is directly bonded using an adhesive layer without providing an air layer on the front surface of a mobile phone liquid crystal panel.
- PDP in order to reduce the weight and thickness, and improve the visibility, it has been studied as a direct color filter system that an optical filter film is directly bonded to a PDP panel.
- Patent Document 2 discloses a resin composition containing an acrylic acid derivative, an acrylic acid derivative polymer, and a high molecular weight cross-linking agent for impact absorption necessary for protecting an image display device or the like. . It is said to be useful for preventing cracks in the image display panel or relieving stress and impact and is excellent in transparency.
- the resin sheet was placed in a high-temperature and high-humidity test tank of 60 ° C. and 90% RH for 50 hours, and as a result of confirmation by visual observation, this resin composition was transparent with little foaming. It is said to be excellent.
- Example 18 in which slight turbidity was observed immediately after production was also evaluated as A (no white turbidity was observed in the moisture absorption test). Therefore, turbidity immediately after production is not considered. This is an inconspicuous phenomenon when a thin resin film such as polyethylene terephthalate (PET) is bonded to one or both sides, but when a gas barrier material such as an acrylic plate and glass or glass is bonded. , White turbidity starts in a few minutes immediately after taking out from the oven in an environment of 60 ° C. and 90% RH, and the white turbidity remains for several hours or more.
- PET polyethylene terephthalate
- Patent Document 3 a copolymer of a (meth) acrylic acid alkyl ester monomer and a carboxyl group-containing monomer is used. Also, in the case of Patent Document 3, as in Patent Document 2, it is clearly stated that the pressure-sensitive adhesive composition does not cause white turbidity of the pressure-sensitive adhesive layer even under environmental conditions of 85 ° C. and 95% RH, and a pressure-sensitive adhesive tape using the same. However, since the (meth) acrylic acid alkyl ester monomer is introduced excessively, it is necessary to irradiate the ultraviolet rays as weak as possible at the time of ultraviolet curing as in the examples for a long time.
- the pressure-sensitive adhesive layer may be clouded even under extremely severe high-temperature and high-humidity environmental conditions such as 85 ° C. and 95% RH, which are applied to an on-vehicle display. It was not a technique that does not float and peel off the adherend and is provided with low productivity and low cost.
- the object of the present invention is to perform an endurance test under an environmental condition at a high temperature and high humidity such as (60 ° C., 90% RH) or (85 ° C., 95% RH) using an oven. It is to provide a pressure-sensitive adhesive composition that does not cause cloudiness of the pressure-sensitive adhesive layer or lift and peel off from the adherend even after being taken out of the oven, a method for producing the same, and a pressure-sensitive adhesive film using the same.
- a hydroxyl group-containing polymer obtained by a polymerization reaction of at least one monomer of a hydroxyl group-containing (meth) acrylate is introduced into the pressure-sensitive adhesive layer to participate in preventing aggregation of water molecules. Therefore, in the present invention, in order to solve the above problems, an acrylic polymer as a main agent is polymerized in advance, and this is a syrup in which at least one kind of hydroxyl group-containing (meth) acrylate monomer is dissolved.
- An adhesive coating solution (a pressure-sensitive adhesive raw material composition to be a precursor of the pressure-sensitive adhesive layer) is prepared.
- the present invention has the following configuration.
- (I) A polymer production process for obtaining a main polymer using a mixed solvent liquid containing at least one kind of acrylic monomer; (2) Bifunctional in an amount of 0.1 equivalent or less with respect to the crosslinking point of the polymer, at least one monomer of a hydroxyl group-containing (meth) acrylate, a photopolymerization initiator, and a polymer crosslinking point.
- a step of preparing a pressure-sensitive adhesive raw material composition containing a crosslinking agent (3)
- a method for producing an adhesive film is provided.
- (III) At least one kind of acrylic monomer having an ester group is polymerized from a monomer containing 85 to 95 parts by weight and at least one kind of acrylic monomer having a carboxyl group is polymerized from 5 to 15 parts by weight.
- Main polymer 100 parts by weight;
- the bifunctional crosslinking agent is 0.1 to 3 equivalents or less with respect to the crosslinking point of the polymer.
- Containing And the molecular weight distribution of the said main ingredient polymer is a raw material composition for adhesives whose number average molecular weight (Mn) is 70,000 or more and whose weight average molecular weight (Mw) is 1 million or more.
- a pressure-sensitive adhesive composition which is present in a necessary quantity in a dispersed state as much as possible. This makes it possible to adsorb moisture under high-temperature and high-humidity environmental conditions to the hydroxyl group-containing polymer, and to prevent the occurrence of white turbidity due to the aggregation of absorbed water molecules even if the pressure-sensitive adhesive layer is thickened to increase buffering properties.
- An agent composition can be provided.
- the water molecules are aggregated after being removed from the environmental conditions at high temperature and high humidity. It is possible to provide a method for producing a pressure-sensitive adhesive composition in which the resulting pressure-sensitive adhesive layer does not become cloudy or does not float or peel off from the adherend. According to the invention described in (II) above, even if the thickness of the pressure-sensitive adhesive layer is increased in order to increase the buffering property, water molecules are aggregated after being removed from the environmental conditions at high temperature and high humidity. It is possible to provide a method for producing a pressure-sensitive adhesive film in which the resulting pressure-sensitive adhesive layer does not become cloudy or does not float or peel off from the adherend.
- FIG. 3A is a graph obtained by enlarging the time in the range of 0 to 40 minutes.
- the pressure sensitive adhesive raw material composition of the present invention crosslinks at least one hydroxyl group-containing monomer (monomer B) with a polymerization initiator for polymerizing the monomer B, the main polymer (polymer A), and the main polymer. It was mixed with a crosslinking agent.
- This raw material composition for pressure-sensitive adhesives contains at least one hydroxyl group-containing (meth) acrylate as a photopolymerizable compound that is polymerized by energy rays.
- the polymer A is not particularly limited as long as it is the main component of the pressure-sensitive adhesive and the acrylic monomer (monomer B) containing a hydroxyl group is easily dispersed.
- the acrylic monomer (monomer B) containing a hydroxyl group is easily dispersed.
- an acrylic polymer is preferable, and a hydrophilic monomer is preferably copolymerized. This is because the monomer B is acrylic and contains a hydroxyl group.
- the polymer A Is preferably an acrylic polymer.
- the raw material composition for pressure-sensitive adhesives of the present invention When the raw material composition for pressure-sensitive adhesives of the present invention is applied to a substrate (or a separator) and dried and then polymerized by light irradiation, a pressure-sensitive adhesive film is obtained.
- the raw material composition for pressure-sensitive adhesives of the present invention contains a cross-linking agent for cross-linking the polymer, and the content of the cross-linking agent is less than 1 equivalent to the cross-linking point of the polymer (preferably, for example, 0.5 Equivalent or less).
- the crosslinking agent can be crosslinked with the hydroxyl group of the polymer B like an isocyanate compound, at least a part of the hydroxyl group of the polymer B is not crosslinked, and the uncrosslinked hydroxyl group is dispersed. Therefore, a pressure-sensitive adhesive layer excellent in moisture adsorption ability can be obtained.
- the amount and type of the crosslinking agent is a bifunctional crosslinking agent in an amount of 0.1 equivalent or less with respect to the crosslinking point of the polymer, so that the deformation of the adherend can be followed.
- the pressure-sensitive adhesive is crosslinked to impart heat resistance, and can be prevented from floating and peeling off from the adherend.
- the pressure-sensitive adhesive film does not particularly need to be distinguished by width, and includes both pressure-sensitive adhesive tapes and pressure-sensitive adhesive sheets specified in JIS Z 0109. Specific examples thereof include a single-sided adhesive tape (or single-sided adhesive sheet) having an adhesive layer on one side of the substrate, a double-sided adhesive tape (or double-sided adhesive sheet) having an adhesive layer on both sides of the substrate, and a substrate. Transfer tape (transfer tape) in which the pressure-sensitive adhesive layer is formed in a film form without having a film.
- the pressure-sensitive adhesive sheet can have a large area, and may be used with its wide width, or may be cut into a tape shape and used as a pressure-sensitive adhesive tape.
- a pressure-sensitive adhesive sheet or pressure-sensitive adhesive tape wound in a roll shape is suitable for an application in which a member is bonded to a display.
- FIG. 1A an example of the single-sided adhesive tape 5 which has the adhesive layer 2 formed using the adhesive composition of this invention is shown typically.
- an adhesive layer 2 is formed on one side of a base material 1 that serves as a support for the adhesive layer 2, and the adhesive surface of the adhesive layer 2 is protected by a separator 3.
- the separator 3 is peeled to expose the adhesive surface, and the base material 1 is laminated on the back surface of the pressure-sensitive adhesive layer 2 and is bonded to the adherend.
- the structure of the double-sided pressure-sensitive adhesive tape having a base material is not particularly shown, but a pressure-sensitive adhesive layer is formed on both surfaces of the base material, and the pressure-sensitive adhesive surface of each pressure-sensitive adhesive layer has a structure protected by a separator.
- FIG. 1B schematically shows an example of the transfer tape 6 having the pressure-sensitive adhesive layer 2 formed using the pressure-sensitive adhesive composition of the present invention.
- separators 3 and 3 are provided on both sides of the pressure-sensitive adhesive layer 2.
- one separator 3 is peeled off, and one adhesive surface is exposed and bonded to the adherend.
- only the film-like pressure-sensitive adhesive layer 2 can be transferred (transferred) to the adherend by peeling off the other separator 3.
- another adherend can be bonded to the new adhesive surface.
- At least one kind of acrylic monomer having an ester group (—COO—) and at least one kind of acrylic monomer having a carboxyl group (—COOH) are contained as monomers that are raw materials for the polymer A.
- various other compounds can be used.
- an acrylic monomer having an ester group (—COO—) for example, a general formula CH 2 ⁇ CR 1 —COOR 2 (wherein R 1 is hydrogen or a methyl group, R 2 is an alkyl group having 1 to 14 carbon atoms) And (meth) acrylates such as hydroxyl group-containing (meth) acrylates.
- alkyl (meth) acrylate represented by the general formula CH 2 ⁇ CR 1 —COOR 2 (wherein R 1 represents hydrogen or a methyl group, and R 2 represents an alkyl group having 1 to 14 carbon atoms)
- R 1 represents hydrogen or a methyl group
- R 2 represents an alkyl group having 1 to 14 carbon atoms
- the alkyl group R 2 has 1 to 14 carbon atoms from the viewpoint of adhesive strength. It is not preferable that the alkyl group has 15 or more carbon atoms because the adhesive strength may be reduced.
- the alkyl group R 2 preferably has 1 to 12 carbon atoms, preferably 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms.
- alkyl (meth) acrylates having 1 to 14 carbon atoms in the alkyl group R 2 alkyl (meth) acrylates having 1 to 3 or 13 to 14 carbon atoms in the alkyl group R 2 are used as a part of the monomer.
- an alkyl (meth) acrylate having 4 to 12 carbon atoms of the alkyl group R 2 as an essential component (for example, 50 to 100 mol%).
- these alkyl groups R 2 may be a straight chain or may be branched.
- Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate. , Polypropylene glycol mono (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, and the like.
- the acrylic monomer containing a carboxyl group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, 2-acryloylethyl succinic acid, and the like.
- acrylic monomers containing alkoxysilyl groups include ⁇ -trimethoxysilylpropyl (meth) acrylate, ⁇ -methyldimethoxysilylpropyl (meth) acrylate, and ⁇ -triethoxysilylpropyl (meth) acrylate.
- non-acrylic monomer containing an alkoxysilyl group include vinylmethoxysilane and vinyltrimethoxysilane.
- organic solvent used in the solution polymerization reaction examples include aromatic hydrocarbons such as toluene and xylene, aliphatic esters such as ethyl acetate and butyl acetate, and alicyclic hydrocarbons such as cyclohexane. , Aliphatic hydrocarbons such as hexane, pentane and the like, but not particularly limited as long as the polymerization reaction is not inhibited. These solvents may be used alone or in combination of two or more. What is necessary is just to determine the usage-amount of a solvent suitably.
- the molecular weight of the polymer produced decreases as the polymerization temperature increases. In carrying out the polymerization reaction at the reflux temperature of the solvent, a polymer can be obtained while removing the heat of polymerization reaction by using a solvent having a boiling point temperature suitable for the polymerization reaction.
- the content of monomer B (the total amount when monomer B is two or more) is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the main polymer (polymer A), and is 85 ° C. 95 In the case where high durability is required such as in a test under a% RH environment, the amount is more preferably 5 to 15 parts by weight.
- the pressure-sensitive adhesive composition comprising a known hydroxyl group-containing acrylic polymer may contain some (meth) acrylate monomers containing hydroxyl groups as unreacted monomers. Compared to the content of hydroxyl group-containing (meth) acrylate in the raw material composition for pressure-sensitive adhesives of the invention, the content is only extremely low.
- the raw material composition for pressure-sensitive adhesives of the present invention is an acrylic syrup containing a main polymer, a hydroxyl group-containing (meth) acrylate monomer, a photopolymerization initiator, and a crosslinking agent, or coated and hydroxyl group-containing.
- the acrylic syrup is prepared as a resin solution dissolved in an organic solvent.
- the organic solvent used in the polymerization reaction is removed, and the obtained liquid syrup is obtained.
- the main polymer is preferably separated and washed with water or an organic solvent as necessary. Thereby, the polymerization reaction of the main polymer can be completely stopped, and unreacted acrylic monomers can be removed from the main polymer.
- the weight of the main polymer can be quantified more accurately, and an acrylic syrup in which the contents of the hydroxyl group-containing monomer, the crosslinking agent, and the photopolymerization initiator used in the next step are more appropriately adjusted can be produced.
- the removal of the organic solvent used in the polymerization reaction may be performed after the hydroxyl group-containing monomer is dissolved in the main polymer.
- the polymerization reaction may proceed when ultraviolet light contained in room light or sunlight acts on the acrylic syrup, making it difficult to manage. Is preferably added immediately before the coating step, which is a subsequent step. This is the same for resin solutions in which acrylic syrup is dissolved in an organic solvent. Care should be taken to prevent the photoinitiator from starting the reaction before coating and film formation due to some external factor. It is.
- the raw material composition for pressure-sensitive adhesives of the present invention is preferably a pressure-sensitive adhesive coating solution containing an appropriate amount of an organic solvent in order to impart fluidity suitable for application to a substrate.
- an organic solvent used in the adhesive coating solution include aromatic hydrocarbons such as toluene and xylene, aliphatic esters such as ethyl acetate and butyl acetate, and alicyclic carbonization such as cyclohexane. Examples thereof include aliphatic hydrocarbons such as hydrogen, hexane, and pentane, but are not particularly limited as long as the purpose of coating and dispersion can be achieved.
- Benzophenone photopolymerization initiators include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, hydroxylbenzophenone, hydroxylpropylbenzophenone, acrylic benzophenone, 4,4'-bis (dimethyl) Amino) benzophenone and the like.
- Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, diethylthioxanthone, and dimethylthioxanthone.
- the bifunctional crosslinking agent is not particularly limited as long as it is a compound having two functional groups that undergo crosslinking reaction in one molecule.
- Examples of such a bifunctional crosslinking agent include a bifunctional epoxy compound and a bifunctional isocyanate.
- the bifunctional epoxy compound include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl glycol diglycidyl ether.
- polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polysulfone, polyethersulfone, polystyrene, polyacrylate, polyetheretherketone, polycarbonate, polyolefin such as polyethylene and polypropylene, polyamide, nylon, polyimide , Fluorine such as triacetyl cellulose (cellulose triacetate), cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly (meth) acrylic acid ester copolymer, polymethyl methacrylate, polytetrafluoroethylene and polytrifluoroethylene Resin, polyvinyl chloride, polyvinylidene chloride copolymer, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol, cellophane, cellulose film, etc.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- Polysulfone polyethersulfone
- polystyrene
- the coating apparatus for applying the adhesive raw material composition to the substrate may be any apparatus as long as it has a means for uniformly supplying and applying the adhesive raw material composition on the base material.
- a device comprising a tank for storing an adhesive raw material composition, a liquid feed pump, piping, a foreign matter removal filter, and a coater head so that the adhesive raw material composition can be supplied and coated on the substrate. Preferred (not shown).
- the coater head is preferably a die coater, for example.
- a thin film layer (coating film) of the pressure-sensitive adhesive raw material composition is formed on one side of the substrate by the coating apparatus.
- the pressure-sensitive adhesive raw material composition immediately after coating with a coating apparatus is uncured and liquid, and has fluidity suitable for coating.
- the thickness of the coating film is preferably between 0.05 and 3 mm, more preferably 0.1 to 2 mm.
- the thickness of the coating film is approximately equal to the thickness of the pressure-sensitive adhesive layer obtained by photopolymerization. Therefore, the thickness of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive film of the present invention is preferably between 0.05 and 3 mm, more preferably 0.1 to 2 mm.
- the thickness of the coating film before drying is thicker than that of the syrup type, and is a number obtained by dividing the thickness of the coating film by the concentration.
- the thickness of the coating film after drying is the same as that of the syrup type. If the coating film is too thin, the thickness of the pressure-sensitive adhesive layer is also reduced, so that the impact absorbing performance is deteriorated. Moreover, when the coating film is too thick, it is disadvantageous in that the cost increases.
