WO2011136141A1 - Solution de résine acrylique, composition adhésive acrylique, adhésif acrylique, feuille adhésive, adhésif acrylique pour élément optique et élément optique comportant une couche adhésive - Google Patents

Solution de résine acrylique, composition adhésive acrylique, adhésif acrylique, feuille adhésive, adhésif acrylique pour élément optique et élément optique comportant une couche adhésive Download PDF

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WO2011136141A1
WO2011136141A1 PCT/JP2011/059928 JP2011059928W WO2011136141A1 WO 2011136141 A1 WO2011136141 A1 WO 2011136141A1 JP 2011059928 W JP2011059928 W JP 2011059928W WO 2011136141 A1 WO2011136141 A1 WO 2011136141A1
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sensitive adhesive
pressure
acrylic
acrylic resin
resin solution
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PCT/JP2011/059928
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English (en)
Japanese (ja)
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晃 山林
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日本合成化学工業株式会社
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Priority to CN201180021239.1A priority Critical patent/CN102858872B/zh
Priority to KR1020127030928A priority patent/KR20130094724A/ko
Publication of WO2011136141A1 publication Critical patent/WO2011136141A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-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
    • 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
    • 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

  • the present invention relates to an acrylic resin solution, an acrylic pressure-sensitive adhesive composition, an acrylic pressure-sensitive adhesive, a pressure-sensitive adhesive sheet, an acrylic pressure-sensitive adhesive for optical members, and an optical member with a pressure-sensitive adhesive layer.
  • the present invention relates to an acrylic resin solution used for producing a suitable non-active energy ray-curable solvent-based acrylic pressure-sensitive adhesive.
  • acrylic adhesives are strong adhesives that are intended to bond adherends firmly for a long period of time, or peel-off types based on the premise that they are peeled off from adherends after being attached.
  • pressure-sensitive adhesives such as pressure-sensitive adhesives, and pressure-sensitive adhesives having optimized adhesive properties are designed and used in various fields.
  • the properties required of adhesives include not only adhesive properties such as adhesive strength, but also transparency and impact resistance to the adhesive layer itself when used for bonding glass substrates in liquid crystal display devices and the like.
  • Absorbency is required, and in such applications, it has been proposed to increase the thickness of the pressure-sensitive adhesive layer in order to improve shock absorption performance.
  • the adhesive is cured by irradiating active energy rays such as ultraviolet rays, and the thick adhesive layer
  • active energy rays such as ultraviolet rays
  • the active energy ray-curable pressure-sensitive adhesive generally does not contain a solvent used for viscosity adjustment with a normal acrylic pressure-sensitive adhesive, and a photopolymerizable unsaturated monomer as a dilution monomer instead of the solvent. Because it is a solvent-free pressure-sensitive adhesive used, there is no need for a drying step to remove the solvent after coating the pressure-sensitive adhesive, and it is possible to obtain a pressure-sensitive adhesive layer efficiently in a short time even when thick coating is applied. It can be done.
  • the support film on which the pressure-sensitive adhesive layer is formed in the pressure-sensitive adhesive tape is required for the followability to the adherend.
  • Thin and soft materials are used.
  • the support film may be damaged by the influence of heat or the like.
  • thick coating can be performed, a thick adhesive layer can be obtained, and a crosslinker curing type solvent-based acrylic having excellent adhesive properties and transparency.
  • an acrylic adhesive composition using the same, an acrylic adhesive, an adhesive sheet, an optical part adhesive, and an optical member with an adhesive layer
  • the present inventor has obtained a specific chain transfer constant and an acrylic resin having a relatively low molecular weight and a low viscosity among the acrylic resins used for ordinary adhesive applications.
  • an adhesive is obtained by applying a thick coating by using an acrylic resin solution (acrylic adhesive composition) having a high solid content and containing an organic solvent as shown in FIG. It has been found that dripping or the like does not sometimes occur, the solvent can be easily dried, and the obtained pressure-sensitive adhesive layer is excellent in adhesive strength, holding power and transparency, and the present invention has been completed.
  • the gist of the present invention includes an acrylic resin (A) having a weight average molecular weight of 50,000 to 300,000 and an organic solvent (B) in which the chain transfer constant of vinyl acetate to an organic solvent at 60 ° C. is 250 or more.
  • the present invention relates to an acrylic resin solution having a solid content concentration of 60% or more.
  • an acrylic pressure-sensitive adhesive composition containing such an acrylic resin solution, an acrylic pressure-sensitive adhesive and a pressure-sensitive adhesive sheet obtained using the acrylic pressure-sensitive adhesive composition, an acrylic pressure-sensitive adhesive for optical members, and a pressure-sensitive adhesive
  • the present invention relates to an optical member with an agent layer.
  • the present invention includes the following aspects.
  • An acrylic resin (A) having a weight average molecular weight of 50,000 to 300,000 and an organic solvent (B) having a chain transfer constant of vinyl acetate to an organic solvent at 60 ° C. of 250 or more, and having a solid content concentration Is an acrylic resin solution characterized by being 60% or more.
  • a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer containing the acrylic pressure-sensitive adhesive according to [8].
  • a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer obtained by coating the acrylic pressure-sensitive adhesive composition according to [6] or [7] on a substrate with a film thickness of 80 ⁇ m or more and drying. The pressure-sensitive adhesive sheet is characterized in that the film thickness of the subsequent pressure-sensitive adhesive layer is 50 ⁇ m or more.
