WO2017104350A1 - Adhesive composition - Google Patents
Adhesive composition Download PDFInfo
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- WO2017104350A1 WO2017104350A1 PCT/JP2016/084411 JP2016084411W WO2017104350A1 WO 2017104350 A1 WO2017104350 A1 WO 2017104350A1 JP 2016084411 W JP2016084411 W JP 2016084411W WO 2017104350 A1 WO2017104350 A1 WO 2017104350A1
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- sensitive adhesive
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- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- 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
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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
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Definitions
- the present invention relates to a pressure-sensitive adhesive composition useful for forming a pressure-sensitive adhesive layer having excellent durability in an optical film with a pressure-sensitive adhesive layer used for a liquid crystal display device or the like.
- An optical film typified by a polarizing plate formed by laminating and laminating a transparent resin film on one or both surfaces of a polarizer is widely used as an optical member constituting an image display device such as a liquid crystal display device.
- An optical film such as a polarizing plate is often used by being bonded to another member (for example, a liquid crystal cell in a liquid crystal display device) via an adhesive layer (see Patent Document 1). For this reason, the optical film with an adhesive layer by which the adhesive layer was previously provided in the one surface as an optical film is known.
- liquid crystal display devices have been deployed in mobile device applications such as smartphones and tablet terminals and in-vehicle devices such as car navigation systems. In such an application, there is a possibility that it may be exposed to a harsh environment as compared with a conventional indoor TV application.
- the pressure-sensitive adhesive layer incorporated in a liquid crystal display device or the like may be placed in a high temperature or high temperature and high humidity environment, or may be placed in an environment where high and low temperatures are repeated.
- the optical film is required to be able to suppress problems such as floating and peeling at the interface between the pressure-sensitive adhesive layer and the optical member to which the optical film is bonded, foaming of the pressure-sensitive adhesive layer, and the like even under these circumstances. It is also required that the optical characteristics do not deteriorate.
- the pressure-sensitive adhesive layer is required to have a higher durability performance than a general optical film due to a strong shrinkage stress in a high temperature environment. Due to the increasing demand for improving the durability of the liquid crystal display device described above, recently, the durability required for the pressure-sensitive adhesive layer has become very severe.
- an object of the present invention is to provide a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer exhibiting excellent durability even under such severe durability conditions.
- a pressure-sensitive adhesive composition comprising a (meth) acrylic resin (A), a crosslinking agent (B), and a silane compound (C),
- the (meth) acrylic resin (A) is represented by the following formula (a1)
- a pressure-sensitive adhesive composition comprising a structural unit derived from a hydroxy group-containing (meth) acrylate and a structural unit derived from 5-hydroxypentyl acrylate.
- the proportion of the structural unit derived from the hydroxy group-containing (meth) acrylate represented by the formula (a1) with respect to 100 parts by weight of all the structural units constituting the (meth) acrylic resin is 1.5 to 4.
- the (meth) acrylic resin is derived from a structural unit derived from an alkyl acrylate (a3-1) having a homopolymer glass transition temperature of less than 0 ° C. and an alkyl acrylate derived from a homopolymer having a glass transition temperature of 0 ° C. or higher.
- [4] A structural unit derived from an alkyl acrylate (a3-1) having a glass transition temperature of the homopolymer of less than 0 ° C., and a structural unit derived from an alkyl acrylate (a3-2) having a glass transition temperature of the homopolymer of 0 ° C. or higher.
- the ratio (weight ratio) of the pressure-sensitive adhesive composition according to [3], wherein (a3-1) / (a3-2) 20/80 to 95/5.
- [5] The pressure-sensitive adhesive composition according to any one of [1] to [4], wherein the (meth) acrylic resin has a weight average molecular weight of 6.0 ⁇ 10 5 to 2.5 ⁇ 10 6 in terms of polystyrene. object.
- B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group.
- —CH 2 — may be substituted with —O— or —CO—
- R 1 represents an alkyl group having 1 to 5 carbon atoms
- R 2 , R 3 , R 4 , R 5 and R 6 are each Independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms
- the pressure-sensitive adhesive composition according to any one of [1] to [7], which is a silane compound represented by the formula: [9] B in the formula (c1) is an alkanediyl group having 1 to 10 carbon atoms
- R 1 is an alkyl group having 1 to 5 carbon atoms
- R 2 , R 3 , R 4 , R 5 and R 6 Are each independently an alkoxy group having 1 to 5 carbon atoms, [8].