- FIG. 2 schematically shows an example of the method for producing the pressure-sensitive adhesive film of the present invention.
- the pressure-sensitive adhesive raw material composition is supplied from the die coater 21 onto the substrate 11 to form the coating film 12.
- Reference numeral 22 denotes a backup roll 22 that is disposed to face the die coater 21 and supports the substrate 11.
- the base material 11 on which the coating film 12 is formed is transported along the longitudinal direction thereof, and dried in the drying chamber 23 so as to remove the solvent in the coating film 12.
- the separator 13 is supplied from the separator supply means 24 onto the coating film 12 and bonded by a nip roll 25.
- the temperature in the drying chamber 23 may be a temperature at which the solvent in the coating film 12 is sufficiently volatilized, and is desirably maintained at a temperature at which the polymerizable compound is not thermally polymerized.
- the separator supply means 24 includes a roll body around which the separator 13 is wound, a shaft that holds the roll body, and the like.
- the nip roll 25 is composed of a pair of rolls that sandwich the base material 11 on which the coating film 12 is formed and the separator 13, and is an apparatus that bonds the two together. It is preferable to provide a pressurizing means for pasting, and at least one of the rolls is preferably made of rubber so that a uniform pressure can be easily applied to the film.
- the separator examples include polycarbonate film, polyarylate film, polyethersulfone film, polysulfone film, polyester film, polyamide film, polyimide film, polystyrene film, polyolefin film, norbornene film, phenoxy ether type polymer film, and organic permeation resistance
- the thickness of the separator is not limited, but it is usually 5 to 500 ⁇ m, preferably 10 to 100 ⁇ m in many cases.
- the separator is selected according to the pressure-sensitive adhesive used and the intended use (peel strength).
- the ultraviolet irradiation device 26 includes a light source unit that generates ultraviolet light and a cooling device that removes heat generated by the light source.
- the light source part is free of lamp light sources such as high-pressure mercury lamps and metal halide lamps, and light-emitting diodes having a light emission peak in the ultraviolet region, as long as they can obtain an ultraviolet irradiation amount that sufficiently cures the polymerizable compound in the coating film 12. Can be selected.
- the coating film 12 polymerizes the polymerizable compound in the coating film 12 by appropriate light irradiation, thereby increasing the cohesive force and expressing adhesiveness.
- a separator is supplied not only as the separator 13 but as the base material 11 for conveyance, and an adhesive. A layer is formed on the separator. Further, when producing a double-sided pressure-sensitive adhesive film having pressure-sensitive adhesive layers on both sides of the support as the pressure-sensitive adhesive film of the present invention, coating and drying of the coating liquid and photopolymerization of the coating film are performed simultaneously or sequentially on each side. Can be done.
- curing for crosslinking reaction is performed.
- the curing method is not particularly limited, for example, an adhesive film wound up on a roll is left under a predetermined temperature and time condition.
- the curing temperature depends on the type of the crosslinking agent and the like, but is preferably heated (for example, 40 to 80 ° C.) as necessary.
- the obtained pressure-sensitive adhesive layer has an adhesive force to glass and acrylic resin when the pressure-sensitive adhesive surface is bonded to an adherend and left in an environment of 23 ° C. and 50% RH for 1 hour and then peeled at a peeling speed of 300 mm / min. Is preferably 10 N / 25 mm or more.
- the storage elastic modulus (G ′) at 23 ° C. and 1 Hz of the adhesive constituting the adhesive layer is 1 ⁇ 10 4 Pa or more and less than 1 ⁇ 10 6 Pa.
- the pressure is more preferably 5 ⁇ 10 4 Pa or more and 5 ⁇ 10 5 Pa or less.
- the storage elastic modulus When the storage elastic modulus is low, the pressure-sensitive adhesive layer is soft and easily deformed, so that it is easy to bond.
- the two members for example, a hard material such as a glass plate or an acrylic plate
- the pressure-sensitive adhesive film of the present invention can be suitably used as a pressure-sensitive adhesive tape for bonding members to various displays such as PDP (plasma display), liquid crystal panel, and organic EL panel.
- PDP plasma display
- LCD liquid crystal panel
- organic EL panel organic EL panel
- Transfer tapes of Examples 1 to 15 and Comparative Examples 1 to 5 were produced by the following production method using the pressure-sensitive adhesive raw material composition shown in Table 1 below. Moreover, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of each main polymer were measured by the method shown in the following (Molecular weight measuring method).
- the epoxy equivalent of the bifunctional epoxy crosslinking agent having the product name EX-931 is 172.
- the equivalent of the crosslinking agent was calculated by using a carboxyl group as a crosslinking point in an epoxy compound and a carboxyl group and a hydroxyl group as a crosslinking point in an isocyanate.
- the addition amount of the crosslinking agent is 0.05 equivalent with respect to the crosslinking point (AA carboxyl group) of the polymer.
- a separator manufactured by Mitsubishi Plastics Co., Ltd .; product name; MRF, thickness 38 ⁇ m
- MRF thickness 38 ⁇ m
- a transfer tape having a pressure-sensitive adhesive layer formed thereon is prepared by performing UV irradiation while adjusting the amount of UV irradiation, causing a photopolymerization reaction using a photopolymerization initiator, curing at 40 ° C. for 7 days or more, and finally forming an adhesive layer. Produced.
- a mixed solvent solution in which 87 parts by weight of 2EHA and 13 parts by weight of AA were dissolved in ethyl acetate used as an organic solvent was prepared.
- a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer.
- the number average molecular weight of this main polymer was 110,000, and the weight average molecular weight was 253,000.
- 15.0 parts by weight of 4HBA, 1.0 part by weight of EX-830, and 0.10 parts by weight of Irgacure (registered trademark) 651 were dissolved in ethyl acetate used as a solvent.
- the prepared main polymer was added to prepare a pressure-sensitive adhesive raw material composition.
- the addition amount of a crosslinking agent is 0.02 equivalent with respect to the crosslinking point of a polymer (carboxyl group of AA). Other than that was carried out similarly to Example 1, and produced the transfer tape.
- a transfer tape was prepared in the same manner as in Example 2 except that the pressure-sensitive adhesive raw material composition was prepared with 2.0 parts by weight of EX-830.
- the addition amount of a crosslinking agent is 0.04 equivalent with respect to the crosslinking point of a polymer (AA carboxyl group).
- a transfer tape was prepared in the same manner as in Example 2 except that the pressure-sensitive adhesive raw material composition was prepared with 10.0 parts by weight of 4HBA and 2.0 parts by weight of EX-830.
- the addition amount of a crosslinking agent is 0.04 equivalent with respect to the crosslinking point of a polymer (AA carboxyl group).
- a mixed solvent solution in which 87 parts by weight of 2EHA and 13 parts by weight of AA were dissolved in ethyl acetate used as an organic solvent was prepared.
- a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer.
- the main polymer had a number average molecular weight of 120,000 and a weight average molecular weight of 4,350,000.
- a transfer tape was produced in the same manner as in Example 5 except that 10.0 parts by weight of 4HBA and 2.0 parts by weight of EX-830 were used.
- the addition amount of a crosslinking agent is 0.04 equivalent with respect to the crosslinking point of a polymer (AA carboxyl group).
- a transfer tape was produced in the same manner as in Example 5 except that 15.0 parts by weight of 4HBA and 2.5 parts by weight of EX-830 were used.
- the addition amount of the crosslinking agent is 0.05 equivalent with respect to the crosslinking point (AA carboxyl group) of the polymer.
- a mixed solvent solution in which 87 parts by weight of 2EHA and 13 parts by weight of AA were dissolved in ethyl acetate used as an organic solvent was prepared.
- a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer.
- the main polymer had a number average molecular weight of 140,000 and a weight average molecular weight of 1,430,000.
- a transfer tape was prepared in the same manner as in Example 8 except that 15.0 parts by weight of 4HBA and 2.5 parts by weight of EX-830 were used.
- the addition amount of the crosslinking agent is 0.05 equivalent with respect to the crosslinking point (AA carboxyl group) of the polymer.
- a transfer tape was produced in the same manner as in Example 7, except that the crosslinking agent was 2.0 parts by weight of polypropylene glycol diglycidyl ether (Nagase ChemteX Corporation; product name EX-931). The addition amount of a crosslinking agent is 0.02 equivalent with respect to the crosslinking point of a polymer (carboxyl group of AA).
- a mixed solvent solution prepared by dissolving 86.5 parts by weight of 2EHA, 13 parts by weight of AA, 0.5 parts by weight of 2-hydroxyethyl acrylate (HEA), and ethyl acetate used as an organic solvent was prepared.
- a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer.
- a transfer tape was produced in the same manner as in Example 12 except that 2.5 parts by weight of A-45N and 0.10 parts by weight of Irgacure (registered trademark) 651 were used.
- the addition amount of the crosslinking agent is 0.08 equivalent with respect to the crosslinking point of the polymer (carboxyl group of AA and hydroxyl group of HEA and 4HBA).
- the molar ratio between the crosslinking point of polymer A (carboxyl group of AA and hydroxyl group of HEA) and the crosslinking point of polymer B (hydroxyl group of 4HBA) is 1: 0.56.
- the former has a higher ratio than the latter.
- a mixed solvent solution in which 92 parts by weight of 2EHA and 8 parts by weight of AA were dissolved in ethyl acetate used as an organic solvent was prepared.
- a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer.
- the main polymer had a number average molecular weight of 90,000 and a weight average molecular weight of 1,260,000.
- a mixed solvent solution in which 95 parts by weight of 2EHA and 5 parts by weight of AA were dissolved in ethyl acetate used as an organic solvent was prepared.
- a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer.
- the main polymer had a number average molecular weight of 300,000 and a weight average molecular weight of 1,440,000.
- Example 1 A mixed solvent solution in which 87 parts by weight of 2EHA and 13 parts by weight of AA were dissolved in ethyl acetate used as an organic solvent was prepared. Using this mixed solvent liquid, a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer. The main polymer had a number average molecular weight of 120,000 and a weight average molecular weight of 4,350,000. Next, the prepared main polymer is added to a solvent solution obtained by dissolving 10.0 parts by weight of 4HBA and 0.05 parts by weight of Irgacure (registered trademark) 651 in a solvent, and then sticking. An agent raw material composition was prepared. In this case, no crosslinking agent is added. Other than that was carried out similarly to Example 1, and produced the transfer tape.
- Irgacure registered trademark
- Example 2 A mixed solvent solution in which 87 parts by weight of 2EHA and 13 parts by weight of AA were dissolved in ethyl acetate used as an organic solvent was prepared. Using this mixed solvent liquid, a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer. The main polymer had a number average molecular weight of 120,000 and a weight average molecular weight of 4,350,000. Next, the prepared main polymer is added to a solvent solution in which 10.0 parts by weight of 4HBA and 2.0 parts by weight of EX-830 are dissolved in the solvent used as a solvent. The ingredients were prepared. The addition amount of a crosslinking agent is 0.04 equivalent with respect to the crosslinking point of a polymer (AA carboxyl group). Other than that was carried out similarly to Example 1, and produced the transfer tape.
- ⁇ Testing method for adhesive tape> Using the adhesive tapes (transfer tapes) of Examples 1 to 15 and Comparative Examples 1 to 5 described above, a sample is prepared, and a bubble confirmation test, a cloudiness confirmation test, a durability test, and an adhesive strength after the pasting are performed. Measurement and storage modulus measurement were performed. (Bubble confirmation test after bonding) Using a bonding device (Climb Products Co., Ltd .; product name SE320), a 50 mm ⁇ 50 mm adhesive tape is bonded to a 2 mm thick glass plate of 75 mm ⁇ 100 mm size, and then an acrylic plate is attached to the opposite surface of the adhesive tape. Pasted.
- Example 6 which concerns on the adhesive tape of this invention is taken out from the oven immediately after taking out from the oven of a high temperature high humidity test. It can be seen that even after 60 minutes, the haze value has not changed at all, and has excellent white turbidity prevention performance. On the other hand, in Comparative Example 2, the haze value increased to about 11% as the maximum value within a few minutes immediately after taking out from the oven of the high temperature and high humidity test, and then the haze value gradually decreased with the passage of the standing time.
- Comparative Example 1 since there is no crosslinking agent, crosslinking is insufficient and it is considered that heat resistance cannot be imparted. In Comparative Example 2, it is considered that the monomer B is not polymerized. In Comparative Example 3, the photopolymerization initiator is considered to be a problem. In Comparative Example 4, since the amount of the crosslinking agent is excessive, it becomes too hard as an adhesive tape, and it is considered that the comparative example 4 is not able to follow the deformation of the adherend and peels off. In Comparative Example 5, since the amount of acrylic acid is too large and the adhesive tape is too hard, it is considered that the acrylic tape was peeled off without being able to follow the deformation of the acrylic plate. In addition, in the case of atmospheric pressure bonding, bubbles will enter (see the bubble confirmation test after bonding above), but it disappears temporarily in the autoclave, but it re-aggregates due to the introduction of environmental test. It is also considered that foaming occurs.
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Abstract
Description
また、本発明の粘着剤組成物及び粘着フィルムは、ディスプレイの前面に各種の光学フィルム及び保護板を貼り合せる場合や、ガラス同士を貼り合せて合わせガラスを作製する場合に使用することができる。 The present invention relates to a method for producing a pressure-sensitive adhesive composition, a method for producing a pressure-sensitive adhesive film, a raw material composition for pressure-sensitive adhesive, and a pressure-sensitive adhesive film, and more particularly, under environmental conditions at high temperature and high humidity using an oven. A method for producing a pressure-sensitive adhesive composition, a method for producing a pressure-sensitive adhesive film, a pressure-sensitive adhesive film having excellent performance without causing cloudiness of the pressure-sensitive adhesive layer and lifting and peeling from the adherend even when the durability test is performed and after taking out from the oven. The present invention relates to an agent raw material composition and an adhesive film.
In addition, the pressure-sensitive adhesive composition and pressure-sensitive adhesive film of the present invention can be used when various optical films and protective plates are bonded to the front surface of the display, or when laminated glass is manufactured by bonding glasses together.
例えば、PDPにおいては、電磁波のシールドフィルム以外に、近赤外線の波長領域を使用している各種のリモコンスイッチの誤作動を防ぐための近赤外線吸収フィルム、その近赤外線吸収フィルムに使用されている近赤外線吸収剤の経時劣化を防ぐための紫外線吸収フィルム、さらには可視光領域の色調調整のためのネオン光カットフィルム、光学フィルターの表面に外光が映り込むのを防ぐための反射防止フィルム等が、ディスプレイ前面に貼り付けられている。これらのフィルムをディスプレイ用光学フィルターとして用いることにより画像の映り具合の改善が図られている。 In recent years, in various displays such as a PDP (plasma display), a liquid crystal panel, and an organic EL panel, various optical films and protective plates are attached to the front surface of the display.
For example, in the PDP, in addition to the electromagnetic wave shielding film, a near-infrared absorbing film for preventing malfunction of various remote control switches using the near-infrared wavelength region, and the near-infrared absorbing film used in the near-infrared absorbing film. UV absorbing film to prevent deterioration of infrared absorber over time, neon light cut film for color tone adjustment in the visible light region, antireflection film to prevent external light from being reflected on the surface of the optical filter, etc. , Pasted on the front of the display. By using these films as an optical filter for a display, the image appearance is improved.
また、PDPでも、軽量化と薄型化、及び視認性の向上を図るため、PDPパネルに直接光学フィルター用のフィルムを貼合することがダイレクトカラーフィルター方式として検討がされている。 Further, in a mobile phone in which a liquid crystal panel is used as a display, a shock absorbing protective plate is attached to the front surface of the liquid crystal panel via an air layer to prevent the liquid crystal panel from cracking. However, recently, in order to reduce weight and thickness, and improve visibility, a thin protective plate is directly bonded using an adhesive layer without providing an air layer on the front surface of a mobile phone liquid crystal panel. Has been done.
Also in PDP, in order to reduce the weight and thickness, and improve the visibility, it has been studied as a direct color filter system that an optical filter film is directly bonded to a PDP panel.
また、ディスプレイ表示装置の出荷前に行なわれるディスプレイの性能試験では、オーブンを使用して行われる高温・高湿度での環境条件下における耐久試験に合格する必要がある。オーブンから取り出した後、粘着剤層が白濁してしまうことがある。片側にフィルムを貼合している場合はその白濁は数時間でなくなり透明になるが、ガラス同士やガラス/アクリル板など硬いもの同士を貼合すると白濁は数日以上残る場合があり、ディスプレイの商品価値を損なうという問題があった。 The above optical film and protective plate are bonded to the front of the display using an adhesive layer, but when using the adhesive layer to bond various optical films and protective plates to the display, bubbles are not generated. There was a problem that microbubbles were generated at the interface between the pressure-sensitive adhesive layer and the adherend due to entrainment.
In addition, in a display performance test performed before shipment of the display device, it is necessary to pass an endurance test under environmental conditions at high temperature and high humidity performed using an oven. After removal from the oven, the pressure-sensitive adhesive layer may become cloudy. When a film is pasted on one side, the cloudiness becomes transparent within a few hours. However, when hard materials such as glass or glass / acrylic plates are pasted together, the cloudiness may remain for several days. There was a problem of damaging the product value.