  • An acrylic pressure-sensitive adhesive for optical members comprising the acrylic pressure-sensitive adhesive according to [8].
  • the acrylic resin solution of the present invention contains a specific acrylic resin and an organic solvent, it is difficult to achieve compatibility with an acrylic resin solution for producing a normal solvent-based acrylic pressure-sensitive adhesive. It becomes possible to have a high solid content concentration, and even when thick coating is performed using such an acrylic resin solution to obtain an acrylic adhesive, dripping or coating streaks occur during coating.
  • the solvent can be easily dried, and the pressure-sensitive adhesive layer obtained has excellent adhesive strength, holding power, transparency, corrosion resistance, and the like.
  • (meth) acryl means acryl or methacryl
  • (meth) acryloyl means acryloyl or methacryloyl
  • (meth) acrylate means acrylate or methacrylate.
  • the acrylic resin (A) used in the present invention comprises a (meth) acrylic acid alkyl ester monomer (a1) as a main component and, if necessary, a functional group-containing monomer (a2) as a copolymerization component. Further, other copolymerizable monomer (a3) can be used as a copolymerization component.
  • the acrylic resin (A) in the present invention uses the functional group monomer (a2) as a copolymerization component, which becomes a cross-linking point of the acrylic resin (A) and adheres to the base material or the adherend. It is preferable in that the property is further increased.
  • the copolymer having the (meth) acrylic acid alkyl ester monomer (a1) as a main component is a copolymer containing the largest amount of the (meth) acrylic acid alkyl ester monomer (a1).
  • the (meth) acrylic acid alkyl ester monomer (a1) is preferably contained in an amount of 50% by weight or more, particularly 55% by weight or more, and more preferably 60% by weight or more based on the polymerization component.
  • the alkyl group usually has 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms.
  • n-butyl (meth) acrylate 2-ethylhexyl (meth) are preferable in terms of copolymerizability, adhesive properties, ease of handling, and availability of raw materials.
  • An acrylate is preferably used, and more preferably n-butyl (meth) acrylate is used in terms of excellent durability.
  • the content of the (meth) acrylic acid alkyl ester monomer (a1) in the copolymer component is preferably 50 to 99.9% by weight, particularly preferably 55 to 99.8% by weight, and more preferably 60 to 99.%. If it is 7% by weight and the amount of the (meth) acrylic acid alkyl ester monomer (a1) is too small, for example, when used as an adhesive, the adhesive strength tends to be insufficient.
  • Examples of the functional group-containing monomer (a2) include a hydroxyl group-containing monomer, an amino group-containing monomer, an acetoacetyl group-containing monomer, an isocyanate group-containing monomer, a carboxyl group-containing monomer, and a glycidyl group-containing monomer.
  • a hydroxyl group-containing monomer and a carboxyl group-containing monomer are preferably used in terms of efficient crosslinking reaction.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meta )
  • Acrylic acid hydroxyalkyl esters such as acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate and other caprolactone-modified monomers, diethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate and other oxyalkylene-modified monomers, other 2-acrylic Primary hydroxyl group-containing monomers such as leuoxyethyl 2-hydroxyethylphthalic acid and N-methylol (meth) acrylamide; 2-hydroxypropyl (meth) acrylic 2 such as 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chlor
  • hydroxyl-containing monomer used by this invention it is also preferable to use a thing with the content rate of di (meth) acrylate which is an impurity 0.5% or less, and also 0.2% or less, especially 0 It is preferable to use a material of 1% or less. Specifically, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are preferable.
  • carboxyl group-containing monomer examples include (meth) acrylic acid, acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamide N-glycolic acid, and cinnamic acid.
  • (meth) acrylic acid is preferably used.
  • amino group-containing monomer examples include t-butylaminoethyl (meth) acrylate, ethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and among others, dimethylamino Ethyl (meth) acrylate and diethylaminoethyl (meth) acrylate are preferably used.
  • acetoacetyl group-containing monomer examples include 2- (acetoacetoxy) ethyl (meth) acrylate and allyl acetoacetate.
  • isocyanate group-containing monomer examples include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate and their alkylene oxide adducts.
  • Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl (meth) acrylate.
  • These functional group-containing monomers (a2) may be used alone or in combination of two or more.
  • a combination of a carboxyl group-containing monomer and an amino group-containing monomer, a hydroxyl group-containing monomer and an amino group-containing A combination of monomers is preferable in terms of excellent sheet forming property because the crosslinking reaction is accelerated.
  • the content ratio of the functional group-containing monomer (a2) in the copolymer component of the acrylic resin (A) is preferably 0.1 to 30% by weight, particularly preferably 0.2 to 25% by weight, and more preferably 0.8%. If it is 3 to 20% by weight and the functional group-containing monomer (a2) is too small, the crosslinking points at the time of crosslinking will be too small, and the cohesive force after crosslinking tends to be insufficient. It tends to be too much. However, when a hydroxyl group-containing monomer is used as the functional group-containing monomer (a2), the content ratio in the copolymer component of the acrylic resin (A) is 20% by weight or more in terms of excellent heat and moisture resistance and transparency. It is preferably 20 to 50% by weight.
  • copolymerizable monomers (a3) include, for example, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, ethoxylated o-phenylphenyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate
  • Aromatic ring-containing monomers such as 2-hydroxy-3-phenoxypropyl (meth) acrylate, styrene, ⁇ -methylstyrene, (meth) acryloylmorpholine, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, (meth) acrylamide, etc.