- the ratio of the silane compound (C) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic resin (A), according to any one of [1] to [9] Adhesive composition.
- the pressure-sensitive adhesive composition according to any one of [1] to [10], wherein the pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition has a gel fraction of 50 to 95%.
- a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is bonded to a glass substrate, and the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer after 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50% is determined by a peeling rate.
- the pressure-sensitive adhesive composition of the present invention can form a pressure-sensitive adhesive layer having excellent durability even under severe durability conditions.
- FIG. 2 is a schematic cross-sectional view showing an example of the layer structure of the polarizing plate.
- FIG. 3 is a schematic cross-sectional view showing another example of the layer configuration of the polarizing plate.
- FIG. 4 is a schematic cross-sectional view showing an example of an optical laminate including an optical film with an adhesive layer formed from the adhesive composition according to the present invention.
- FIG. 5 is a schematic sectional drawing which shows an example of the optical laminated body containing the optical film with an adhesive layer formed from the adhesive composition which concerns on this invention.
- FIG. 6 is a schematic cross-sectional view showing still another example of an optical laminate including an optical film with an adhesive layer formed from the adhesive composition according to the present invention.
- FIG. 7 is a schematic sectional drawing which shows another example of the optical laminated body containing the optical film with an adhesive layer formed from the adhesive composition which concerns on this invention.
- FIG. 8 is a schematic sectional drawing which shows another example of the optical laminated body containing the optical film with an adhesive layer formed from the adhesive composition which concerns on this invention.
- the pressure-sensitive adhesive composition of the present invention contains a (meth) acrylic resin (A), a crosslinking agent (B), and a silane compound (C).
- the (meth) acrylic resin (A) is a polymer or copolymer having a structural unit derived from a (meth) acrylic monomer as a main component (preferably containing 50% by weight or more), and represented by the following formula (a1 And a structural unit derived from a hydroxy group-containing (meth) acrylate and a structural unit derived from 5-hydroxypentyl acrylate.
- n represents an integer of 1 to 4, A 1 represents a hydrogen atom or an alkyl group, X 1 represents an optionally substituted methylene group, and when n is 2 or more, The substituents may be the same or different)
- (meth) acrylic resin (A) of the present invention has hydroxyalkyl groups having predetermined different carbon chain lengths in the side chain, in the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, (meth) acrylic It is estimated that the crosslink density between the system resins can be optimized. By optimizing the cross-linking density, it is possible to form a pressure-sensitive adhesive layer with an excellent balance between hardness and softness (or having the optimum hardness), so that durability can be improved and peeling of the interface is possible even in a high-temperature environment. (Or floating) and foaming can be effectively suppressed.
- the pressure-sensitive adhesive layer can effectively relieve the stress, so that white spots due to the shrinkage of the optical film (for example, the deflection plate) can be prevented. Furthermore, the reworkability (peelability) can be improved by optimizing the crosslinking density.
- the term “durability” refers to the interface between the pressure-sensitive adhesive layer and the optical member adjacent thereto, for example, in a high temperature environment, a high temperature and high humidity environment, or an environment where high and low temperatures are repeated.
- cohesive failure resistance means the characteristic which can suppress the cohesive failure (or tearing) of an adhesive layer.
- X 1 represents a methylene group which may have a substituent.
- substituents include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (eg, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group, a t-butyl group).
- C 1-10 alkyl group such as butyl group, pentyl group, hexyl group, preferably C 1-6 alkyl group, more preferably C 1-3 alkyl group), cycloalkyl group (cyclopentyl group, cyclohexyl group, etc.)
- An aryl group [phenyl group, alkylphenyl group (tolyl group, xylyl group, etc.)] aralkyl group (benzyl group, etc.), alkoxy group (for example, C 1-4 alkoxy group such as methoxy group, ethoxy group, etc.), polyoxyalkylene groups (e.g., such as dioxyethylene group), C of such cycloalkoxy groups (e.g., hexyloxy group cyclohexylene Such as -10 cycloalkyloxy group), an aryloxy group (e.g., phenoxy group), aralkyloxy group (e.g., benzyl
- halogen atom an alkyl group, an alkoxy group, an aryloxy group, and the like are preferable, and an alkyl group (for example, a methyl group, an ethyl group, and the like) is particularly preferable.