具体的には、アルキル基の炭素数が7~18のアルキル(メタ)アクリレートと水酸基含有モノマーとの重量比率が100:0.01~5で含有するポリマー及び水酸基と反応する官能基を2つ以上有する化合物を含有する組成物の架橋物により形成された粘着剤層である。この粘着剤層を用いた光学フィルムをガラスに貼り合せた後、50℃×0.05MPa雰囲気下に5分間放置し、粘着剤層での微小気泡の発生の有無を目視にて確認する方法により気泡の有無を検査しているが、微小気泡の発生が防止できているとしている。 For example, Patent Document 1 discloses a pressure-sensitive adhesive optical film using a pressure-sensitive adhesive layer that improves the repair performance when a depression is generated on the surface of the pressure-sensitive adhesive layer and prevents entrainment of bubbles.
Specifically, a polymer containing an alkyl (meth) acrylate having an alkyl group having 7 to 18 carbon atoms and a hydroxyl group-containing monomer in a weight ratio of 100: 0.01 to 5 and two functional groups that react with the hydroxyl group. It is a pressure-sensitive adhesive layer formed from a crosslinked product of the composition containing the compound as described above. After the optical film using the pressure-sensitive adhesive layer is bonded to glass, it is left in an atmosphere of 50 ° C. × 0.05 MPa for 5 minutes, and the presence or absence of microbubbles in the pressure-sensitive adhesive layer is visually confirmed. Although the presence or absence of bubbles is inspected, the generation of microbubbles is prevented.
吸湿試験として、樹脂シートを60℃、90%RHの高温高湿試験槽に50時間入れることで行い、目視観察で評価を行なう方法で確認した結果、この樹脂組成物であれば発泡が少なく透明性に優れているとしている。
As a moisture absorption test, the resin sheet was placed in a high-temperature and high-humidity test tank of 60 ° C. and 90% RH for 50 hours, and as a result of confirmation by visual observation, this resin composition was transparent with little foaming. It is said to be excellent.
吸湿試験として、樹脂フィルムに積層した粘着剤層介してガラス板に貼り合せた積層体を60℃、90%RHの環境下に120時間放置した後、常温(25℃)下で30分間放置した後、ヘイズ値を測定して積層体の透明性を判定している。この粘着剤組成物によれば、高温高湿下で放置された後でも、発泡が少なくて高い透明性を維持できるとしている。
As a moisture absorption test, a laminate bonded to a glass plate through an adhesive layer laminated to a resin film was left in an environment of 60 ° C. and 90% RH for 120 hours, and then left at room temperature (25 ° C.) for 30 minutes. Thereafter, the haze value is measured to determine the transparency of the laminate. According to this pressure-sensitive adhesive composition, even after being left under high temperature and high humidity, it is said that high transparency can be maintained with less foaming.
ところで、特許文献3に関しては、供試用の粘着剤層を60℃、90%RHの環境下のオーブンにて試験し、およびそこから取り出した後、常温(25℃)下で30分間放置するという試験方法を採用している。つまり、特許文献3の試験方法は、粘着剤層の白濁はオーブンから取り出した直後から数分の間に白濁が始まり、30分後には目立たなくなる場合にも合格と判定される可能性がある。実際、特許文献2に関しては、吸湿試験後も白濁を維持した実施例19と違い、作製直後は若干の濁りが観察されたという実施例18もA(吸湿試験で白濁は認められない)と評価され、作製直後の濁りは考慮されていない。
これは、ポリエチレンテレフタレート(PET)などの薄い樹脂フィルムを片側もしくは両面に貼合する場合にはあまり目立たない現象であるが、アクリル板とガラス、ガラス同士などガスバリア性の高い材料を貼合した場合、60℃、90%RHの環境下にあるオーブンから取り出した直後から数分の間に白濁が始まり、その白濁が数時間以上に渡って残ってしまうという現象が生じる。従って、この粘着剤層を使用する環境によっては大きな問題となる。
また、近年、ディスプレイの用途が拡大していることに伴い、従来の環境試験条件に比較して、更に厳しい環境条件下での耐久性能が求められている。例えば、車載用のディスプレイに使用される光学フィルムを貼り合せる粘着テープでは、85℃、95%RHの環境条件下においても粘着剤層の白濁や被着体からの浮き及び剥がれが生じない粘着剤組成物、及びそれを用いた粘着テープが必要とされている。 The pressure-sensitive adhesive composition and pressure-sensitive adhesive layer described in Patent Documents 1 to 3 described above are performed under an environment of 60 ° C. and 90% RH at most as high-temperature and high-humidity environmental conditions.
By the way, with respect to
This is an inconspicuous phenomenon when a thin resin film such as polyethylene terephthalate (PET) is bonded to one or both sides, but when a gas barrier material such as an acrylic plate and glass or glass is bonded. , White turbidity starts in a few minutes immediately after taking out from the oven in an environment of 60 ° C. and 90% RH, and the white turbidity remains for several hours or more. Therefore, depending on the environment in which this pressure-sensitive adhesive layer is used, it becomes a big problem.
In recent years, with the expansion of display applications, durability performance under severer environmental conditions is required as compared with conventional environmental test conditions. For example, in an adhesive tape that bonds an optical film used in an on-vehicle display, the adhesive layer does not cause white turbidity and does not float or peel off from the adherend even under environmental conditions of 85 ° C. and 95% RH. There is a need for a composition and an adhesive tape using the composition.
従って、過酷な高温高湿の環境条件下では、粘着層が厚い視認性向上用粘着テープとして使用すると、水分に起因する粘着剤層の白濁や高温環境下にさらされたことによる被着体の変形による被着体からの浮き及び剥がれを防止できないという問題があった。 However, the pressure-sensitive adhesive composition described in Patent Document 1 imparts a hydroxyl group to an acrylic polymer and an alkyl (meth) acrylate (A) having 7 to 18 carbon atoms in the alkyl group serving as the skeleton of the acrylic polymer. After forming a copolymer with the hydroxyl group-containing monomer (B), a composition (crosslinking agent) containing a compound having two or more functional groups that react with a hydroxyl group is added to perform a crosslinking reaction. The weight ratio of (B) to (A) is 100: 0.01 to 5, and the amount of (B) added is small, which contributes to retention of moisture and increases the temperature. There is too little absolute amount of the hydroxyl group considered to be effective for preventing foaming in the environmental test under humidity. Furthermore, the hydroxyl group imparted to the copolymer is consumed in the crosslinking reaction, and the number of hydroxyl groups remaining after the crosslinking reaction is limited.
Therefore, under severe environmental conditions of high temperature and high humidity, when used as a pressure-sensitive adhesive tape with a thick adhesive layer, the adhesive layer may become clouded due to moisture or exposed to high temperatures. There has been a problem that the floating and peeling from the adherend due to deformation cannot be prevented.
また特許文献3の場合も特許文献2と同様に85℃、95%RHの環境条件下においても粘着層の白濁が生じない粘着剤組成物、及びそれを用いた粘着テープであることは明言されておらず、(メタ)アクリル酸アルキルエステルモノマーを過剰に導入しているため、実施例のように紫外線硬化時に可能な限り弱い紫外線を長時間照射する必要がある。また、60℃、90%RHの環境条件下においても粘着層の白濁が生じない粘着剤組成物、及びそれを用いた粘着テープであると明言されているが、弱い紫外線を長時間照射する必要があるため生産性が悪い。 In the pressure-sensitive adhesive composition described in
Also, in the case of
さらに、被着体からの浮き及び剥がれを防止するため、粘着剤を架橋して耐熱性を付与するとともに、高温環境下にさらされて被着体に変形が生じても架橋した粘着剤が被着体の変形に追従できるようにする。 In order to prevent cloudiness of the pressure-sensitive adhesive layer without causing aggregation of water molecules due to a sudden change in the external environment, in the present invention, in the production of an acrylic polymer having a hydroxyl group, a monomer having no hydroxyl group The technical idea is to obtain a pressure-sensitive adhesive composition in which water molecules are dispersed in such a way that they are invisible so as to be polymerized as a single substance as much as possible.
Furthermore, in order to prevent lifting and peeling from the adherend, the pressure-sensitive adhesive is crosslinked to impart heat resistance, and the crosslinked pressure-sensitive adhesive is not covered even if the adherend is deformed by exposure to a high temperature environment. To be able to follow the deformation of the kimono.
そこで、本発明では、上記問題点を解決するために、主剤となるアクリル系ポリマーをあらかじめ重合させておき、これを、ヒドロキシル基含有の(メタ)アクリレートのモノマーの少なくとも1種類を溶解させたシロップ、もしくは有機溶媒液に溶解して得られた溶剤系アクリル樹脂に、ポリマーの架橋点に対して0.1当量以下となる量の2官能性の架橋剤と、光重合開始剤とともに加えて粘着剤塗布液(粘着剤層の前駆体となる粘着剤用原料組成物)を調製する。この塗布液を基材に塗布・乾燥・光照射・養生して、水分子の凝集防止に関与するヒドロキシル基を含有し、かつ被着体の変形に追従できる程度に架橋された粘着剤組成物を得る。これにより、ヒドロキシル基を有するアクリル系ポリマーを効率良く作製し、かつ均一に混ざりにくいポリマー同士を問題なく混合することができ、光学特性に優れた粘着剤組成物を得る。さらに、本発明においては、あらかじめ重合させておいた主剤となるアクリル系ポリマーに対するモノマーの添加量を従来技術と比較して少なくできるため、生産性の高い粘着フィルムを提供できる。 In the present invention, a hydroxyl group-containing polymer obtained by a polymerization reaction of at least one monomer of a hydroxyl group-containing (meth) acrylate is introduced into the pressure-sensitive adhesive layer to participate in preventing aggregation of water molecules.
Therefore, in the present invention, in order to solve the above problems, an acrylic polymer as a main agent is polymerized in advance, and this is a syrup in which at least one kind of hydroxyl group-containing (meth) acrylate monomer is dissolved. Or a solvent-based acrylic resin obtained by dissolving in an organic solvent solution together with a bifunctional crosslinking agent in an amount of 0.1 equivalent or less with respect to the crosslinking point of the polymer and a photopolymerization initiator An adhesive coating solution (a pressure-sensitive adhesive raw material composition to be a precursor of the pressure-sensitive adhesive layer) is prepared. A pressure-sensitive adhesive composition containing a hydroxyl group involved in preventing aggregation of water molecules by coating, drying, irradiating and curing this coating solution on a base material, and being crosslinked to the extent that it can follow the deformation of the adherend. Get. Thereby, the acrylic polymer which has a hydroxyl group can be produced efficiently, and the polymer which is hard to mix uniformly can be mixed without a problem, and the adhesive composition excellent in the optical characteristic is obtained. Furthermore, in this invention, since the addition amount of the monomer with respect to the acrylic polymer used as the main ingredient previously polymerized can be reduced compared with a prior art, an adhesive film with high productivity can be provided.
(I) (1)アクリル系モノマーの少なくとも1種類を含有する混合溶媒液を用いて、主剤ポリマーを得るポリマー製造工程;
(2)前記主剤ポリマーと、ヒドロキシル基含有の(メタ)アクリレートのモノマーの少なくとも1種類と、光重合開始剤と、ポリマーの架橋点に対して0.1当量以下となる量の2官能性の架橋剤とを含有する粘着剤用原料組成物を調製する工程;及び
(3)前記粘着剤用原料組成物を用い、光照射による重合反応及び架橋反応をさせて粘着剤組成物を得る工程;
を含む、粘着剤組成物の製造方法。 In order to solve the above problems, the present invention has the following configuration.
(I) (1) A polymer production process for obtaining a main polymer using a mixed solvent liquid containing at least one kind of acrylic monomer;
(2) Bifunctional in an amount of 0.1 equivalent or less with respect to the crosslinking point of the polymer, at least one monomer of a hydroxyl group-containing (meth) acrylate, a photopolymerization initiator, and a polymer crosslinking point. A step of preparing a pressure-sensitive adhesive raw material composition containing a crosslinking agent; and (3) a step of obtaining a pressure-sensitive adhesive composition by performing a polymerization reaction and a crosslinking reaction by light irradiation using the pressure-sensitive adhesive raw material composition;
The manufacturing method of the adhesive composition containing this.
(2)前記主剤ポリマーと、ヒドロキシル基含有の(メタ)アクリレートのモノマーの少なくとも1種類と、光重合開始剤と、ポリマーの架橋点に対して0.1当量以下となる量の2官能性の架橋剤とを含有する粘着剤用原料組成物を調製する工程;
(3)前記粘着剤用原料組成物を、粘着フィルムの基材またはセパレーター上に塗布及び乾燥して粘着剤塗布膜を形成する工程;及び
(4)前記粘着剤塗布膜への光照射による重合反応及び架橋反応をさせて粘着剤層を得る工程;
を含む、粘着フィルムの製造方法を提供する。 (II) (1) A polymer production process for obtaining a main polymer using a mixed solvent liquid containing at least one kind of acrylic monomer;
(2) Bifunctional in an amount of 0.1 equivalent or less with respect to the crosslinking point of the polymer, at least one monomer of a hydroxyl group-containing (meth) acrylate, a photopolymerization initiator, and a polymer crosslinking point. A step of preparing a pressure-sensitive adhesive raw material composition containing a crosslinking agent;
(3) A step of applying and drying the pressure-sensitive adhesive raw material composition on a base material or a separator of the pressure-sensitive adhesive film to form a pressure-sensitive adhesive coating film; and (4) polymerization by light irradiation on the pressure-sensitive adhesive coating film. A step of carrying out a reaction and a crosslinking reaction to obtain an adhesive layer;
A method for producing an adhesive film is provided.
(B)ヒドロキシル基含有の(メタ)アクリレートのモノマーの少なくとも1種類:5~20重量部;
(C)光重合開始剤:0.01~0.5重量部;及び
(D)2官能性の架橋剤を、ポリマーの架橋点に対して0.1当量以下となる1.0~3.0重量部;
を含有し、
かつ前記主剤ポリマーの分子量分布が、数平均分子量(Mn)で7万以上、重量平均分子量(Mw)で100万以上である、粘着剤用原料組成物。 (III) (A) At least one kind of acrylic monomer having an ester group is polymerized from a monomer containing 85 to 95 parts by weight and at least one kind of acrylic monomer having a carboxyl group is polymerized from 5 to 15 parts by weight. Main polymer: 100 parts by weight;
(B) at least one kind of hydroxyl group-containing (meth) acrylate monomer: 5 to 20 parts by weight;
(C) Photopolymerization initiator: 0.01 to 0.5 parts by weight; and (D) The bifunctional crosslinking agent is 0.1 to 3 equivalents or less with respect to the crosslinking point of the polymer. 0 parts by weight;
Containing
And the molecular weight distribution of the said main ingredient polymer is a raw material composition for adhesives whose number average molecular weight (Mn) is 70,000 or more and whose weight average molecular weight (Mw) is 1 million or more.
当該粘着剤層が、上記(III)の粘着剤用原料組成物を、基材またはセパレーター上に塗布した後、光照射により重合反応及び架橋反応をさせて得られる、厚みが0.05~3mmである粘着フィルム。 (IV) including a base material or a separator, and an adhesive layer,
The pressure-sensitive adhesive layer is obtained by applying the above-mentioned pressure-sensitive adhesive raw material composition (III) on a substrate or a separator, followed by polymerization reaction and cross-linking reaction by light irradiation, and has a thickness of 0.05 to 3 mm. Is an adhesive film.
(VI) ディスプレイに部材を貼り合わせる用途の粘着テープ。 (V) The pressure-sensitive adhesive layer is bonded to glass and acrylic resin when the pressure-sensitive adhesive surface is bonded to an adherend and left in a 23 ° C., 50% RH environment for 1 hour and then peeled at a peeling speed of 300 mm / min. The above, wherein the force is 10 N / 25 mm or more and the storage elastic modulus (G ′) at 23 ° C. and 1 Hz of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is 1 × 10 4 Pa or more and less than 1 × 10 6 Pa ( IV).
(VI) Adhesive tape for attaching materials to the display.
また、粘着剤塗布液の流動性を適切に調整することによって基材への塗布厚みをより厚くすることが可能であり、緩衝性の高い粘着剤テープを提供することができる。
さらに、架橋剤の量を、ポリマーの架橋点に対して0.1当量以下となる量とし、架橋剤の種類を2官能性のものとすることにより、高温環境下にさらされたことによる被着体の変形に追従できる程度に粘着剤が架橋され、更に耐熱性も付与され、より過酷な条件下での被着体からの浮き及び剥がれを防止することができる。 According to the present invention described above, by suppressing the crosslinking reaction of the acrylic polymer to a minimum, the number of hydroxyl groups introduced into the polymer can be prevented from being consumed and reduced, and a hydroxyl group capable of adsorbing water molecules is possible. Provided is a pressure-sensitive adhesive composition which is present in a necessary quantity in a dispersed state as much as possible. This makes it possible to adsorb moisture under high-temperature and high-humidity environmental conditions to the hydroxyl group-containing polymer, and to prevent the occurrence of white turbidity due to the aggregation of absorbed water molecules even if the pressure-sensitive adhesive layer is thickened to increase buffering properties. An agent composition can be provided.
In addition, by appropriately adjusting the fluidity of the pressure-sensitive adhesive coating solution, it is possible to increase the coating thickness on the substrate, and it is possible to provide a pressure-sensitive adhesive tape with high buffering properties.