  • Amide monomers 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- Butoxydiethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, octoxypolyethylene Monomers containing alkoxy groups and oxyalkylene groups, such as glycol-polypropylene glycol-mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate, acrylonitrile, methacrylon
  • the content of the other copolymerizable monomer (a3) in the copolymerization component is preferably 0 to 40% by weight, particularly preferably 0 to 30% by weight, and more preferably 0 to 25% by weight. When there is too much (a3), there exists a tendency for an adhesive characteristic to fall easily.
  • the (meth) acrylic acid alkyl ester monomer component (a1) is preferably polymerized with the functional group-containing monomer (a2) and, if necessary, the copolymerizable monomer (a3) as a copolymerization component.
  • the resin (A) is produced, and the polymerization can be performed by a conventionally known method such as solution radical polymerization, suspension polymerization, bulk polymerization, emulsion polymerization or the like.
  • a monomer component such as a (meth) acrylic acid alkyl ester monomer (a1), a functional group-containing monomer (a2), another copolymerizable monomer (a3), or a polymerization initiator is mixed or dropped in an organic solvent. Polymerization is carried out at reflux or at 50 to 98 ° C. for 2 to 20 hours.
  • organic solvent used in the polymerization examples include aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, aliphatic alcohols such as n-propyl alcohol and isopropyl alcohol, acetone, methyl ethyl ketone, methyl Examples thereof include ketones such as isobutyl ketone and cyclohexanone.
  • polymerization initiator used for such polymerization examples include azo-based polymerization initiators such as azobisisobutyronitrile and azobisdimethylvaleronitrile, which are ordinary radical polymerization initiators, benzoyl peroxide, lauroyl peroxide, di-t Specific examples thereof include peroxide polymerization initiators such as butyl peroxide and cumene hydroperoxide.
  • the acrylic resin (A) obtained above has a weight average molecular weight of 50,000 to 300,000 in order to reduce the viscosity of the acrylic resin solution and obtain a thick adhesive layer. It is necessary in terms of facilitating necessary high solid differentiation, preferably 60,000 to 250,000, particularly preferably 70,000 to 200,000, particularly preferably 80,000 to 180,000. If the weight average molecular weight is too small, the cohesive force tends to be insufficient. If the weight average molecular weight is too large, the viscosity of the acrylic resin solution tends to be high, and it tends to be difficult to obtain a clean coated surface.
  • the number average molecular weight of the acrylic resin (A) is usually 3,000 to 150,000, preferably 5,000 to 130,000, particularly preferably 8,000 to 100,000, and particularly preferably 10,000 to 80,000. is there. If the number average molecular weight is too small, the cohesive force tends to be insufficient. If the number average molecular weight is too large, the viscosity of the acrylic resin solution tends to be high, and it tends to be difficult to obtain a clean coated surface.
  • the degree of dispersion (weight average molecular weight / number average molecular weight) of the acrylic resin (A) is preferably 20 or less, particularly preferably 10 or less, more preferably 7 or less, and particularly preferably 4 or less. preferable. When the degree of dispersion is too high, the durability performance of the pressure-sensitive adhesive layer is lowered, and foaming or the like tends to occur when a durability test is performed.
  • the lower limit of the degree of dispersion is usually 2 from the viewpoint of production limit.
  • the glass transition temperature of the acrylic resin (A) is usually ⁇ 75 to ⁇ 10 ° C., preferably ⁇ 70 to ⁇ 15 ° C., more preferably ⁇ 60 to ⁇ 20 ° C. If the glass transition temperature is too high, Adhesive properties tend to be difficult to obtain, and if it is too low, the adhesive strength tends to decrease.
  • said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, and it is a column in high performance liquid chromatography (The Japan Waters company “Waters 2695 (main body)” and “Waters 2414 (detector)”).
  • Shodex GPC KF-806L exclusion limit molecular weight: 2 ⁇ 10 7 , separation range: 100 to 2 ⁇ 10 7 , theoretical plate number: 10,000 plates / piece
  • filler material styrene-divinylbenzene copolymer
  • the number average molecular weight can also be measured by the same method.
  • the degree of dispersion is determined from the weight average molecular weight and the number average molecular weight.
  • the glass transition temperature (Tg) is calculated from the following Fox equation.
  • (A) does not contain an acidic group.
  • the organic solvent (B) used in the present invention is required to have a chain transfer constant of vinyl acetate to an organic solvent at 60 ° C. of 250 or more.
  • the chain transfer constant C in the present invention means that when the vinyl acetate monomer is polymerized at 60 ° C., the reaction rate constants of the vinyl acetate growth terminal radical to vinyl acetate and the organic solvent are kp and ktr, respectively. Is calculated by the following equation.
  • the chain transfer constant is preferably 300 or more, particularly preferably 400 or more, more preferably 500 or more, and the upper limit is usually 10,000. If the chain transfer constant is too small, the molecular weight of the acrylic resin tends to be high and thick film coating tends to be difficult.
  • the organic solvent (B) As the organic solvent (B), as long as the chain transfer constant of the organic solvent (B) is 250 or more, the organic solvent may be used alone, or two or more organic solvents may be used in combination.
  • the chain transfer constant of the organic solvent (B) is represented by an average chain transfer constant.