- a 1 represents a hydrogen atom or an alkyl group, and the alkyl group may be an alkyl group exemplified in X 1 (preferably a methyl group or the like).
- X 1 preferably a methyl group or the like.
- n represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2.
- hydroxy group-containing (meth) acrylate (a1) examples include 1-hydroxymethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 1-hydroxyheptyl (meth) acrylate, and (meth) acrylic.
- 1-hydroxybutyl acid, 1-hydroxyC 1-8 alkyl (meth) acrylate such as 1-hydroxypentyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate (Meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 2-hydroxypentyl, (meth) acrylic acid 2-hydroxyhexyl and the like (meth) acrylic acid 2-hydroxy C 2-9 alkyl; (meth) acrylic 3-hydroxypropyl acid, 3-hydroxybutyl (meth) acrylate, ( Data) acrylate, 3-hydroxypentyl, (meth) acrylate, 3-hydroxyhexyl, (meth) (meth) acrylic acid such as acrylic acid 3-hydroxy-heptyl 3-hydroxy C 3-10 alkyl; (meth) acrylic acid 4 -(Meth) acrylic acid such as hydroxybutyl, 4-hydroxypentyl (meth) acrylate, 4-hydroxyhexyl (meth) acrylate,
- hydroxy-containing (meth) acrylates in which n is 2, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate; Hydroxy-containing (meth) acrylates where n is 3 such as 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate and 3-hydroxypentyl (meth) acrylate are preferred.
- the hydroxy-containing (meth) acrylate in which n is 2 is preferable, and among these, 2-hydroxyethyl (meth) acrylate is preferable.
- the proportion of the structural unit derived from the hydroxy group-containing (meth) acrylate represented by the formula (a1) is 1.5 to 4.5 parts by weight with respect to 100 parts by weight of all the structural units constituting the (meth) acrylic resin.
- the proportion of the structural unit derived from 5-hydroxypentyl acrylate (a2) is preferably 0.25 to 1.0 part by weight.
- the ratio (weight ratio) of the structural unit derived from the hydroxy group-containing (meth) acrylate represented by the formula (a1) and the structural unit derived from 5-hydroxypentyl acrylate (a2) is particularly within the above range.
- (a1) / (a2) 13/1 to 3/1 (for example, 11/1 to 3/1), more preferably 9/1 to 4/1, particularly 7/1 to 5 / 1 may be sufficient.
- (a1) / (a2) 13/1 to 3/1 (for example, 11/1 to 3/1)
- more preferably 9/1 to 4/1, particularly 7/1 to 5 / 1 may be sufficient.
- the (meth) acrylic resin (A) may contain a structural unit derived from an alkyl acrylate (a3) and a structural unit derived from a substituent-containing alkyl acrylate (a4).
- examples of the alkyl acrylate (a3-1) having a glass transition temperature (Tg) of the homopolymer of less than 0 ° C. include ethyl acrylate, n- and i-propyl acrylate, n- and i- Butyl acrylate, n-pentyl acrylate, n- and i-hexyl acrylate, n-heptyl acrylate, n- and i-octyl acrylate, 2-ethylhexyl acrylate, n- and i-nonyl acrylate, n- and i- Examples thereof include linear or branched alkyl acrylates having about 2 to 12 carbon atoms in the alkyl group such as decyl acrylate and n-dodecyl acrylate.
- the alkyl acrylate (a3) may be an alkyl acrylate (cycloalkyl acrylate) having an alicyclic structure, but has 2 to 10 carbon atoms from the viewpoint of followability (or flexibility and adhesiveness) to the optical film.
- Alkyl acrylates preferably alkyl acrylates having 3 to 8 carbon atoms, more preferably alkyl acrylates having 4 to 6 carbon atoms, particularly n-butyl alkyl acrylate.
- n-butyl alkyl acrylate is used, the followability can be enhanced, and for example, it is advantageous in peeling resistance.
- These alkyl acrylates (a3-1) can be used alone or in combination of two or more.
- alkyl acrylate (a3-2) having a homopolymer Tg of 0 ° C. or higher examples include methyl acrylate, cycloalkyl acrylate (eg, cyclohexyl acrylate, isobornyl acrylate), stearyl acrylate, t-butyl acrylate, etc. Methyl acrylate is particularly preferred. When methyl acrylate is used, the strength can be increased, which is advantageous for cohesive failure, for example.
- These alkyl acrylates (a3-2) can be used alone or in combination of two or more.