Further, the amount of the crosslinking agent is 0.1 equivalent or less with respect to the crosslinking point of the polymer, and the type of the crosslinking agent is bifunctional, so that the coating caused by exposure to a high temperature environment. The pressure-sensitive adhesive is cross-linked to such an extent that it can follow the deformation of the adherend, and is further imparted with heat resistance, and can be prevented from floating and peeling off from the adherend under more severe conditions.
上記(II)に記載の発明によれば、緩衝性を高めるために粘着剤層の厚みを厚くしても、高温・高湿度での環境条件下およびそれより取り出した後における水分子の凝集に起因する粘着剤層の白濁や被着体からの浮き及び剥がれが生じない粘着フィルムの製造方法を提供できる。 According to the invention described in the above (I), even if the thickness of the pressure-sensitive adhesive layer is increased in order to enhance the buffering property, the water molecules are aggregated after being removed from the environmental conditions at high temperature and high humidity. It is possible to provide a method for producing a pressure-sensitive adhesive composition in which the resulting pressure-sensitive adhesive layer does not become cloudy or does not float or peel off from the adherend.
According to the invention described in (II) above, even if the thickness of the pressure-sensitive adhesive layer is increased in order to increase the buffering property, water molecules are aggregated after being removed from the environmental conditions at high temperature and high humidity. It is possible to provide a method for producing a pressure-sensitive adhesive film in which the resulting pressure-sensitive adhesive layer does not become cloudy or does not float or peel off from the adherend.
上記(IV)~(VI)に記載の発明によれば、緩衝性を高めるために粘着剤層を厚くしても、高温・高湿度での環境条件下およびそれより取り出した後における水分子の凝集に起因する粘着剤層の白濁や被着体からの浮き及び剥がれが生じない粘着フィルムを提供できる。 According to the invention described in (III) above, even if the pressure-sensitive adhesive layer is thickened to increase the buffering property, it is caused by the aggregation of water molecules after environmental conditions at high temperature and high humidity and after removal from the environmental layer. It is possible to provide a pressure-sensitive adhesive coating liquid (a pressure-sensitive adhesive raw material composition) in which the pressure-sensitive adhesive layer does not become cloudy or does not float or peel off from the adherend.
According to the inventions described in the above (IV) to (VI), even if the pressure-sensitive adhesive layer is thickened to enhance the buffering property, the water molecules are removed under environmental conditions at high temperature and high humidity and after removal from the environmental layer. It is possible to provide an adhesive film in which the pressure-sensitive adhesive layer is not clouded due to aggregation, and is not lifted from or peeled off from the adherend.
本発明の粘着剤用原料組成物は、少なくとも1種類のヒドロキシル基含有モノマー(モノマーB)を、そのモノマーBを重合させるための重合開始剤、主剤ポリマー(ポリマーA)および主剤ポリマーを架橋するための架橋剤に混合したものである。この粘着剤用原料組成物は、エネルギー線により重合する光重合性化合物として、少なくとも1種類のヒドロキシル基含有の(メタ)アクリレートを含有する。(メタ)アクリレートのモノマーは、光重合開始剤とラジカル重合可能なビニル基である(メタ)アクリル基を有する重合性化合物であって、例えば、300nm~400nmの範囲内の紫外線に対して硬化性を有する紫外線硬化性樹脂材料である。
なお、本明細書において、(メタ)アクリレートとは、アクリレート及びメタクリレートの総称である。 Hereinafter, preferred embodiments of the present invention will be described.
The pressure sensitive adhesive raw material composition of the present invention crosslinks at least one hydroxyl group-containing monomer (monomer B) with a polymerization initiator for polymerizing the monomer B, the main polymer (polymer A), and the main polymer. It was mixed with a crosslinking agent. This raw material composition for pressure-sensitive adhesives contains at least one hydroxyl group-containing (meth) acrylate as a photopolymerizable compound that is polymerized by energy rays. The monomer of (meth) acrylate is a polymerizable compound having a (meth) acryl group which is a vinyl group capable of radical polymerization with a photopolymerization initiator, and is curable, for example, in the range of 300 nm to 400 nm. Is an ultraviolet curable resin material.
In this specification, (meth) acrylate is a general term for acrylate and methacrylate.
モノマーBが分散しやすいためにはアクリル系ポリマーであることが好ましく、さらには親水性モノマーを共重合していることが好ましい。これはモノマーBがアクリル系であることとヒドロキシル基を含有しているためである。また、本発明の粘着剤用原料組成物は、光学用途に使用した場合には透明性を有することが必要であり、かつ粘着力の強弱を制御することが簡便であることからも、ポリマーAはアクリル系ポリマーであることが好ましい。 The polymer A is not particularly limited as long as it is the main component of the pressure-sensitive adhesive and the acrylic monomer (monomer B) containing a hydroxyl group is easily dispersed.
In order to easily disperse the monomer B, an acrylic polymer is preferable, and a hydrophilic monomer is preferably copolymerized. This is because the monomer B is acrylic and contains a hydroxyl group. Moreover, since the raw material composition for pressure-sensitive adhesives of the present invention needs to have transparency when used for optical applications, and it is easy to control the strength of the pressure-sensitive adhesive, the polymer A Is preferably an acrylic polymer.
さらに、本発明においては、架橋剤の量及び種類をポリマーの架橋点に対して0.1当量以下となる量の2官能性の架橋剤とすることにより、被着体の変形に追従できる程度に粘着剤を架橋して耐熱性が付与され、被着体からの浮き及び剥がれを防止することができる。 When the raw material composition for pressure-sensitive adhesives of the present invention is applied to a substrate (or a separator) and dried and then polymerized by light irradiation, a pressure-sensitive adhesive film is obtained. Moreover, the raw material composition for pressure-sensitive adhesives of the present invention contains a cross-linking agent for cross-linking the polymer, and the content of the cross-linking agent is less than 1 equivalent to the cross-linking point of the polymer (preferably, for example, 0.5 Equivalent or less). As a result, even if the crosslinking agent can be crosslinked with the hydroxyl group of the polymer B like an isocyanate compound, at least a part of the hydroxyl group of the polymer B is not crosslinked, and the uncrosslinked hydroxyl group is dispersed. Therefore, a pressure-sensitive adhesive layer excellent in moisture adsorption ability can be obtained.
Furthermore, in the present invention, the amount and type of the crosslinking agent is a bifunctional crosslinking agent in an amount of 0.1 equivalent or less with respect to the crosslinking point of the polymer, so that the deformation of the adherend can be followed. The pressure-sensitive adhesive is crosslinked to impart heat resistance, and can be prevented from floating and peeling off from the adherend.
基材を有する両面粘着テープの構造については特に図示しないが、基材の両面に粘着剤層が形成され、それぞれの粘着剤層の粘着面がセパレーターで保護された構造を有する。 In FIG. 1A, an example of the single-sided
The structure of the double-sided pressure-sensitive adhesive tape having a base material is not particularly shown, but a pressure-sensitive adhesive layer is formed on both surfaces of the base material, and the pressure-sensitive adhesive surface of each pressure-sensitive adhesive layer has a structure protected by a separator.
本発明における、高温・高湿度での環境条件下における白濁の発生を防止できる改善効果については、トランスファーテープの形態で貼り合わせるガラス(無機ガラス)やアクリル樹脂(アクリルガラス)などの水分の透過性が悪いものの場合に、特に著しい効果が得られる。これは次の理由による。
水分子の透過性の良い樹脂フィルムを貼合する場合は、粘着テープ層に分散している水分子が樹脂フィルムの場合は簡単に透過して通り抜けることができるため、水分子の凝集する確率が減ることと、仮に水分子が凝集したとしてもすぐに樹脂フィルムを通して抜けていくため、白濁している時間が短いことになる。しかし、水分子の透過性の悪い材料を貼合する場合は、水分子が凝集し白濁してしまうと、粘着テープの周辺端に水分子が拡散した後に抜けるため、長時間に渡り白濁が続くことになるからである。 FIG. 1B schematically shows an example of the
About the improvement effect that can prevent the occurrence of white turbidity under environmental conditions at high temperature and high humidity in the present invention, the permeability of moisture such as glass (inorganic glass) or acrylic resin (acrylic glass) to be bonded in the form of transfer tape In particular, a remarkable effect can be obtained in the case of a bad one. This is due to the following reason.
When pasting a resin film with good water molecule permeability, the water molecules dispersed in the adhesive tape layer can be easily penetrated and passed through in the case of a resin film. If the water molecules are reduced, even if water molecules are aggregated, the water molecules are immediately removed through the resin film. However, when pasting a material with poor water molecule permeability, if water molecules aggregate and become cloudy, the water molecules diffuse after spreading to the peripheral edge of the adhesive tape, and thus the cloudiness continues for a long time. Because it will be.
アルキル(メタ)アクリレートは、粘着力の観点から、アルキル基R2の炭素数が1~14とされる。アルキル基の炭素数が15以上であると、粘着力が低下する可能性があるので好ましくない。このアルキル基R2は、炭素数が1~12であることが好ましく、炭素数が4~12であることが好ましく、炭素数が4~8であることがより好ましい。
また、アルキル基R2の炭素数が1~14のアルキル(メタ)アクリレートのうち、アルキル基R2の炭素数が1~3または13~14のアルキル(メタ)アクリレートをモノマーの一部分として用いても良いが、アルキル基R2の炭素数が4~12のアルキル(メタ)アクリレートを必須として(例えば50~100モル%)用いることが好ましい。
なお、これらのアルキル基R2は、直鎖であっても、分岐鎖であってもよい。 Examples of the alkyl (meth) acrylate represented by the general formula CH 2 ═CR 1 —COOR 2 (wherein R 1 represents hydrogen or a methyl group, and R 2 represents an alkyl group having 1 to 14 carbon atoms) include Includes methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate , N-pentyl (meth) acrylate, isopentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate , Decyl (meth) acrylate, Sil (meth) acrylate and the like, it may be used singly or in combination of two or more. Of these, 2-ethylhexyl (meth) acrylate and n-butyl (meth) acrylate are preferably used.
In the alkyl (meth) acrylate, the alkyl group R 2 has 1 to 14 carbon atoms from the viewpoint of adhesive strength. It is not preferable that the alkyl group has 15 or more carbon atoms because the adhesive strength may be reduced. The alkyl group R 2 preferably has 1 to 12 carbon atoms, preferably 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms.
Further, among the alkyl (meth) acrylates having 1 to 14 carbon atoms in the alkyl group R 2 , alkyl (meth) acrylates having 1 to 3 or 13 to 14 carbon atoms in the alkyl group R 2 are used as a part of the monomer. However, it is preferable to use an alkyl (meth) acrylate having 4 to 12 carbon atoms of the alkyl group R 2 as an essential component (for example, 50 to 100 mol%).
Incidentally, these alkyl groups R 2 may be a straight chain or may be branched.
また、カルボキシル基を含有するアクリル系モノマーとしては、例えば、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、2-アクリロイルエチル琥珀酸などが挙げられる。 Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate. , Polypropylene glycol mono (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, and the like.
Examples of the acrylic monomer containing a carboxyl group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, 2-acryloylethyl succinic acid, and the like.
ポリマーAを構成するモノマーのうち、アルキル(メタ)アクリレートと親水基を有するモノマーとの配合比は、粘着剤に求められる特性やモノマーの種類、1分子中に親水基が占める重量比などによっても異なるが、例えば5~50重量%が親水基を有するモノマーであり、95~50重量%がアルキル(メタ)アクリレートであることが好ましい。 Another monomer can be added to the raw material monomer of the polymer A. For example, a monomer having a hydrophilic group such as a carboxyl group, an alkoxysilyl group, an amino group, a hydroxyl group, or a sulfonic acid group can be selected and used.
Among the monomers constituting the polymer A, the blending ratio of the alkyl (meth) acrylate and the monomer having a hydrophilic group depends on the characteristics required for the pressure-sensitive adhesive, the type of monomer, the weight ratio of the hydrophilic group in one molecule, and the like. Although different, for example, 5 to 50% by weight is preferably a monomer having a hydrophilic group, and 95 to 50% by weight is preferably an alkyl (meth) acrylate.
また、アルコキシシリル基を含有する非アクリル系モノマーとしては、例えば、ビニルメトキシシラン、ビニルトリメトキシシランなどが挙げられる。
また、アミノ基を含有するアクリル系モノマーとしては、例えば、ジメチルアミノエチル(メタ)アクリレート、ジメチルアミノプロピル(メタ)アクリレート、t-ブチルアミノエチル(メタ)アクリレート、モノメチルアミノエチル(メタ)アクリレート等のアミノ基を含有する(メタ)アクリレートのほか、(メタ)アクリル酸アミド、イタコン酸アミド、ジメチルアミノプロピル(メタ)アクリルアミド、ジメチルアミノエチル(メタ)アクリルアミド、N-メトキシメチルアクリルアミド、N-エトキシメチル(メタ)アクリルアミド、N-メトキシメチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミドなどが挙げられる。 Examples of acrylic monomers containing alkoxysilyl groups include γ-trimethoxysilylpropyl (meth) acrylate, γ-methyldimethoxysilylpropyl (meth) acrylate, and γ-triethoxysilylpropyl (meth) acrylate. Can be mentioned.
Examples of the non-acrylic monomer containing an alkoxysilyl group include vinylmethoxysilane and vinyltrimethoxysilane.
Examples of the acrylic monomer containing an amino group include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, and monomethylaminoethyl (meth) acrylate. In addition to (meth) acrylates containing amino groups, (meth) acrylic acid amide, itaconic acid amide, dimethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, N-methoxymethylacrylamide, N-ethoxymethyl ( Examples include meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide.
ポリマーAを構成するアクリル系モノマー及び任意に配合される非アクリル系モノマーを重合させるには、溶液重合、塊状重合、懸濁重合、乳化重合等の公知の方法により行うことができるが、除熱の容易な溶液重合が好適に用いられる。溶液重合反応において使用される有機溶媒としては、具体的には、例えば、トルエン、キシレン等の芳香族炭化水素類、酢酸エチル、酢酸ブチル等の脂肪族エステル類、シクロヘキサン等の脂環族炭化水素類、ヘキサン、ペンタン等の脂肪族炭化水素類等が挙げられるが、上記重合反応を阻害しなければ、特に限定されない。これらの溶媒は、1種類のみを用いてもよく、2種類以上を混合して用いてもよい。溶媒の使用量は、適宜に決定すればよい。
一般的に、溶液重合反応においては、重合温度が高くなるに従い、生成されるポリマーの分子量は低下する。重合反応を溶媒の還流温度で行わせるに当たり、重合反応に適した沸点温度を有する溶媒を使用することにより、重合反応熱を除去しながらポリマーを得ることができる。 The polymer A is preferably composed of an acrylic monomer (an alkyl (meth) acrylate and an acrylic monomer having a hydrophilic group) for the most part (for example, 50% by weight or more, more preferably 80% by weight or more) Monomers other than acrylic monomers (non-acrylic monomers) can be used in combination so as not to impair the effects of the present invention.
Polymerization of the acrylic monomer constituting the polymer A and the optionally blended non-acrylic monomer can be carried out by a known method such as solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, etc. The easy solution polymerization is preferably used. Specific examples of the organic solvent used in the solution polymerization reaction include aromatic hydrocarbons such as toluene and xylene, aliphatic esters such as ethyl acetate and butyl acetate, and alicyclic hydrocarbons such as cyclohexane. , Aliphatic hydrocarbons such as hexane, pentane and the like, but not particularly limited as long as the polymerization reaction is not inhibited. These solvents may be used alone or in combination of two or more. What is necessary is just to determine the usage-amount of a solvent suitably.
In general, in the solution polymerization reaction, the molecular weight of the polymer produced decreases as the polymerization temperature increases. In carrying out the polymerization reaction at the reflux temperature of the solvent, a polymer can be obtained while removing the heat of polymerization reaction by using a solvent having a boiling point temperature suitable for the polymerization reaction.
分子量が大きすぎると粘度が高すぎて加工適性が悪くなる。塗料の温度を上げるなど塗工方法を工夫することでこの上限はさらに広げられると考えられるが、室温で塗工をする場合、例えば、Mw500万未満の材料が好ましいと考えられる。 The molecular weight distribution of the polymer A is preferably 70,000 or more in terms of number average molecular weight (Mn) and 1,000,000 or more in terms of weight average molecular weight (Mw). Furthermore, the weight average molecular weight (Mw) is more preferably 12 million or more. Thus, when the molecular weight of the polymer A is large, the heat resistance and the weather resistance are more excellent.
If the molecular weight is too large, the viscosity is too high and the processability is deteriorated. It is considered that this upper limit can be further widened by devising the coating method such as raising the temperature of the paint. However, when coating is performed at room temperature, for example, a material having an Mw of less than 5 million is considered preferable.
本発明の粘着剤用原料組成物の一つの好ましい実施態様においては、ヒドロキシル基を含有しないアルキル(メタ)アクリレート及びアクリル酸のモノマーを重合させて得られたアクリル系ポリマーと、ヒドロキシル基含有の(メタ)アクリレートのモノマーとが、共重合しないで別々に分散した混合状態で存在する。また、別の好ましい実施態様においては、親水性モノマーを含むモノマーを重合させて得られたポリマーAと、ヒドロキシル基含有の(メタ)アクリレートのモノマーとが、粘着剤用原料組成物中に含まれる。 Moreover, the raw material composition for pressure-sensitive adhesives of the present invention contains at least one monomer (monomer B) of a hydroxyl group-containing (meth) acrylate.