  • the average chain transfer constant when using two or more organic solvents is When using n kinds of organic solvents (X1, X2,... Xn), The chain transfer constant of each organic solvent is A1, A2,.
  • the content ratio (% by weight) of each organic solvent is B1, B2,... Bn Then, it is calculated by the following formula.
  • the chain transfer constants of the main organic solvents that are usually generally blended with acrylic adhesives are, for example, methyl ethyl ketone (738), toluene (208.9), acetone (117), and ethyl acetate (33).
  • the numbers in parentheses are those in J. brandrup, E .; H. Immergut "Polymer Handbook", p. The value is based on II-91, Interscience (1965).
  • 50% by weight or more of the organic solvent (B) is preferably methyl ethyl ketone, particularly preferably 60% by weight or more, and more preferably 70% by weight. % Or more is methyl ethyl ketone.
  • Preferred examples of the solvent combined with methyl ethyl ketone include toluene, acetone, ethyl acetate, and the like, and toluene is particularly preferred because a good coating surface can be easily obtained.
  • the said organic solvent (B) may be mix
  • it is preferably used as a polymerization solvent for polymerization from the viewpoint of easily obtaining an acrylic resin solution having a solid content concentration suitable for thick coating and industrial productivity.
  • the content of the organic solvent (B) is preferably 70 parts by weight or less, particularly preferably 40 parts by weight or less, more preferably 30 parts by weight or less with respect to 100 parts by weight of the acrylic resin (A). is there.
  • the lower limit of the content is usually 10 parts by weight. If the content of the organic solvent (B) is too large, thick coating tends to be difficult.
  • an acrylic resin solution containing the acrylic resin (A) and the organic solvent (B) of the present invention is obtained.
  • the acrylic resin solution has a solid content concentration in a specific range.
  • an acrylic pressure-sensitive adhesive composition containing a cross-linking agent (C) described later an essential requirement for enabling thick coating when applied to a substrate It has become.
  • the acrylic resin solution of the present invention is required to have a solid content concentration of 60% by weight or more, preferably 65% by weight or more, particularly preferably 70% by weight or more, more preferably 75% by weight or more,
  • the upper limit of the solid content concentration is usually 90% by weight. If the solid content concentration is too low, thick coating is difficult and a thick adhesive layer tends to be difficult to obtain.
  • the solid content concentration (% by weight) of the acrylic resin solution is determined by, for example, accurately weighing 1 g of a sample on an aluminum foil and heating it with a ket (infrared dryer, 185 W, height 5 cm) for 45 minutes. Can be calculated.
  • the acrylic resin solution it is preferable that 60% by weight or more of the total solid content is the acrylic resin (A) in terms of ensuring cohesion, and particularly preferably 70% by weight or more.
  • Preferably 80 weight% or more is an acrylic resin (A).
  • the upper limit of the content ratio of the acrylic resin (A) with respect to the total solid content is 100% by weight.
  • the acrylic resin solution of the present invention preferably has a viscosity of 20,000 mPa ⁇ s / 25 ° C. or less from the viewpoint of coating properties, particularly preferably 18,000 mPa ⁇ s / 25 ° C. or less, more preferably 15,000 mPa ⁇ s / 25 ° C. or lower.
  • the lower limit of the viscosity is 100 mPa ⁇ s / 25 ° C. If the viscosity is too high, the coating tends to be difficult due to, for example, the appearance of coating stripes.
  • the acrylic resin solution is preferably further blended with a crosslinking agent (C) to form an acrylic pressure-sensitive adhesive composition.
  • a crosslinking agent (C) to form an acrylic pressure-sensitive adhesive composition.
  • the acrylic pressure-sensitive adhesive composition is used.
  • the product becomes an acrylic pressure-sensitive adhesive by being crosslinked by the crosslinking agent (C).
  • Such a crosslinking agent (C) exhibits an excellent adhesive force by reacting with a functional group derived from the functional group-containing monomer (a2) which is a constituent monomer of the acrylic resin (A).
  • a functional group derived from the functional group-containing monomer (a2) which is a constituent monomer of the acrylic resin (A) examples include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, aziridine-based crosslinking agents, melamine-based crosslinking agents, aldehyde-based crosslinking agents, amine-based crosslinking agents, and metal chelate-based crosslinking agents.
  • an isocyanate type crosslinking agent is suitably used from the point of improving the adhesiveness with the base material and the reactivity with the acrylic resin (A).
  • isocyanate crosslinking agent examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, hexamethylene.
  • adducts of polyol compounds such as trimethylolpropane, burettes and isocyanurates of these polyisocyanate compounds, Among these, adducts, burettes, and isocyanurates of tolylene diisocyanate and hexamethylene diisocyanate polyol compounds are preferably used, and 2,4-tolylene diisocyanate adduct of trimethylol propane and 2 of trimethylol propane. 1,6-tolylene diisocyanate adduct or a mixture thereof is particularly preferably used.
  • epoxy crosslinking agent examples include N, N, N ′, N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, etherene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, Pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycol In addition to diyl ether, adipic
  • aziridine-based crosslinking agent examples include tetramethylolmethane-tri- ⁇ -aziridinylpropionate, trimethylolpropane-tri- ⁇ -aziridinylpropionate, N, N′-diphenylmethane-4,4.
  • Examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexaptoxymethyl melamine, hexapentyloxymethyl melamine, hexahexyloxymethyl melamine, and melamine resin. .