- Tg of the alkyl acrylate homopolymer reference values such as POLYMER HANDBOOK (Wiley-Interscience) can be referred to.
- the proportion of structural units derived from alkyl acrylate in (meth) acrylic resin (A) is 100 weights of all structural units constituting (meth) acrylic resin (A) from the viewpoints of durability and reworkability of the pressure-sensitive adhesive layer.
- Part by weight for example, 40 parts by weight or more (eg 50 to 98 parts by weight), preferably 60 parts by weight or more (eg 70 to 95 parts by weight), more preferably 70 parts by weight or more (eg 80 ⁇ 90 parts by weight).
- (A3-1) / (a3-2) 20/80 to 95/5 (for example, 30/70 to 90/10), preferably 40/60 to 85/15, more preferably 55/45 to 75/25.
- the followability improves as the proportion of the structural unit derived from the alkyl acrylate (a3-1) having a glass transition temperature of less than 0 ° C. increases.
- the proportion of the structural unit derived from the alkyl acrylate (a3-2) having a glass transition temperature of 0 ° C. or higher is increased, the cohesive fracture resistance is improved.
- Examples of the substituent-containing alkyl acrylate (a4) include alkyl acrylates in which a substituent is introduced into the alkyl group in the alkyl acrylate (a3-1) (the hydrogen atom of the alkyl group is substituted with a substituent).
- the substituent may be, for example, an aryl group (such as a phenyl group), an aryloxy group (phenoxy group), an alkoxy group (such as a methoxy group, an ethoxy group).
- Examples of the substituent-containing alkyl acrylate (a3-3) include, for example, alkoxyalkyl acrylate (eg, 2-methoxyethyl acrylate, ethoxymethyl acrylate, etc.), aryloxyalkyl acrylate (eg, phenoxyethyl acrylate, etc.), aryloxypolyalkylene glycol mono Examples include acrylate and polyalkylene glycol monoacrylate. These alkyl acrylates (a3-3) can be used alone or in combination of two or more. By including an alkyl acrylate containing an aromatic ring such as an aryl group or an aryloxy group, white spots of the polarizing plate during the durability test can be improved.
- alkoxyalkyl acrylate eg, 2-methoxyethyl acrylate, ethoxymethyl acrylate, etc.
- aryloxyalkyl acrylate eg, phenoxyethyl acrylate, etc.
- the alkylene group of the aryloxy polyalkylene glycol monoacrylate and the polyalkylene glycol monoacrylate may be, for example, a C 1-6 alkylene group such as a methylene group, an ethylene group, or a propylene group (preferably an ethylene group).
- the repeating unit of the oxyalkylene group may be, for example, 2 to 7, preferably 2 to 5 (particularly 2) from the viewpoint of durability of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition.
- the pressure-sensitive adhesive composition contains the (meth) acrylic resin (A) and the crosslinking agent (B) described later, and can form an optimal crosslinked structure (or crosslinking density), so the number of repeating units of the oxyalkylene group Even if is relatively small, good reworkability is exhibited.
- Specific examples include phenoxy di to hepta C 1-3 alkylene glycol acrylate such as phenoxy diethylene glycol acrylate, and di to hepta C 1-3 alkylene mono acrylate such as diethylene glycol monoacrylate.
- the proportion of the structural unit derived from the substituent-containing alkyl acrylate is, for example, 0 to 30 parts by weight (for example, 1 to 25 parts by weight) with respect to 100 parts by weight of all the structural units constituting the (meth) acrylic resin (A).
- the amount is preferably 3 to 20 parts by weight, more preferably 5 to 15 parts by weight.
- the (meth) acrylic resin (A) is composed of hydroxy group-containing (meth) acrylate (a1) and 5-hydroxypentyl acrylate (a2), alkyl acrylate (a3) and substituent-containing alkyl acrylate (a4).
- a structural unit derived from the monomer (a5) can be included.
- Other monomers can be used alone or in combination of two or more.
- Examples of the other monomer (a5) include a monomer (a5-1) having a polar functional group other than a hydroxy group, an acrylamide monomer (a5-2), a methacrylate (methacrylate ester) (a5- 3) a methacrylamide monomer (a5-4), a styrene monomer (a5-5), a vinyl monomer (a5-6), a single monomer having a plurality of (meth) acryloyl groups in the molecule And a monomer (a5-7).