In one preferable embodiment of the raw material composition for pressure-sensitive adhesives of the present invention, an acrylic polymer obtained by polymerizing a monomer of alkyl (meth) acrylate and acrylic acid not containing a hydroxyl group, and a hydroxyl group-containing ( The monomer of (meth) acrylate exists in the state of being mixed separately without being copolymerized. In another preferred embodiment, the polymer A obtained by polymerizing a monomer containing a hydrophilic monomer and a hydroxyl group-containing (meth) acrylate monomer are contained in the pressure-sensitive adhesive raw material composition. .
なお、公知のヒドロキシル基を含有するアクリル系ポリマーからなる粘着剤組成物において、未反応モノマーとしてヒドロキシル基を含有する(メタ)アクリレートのモノマーを若干含有することがあるが、その含有率は、本発明の粘着剤用原料組成物におけるヒドロキシル基含有の(メタ)アクリレートの含有率に比べると、著しく低いものに過ぎない。 The content of monomer B (the total amount when monomer B is two or more) is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the main polymer (polymer A), and is 85 ° C. 95 In the case where high durability is required such as in a test under a% RH environment, the amount is more preferably 5 to 15 parts by weight.
The pressure-sensitive adhesive composition comprising a known hydroxyl group-containing acrylic polymer may contain some (meth) acrylate monomers containing hydroxyl groups as unreacted monomers. Compared to the content of hydroxyl group-containing (meth) acrylate in the raw material composition for pressure-sensitive adhesives of the invention, the content is only extremely low.
また、アクリルシロップに光重合開始剤を添加した後は、室内光や太陽光に含まれる紫外光がアクリルシロップに作用すると重合反応が進行するおそれがあり、管理が難しくなるため、光重合開始剤は、後工程である塗布工程のなるべく直前に添加することが好ましい。これは、アクリルシロップが有機溶媒に溶解している樹脂溶液でも同様の扱いで、注意すべきは光開始剤が何らかの外的要因で塗布・製膜前に反応を開始してしまうことを防ぐことである。 In the step of dissolving the hydroxyl group-containing monomer in the main polymer to obtain an acrylic syrup, before dissolving the hydroxyl group-containing monomer in the main polymer, the organic solvent used in the polymerization reaction is removed, and the obtained liquid syrup is obtained. The main polymer is preferably separated and washed with water or an organic solvent as necessary. Thereby, the polymerization reaction of the main polymer can be completely stopped, and unreacted acrylic monomers can be removed from the main polymer. In addition, the weight of the main polymer can be quantified more accurately, and an acrylic syrup in which the contents of the hydroxyl group-containing monomer, the crosslinking agent, and the photopolymerization initiator used in the next step are more appropriately adjusted can be produced. When preparing an acrylic syrup, the removal of the organic solvent used in the polymerization reaction may be performed after the hydroxyl group-containing monomer is dissolved in the main polymer.
In addition, after adding a photopolymerization initiator to an acrylic syrup, the polymerization reaction may proceed when ultraviolet light contained in room light or sunlight acts on the acrylic syrup, making it difficult to manage. Is preferably added immediately before the coating step, which is a subsequent step. This is the same for resin solutions in which acrylic syrup is dissolved in an organic solvent. Care should be taken to prevent the photoinitiator from starting the reaction before coating and film formation due to some external factor. It is.
ヒドロキシル基含有の(メタ)アクリレートとしては、二価アルコール(ジオール化合物)の有する2つのヒドロキシル基のうち一つのヒドロキシル基を、アクリル酸またはメタクリル酸でエステル化して得られ、1分子にヒドロキシル基及びビニル基を1つずつ有する、ヒドロキシアルキル(メタ)アクリレートが好適に用いられる。 The hydroxyl group-containing (meth) acrylate monomers used as monomer B in the present invention are 2-hydroxylethyl (meth) acrylate, 2-hydroxylpropyl (meth) acrylate, 3-hydroxylpropyl (meth) acrylate, 4- Hydroxylbutyl (meth) acrylate, 5-hydroxylpentyl (meth) acrylate, 6-hydroxylhexyl (meth) acrylate, 7-hydroxylheptyl (meth) acrylate, 8-hydroxyloctyl (meth) acrylate, 7-methyl-8-hydroxyl Octyl (meth) acrylate, 2-methyl-8-hydroxyloctyl (meth) acrylate, 9-hydroxylnonyl (meth) acrylate, 10-hydroxyldecyl (meth) acrylate, 12-hy B hexyl lauryl (meth) acrylate and the like, they may be used in combination of two or more may be used alone. In particular, 2-hydroxylethyl (meth) acrylate, hydroxylpropyl (meth) acrylate, and 4-hydroxylbutyl (meth) acrylate are preferably used.
The hydroxyl group-containing (meth) acrylate is obtained by esterifying one hydroxyl group of two hydroxyl groups of a dihydric alcohol (diol compound) with acrylic acid or methacrylic acid. A hydroxyalkyl (meth) acrylate having one vinyl group at a time is preferably used.
アセトフェノン系光重合開始剤としては、アセトフェノン、p-(tert-ブチル)1’,1’,1’-トリクロロアセトフェノン、クロロアセトフェノン、2’,2’-ジエトキシアセトフェノン、ヒドロキシルアセトフェノン、2,2-ジメトキシ-2’-フェニルアセトフェノン、2-アミノアセトフェノン、ジアルキルアミノアセトフェノン等が挙げられる。
ベンゾイン系光重合開始剤としては、ベンジル、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、1-ヒドロキシルシクロヘキシルフェニルケトン、2-ヒドロキシル2-メチル-1-フェニル-2-メチルプロパン-1-オン、1-(4-イソプロピルフェニル)-2-ヒドロキシル2-メチルプロパン-1-オン、ベンジルジメチルケタール等が挙げられる。
ベンゾフェノン系光重合開始剤としては、ベンゾフェノン、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、メチル-o-ベンゾイルベンゾエート、4-フェニルベンゾフェノン、ヒドロキシルベンゾフェノン、ヒドロキシルプロピルベンゾフェノン、アクリルベンゾフェノン、4,4’-ビス(ジメチルアミノ)ベンゾフェノン等が挙げられる。
チオキサントン系光重合開始剤としては、チオキサントン、2-クロロチオキサントン、2-メチルチオキサントン、ジエチルチオキサントン、ジメチルチオキサントン等が挙げられる。
その他の光重合開始剤としては、α-アシルオキシムエステル、ベンジル-(o-エトキシカルボニル)-α-モノオキシム、アシルホスフィンオキサイド、グリオキシエステル、3-ケトクマリン、2-エチルアンスラキノン、カンファーキノン、テトラメチルチウラムスルフィド、アゾビスイソブチロニトリル、ベンゾイルペルオキシド、ジアルキルペルオキシド、tert-ブチルペルオキシピバレート等が挙げられる。 Although it does not specifically limit as a photoinitiator (polymerization catalyst), For example, an acetophenone type photoinitiator, a benzoin type photoinitiator, a benzophenone type photoinitiator, a thioxanthone type photoinitiator, a thioxanthone type photopolymerization An initiator etc. are mentioned.
As the acetophenone photopolymerization initiator, acetophenone, p- (tert-butyl) 1 ′, 1 ′, 1′-trichloroacetophenone, chloroacetophenone, 2 ′, 2′-diethoxyacetophenone, hydroxylacetophenone, 2,2- Examples include dimethoxy-2′-phenylacetophenone, 2-aminoacetophenone, dialkylaminoacetophenone, and the like.
Benzoin photopolymerization initiators include benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxyl cyclohexyl phenyl ketone, 2-hydroxyl 2-methyl-1-phenyl-2-methyl Propan-1-one, 1- (4-isopropylphenyl) -2-hydroxyl 2-methylpropan-1-one, benzyldimethyl ketal and the like can be mentioned.
Benzophenone photopolymerization initiators include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, hydroxylbenzophenone, hydroxylpropylbenzophenone, acrylic benzophenone, 4,4'-bis (dimethyl) Amino) benzophenone and the like.
Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, diethylthioxanthone, and dimethylthioxanthone.
Other photopolymerization initiators include α-acyl oxime ester, benzyl- (o-ethoxycarbonyl) -α-monooxime, acyl phosphine oxide, glyoxy ester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, tetra Examples thereof include methyl thiuram sulfide, azobisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, tert-butyl peroxypivalate and the like.
また、上述したように、主剤ポリマー100重量部に対して、ヒドロキシル基含有の(メタ)アクリレートのモノマー(2種類以上用いる場合は合計量)は5~20重量部であることが好ましく、85℃95%RH環境下での試験を行うなど高耐久性を必要とする場合、5~15重量部であることがより好ましいので、主剤ポリマー100重量部を基準とした光重合開始剤の含有量は、0.01~0.5重量部が好ましい。 These photopolymerization initiators may be used alone or in combination of two or more. The content of the photopolymerization initiator is 0.02 to 10% by mass in a weight percentage where the total amount of the polymerizable compound (in the present invention, hydroxyl group-containing (meth) acrylate) is 100% by mass. The content is preferably 0.1 to 5% by mass. If the content of the photopolymerization initiator is 0.02% by mass or more, the polymerizable compound can be polymerized in a short time, and if it is 10% by mass or less, the residue of the photopolymerization initiator hardly remains in the cured product. .
Further, as described above, the hydroxyl group-containing (meth) acrylate monomer (total amount when two or more types are used) is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the main polymer. In the case where high durability is required such as in a test under a 95% RH environment, the content is more preferably 5 to 15 parts by weight. Therefore, the content of the photopolymerization initiator based on 100 parts by weight of the main polymer is 0.01 to 0.5 part by weight is preferable.
2官能性エポキシ化合物としては、エチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ジプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル等の脂肪族の2官能性エポキシ化合物や、水添ビスフェノールAジグリシジルエーテル、o-フタル酸ジグリシジルエステル、テレフタル酸ジグリシジルエステル、レゾルシンジグリシジルエーテル等の芳香族の2官能性エポキシ化合物が挙げられる。2官能性エポキシ化合物のエポキシ基は、ポリマーのカルボキシル基と架橋反応することができる。
2官能性イソシアネートとしては、ヘキサメチレンジイソシアネートやイソホロンジイソシアネート(IPDI)等の脂肪族の2官能性イソシアネートや、トリレンジイソシアネートやジフェニルメタンジイソシアネート等の芳香族の2官能性イソシアネートが挙げられる。2官能性イソシアネートのNCO基は、ポリマーのカルボキシル基やヒドロキシル基と架橋反応することができる。
2官能性の架橋剤の含有量は、ポリマーの架橋点に対して0.1当量以下となる範囲で、例えば、主剤ポリマー100重量部に対して1.0~3.0重量部が好ましい。 The bifunctional crosslinking agent is not particularly limited as long as it is a compound having two functional groups that undergo crosslinking reaction in one molecule. Examples of such a bifunctional crosslinking agent include a bifunctional epoxy compound and a bifunctional isocyanate.
Examples of the bifunctional epoxy compound include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl glycol diglycidyl ether. Aliphatic bifunctional epoxy compounds such as 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, o-phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, resorcin diglycidyl ether, etc. Aromatic bifunctional epoxy compounds can be mentioned. The epoxy group of the bifunctional epoxy compound can crosslink with the carboxyl group of the polymer.
Examples of the bifunctional isocyanate include aliphatic bifunctional isocyanates such as hexamethylene diisocyanate and isophorone diisocyanate (IPDI), and aromatic bifunctional isocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate. The NCO group of the bifunctional isocyanate can undergo a crosslinking reaction with the carboxyl group or hydroxyl group of the polymer.
The content of the bifunctional crosslinking agent is preferably in the range of 0.1 equivalent or less with respect to the crosslinking point of the polymer, for example, 1.0 to 3.0 parts by weight with respect to 100 parts by weight of the main polymer.
特に前記基材のうち、耐熱性、紫外線透過性、及び価格の面から、ポリエチレンテレフタレートを用いることが好ましい。
なお、基材の厚みは16μm~200μmを有することが好ましく、50μm~188μmを有することが更に好ましい。基材の厚みが薄過ぎるとハンドリング性が悪く、また、基材の厚みが厚過ぎると、コスト面、ハンドリング性で不利である。 Here, the material of the base material used when the pressure sensitive adhesive raw material composition is applied to form the pressure sensitive adhesive film has transparency and heat resistance, and inhibits the curing of the ultraviolet curable resin composition. Those having small scattering and absorption in the ultraviolet region near 350 nm to 400 nm are preferable. For example, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polysulfone, polyethersulfone, polystyrene, polyacrylate, polyetheretherketone, polycarbonate, polyolefin such as polyethylene and polypropylene, polyamide, nylon, polyimide , Fluorine such as triacetyl cellulose (cellulose triacetate), cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly (meth) acrylic acid ester copolymer, polymethyl methacrylate, polytetrafluoroethylene and polytrifluoroethylene Resin, polyvinyl chloride, polyvinylidene chloride copolymer, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol, cellophane, cellulose film, etc. It can be mentioned. These materials may be used alone or in combination of two or more.
In particular, among the substrates, it is preferable to use polyethylene terephthalate from the viewpoints of heat resistance, ultraviolet light transmittance, and cost.
The base material preferably has a thickness of 16 μm to 200 μm, more preferably 50 μm to 188 μm. If the thickness of the substrate is too thin, the handling properties are poor, and if the thickness of the substrate is too thick, it is disadvantageous in terms of cost and handling properties.
塗布装置により、基材の片面に粘着剤用原料組成物の薄膜層(塗布膜)が形成される。塗布装置で塗布した直後の粘着剤用原料組成物は、未硬化でかつ液状であり、塗布に適した流動性を有する。 The coating apparatus for applying the adhesive raw material composition to the substrate may be any apparatus as long as it has a means for uniformly supplying and applying the adhesive raw material composition on the base material. A device comprising a tank for storing an adhesive raw material composition, a liquid feed pump, piping, a foreign matter removal filter, and a coater head so that the adhesive raw material composition can be supplied and coated on the substrate. Preferred (not shown). The coater head is preferably a die coater, for example.
A thin film layer (coating film) of the pressure-sensitive adhesive raw material composition is formed on one side of the substrate by the coating apparatus. The pressure-sensitive adhesive raw material composition immediately after coating with a coating apparatus is uncured and liquid, and has fluidity suitable for coating.
粘着剤用原料組成物が溶液タイプの場合は、乾燥前の塗布膜の厚みはシロップタイプより厚くなり、上記の塗布膜の厚みを濃度で割った数字となる。乾燥後の塗布膜の厚みはシロップタイプと同様である。
塗布膜が薄すぎると、粘着剤層の厚さも薄くなるので、衝撃吸収性能が悪くなる。また、塗布膜が厚過ぎるとコストが上昇する点で不利である。 When the pressure sensitive adhesive composition is a syrup type, the thickness of the coating film is preferably between 0.05 and 3 mm, more preferably 0.1 to 2 mm. The thickness of the coating film is approximately equal to the thickness of the pressure-sensitive adhesive layer obtained by photopolymerization. Therefore, the thickness of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive film of the present invention is preferably between 0.05 and 3 mm, more preferably 0.1 to 2 mm.
When the raw material composition for the pressure-sensitive adhesive is a solution type, the thickness of the coating film before drying is thicker than that of the syrup type, and is a number obtained by dividing the thickness of the coating film by the concentration. The thickness of the coating film after drying is the same as that of the syrup type.
If the coating film is too thin, the thickness of the pressure-sensitive adhesive layer is also reduced, so that the impact absorbing performance is deteriorated. Moreover, when the coating film is too thick, it is disadvantageous in that the cost increases.
セパレーター供給手段24は、セパレーター13が巻き取られたロール体と、そのロール体を保持する軸等から構成される。
ニップロール25は、塗布膜12が形成された基材11と、セパレーター13とを挟み込む1対のロールからなり、両者を貼合する装置である。貼合のための加圧手段を備えることが好ましく、また、フィルムに対して均一な圧力をかけ易いよう、少なくとも一方のロールがゴム製であることが好ましい。 The temperature in the drying chamber 23 may be a temperature at which the solvent in the
The separator supply means 24 includes a roll body around which the
The
塗布膜12は、塗布膜12中の重合性化合物が適度な光照射により重合することで、凝集力を高め、粘着性を発現する。 The
The
また、本発明の粘着フィルムとして支持体の両面に粘着剤層を有する両面粘着フィルムを製造する場合は、それぞれの面で同時に、または逐次に、塗布液の塗布・乾燥と塗布膜の光重合を行なうことができる。 Moreover, when manufacturing the double-sided adhesive film which does not have a support body like a transfer tape as an adhesive film of this invention, a separator is supplied not only as the
Further, when producing a double-sided pressure-sensitive adhesive film having pressure-sensitive adhesive layers on both sides of the support as the pressure-sensitive adhesive film of the present invention, coating and drying of the coating liquid and photopolymerization of the coating film are performed simultaneously or sequentially on each side. Can be done.
〈トランスファーテープの作製〉
下記の表1に示す配合の粘着剤原料組成物を用いて、下記の製造方法により実施例1~15および比較例1~5のトランスファーテープを作製した。また、各主剤ポリマーの数平均分子量(Mn)および重量平均分子量(Mw)は、下記の(分子量測定方法)に示す方法により測定した。 Hereinafter, the present invention will be specifically described with reference to examples.