  • aldehyde-based crosslinking agent examples include glyoxal, malondialdehyde, succindialdehyde, maleindialdehyde, glutardialdehyde, formaldehyde, acetaldehyde, benzaldehyde and the like.
  • amine-based crosslinking agent examples include hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetraamine, diethylenetriamine, triethyltetraamine, isophoronediamine, amino resin, and polyamide.
  • metal chelate-based crosslinking agent examples include acetylacetone and acetoacetyl ester coordination compounds of multimetals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, panadium, chromium, and zirconium. It is done.
  • cross-linking agents (C) may be used alone or in combination of two or more.
  • the content of the crosslinking agent (C) is usually preferably 0.01 to 20 parts by weight, more preferably 0.05 to 15 parts by weight, with respect to 100 parts by weight of the acrylic resin (A). Particularly preferred is 0.1 to 10 parts by weight. If the amount of the crosslinking agent (C) is too small, the cohesive force tends to be insufficient and sufficient durability cannot be obtained. If the amount is too large, the flexibility and the adhesive force tend to decrease.
  • crosslinking accelerators include tertiary amines such as benzylmethylamine and triethylenediamine, imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole, acids such as paratoluenesulfonic acid and phosphoric acid. Examples thereof include catalysts and metal oxides of tin and zinc.
  • the acrylic pressure-sensitive adhesive composition further includes a silane coupling agent, an antistatic agent, other acrylic pressure-sensitive adhesives, other pressure-sensitive adhesives, urethane resin, rosin, and rosin ester as long as the effects of the present invention are not impaired.
  • Hydrogenated rosin esters phenol resins, aromatic modified terpene resins, aliphatic petroleum resins, alicyclic petroleum resins, styrene resins, xylene resins, etc.
  • colorants such as ultraviolet absorbers and functional dyes, and compounds that cause coloration or discoloration upon irradiation with ultraviolet rays or radiation can be blended. It is preferably 30% by weight or less, particularly preferably 20% by weight or less, and a low molecular component having a molecular weight lower than 10,000 as a compounding agent is contained as much as possible. It is preferred from the viewpoint of excellent durability.
  • a small amount of impurities and the like contained in the raw materials for producing the constituent components of the pressure-sensitive adhesive composition may be contained.
  • the acrylic pressure-sensitive adhesive composition is cured (cross-linked) with the cross-linking agent (C) to obtain an acrylic pressure-sensitive adhesive.
  • the acrylic pressure-sensitive adhesive of the present invention is preferably used for a pressure-sensitive adhesive sheet containing a pressure-sensitive adhesive layer made of an acrylic pressure-sensitive adhesive and a base material.
  • the pressure-sensitive adhesive sheet can be produced according to a known method for producing a pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive sheet can be obtained by drying and curing after an acrylic pressure-sensitive adhesive composition is provided on a substrate.
  • the substrate on which the acrylic pressure-sensitive adhesive composition is provided is not particularly limited, and examples thereof include polyester resins such as polyethylene naphthalate, polyethylene terephthalate, boribylene terephthalate, polyethylene terephthalate / isophthalate copolymer; polyethylene, polypropylene, Polyolefin resins such as polymethylpentene; Polyfluorinated ethylene resins such as polyvinyl fluoride, polyvinylidene fluoride, and polyfluorinated ethylene; Polyamides such as nylon 6 and nylon 6, 6; Polyvinyl chloride, polyvinyl chloride / vinyl acetate copolymer Polymers, vinyl polymers such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol and vinylon; cellulose resins such as cellulose triacetate and cellophane; Acrylic resin such as polyethyl methacrylate, polyethyl acrylate, polybuty
  • the acrylic pressure-sensitive adhesive is preferably used as a pressure-sensitive adhesive for optical members.
  • a pressure-sensitive adhesive layer made of the acrylic pressure-sensitive adhesive is formed on the optical member.
  • an optical with a pressure-sensitive adhesive layer is formed. A member can be obtained.
  • the optical member examples include a transparent electrode film such as an ITO electrode film, a polarizing plate, a retardation plate, an elliptically polarizing plate, an optical compensation film, a brightness enhancement film, an electromagnetic wave shielding film, a near-infrared absorbing film, and an AR film.
  • a transparent electrode film such as an ITO electrode film, a polarizing plate, a retardation plate, an elliptically polarizing plate, an optical compensation film, a brightness enhancement film, an electromagnetic wave shielding film, a near-infrared absorbing film, and an AR film.
  • a transparent electrode film when it is a transparent electrode film, the effect of this invention can be exhibited notably and it is preferable at the point from which high adhesive force is acquired, Especially preferably, it is an ITO (indium tin oxide) electrode film.
  • the acrylic resin (A) does not contain an acidic group, corrosion is particularly difficult to occur.
  • a release sheet on the surface opposite to the optical member surface of the pressure-sensitive adhesive layer.
  • An adhesive layer and an adherend will be bonded.
  • a silicon-based release sheet is preferably used as such a release sheet.
  • [1] Apply the acrylic pressure-sensitive adhesive composition on the optical member. After drying, a method of pasting a release sheet and performing an aging treatment, [2] An acrylic pressure-sensitive adhesive composition is applied on the release sheet, and after drying, an optical member is pasted, and aging is performed. This can be done by a method of processing. Among these, the method [2] is preferable in terms of not damaging the optical member, workability, and stable production.
  • a crosslinking agent (C) for an acrylic adhesive composition it is preferable to perform an aging process after manufacturing the optical member with an adhesive layer using the said method.
  • Such an aging treatment is carried out to balance the physical properties of the adhesive.
  • the temperature is usually from room temperature to 70 ° C.
  • the time is usually from 1 day to 30 days.
  • the treatment may be carried out under the conditions of 1 day to 20 days at 23 ° C., preferably 3 to 10 days at 23 ° C., 1 to 7 days at 40 ° C.
  • the application (coating) of the acrylic pressure-sensitive adhesive composition is performed by a conventional method such as roll coating, die coating, gravure coating, comma coating, or screen printing.
  • the pressure-sensitive adhesive that bonds the pressure-sensitive adhesive layer and the adherend (other optical members) after peeling off the release sheet.
  • a double-sided pressure-sensitive adhesive sheet having a known general configuration may be applied using the above acrylic pressure-sensitive adhesive, but in particular, it is excellent in transparency and has a high adhesive force with respect to the thickness to constitute.
  • a double-sided pressure-sensitive adhesive sheet is preferred.
  • Such a substrate-less double-sided pressure-sensitive adhesive sheet is formed by forming a pressure-sensitive adhesive layer made of the above acrylic pressure-sensitive adhesive on a release sheet, and then sticking another release sheet to the side of the pressure-sensitive adhesive layer that does not have a release sheet. It can be obtained by combining.
  • the other release sheet may be peeled off and bonded to the adherend.
  • the gel fraction of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive layer of the optical member with the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer of the double-sided pressure-sensitive adhesive sheet is 30 to 98% from the viewpoint of durability and adhesive strength. 40 to 95% is particularly preferable, and 50 to 90% is particularly preferable. If the gel fraction is too low, durability tends to be insufficient due to insufficient cohesive force. On the other hand, if the gel fraction is too high, the adhesive force tends to decrease due to an increase in cohesive force.
  • the gel fraction of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive for optical members, and the pressure-sensitive adhesive layer of the double-sided pressure-sensitive adhesive sheet is achieved by adjusting the type and amount of the crosslinking agent. Is done.
  • the gel fraction is a measure of the degree of crosslinking (curing degree), and is calculated, for example, by the following method. That is, a pressure-sensitive adhesive sheet (not provided with a separator) in which a pressure-sensitive adhesive layer is formed on a polymer sheet (for example, polyethylene terephthalate film or the like) as a base material is wrapped with a 200-mesh SUS wire mesh, and 23 in toluene.
  • the weight percentage of the insoluble pressure-sensitive adhesive component that was immersed in the wire mesh for 24 hours and remained in the wire mesh with respect to the pressure-sensitive adhesive layer before being immersed in toluene is defined as a gel fraction. However, the weight of the substrate is subtracted.
  • the thickness (post-drying film thickness) of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet, the optical member with the pressure-sensitive adhesive layer, and the double-sided pressure-sensitive adhesive sheet is usually preferably 3 to 200 ⁇ m, particularly preferably 5 to 150 ⁇ m. Further, it is preferably 10 to 100 ⁇ m. If the thickness of the pressure-sensitive adhesive layer is too thin, the adhesive physical properties tend to be difficult to stabilize, and if it is too thick, the thickness of the entire optical member tends to increase too much.
  • the acrylic pressure-sensitive adhesive composition of the present invention since the acrylic resin solution contained in the composition has a high solid content concentration and a low viscosity, it is generally used generally. It is possible to obtain a thick adhesive layer that could not be obtained by coating and drying with an acrylic adhesive composition with a low solid content diluted with a solvent to reduce viscosity It becomes.
  • the above thick adhesive layer When obtaining the above thick adhesive layer, it is preferably applied with a film thickness of 80 ⁇ m or more, particularly preferably 110 ⁇ m or more, more preferably 140 ⁇ m or more, and the film thickness of the adhesive layer obtained after drying. It is preferably 50 ⁇ m or more, particularly preferably 80 ⁇ m or more, and further preferably 100 ⁇ m or more.
  • the film thickness at the time of coating is usually 3000 ⁇ m, and the film thickness after drying is usually 2000 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer after drying is preferably 100 ⁇ m or more, particularly preferably 120 ⁇ m or more. Is usually 2000 ⁇ m.
  • the adhesive strength of the pressure-sensitive adhesive layer of the present invention is appropriately determined according to the material of the adherend, and is adhered to, for example, a PET sheet on which a glass substrate, a polycarbonate plate, a polymethyl methacrylate plate, or an ITO layer is deposited.
  • the adhesive strength is preferably 5 N / 25 mm to 500 N / 25 mm, more preferably 10 N / 25 mm to 100 N / 25 mm.
  • the said adhesive force (N / 25mm) is computed as follows.
  • PET polyethylene terephthalate
  • the release sheet is peeled off, and the pressure-sensitive adhesive layer side of the 25 mm ⁇ 100 mm PET sheet with the pressure-sensitive adhesive layer is added to soda glass or the like by reciprocating 2 kg rubber rollers in an atmosphere of 23 ° C. and 50% relative humidity. Apply pressure and leave in the same atmosphere for 30 minutes.
  • the 180 ° peel strength (N / 25 mm) is measured at room temperature at a peel rate of 300 mm / min, and the resulting value is defined as the adhesive strength (N / 25 mm).