<Production of transfer tape>
Transfer tapes of Examples 1 to 15 and Comparative Examples 1 to 5 were produced by the following production method using the pressure-sensitive adhesive raw material composition shown in Table 1 below. Moreover, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of each main polymer were measured by the method shown in the following (Molecular weight measuring method).
ここで、製品名:Irgacure(登録商標)651の光重合開始剤は、ベンジルジメチルケタールを有効成分とするものである。
製品名:EX-830の2官能性エポキシ架橋剤のエポキシ当量(g/エポキシ基1mol)は268である。また、製品名:EX-931の2官能性エポキシ架橋剤のエポキシ当量は172である。
架橋剤の当量は、エポキシ化合物ではカルボキシル基を架橋点とし、イソシアネートではカルボキシル基及びヒドロキシル基を架橋点として計算した。 In Table 1, “2EHA” represents 2-ethylhexyl acrylate, “AA” represents acrylic acid, “HEA” represents 2-hydroxylethyl acrylate, “4HBA” represents 4-hydroxylbutyl acrylate, “Irg651” represents Irgacure (registered trademark) 651. Moreover, the kind of crosslinking agent was shown using the product name quoted in the following manufacturing method, respectively.
Here, the photopolymerization initiator of product name: Irgacure (registered trademark) 651 contains benzyl dimethyl ketal as an active ingredient.
The epoxy equivalent (g / epoxy group 1 mol) of the bifunctional epoxy crosslinking agent of product name: EX-830 is 268. In addition, the epoxy equivalent of the bifunctional epoxy crosslinking agent having the product name EX-931 is 172.
The equivalent of the crosslinking agent was calculated by using a carboxyl group as a crosslinking point in an epoxy compound and a carboxyl group and a hydroxyl group as a crosslinking point in an isocyanate.
各主剤ポリマーについて濃度2%に希釈し、移動相をテトラヒドロフラン(THF)、流速0.5ml/minでGPC分析装置(ウォーターズ社;装置名 Alliance2695-2414RI検出器)により測定を行い、ポリスチレン換算により分子量を算出した。 (Molecular weight measurement method)
Each main polymer was diluted to a concentration of 2%, the mobile phase was measured with a GPC analyzer (Waters, Inc .; apparatus name Alliance 2695-2414 RI detector) at a flow rate of 0.5 ml / min, and the molecular weight was calculated in terms of polystyrene. Was calculated.
次に、モノマーBとして、4-ヒドロキシルブチルアクリレート(大阪有機材料工業株式会社;4HBA)を15.0重量部と、2官能性のエポキシ系架橋剤として、ポリエチレングリコールジグリシジルエーテル(ナガセケムテックス株式会社;製品名:EX-830)を2.0重量部、アルキルフェノン系の光重合開始剤(チバ・ジャパン株式会社製;製品名:Irgacure(登録商標)651)を0.10重量部とを、溶媒として用いた酢酸エチルに溶解した溶媒液に、前記作製済みの主剤ポリマーを加えて粘着剤原料組成物を調合した。
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基)に対して0.05当量である。
その粘着剤原料組成物を、基材として用いたセパレーター(東洋紡績株式会社製;製品名:K1504、厚み75μm)の上面に、アプリケーターを用いて、乾燥後における粘着剤層の厚みが200μmとなるように塗布した後、乾燥させて粘着剤層の積層体を作製した。
次に、得られた積層体の粘着剤層の上面に、セパレーター(三菱樹脂株式会社製;製品名;MRF、厚み38μm)を貼合し、粘着剤の積層フィルムを作製した。
その後、基材を搬送しながら高圧水銀ランプで照射する連続UV照射装置を用いて、照射量約200mJ(波長300nm~400nm)となるように、基材である粘着剤の積層フィルムの搬送スピード、UV照射の光量などを調整しながらUV照射を行い、光重合開始剤を用いて光重合反応を行わせ、40℃で7日間以上養生し、最終的に粘着剤層が形成されたトランスファーテープを作製した。 A mixed solvent solution was prepared by dissolving 90 parts by weight of 2-ethylhexyl acrylate (2EHA) and 10 parts by weight of acrylic acid (AA) in ethyl acetate used as an organic solvent. Using this mixed solvent liquid, a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer. The main polymer had a number average molecular weight of 70,000 and a weight average molecular weight of 1,260,000.
Next, 15.0 parts by weight of 4-hydroxylbutyl acrylate (Osaka Organic Materials Co., Ltd .; 4HBA) as monomer B and polyethylene glycol diglycidyl ether (Nagase ChemteX Corporation) as a bifunctional epoxy crosslinking agent Company: Product name: EX-830) 2.0 parts by weight, alkylphenone photopolymerization initiator (Ciba Japan KK; product name: Irgacure (registered trademark) 651) 0.10 parts by weight Then, the prepared main polymer was added to a solvent solution dissolved in ethyl acetate used as a solvent to prepare an adhesive material composition.
The addition amount of the crosslinking agent is 0.05 equivalent with respect to the crosslinking point (AA carboxyl group) of the polymer.
Using the applicator on the upper surface of a separator (manufactured by Toyobo Co., Ltd .; product name: K1504, thickness 75 μm) using the pressure-sensitive adhesive raw material composition as a base material, the thickness of the pressure-sensitive adhesive layer after drying becomes 200 μm. After coating, the laminate of the pressure-sensitive adhesive layer was produced by drying.
Next, a separator (manufactured by Mitsubishi Plastics Co., Ltd .; product name; MRF, thickness 38 μm) was bonded to the upper surface of the pressure-sensitive adhesive layer of the obtained laminate to produce a pressure-sensitive adhesive laminated film.
Then, using a continuous UV irradiation device that irradiates the substrate with a high-pressure mercury lamp while conveying the substrate, the conveyance speed of the adhesive laminated film as the substrate is adjusted so that the irradiation amount is about 200 mJ (wavelength 300 nm to 400 nm). A transfer tape having a pressure-sensitive adhesive layer formed thereon is prepared by performing UV irradiation while adjusting the amount of UV irradiation, causing a photopolymerization reaction using a photopolymerization initiator, curing at 40 ° C. for 7 days or more, and finally forming an adhesive layer. Produced.
次に、4HBAを15.0重量部と、EX-830を1.0重量部、Irgacure(登録商標)651を0.10重量部とを、溶媒として用いた酢酸エチルに溶解した溶媒液に、前記作製済みの主剤ポリマーを加えて粘着剤原料組成物を調合した。
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基)に対して0.02当量である。
それ以外は、実施例1と同様にしてトランスファーテープを作製した。 A mixed solvent solution in which 87 parts by weight of 2EHA and 13 parts by weight of AA were dissolved in ethyl acetate used as an organic solvent was prepared. Using this mixed solvent liquid, a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer. The number average molecular weight of this main polymer was 110,000, and the weight average molecular weight was 253,000.
Next, 15.0 parts by weight of 4HBA, 1.0 part by weight of EX-830, and 0.10 parts by weight of Irgacure (registered trademark) 651 were dissolved in ethyl acetate used as a solvent. The prepared main polymer was added to prepare a pressure-sensitive adhesive raw material composition.
The addition amount of a crosslinking agent is 0.02 equivalent with respect to the crosslinking point of a polymer (carboxyl group of AA).
Other than that was carried out similarly to Example 1, and produced the transfer tape.
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基)に対して0.04当量である。 A transfer tape was prepared in the same manner as in Example 2 except that the pressure-sensitive adhesive raw material composition was prepared with 2.0 parts by weight of EX-830.
The addition amount of a crosslinking agent is 0.04 equivalent with respect to the crosslinking point of a polymer (AA carboxyl group).
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基)に対して0.04当量である。 A transfer tape was prepared in the same manner as in Example 2 except that the pressure-sensitive adhesive raw material composition was prepared with 10.0 parts by weight of 4HBA and 2.0 parts by weight of EX-830.
The addition amount of a crosslinking agent is 0.04 equivalent with respect to the crosslinking point of a polymer (AA carboxyl group).
次に、4HBAを5.0重量部と、EX-830を1.5重量部、Irgacure(登録商標)651を0.05重量部とを、溶媒として用いた酢酸エチルに溶解した溶媒液に、前記作製済みの主剤ポリマーを加えて粘着剤原料組成物を調合した。
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基)に対して0.03当量である。
それ以外は、実施例1と同様にしてトランスファーテープを作製した。 A mixed solvent solution in which 87 parts by weight of 2EHA and 13 parts by weight of AA were dissolved in ethyl acetate used as an organic solvent was prepared. Using this mixed solvent liquid, a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer. The main polymer had a number average molecular weight of 120,000 and a weight average molecular weight of 4,350,000.
Next, in a solvent solution in which 5.0 parts by weight of 4HBA, 1.5 parts by weight of EX-830 and 0.05 parts by weight of Irgacure (registered trademark) 651 were dissolved in ethyl acetate used as a solvent, The prepared main polymer was added to prepare a pressure-sensitive adhesive raw material composition.
The addition amount of a crosslinking agent is 0.03 equivalent with respect to the crosslinking point (AA carboxyl group) of a polymer.
Other than that was carried out similarly to Example 1, and produced the transfer tape.
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基)に対して0.04当量である。 A transfer tape was produced in the same manner as in Example 5 except that 10.0 parts by weight of 4HBA and 2.0 parts by weight of EX-830 were used.
The addition amount of a crosslinking agent is 0.04 equivalent with respect to the crosslinking point of a polymer (AA carboxyl group).
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基)に対して0.05当量である。 A transfer tape was produced in the same manner as in Example 5 except that 15.0 parts by weight of 4HBA and 2.5 parts by weight of EX-830 were used.
The addition amount of the crosslinking agent is 0.05 equivalent with respect to the crosslinking point (AA carboxyl group) of the polymer.
次に、4HBAを5.0重量部と、EX-830を1.5重量部、Irgacure(登録商標)651を0.10重量部とを、溶媒として用いた酢酸エチルに溶解した溶媒液に、前記作製済みの主剤ポリマーを加えて粘着剤原料組成物を調合した。
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基)に対して0.03当量である。
それ以外は、実施例1と同様にしてトランスファーテープを作製した。 A mixed solvent solution in which 87 parts by weight of 2EHA and 13 parts by weight of AA were dissolved in ethyl acetate used as an organic solvent was prepared. Using this mixed solvent liquid, a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer. The main polymer had a number average molecular weight of 140,000 and a weight average molecular weight of 1,430,000.
Next, in a solvent solution in which 5.0 parts by weight of 4HBA, 1.5 parts by weight of EX-830 and 0.10 parts by weight of Irgacure (registered trademark) 651 were dissolved in ethyl acetate used as a solvent, The prepared main polymer was added to prepare a pressure-sensitive adhesive raw material composition.
The addition amount of a crosslinking agent is 0.03 equivalent with respect to the crosslinking point (AA carboxyl group) of a polymer.
Other than that was carried out similarly to Example 1, and produced the transfer tape.
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基)に対して0.04当量である。 A transfer tape was produced in the same manner as in Example 8 except that 10.0 parts by weight of 4HBA and 2.0 parts by weight of EX-830 were used.
The addition amount of a crosslinking agent is 0.04 equivalent with respect to the crosslinking point of a polymer (AA carboxyl group).
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基)に対して0.05当量である。 A transfer tape was prepared in the same manner as in Example 8 except that 15.0 parts by weight of 4HBA and 2.5 parts by weight of EX-830 were used.
The addition amount of the crosslinking agent is 0.05 equivalent with respect to the crosslinking point (AA carboxyl group) of the polymer.
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基)に対して0.02当量である。 A transfer tape was produced in the same manner as in Example 7, except that the crosslinking agent was 2.0 parts by weight of polypropylene glycol diglycidyl ether (Nagase ChemteX Corporation; product name EX-931).
The addition amount of a crosslinking agent is 0.02 equivalent with respect to the crosslinking point of a polymer (carboxyl group of AA).
次に、4HBAを15.0重量部と、架橋剤としてイソホロンジイソシアネート(三井化学ポリウレタン株式会社;製品名:A-45N)を1.5重量部、Irgacure(登録商標)651を0.05重量部とを、溶媒として用いた酢酸エチルに溶解した溶媒液に、前記作製済みの主剤ポリマーを加えて粘着剤原料組成物を調合した。
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基およびHEAと4HBAのヒドロキシル基)に対して0.05当量である。
それ以外は、実施例1と同様にしてトランスファーテープを作製した。 A mixed solvent solution prepared by dissolving 86.5 parts by weight of 2EHA, 13 parts by weight of AA, 0.5 parts by weight of 2-hydroxyethyl acrylate (HEA), and ethyl acetate used as an organic solvent was prepared. Using this mixed solvent liquid, a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer.
Next, 15.0 parts by weight of 4HBA, 1.5 parts by weight of isophorone diisocyanate (Mitsui Chemical Polyurethane Co., Ltd .; product name: A-45N) as a crosslinking agent, and 0.05 parts by weight of Irgacure (registered trademark) 651 Was added to the solvent solution dissolved in ethyl acetate used as a solvent, and the prepared main polymer was added to prepare an adhesive raw material composition.
The addition amount of the crosslinking agent is 0.05 equivalent with respect to the crosslinking point of the polymer (carboxyl group of AA and hydroxyl group of HEA and 4HBA).
Other than that was carried out similarly to Example 1, and produced the transfer tape.
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基およびHEAと4HBAのヒドロキシル基)に対して0.08当量である。
なお、実施例12,13において、ポリマーAの架橋点(AAのカルボキシル基およびHEAのヒドロキシル基)とポリマーBの架橋点(4HBAのヒドロキシル基)とのモル比は1:0.56であり、前者が後者より多い比率になっている。 A transfer tape was produced in the same manner as in Example 12 except that 2.5 parts by weight of A-45N and 0.10 parts by weight of Irgacure (registered trademark) 651 were used.
The addition amount of the crosslinking agent is 0.08 equivalent with respect to the crosslinking point of the polymer (carboxyl group of AA and hydroxyl group of HEA and 4HBA).
In Examples 12 and 13, the molar ratio between the crosslinking point of polymer A (carboxyl group of AA and hydroxyl group of HEA) and the crosslinking point of polymer B (hydroxyl group of 4HBA) is 1: 0.56. The former has a higher ratio than the latter.
次に、4HBAを17.2重量部と、EX-830を1.7重量部、Irgacure(登録商標)651を0.06重量部とを、溶媒として用いた酢酸エチルに溶解した溶媒液に、前記作製済みの主剤ポリマーを加えて粘着剤原料組成物を調合した。
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基)に対して0.06当量である。
それ以外は、実施例1と同様にしてトランスファーテープを作製した。 A mixed solvent solution in which 92 parts by weight of 2EHA and 8 parts by weight of AA were dissolved in ethyl acetate used as an organic solvent was prepared. Using this mixed solvent liquid, a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer. The main polymer had a number average molecular weight of 90,000 and a weight average molecular weight of 1,260,000.
Next, in a solvent solution in which 17.2 parts by weight of 4HBA, 1.7 parts by weight of EX-830 and 0.06 parts by weight of Irgacure (registered trademark) 651 were dissolved in ethyl acetate used as a solvent, The prepared main polymer was added to prepare a pressure-sensitive adhesive raw material composition.
The addition amount of a crosslinking agent is 0.06 equivalent with respect to the crosslinking point (AA carboxyl group) of a polymer.
Other than that was carried out similarly to Example 1, and produced the transfer tape.
次に、4HBAを10.0重量部と、EX-830を1.5重量部、Irgacure(登録商標)651を0.05重量部とを、溶媒として用いた酢酸エチルに溶解した溶媒液に、前記作製済みの主剤ポリマーを加えて粘着剤原料組成物を調合した。
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基)に対して0.08当量である。
それ以外は、実施例1と同様にしてトランスファーテープを作製した。 A mixed solvent solution in which 95 parts by weight of 2EHA and 5 parts by weight of AA were dissolved in ethyl acetate used as an organic solvent was prepared. Using this mixed solvent liquid, a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer. The main polymer had a number average molecular weight of 300,000 and a weight average molecular weight of 1,440,000.
Next, in a solvent solution in which 10.0 parts by weight of 4HBA, 1.5 parts by weight of EX-830, and 0.05 parts by weight of Irgacure (registered trademark) 651 were dissolved in ethyl acetate used as a solvent, The prepared main polymer was added to prepare a pressure-sensitive adhesive raw material composition.
The addition amount of the crosslinking agent is 0.08 equivalent with respect to the crosslinking point of the polymer (AA carboxyl group).
Other than that was carried out similarly to Example 1, and produced the transfer tape.
2EHAを87重量部と、AAを13重量部とを、有機溶媒として用いた酢酸エチルに溶解させた混合溶媒液を調製した。この混合溶媒液を用い、有機溶媒を沸点において還流させながら溶液重合反応を行なわせて、主剤ポリマーを作製した。この主剤ポリマーの数平均分子量は12万、重量平均分子量453万であった。
次に、4HBAを10.0重量部と、Irgacure(登録商標)651を0.05重量部とを、溶媒として用いた酢酸エチルに溶解した溶媒液に、前記作製済みの主剤ポリマーを加えて粘着剤原料組成物を調合した。この場合、架橋剤は添加されていない。
それ以外は、実施例1と同様にしてトランスファーテープを作製した。 (Comparative Example 1)
A mixed solvent solution in which 87 parts by weight of 2EHA and 13 parts by weight of AA were dissolved in ethyl acetate used as an organic solvent was prepared. Using this mixed solvent liquid, a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer. The main polymer had a number average molecular weight of 120,000 and a weight average molecular weight of 4,350,000.