  • the total light transmittance of the pressure-sensitive adhesive layer of the present invention is preferably 90% or more, particularly preferably 92% or more. If the total light transmittance is too low, the transmittance is low, so that it tends to be difficult to use in display applications.
  • the upper limit of the total light transmittance is usually 95%.
  • the haze value of the pressure-sensitive adhesive layer of the present invention is preferably 10% or less, particularly preferably 2% or less. If the haze value is too high, the image tends to be unclear when used for display.
  • the lower limit of the haze value is usually 0.00%.
  • the above-mentioned total light transmittance and haze value are values measured using a haze meter based on JIS K7361-1.
  • the total light transmittance of the pressure-sensitive adhesive layer can be measured using HAZE MATER NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS K7361-1.
  • the diffusion transmittance of the pressure-sensitive adhesive layer can be measured using, for example, HAZE MATER NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS K7361-1.
  • the pressure-sensitive adhesive composed of the pressure-sensitive adhesive composition of the present invention can be suitably used as a double-sided pressure-sensitive adhesive sheet, particularly a double-sided pressure-sensitive adhesive sheet having no base material (base material-less). Excellent in reliability and impact resistance, has high light transmittance, hardly generates haze, and is made of glass, ITO transparent electrode sheet, polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), etc. It is useful for attaching optical members such as optical sheets, polarizing films, retardation films, optical compensation films, and brightness enhancement films. Furthermore, it can use suitably with respect to the touchscreen which comprises these optical members.
  • acrylic resin solution (I) various acrylic resin solutions (hereinafter sometimes referred to as “acrylic resin solution (I)”) were prepared as follows. In addition, about the measurement of the weight average molecular weight of acrylic resin solution (I), a number average molecular weight, and a glass transition temperature, it measured according to the above-mentioned method.
  • the acrylic resin solution (I) has a solid content of 1 to 2 g of an acrylic resin solution on an aluminum foil, heated and dried for 45 minutes in a ket (infrared dryer, 185 W, height 5 cm), and weight before and after drying. Changes were measured and calculated. The viscosity of the acrylic resin solution (I) was measured according to the JIS K5400 (1990) 4.5.3 rotational viscometer method.
  • polymerization was carried out for 7 hours while successively adding a polymerization catalyst solution in which 0.06 part of AIBN was dissolved in 2 parts of ethyl acetate, and the acrylic resin solution (I-1) (solid content concentration 72.5%, viscosity) 4,700 mPa ⁇ s / 25 ° C., a weight average molecular weight of 127,000, a number average molecular weight of 47,200, a dispersity of 2.69, and a glass transition temperature of ⁇ 53.3 ° C.).
  • a polymerization catalyst solution in which 0.06 part of AIBN was dissolved in 2 parts of ethyl acetate, and the acrylic resin solution (I-1) (solid content concentration 72.5%, viscosity) 4,700 mPa ⁇ s / 25 ° C., a weight average molecular weight of 127,000, a number average molecular weight of 47,200, a dispersity of 2.69, and a glass transition temperature of ⁇ 53.3 °
  • an acrylic resin solution (I-2) (solid content concentration 72.5%, viscosity 14) was added for 7 hours while successively adding a polymerization catalyst solution in which 0.06 part of AIBN was dissolved in 2 parts of ethyl acetate. 400 mPa ⁇ s / 25 ° C., weight average molecular weight 134,000, number average molecular weight 50,200, dispersity 2.67, glass transition temperature ⁇ 31.5 ° C.).
  • an acrylic resin solution (I-3) (solid content concentration 70%, viscosity 8,000 mPas) was added for 7 hours while successively adding a polymerization catalyst solution in which 0.06 part of AIBN was dissolved in 2 parts of ethyl acetate. S / 25 ° C., weight average molecular weight 235,000, number average molecular weight 78,900, dispersity 2.98, glass transition temperature ⁇ 49.3 ° C.).
  • an acrylic resin solution (I-4) (solid content concentration 65%, viscosity 7,800 mPa) was polymerized for 7 hours while successively adding a polymerization catalyst solution in which 0.06 part of AIBN was dissolved in 13 parts of ethyl acetate. S / 25 ° C., weight average molecular weight 262,000, number average molecular weight 84,500, dispersity 3.12, glass transition temperature ⁇ 49.3 ° C.).
  • an acrylic resin solution (I-5) (solid content concentration: 72.5%, viscosity: 10%) was polymerized for 7 hours while sequentially adding a polymerization catalyst solution in which 0.06 part of AIBN was dissolved in 2 parts of ethyl acetate. 400 mPa ⁇ s / 25 ° C., weight average molecular weight 118,000, number average molecular weight 43,700, dispersity 2.70, glass transition temperature ⁇ 31.5 ° C.).
  • an acrylic resin solution (I-6) (solid content concentration 70%, viscosity 8,900 mPa) was polymerized for 7 hours while successively adding a polymerization catalyst solution in which 0.06 part of AIBN was dissolved in 2 parts of ethyl acetate. S / 25 ° C., weight average molecular weight 107,000, number average molecular weight 40,200, dispersity 2.66, glass transition temperature-38.9 ° C.).
  • an acrylic resin solution (I-7) (solid content concentration 70%, viscosity 8,200 mPas) was added for 7 hours while successively adding a polymerization catalyst solution in which 0.06 part of AIBN was dissolved in 2 parts of ethyl acetate. S / 25 ° C., weight average molecular weight 215,000, number average molecular weight 76,800, dispersity 2.80, glass transition temperature ⁇ 50.6 ° C.).