Next, the prepared main polymer is added to a solvent solution obtained by dissolving 10.0 parts by weight of 4HBA and 0.05 parts by weight of Irgacure (registered trademark) 651 in a solvent, and then sticking. An agent raw material composition was prepared. In this case, no crosslinking agent is added.
Other than that was carried out similarly to Example 1, and produced the transfer tape.
2EHAを87重量部と、AAを13重量部とを、有機溶媒として用いた酢酸エチルに溶解させた混合溶媒液を調製した。この混合溶媒液を用い、有機溶媒を沸点において還流させながら溶液重合反応を行なわせて、主剤ポリマーを作製した。この主剤ポリマーの数平均分子量は12万、重量平均分子量453万であった。
次に、4HBAを10.0重量部と、EX-830を2.0重量部とを、溶媒として用いた酢酸エチルに溶解した溶媒液に、前記作製済みの主剤ポリマーを加えて粘着剤原料組成物を調合した。
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基)に対して0.04当量である。
それ以外は、実施例1と同様にしてトランスファーテープを作製した。 (Comparative Example 2)
A mixed solvent solution in which 87 parts by weight of 2EHA and 13 parts by weight of AA were dissolved in ethyl acetate used as an organic solvent was prepared. Using this mixed solvent liquid, a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer. The main polymer had a number average molecular weight of 120,000 and a weight average molecular weight of 4,350,000.
Next, the prepared main polymer is added to a solvent solution in which 10.0 parts by weight of 4HBA and 2.0 parts by weight of EX-830 are dissolved in the solvent used as a solvent. The ingredients were prepared.
The addition amount of a crosslinking agent is 0.04 equivalent with respect to the crosslinking point of a polymer (AA carboxyl group).
Other than that was carried out similarly to Example 1, and produced the transfer tape.
2EHAを87重量部と、AAを13重量部とを、有機溶媒として用いた酢酸エチルに溶解させた混合溶媒液を調製した。この混合溶媒液を用い、有機溶媒を沸点において還流させながら溶液重合反応を行なわせて、主剤ポリマーを作製した。この主剤ポリマーの数平均分子量は12万、重量平均分子量453万であった。
次に、EX-830を2.0重量部と、Irgacure(登録商標)651を0.05重量部とを、溶媒として用いた酢酸エチルに溶解した溶媒液に、前記作製済みの主剤ポリマーを加えて粘着剤原料組成物を調合した。この場合、モノマーBは添加されていない。
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基)に対して0.04当量である。
それ以外は、実施例1と同様にしてトランスファーテープを作製した。 (Comparative Example 3)
A mixed solvent solution in which 87 parts by weight of 2EHA and 13 parts by weight of AA were dissolved in ethyl acetate used as an organic solvent was prepared. Using this mixed solvent liquid, a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer. The main polymer had a number average molecular weight of 120,000 and a weight average molecular weight of 4,350,000.
Next, the prepared main polymer is added to a solvent solution in which 2.0 parts by weight of EX-830 and 0.05 parts by weight of Irgacure (registered trademark) 651 are dissolved in ethyl acetate used as a solvent. A pressure-sensitive adhesive raw material composition was prepared. In this case, monomer B is not added.
The addition amount of a crosslinking agent is 0.04 equivalent with respect to the crosslinking point of a polymer (AA carboxyl group).
Other than that was carried out similarly to Example 1, and produced the transfer tape.
2EHAを87重量部と、AAを13重量部とを、有機溶媒として用いた酢酸エチルに溶解させた混合溶媒液を調製した。この混合溶媒液を用い、有機溶媒を沸点において還流させながら溶液重合反応を行なわせて、主剤ポリマーを作製した。この主剤ポリマーの数平均分子量は12万、重量平均分子量453万であった。
次に、4HBAを10重量部と、EX-830を7.5重量部、Irgacure(登録商標)651を0.05重量部とを、溶媒として用いた酢酸エチルに溶解した溶媒液に、前記作製済みの主剤ポリマーを加えて粘着剤原料組成物を調合した。
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基)に対して0.16当量である。
それ以外は、実施例1と同様にしてトランスファーテープを作製した。 (Comparative Example 4)
A mixed solvent solution in which 87 parts by weight of 2EHA and 13 parts by weight of AA were dissolved in ethyl acetate used as an organic solvent was prepared. Using this mixed solvent liquid, a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer. The main polymer had a number average molecular weight of 120,000 and a weight average molecular weight of 4,350,000.
Next, 10 parts by weight of 4HBA, 7.5 parts by weight of EX-830 and 0.05 parts by weight of Irgacure (registered trademark) 651 were dissolved in ethyl acetate used as a solvent in the above-mentioned preparation. An adhesive raw material composition was prepared by adding the used main polymer.
The addition amount of a crosslinking agent is 0.16 equivalent with respect to the crosslinking point of a polymer (AA carboxyl group).
Other than that was carried out similarly to Example 1, and produced the transfer tape.
2EHAを80重量部と、AAを20重量部とを、有機溶媒として用いた酢酸エチルに溶解させた混合溶媒液を調製した。この混合溶媒液を用い、有機溶媒を沸点において還流させながら溶液重合反応を行なわせて、主剤ポリマーを作製した。
次に、4HBAを15重量部と、EX-830を2.0重量部と、Irgacure(登録商標)651を0.10重量部とを、溶媒として用いた酢酸エチルに溶解した溶媒液に、前記作製済みの主剤ポリマーを加えて粘着剤原料組成物を調合した。
架橋剤の添加量は、ポリマーの架橋点(AAのカルボキシル基)に対して0.03当量である。
それ以外は、実施例1と同様にしてトランスファーテープを作製した。 (Comparative Example 5)
A mixed solvent solution in which 80 parts by weight of 2EHA and 20 parts by weight of AA were dissolved in ethyl acetate used as an organic solvent was prepared. Using this mixed solvent liquid, a solution polymerization reaction was performed while refluxing the organic solvent at the boiling point to prepare a main polymer.
Next, in a solvent solution in which 15 parts by weight of 4HBA, 2.0 parts by weight of EX-830, and 0.10 parts by weight of Irgacure (registered trademark) 651 were dissolved in ethyl acetate used as a solvent, The prepared main ingredient polymer was added to prepare an adhesive raw material composition.
The addition amount of a crosslinking agent is 0.03 equivalent with respect to the crosslinking point (AA carboxyl group) of a polymer.
Other than that was carried out similarly to Example 1, and produced the transfer tape.
上記の実施例1~15及び比較例1~5の粘着テープ(トランスファーテープ)を用いて、貼合サンプルを作製して、貼合後の気泡確認試験、白濁確認試験、耐久性試験、粘着力測定、貯蔵弾性率測定を行なった。(貼合後の気泡確認試験)
貼合装置(株式会社クライムプロダクツ;製品名 SE320)を使用し、75mm×100mmサイズの2mm厚のガラス板に50mm×50mmの粘着テープを貼合し、その後、粘着テープの反対面にアクリル板を貼合した。アクリル板の側から貼合後の外観を目視にて確認し、気泡が確認できるものを(×)、確認できないものを(○)と評価した。(白濁確認試験)
気泡確認試験で作製した貼合品を85℃×95%RHの環境下へ投入し、12時間後に取り出した。その後23℃50%RH環境下に放置し外観変化を目視にて確認した。白濁したものを(×)、白濁が確認できないものを(○)と評価した。
また、実施例6及び比較例2により得られた粘着テープを、耐熱耐湿環境試験条件として、85℃×95%RHの条件に調整したオーブンへ投入して、12時間保持後に取り出した。供試したサンプルのヘイズ値を、オーブンから取り出した直後から180分経過まで測定し、得られた高温高湿度試験から取り出した後のヘイズ値の変化を図3に示す。
なお、ヘイズ値の測定は、ヘイズメータ(製造者:日本電色株式会社、型式:Haze Meter、NDH2000)を用いて行った。 <Testing method for adhesive tape>
Using the adhesive tapes (transfer tapes) of Examples 1 to 15 and Comparative Examples 1 to 5 described above, a sample is prepared, and a bubble confirmation test, a cloudiness confirmation test, a durability test, and an adhesive strength after the pasting are performed. Measurement and storage modulus measurement were performed. (Bubble confirmation test after bonding)
Using a bonding device (Climb Products Co., Ltd .; product name SE320), a 50 mm × 50 mm adhesive tape is bonded to a 2 mm thick glass plate of 75 mm × 100 mm size, and then an acrylic plate is attached to the opposite surface of the adhesive tape. Pasted. The appearance after bonding was visually confirmed from the side of the acrylic plate, and the case where bubbles could be confirmed was evaluated as (x), and the case where the bubbles could not be confirmed was evaluated as (◯). (White turbidity confirmation test)
The bonded product produced in the bubble confirmation test was put in an environment of 85 ° C. × 95% RH and taken out after 12 hours. Thereafter, it was left in an environment of 23 ° C. and 50% RH, and the appearance change was visually confirmed. A cloudy product was evaluated as (x), and a sample in which cloudiness was not confirmed was evaluated as (◯).
Moreover, the adhesive tape obtained by Example 6 and the comparative example 2 was thrown into the oven adjusted to the conditions of 85 degreeC x 95% RH as heat-and-moisture-proof environment test conditions, and it took out after holding | maintaining for 12 hours. The haze value of the tested sample was measured from immediately after taking out from the oven until 180 minutes elapsed, and the change in haze value after taking out from the obtained high temperature and high humidity test is shown in FIG.
The haze value was measured using a haze meter (manufacturer: Nippon Denshoku Co., Ltd., model: Haze Meter, NDH2000).
75mm×100mmサイズの2mm厚のガラス板に50mm×50mmの粘着テープを貼合し、その後、粘着テープの反対面に0.8mm厚のアクリル板(三菱樹脂製;製品名:MR-200)を真空環境下で貼合した。貼合条件は真空度が1.0×101Paに到達した時点で、押圧力3.0MPa、時間20秒で押圧する条件とした。この時点では気泡無くきれいに貼合ができていることを確認した。次に、オートクレーブ処理を60℃×0.5MPa×30分間実施し、貼合品のサンプルを完成した。
耐久性試験は、作製した貼合品のサンプルを、85℃dry、60℃×90%RH、85℃×95%RHの高温高湿度環境に投入し、12時間経過時点で取り出し、目視による確認を実施し、浮き・剥がれのあるものは(×)と評価した。この時点で浮き・剥がれの無いサンプルに関してはさらに500時間投入し、取り出した後で目視による確認を実施し、浮き・剥がれのあるものは(×)、無いものを(○)と評価した。(耐久性試験・大気圧貼合)
75mm×100mmサイズの2mm厚のガラス板に50mm×50mmの粘着テープを貼合し、その後、粘着テープの反対面に0.8mm厚のガラス板を大気圧下で貼合を行った。貼合にはクライムプロダクツ製のSE320を使用した。この時点で気泡無くきれいに貼合ができていることを確認できたサンプルについてオートクレーブ処理を60℃×0.5MPa×30分間実施し、貼合品のサンプルを完成した。
耐久性試験は、作製した貼合品のサンプルを、85℃×95%RHの高温高湿度環境に投入し、12時間経過時点で取り出し、目視による確認を実施し、浮き・剥がれのあるものは(×)と評価した。この時点で浮き・剥がれの無いサンプルに関してはさらに500時間投入し、取り出した後で目視による確認を実施し、浮き・剥がれのあるものは(×)、無いものを(○)と評価した。 (Durability test and vacuum bonding)
Adhere a 50mm x 50mm adhesive tape to a 2mm thick glass plate of 75mm x 100mm size, and then place a 0.8mm thick acrylic plate (Mitsubishi Resin; product name: MR-200) on the opposite side of the adhesive tape. Bonding was performed in a vacuum environment. The bonding conditions were such that when the degree of vacuum reached 1.0 × 10 1 Pa, pressing was performed at a pressure of 3.0 MPa for 20 seconds. At this point in time, it was confirmed that the laminating was completed without bubbles. Next, autoclaving was performed at 60 ° C. × 0.5 MPa × 30 minutes to complete a sample of the bonded product.
In the durability test, a sample of the produced bonded product is put into a high temperature and high humidity environment of 85 ° C. dry, 60 ° C. × 90% RH, 85 ° C. × 95% RH, taken out after 12 hours, and visually confirmed. And those with floating / peeling were evaluated as (×). At this time, the sample without floating / peeling was put in for another 500 hours, and after taking it out, visual confirmation was carried out. The sample with floating / peeling was evaluated as (X), and the sample without float was evaluated as (O). (Durability test and atmospheric pressure bonding)
A 50 mm × 50 mm adhesive tape was bonded to a 75 mm × 100
In the durability test, a sample of the produced bonded product is put into a high-temperature and high-humidity environment of 85 ° C. × 95% RH, taken out after 12 hours, and checked visually. (×) was evaluated. At this time, the sample without floating / peeling was put in for another 500 hours, and after taking it out, visual confirmation was carried out. The sample with floating / peeling was evaluated as (X), and the sample without float was evaluated as (O).
複数枚の粘着テープを重ねて貼合し、60℃×0.5MPa×30分間のオートクレーブを実施し、厚み1mmの動的粘弾性試験用サンプルを作製した。このサンプルをせん断型レオメーター(AntonPaar社;装置名 MCR301)にて線形領域内、周波数1Hzの条件で動的粘弾性試験を行なった。貯蔵弾性率の測定は、-40℃~+150℃の温度範囲で、昇温速度3m/minの条件により、室温23℃における値を読み取った。 (Storage elastic modulus measurement)
A plurality of pressure-sensitive adhesive tapes were stacked and bonded, and autoclaving at 60 ° C. × 0.5 MPa × 30 minutes was performed to prepare a sample for a dynamic viscoelasticity test having a thickness of 1 mm. This sample was subjected to a dynamic viscoelasticity test using a shear type rheometer (AntonPaar; apparatus name: MCR301) in a linear region at a frequency of 1 Hz. The storage elastic modulus was measured at a room temperature of 23 ° C. under a temperature range of −40 ° C. to + 150 ° C. and a temperature increase rate of 3 m / min.
粘着テープ(ここではトランスファーテープ)の一方のセパレーターを剥離して粘着剤層の片面を厚さ38μmのポリエチレンテレフタレート(PET)フィルムに貼合し、さらに他方のセパレーターを剥離して粘着剤層の逆面を被着体(ガラス板またはアクリル板)に貼合後23℃、50%RH環境下に1時間放置後、剥離速度300mm/minで剥離させ、その180°剥離強度を測定した。 (Adhesive strength measurement)
One separator of the adhesive tape (here transfer tape) is peeled off, one side of the adhesive layer is bonded to a 38 μm thick polyethylene terephthalate (PET) film, and the other separator is peeled off to reverse the adhesive layer. After the surface was bonded to an adherend (glass plate or acrylic plate), it was allowed to stand in an environment of 23 ° C. and 50% RH for 1 hour, and then peeled off at a peeling speed of 300 mm / min.
上記試験の結果を表2に示す。 <Test results>
The results of the test are shown in Table 2.
実施例1~15については、気泡無く貼合ができることが確認できた。比較例1~4では気泡無く貼合ができることが確認できた。比較例5では気泡が確認された。これは比較例5では主剤ポリマー中のAAの割合が多く、樹脂が硬くなり、被着体への追従性が悪くなっているためであると考えられる。 (Result of air bubble confirmation test after bonding)
In Examples 1 to 15, it was confirmed that bonding could be performed without bubbles. In Comparative Examples 1 to 4, it was confirmed that bonding was possible without bubbles. In Comparative Example 5, bubbles were confirmed. This is presumably because, in Comparative Example 5, the ratio of AA in the main polymer is large, the resin is hard, and the followability to the adherend is poor.
実施例1~15については、白濁は確認できなかった。比較例1、4、5においても白濁は確認できなかった。比較例2、3においては白濁が確認された。
比較例2は光重合開始剤が導入されていないため、UV照射を行ってもモノマーBが重合しない。比較例2では白濁改善効果のある粘着剤になっていないことから、モノマーBを重合させることが白濁改善に効果があることが確認できた。
また、比較例3ではモノマーBが存在しないため、UV照射を行うことで光開始剤が反応はするものの、白濁改善効果のあるモノマーBの重合物が生成しない。比較例3では白濁してしまうことから、モノマーBの重合品の存在が重要であることが確認できた。
また、図3の高温高湿度試験から取り出した後のヘイズ値の変化を示すグラフにおいて、本発明の粘着テープに係わる実施例6は、高温高湿度試験のオーブンから取り出した直後、及びオーブンから取り出して60分経過しても、全くヘイズ値が変化しておらず、優れた白濁防止性能を有することが分かる。
一方、比較例2においては、高温高湿度試験のオーブンから取り出した直後から数分でヘイズ値が最大値として約11%に上昇した後、放置時間の経過と共に、徐々にヘイズ値が低下する傾向を示すが、白濁した状態が120分以上も継続することが分かる。
本評価は、セパレーター同士もしくはポリエチレンテレフタレート(PET)などの樹脂フィルム同士で実施した場合に起こる変化であるが、ガス透過性の悪いガラス同士やアクリル板とガラスなどのサンプルでは白濁するタイミングは同じであるが、白濁が消滅する状況は数日かかることもある。
なお、耐熱耐湿環境試験において発生した、いずれの白濁も室温において数時間放置することにより、白濁は消滅して透明となった。 (Result of cloudiness confirmation test of adhesive tape)
In Examples 1 to 15, no cloudiness was observed. In Comparative Examples 1, 4, and 5, no cloudiness could be confirmed. In Comparative Examples 2 and 3, cloudiness was confirmed.