  • polymerization was carried out for 7 hours while successively adding a polymerization catalyst solution in which 0.05 part of AIBN was dissolved in 6 parts of toluene, and then diluted with 84 parts of toluene to obtain an acrylic resin solution (I-8) (solid content concentration).
  • I-8 solid content concentration
  • I-9 solid
  • Table 1 shows the type and weight ratio of the organic solvent (B), the chain transfer constant, and the blending amount (parts) in the acrylic resin solutions (I-1) to (I-9).
  • Crosslinking agent (C) The following were prepared as the crosslinking agent (C-1). ⁇ 55% ethyl acetate solution of tolylene diisocyanate adduct of trimethylolpropane (Nippon Polyurethane Co., Ltd., “Coronate L-55E”)
  • the acrylic pressure-sensitive adhesive composition obtained above was applied to a polyester release sheet at a thickness of 250 ⁇ m, dried at 90 to 100 ° C. for 3 minutes, and a pressure-sensitive adhesive layer having a thickness of 175 ⁇ m after drying was formed. Formed. Then, the formed pressure-sensitive adhesive layer side was bonded with a polyester release sheet and aged at 40 ° C. for 10 days to obtain a substrate-less double-sided pressure-sensitive adhesive sheet.
  • a PET film with a pressure-sensitive adhesive layer was produced as follows, and the gel fraction, adhesive strength, holding power, and corrosion resistance were measured according to the following methods. evaluated. These results are also shown in Table 2 below.
  • the acrylic pressure-sensitive adhesive composition obtained above is applied to a polyester release sheet with a thickness of 250 ⁇ m and dried at 90 to 100 ° C. for 3 minutes to form a pressure-sensitive adhesive layer with a thickness of 175 ⁇ m after drying.
  • the state of the pressure-sensitive adhesive layer was visually observed.
  • ⁇ No bubbles are observed in the coating film.
  • ⁇ Under the above-mentioned conditions, bubbles are slightly generated in the coating film. However, when the coating is further dried at 100 ° C. for 2 minutes, the bubbles disappear.
  • X Bubbles are generated in the coating film. Even if the drying time is extended, bubbles do not disappear.
  • an optical PET film with a pressure-sensitive adhesive layer was prepared as follows, and the total light transmittance and haze value were measured and evaluated according to the following methods. These results are also shown in Table 2 below.
  • the substrate-less double-sided pressure-sensitive adhesive sheet is cut into 3 cm ⁇ 4 cm, the release sheet on one side is peeled off, the pressure-sensitive adhesive layer side is pressed against the optical PET film, and the other release sheet is further peeled off. A sample for measuring light transmittance and haze value was obtained.
  • the pressure-sensitive adhesive layers obtained by curing the acrylic pressure-sensitive adhesive compositions of Examples 1 to 7 are all good although they are thick-film pressure-sensitive adhesive layers obtained by coating thicker than usual. A coated surface is obtained, excellent in optical properties such as total light transmittance and haze value, and excellent in adhesive properties.
  • Comparative Examples 1 and 2 since the acrylic resin contained in the acrylic resin solution has a high weight average molecular weight and a high viscosity, it must be diluted with an organic solvent to a viscosity that can be applied. The system resin solution has a low solid content concentration. Therefore, even if the coating is thick as in Examples 1 to 7, the organic solvent cannot be completely removed during drying, and many bubbles are generated on the coated surface of the produced pressure-sensitive adhesive layer, resulting in optical properties. It is inferior to.
  • the pressure-sensitive adhesive composed of the pressure-sensitive adhesive composition of the present invention can be suitably used as a double-sided pressure-sensitive adhesive sheet, particularly a double-sided pressure-sensitive adhesive sheet having no base material (base material-less).
  • optical members such as optical sheets such as PET), polycarbonate (PC), and polymethyl methacrylate (PMMA), polarizing films, retardation films, optical compensation films, and brightness enhancement films. Furthermore, it can use suitably with respect to the touchscreen which comprises these optical members.

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Abstract

La présente invention concerne un adhésif acrylique à base de solvant de type durcissable au moyen d'un agent de réticulation, ledit adhésif pouvant être appliqué selon une forte épaisseur et permettant d'obtenir une couche adhésive sous forme de film épais. L'invention concerne spécifiquement un solvant de résine acrylique caractérisé en ce qu'il contient une résine acrylique (A) dont le poids moléculaire moyen en poids varie de 50 000 à 300 000 et un solvant organique (B) tel que la constante de transfert de chaîne de l'acétate de vinyle dans le solvant est égale ou supérieure à 250, à 60 °C, la concentration en solides étant égale ou supérieure à 60 %.
PCT/JP2011/059928 2010-04-27 2011-04-22 Solution de résine acrylique, composition adhésive acrylique, adhésif acrylique, feuille adhésive, adhésif acrylique pour élément optique et élément optique comportant une couche adhésive WO2011136141A1 (fr)

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KR1020127030928A KR20130094724A (ko) 2010-04-27 2011-04-22 아크릴계 수지 용액, 아크릴계 점착제 조성물, 아크릴계 점착제, 점착 시트, 광학 부재용 아크릴계 점착제, 점착제층 부착 광학 부재

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CN102858872B (zh) 2016-06-29
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