In Comparative Example 2, since no photopolymerization initiator is introduced, the monomer B does not polymerize even when UV irradiation is performed. In Comparative Example 2, since it was not a pressure-sensitive adhesive having an effect of improving white turbidity, it was confirmed that polymerizing monomer B was effective in improving white turbidity.
Moreover, since the monomer B does not exist in the comparative example 3, although a photoinitiator reacts by performing UV irradiation, the polymer of the monomer B which has a cloudiness improvement effect is not produced | generated. Since it became cloudy in Comparative Example 3, it was confirmed that the presence of the polymerized monomer B was important.
Moreover, in the graph which shows the change of the haze value after taking out from the high temperature high humidity test of FIG. 3, Example 6 which concerns on the adhesive tape of this invention is taken out from the oven immediately after taking out from the oven of a high temperature high humidity test. It can be seen that even after 60 minutes, the haze value has not changed at all, and has excellent white turbidity prevention performance.
On the other hand, in Comparative Example 2, the haze value increased to about 11% as the maximum value within a few minutes immediately after taking out from the oven of the high temperature and high humidity test, and then the haze value gradually decreased with the passage of the standing time. It can be seen that the cloudy state continues for 120 minutes or longer.
This evaluation is a change that occurs when separators or resin films such as polyethylene terephthalate (PET) are used. However, the timing of cloudiness is the same for samples such as glasses with poor gas permeability or acrylic plates and glasses. However, it can take several days for the cloudiness to disappear.
In addition, any cloudiness generated in the heat and humidity resistance test was allowed to stand at room temperature for several hours, and the cloudiness disappeared and became transparent.
85℃dryや60℃×90%RHの条件の場合、アクリル板を被着体とした大気圧貼合においても、ガラス板を被着体とした真空下貼合においても、実施例1~15においては、目視による浮き・剥がれは確認できなかった。比較例2においても、目視による浮き・剥がれは確認できなかった。比較例1、3~5においては目視による浮き・剥がれが確認できた。
85℃×95%RHの条件の場合、アクリル板を被着体とした大気圧貼合においても、ガラス板を被着体とした真空下貼合においても、実施例1~13においては、目視による浮き・剥がれは確認できなかった。比較例1~5においては目視による浮き・剥がれが確認できた。
比較例1は架橋剤が無いため架橋が不十分であり、耐熱性を付与できていないと考えられる。
比較例2はモノマーBが重合していないことが問題となっていると考えられる。
比較例3は光重合開始剤が問題になっていると考えられる。
比較例4は架橋剤の量が過剰すぎるため、粘着テープとして硬くなりすぎ、被着体の変形に追従できずに剥がれてしまうと考えられる。
比較例5はアクリル酸の量が多すぎて粘着テープが硬すぎるため、アクリル板の変形に追従できずに剥がれてしまったと考えられる。また、大気圧貼合の場合には、気泡が入ってしまうため(上記貼合後の気泡確認試験を参照)、それがオートクレーブで一時的に消滅するが、環境試験験投入により再凝集して発泡してしまうことも考えられる。 (Durability test results)
In the case of 85 ° C. dry or 60 ° C. × 90% RH, Examples 1 to 15 were used in both atmospheric pressure bonding using an acrylic plate as an adherend and in vacuum bonding using a glass plate as an adherend. In, floating and peeling by visual observation could not be confirmed. Also in Comparative Example 2, no floating or peeling by visual observation could be confirmed. In Comparative Examples 1 and 3 to 5, floating / peeling was visually confirmed.
In the case of 85 ° C. × 95% RH, both the atmospheric pressure bonding using the acrylic plate as the adherend and the vacuum bonding using the glass plate as the adherend were visually observed in Examples 1 to 13. No floating or peeling due to In Comparative Examples 1 to 5, floating / peeling was visually confirmed.
In Comparative Example 1, since there is no crosslinking agent, crosslinking is insufficient and it is considered that heat resistance cannot be imparted.
In Comparative Example 2, it is considered that the monomer B is not polymerized.
In Comparative Example 3, the photopolymerization initiator is considered to be a problem.
In Comparative Example 4, since the amount of the crosslinking agent is excessive, it becomes too hard as an adhesive tape, and it is considered that the comparative example 4 is not able to follow the deformation of the adherend and peels off.
In Comparative Example 5, since the amount of acrylic acid is too large and the adhesive tape is too hard, it is considered that the acrylic tape was peeled off without being able to follow the deformation of the acrylic plate. In addition, in the case of atmospheric pressure bonding, bubbles will enter (see the bubble confirmation test after bonding above), but it disappears temporarily in the autoclave, but it re-aggregates due to the introduction of environmental test. It is also considered that foaming occurs.
光学用途の粘着テープの分子量は高分子量であるほうが好ましいといわれている。分子量が大きいと耐熱性が良くなる傾向や耐候性試験においても良い方向に進むと言われているためである。
実施例1からは、主剤のモノマー比が2EHA/AA=90/10の場合はMwが100万以上で良好と思われる。実施例2~11、比較例6の結果の対比から、主剤のモノマー比が2EHA/AA=87/13の場合もMwが100万以上の材料であればより好ましい範囲と思われる。実施例14の2EHA/AA=92/8、実施例15の2EHA/AA=95/5の場合もMwが100万以上の材料である。よって、主剤中のモノマー比によらず好ましい範囲はMwが100万以上、より好ましくは120万を超える範囲であると考えられる。
分子量が大きすぎると粘度が高すぎて加工適性が悪くなる。塗料の温度を上げるなど塗工方法を工夫することでこの上限はさらに広げられると考えられるが、室温で塗工をする場合、実施例1~11、14、15で使用したMw500万未満の材料が好ましいと考えられる。 (Results of molecular weight distribution measurement)
It is said that the molecular weight of the pressure-sensitive adhesive tape for optical use is preferably a high molecular weight. This is because it is said that when the molecular weight is large, the heat resistance tends to improve and the weather resistance test proceeds in a good direction.
From Example 1, when the monomer ratio of the main agent is 2EHA / AA = 90/10, it seems that Mw is 1 million or more and is good. From the comparison of the results of Examples 2 to 11 and Comparative Example 6, it is considered that a material having an Mw of 1 million or more is more preferable when the monomer ratio of the main agent is 2EHA / AA = 87/13. In the case of 2EHA / AA = 92/8 in Example 14 and 2EHA / AA = 95/5 in Example 15, the Mw is 1 million or more. Therefore, it is considered that a preferable range regardless of the monomer ratio in the main agent is a range where Mw is 1 million or more, and more preferably exceeds 1.2 million.
If the molecular weight is too large, the viscosity is too high and the processability is deteriorated. It is thought that this upper limit can be further expanded by devising the coating method such as raising the temperature of the paint. However, when coating at room temperature, the material having an Mw of less than 5 million used in Examples 1 to 11, 14, and 15 Is considered preferable.
85℃dryや60℃×90%RHの耐久性を満足するには、実施例1~15のとおり粘着テープの弾性率(単位Pa)は104~105オーダーであれば良いと思われる。しかし、アクリル板の変形が大きくなる85℃×95%RH環境下では、実施例1~13のとおり弾性率は105オーダーが好ましいことが分かる。
実施例14、15のように104オーダーで粘着テープを柔らかくすると、被着体への貼合性は良くなるが、主剤のアクリル酸の量を減らす必要がある。アクリル酸の量が減ると被着体に対する粘着力が下がってしまい85℃×95%RH環境下では浮き・剥がれが発生したと考えられる。剥がれる場所がガラスと粘着テープの界面になるため、対ガラスの粘着力が低いことが問題になると考えられる。
逆に比較例5のように貯蔵弾性率が106オーダーになると被着体への貼合性は悪くなる。
このことから、貼合後の気泡については、弾性率は105オーダー以下が好ましく、耐久性からすると85℃dry、60℃×90%RHであれば104~105オーダー、85℃×95%RHの高耐久が必要であれば、105オーダーであることが好ましく、より好ましくは105オーダー前半であると考えられる。
貯蔵弾性率(G′)は、主剤の組成、特にアクリル酸の配合比によるところが多いが架橋剤の添加量でも大きく変化する可能性はある。しかし、本発明による架橋剤の配合割合であれば同じモノマー組成の場合、オーダーが変わるほどではないため、実測値の無い部分(表1に「(推定)」と表示した部分)は同組成品と同じオーダーの弾性率、例えば実施例1,6や比較例5を参照すれば1×105~2×105程度であり、そうでないとしても、少なくとも5×104~5×105の範囲には収まっている、と考えられる。 (Results of storage modulus measurement)
In order to satisfy the durability of 85 ° C. dry and 60 ° C. × 90% RH, it is considered that the elastic modulus (unit Pa) of the adhesive tape should be on the order of 10 4 to 10 5 as in Examples 1 to 15. However, the deformation under 85 ℃ × 95% RH environment increases the acrylic plate, as the elastic modulus of Examples 1 to 13 it can be seen that 10 5 orders are preferred.
When softening the
Conversely, when the storage elastic modulus is on the order of 10 6 as in Comparative Example 5, the bonding property to the adherend deteriorates.
From this, the elastic modulus of the air bubbles after pasting is preferably 10 5 order or less, and from the viewpoint of durability, if it is 85 ° C. dry, 60 ° C. × 90% RH, 10 4 to 10 5 order, 85 ° C. × 95 if you need high durability of RH%, preferably from 10 5 order, considered more preferably 10 5 orders early.
The storage elastic modulus (G ′) depends largely on the composition of the main agent, particularly the blending ratio of acrylic acid, but there is a possibility that the storage elastic modulus (G ′) will change greatly depending on the amount of crosslinking agent added. However, in the case of the same monomer composition with the blending ratio of the cross-linking agent according to the present invention, the order is not changed so much, the part having no actual measurement value (the part indicated as “(estimated)” in Table 1) For example, about 1 × 10 5 to 2 × 10 5 when referring to Examples 1, 6 and Comparative Example 5, and if not, at least 5 × 10 4 to 5 × 10 5 It is thought that it is within the range.
粘着力がある程度高くなければ耐久試験時の被着体であるガラス板やアクリル板の変形により剥がれてしまう。実施例1~15の結果から、対ガラスでは10N/25mm以上、対アクリル板に対しては10N/25mm以上あると、耐久性で良好と判断できることが分かる。 (Results of adhesive strength measurement)
If the adhesive strength is not high to some extent, the glass plate or acrylic plate, which is the adherend during the durability test, will peel off due to deformation. From the results of Examples 1 to 15, it can be seen that durability is good when it is 10 N / 25 mm or more for glass and 10 N / 25 mm or more for acrylic plate.
Claims (6)
- (1)アクリル系モノマーの少なくとも1種類を含有する混合溶媒液を用いて、主剤ポリマーを得るポリマー製造工程;
(2)前記主剤ポリマーと、ヒドロキシル基含有の(メタ)アクリレートのモノマーの少なくとも1種類と、光重合開始剤と、ポリマーの架橋点に対して0.1当量以下となる量の2官能性の架橋剤とを含有する粘着剤用原料組成物を調製する工程;及び
(3)前記粘着剤用原料組成物を用い、光照射による重合反応及び架橋反応をさせて粘着剤組成物を得る工程;
を含む、粘着剤組成物の製造方法。 (1) A polymer production process for obtaining a main polymer using a mixed solvent liquid containing at least one kind of acrylic monomer;
(2) Bifunctional in an amount of 0.1 equivalent or less with respect to the crosslinking point of the polymer, at least one monomer of a hydroxyl group-containing (meth) acrylate, a photopolymerization initiator, and a polymer crosslinking point. A step of preparing a pressure-sensitive adhesive raw material composition containing a crosslinking agent; and (3) a step of obtaining a pressure-sensitive adhesive composition by performing a polymerization reaction and a crosslinking reaction by light irradiation using the pressure-sensitive adhesive raw material composition;
The manufacturing method of the adhesive composition containing this. - (1)アクリル系モノマーの少なくとも1種類を含有する混合溶媒液を用いて、主剤ポリマーを得るポリマー製造工程;
(2)前記主剤ポリマーと、ヒドロキシル基含有の(メタ)アクリレートのモノマーの少なくとも1種類と、光重合開始剤と、ポリマーの架橋点に対して0.1当量以下となる量の2官能性の架橋剤とを含有する粘着剤用原料組成物を調製する工程;
(3)前記粘着剤用原料組成物を、粘着フィルムの基材またはセパレーター上に塗布及び乾燥して粘着剤塗布膜を形成する工程;及び
(4)前記粘着剤塗布膜への光照射による重合反応及び架橋反応をさせて粘着剤層を得る工程、
を含む、粘着フィルムの製造方法。 (1) A polymer production process for obtaining a main polymer using a mixed solvent liquid containing at least one kind of acrylic monomer;
(2) Bifunctional in an amount of 0.1 equivalent or less with respect to the crosslinking point of the polymer, at least one monomer of a hydroxyl group-containing (meth) acrylate, a photopolymerization initiator, and a polymer crosslinking point. A step of preparing a pressure-sensitive adhesive raw material composition containing a crosslinking agent;
(3) A step of applying and drying the pressure-sensitive adhesive raw material composition on a base material or a separator of the pressure-sensitive adhesive film to form a pressure-sensitive adhesive coating film; and (4) polymerization by light irradiation on the pressure-sensitive adhesive coating film. A step of performing a reaction and a crosslinking reaction to obtain a pressure-sensitive adhesive layer;
A method for producing an adhesive film, comprising: - (A)エステル基を有するアクリル系モノマーの少なくとも1種類が85~95重量部と、カルボキシル基を有するアクリル系モノマーの少なくとも1種類が5~15重量部とを含有するモノマーから重合された主剤ポリマー:100重量部;
(B)ヒドロキシル基含有の(メタ)アクリレートのモノマーの少なくとも1種類:5~20重量部;
(C)光重合開始剤:0.01~0.5重量部;及び
(D)2官能性の架橋剤を、ポリマーの架橋点に対して0.1当量以下となる1.0~3.0重量部;
を含有し、
前記主剤ポリマーの分子量分布が、数平均分子量(Mn)で7万以上、重量平均分子量(Mw)で100万以上である、粘着剤用原料組成物。 (A) Main polymer polymerized from a monomer containing 85 to 95 parts by weight of at least one acrylic monomer having an ester group and 5 to 15 parts by weight of at least one acrylic monomer having a carboxyl group : 100 parts by weight;
(B) at least one kind of hydroxyl group-containing (meth) acrylate monomer: 5 to 20 parts by weight;
(C) Photopolymerization initiator: 0.01 to 0.5 parts by weight; and (D) The bifunctional crosslinking agent is 0.1 to 3 equivalents or less with respect to the crosslinking point of the polymer. 0 parts by weight;
Containing
The pressure-sensitive adhesive raw material composition in which the molecular weight distribution of the main polymer is 70,000 or more in terms of number average molecular weight (Mn) and 1,000,000 or more in terms of weight average molecular weight (Mw). - 基材又はセパレータ、及び粘着剤層を含み、
当該粘着剤層が、請求項3に記載の粘着剤用原料組成物を、基材またはセパレーター上に塗布した後、光照射により重合反応及び架橋反応をさせて得られる、厚みが0.05~3mmものである、粘着フィルム。 Including a substrate or separator, and an adhesive layer,
The pressure-sensitive adhesive layer is obtained by applying the raw material composition for pressure-sensitive adhesive according to claim 3 on a base material or a separator, and then performing a polymerization reaction and a crosslinking reaction by light irradiation. An adhesive film that is 3 mm. - 前記粘着剤層は、その粘着面を被着体に貼合後23℃、50%RH環境下に1時間放置後、剥離速度300mm/minで剥離したときのガラスおよびアクリル樹脂に対する粘着力が10N/25mm以上であり、かつ前記粘着剤層を構成する粘着剤の23℃、1Hzでの貯蔵弾性率(G′)が1×104Pa以上かつ1×106Pa未満である、請求項4に記載の粘着フィルム。 The pressure-sensitive adhesive layer has an adhesive strength of 10 N against glass and acrylic resin when the pressure-sensitive adhesive surface is bonded to an adherend and left at 23 ° C. and 50% RH for 1 hour and then peeled at a peeling speed of 300 mm / min. The storage elastic modulus (G ′) at 23 ° C. and 1 Hz of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is 1 × 10 4 Pa or more and less than 1 × 10 6 Pa. The adhesive film as described in 2.
- ディスプレイに部材を貼り合わせる用途の粘着テープである請求項4または5に記載の粘着フィルム。 The pressure-sensitive adhesive film according to claim 4 or 5, wherein the pressure-sensitive adhesive tape is used for attaching a member to a display.
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KR1020127009266A KR101378451B1 (en) | 2009-10-06 | 2010-10-01 | Process for production of pressure-sensitive adhesive composition, process for production of pressure-sensitive adhesive film, raw material composition for pressure-sensitive adhesive, and pressure-sensitive adhesive film |
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