- a monomer (a5-1) having a polar functional group other than a hydroxy group an acrylamide monomer (a5-2), a methacrylate (methacrylate ester) (a5- 3) a methacrylamide monomer (a5-4), a styrene monomer (a5-5), a vinyl monomer (a5-6), a single monomer having a plurality of (meth) acryloyl groups in the molecule
- Examples of the monomer (a5-1) having a polar functional group other than a hydroxy group include (meth) acrylates having a substituent such as a carboxyl group, a substituted or unsubstituted amino group, and a heterocyclic group such as an epoxy group. .
- acryloylmorpholine vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl Monomers having a heterocyclic group such as (meth) acrylate and 2,5-dihydrofuran; aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, etc.
- a monomer having a substituted or unsubstituted amino group (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, carboxyalkyl (meth) acrylate (for example, carboxyethyl (meth) acrylate, Monomers are exemplified with a carboxyl group such as Rubokishipenchiru (meth) acrylate). These monomers can be used alone or in combination of two or more.
- the structural unit derived from the monomer which has an amino group is not included substantially from a viewpoint of preventing the fall of the peelability of the separate film which can be laminated
- the present invention since it shows high durability even if it does not contain a structural unit derived from a monomer having a carboxy group that is considered to increase ITO corrosivity (a structural unit derived from a carboxyl group-containing (meth) acrylate). It is possible to achieve both durability and ITO corrosion resistance.
- a structural unit derived from a monomer having a carboxy group [a structural unit derived from a carboxyl group-containing (meth) acrylate] is contained, the durability can be further improved.
- the durability can be effectively improved even if the proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate is small, it is possible to improve the durability while suppressing the corrosion of ITO.
- the proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate is, for example, 5.0 parts by weight or less (for example, 0 to 3 parts by weight), preferably 1 with respect to 100 parts by weight of the structural unit derived from (meth) acrylate.
- 0.0 parts by weight or less eg, 0 to 0.8 parts by weight
- more preferably 0.5 parts by weight or less eg, 0.001 to 0.5 parts by weight
- 0.005 to 0.3 parts by weight particularly 0.2 parts by weight or less (eg 0.01 to 0.2 parts by weight), especially 0.15 parts by weight or less (eg 0.05 to 0.15 parts by weight). is there. If it is less than the upper limit, ITO corrosivity can be suppressed, and if it is more than the lower limit, durability can be improved.
- Examples of the acrylamide monomer (a5-2) include N-methylol acrylamide, N- (2-hydroxyethyl) acrylamide, N- (3-hydroxypropyl) acrylamide, N- (4-hydroxybutyl) acrylamide, N- (5-hydroxypentyl) acrylamide, N- (6-hydroxyhexyl) acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N- (3-dimethylaminopropyl) acrylamide, N- (1,1-dimethyl-3-oxobutyl) acrylamide, N- [2- (2-oxo-1-imidazolidinyl) ethyl] acrylamide, 2-acryloylamino-2-methyl-1-propanesulfonic acid, N- (Methoxymethyl) Kurylamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (1-methylethoxymethyl
- N- (methoxymethyl) acrylamide N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (butoxymethyl) acrylamide, N- (2-methylpropoxymethyl) acrylamide and the like are preferable.
- methacrylate (methacrylic acid ester) (a5-3) examples include linear alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, lauryl methacrylate; i-butyl methacrylate Branched alkyl methacrylates such as 2-ethylhexyl methacrylate and i-octyl methacrylate; isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, cyclododecyl methacrylate, methyl cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate, t-butyl cyclohexyl methacrylate, Mono or di, such as cyclohexyl phenyl methacrylate Black alkyl
- Examples of the methacrylamide monomer (a5-4) include a methacrylamide monomer corresponding to the acrylamide monomer described in (a5-2).
- styrene monomer (a5-5) examples include styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, and the like.
- Alkyl styrene Alkyl styrene; halogenated styrene such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, and iodostyrene; nitrostyrene; acetylstyrene; methoxystyrene; divinylbenzene, and the like.
- vinyl-based monomer (a5-6) examples include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate and vinyl laurate; halogens such as vinyl chloride and vinyl bromide Vinyl halides; vinylidene halides such as vinylidene chloride; nitrogen-containing aromatic vinyls such as vinyl pyridine, vinyl pyrrolidone and vinyl carbazole; conjugated diene monomers such as butadiene, isoprene and chloroprene; unsaturated nitriles such as acrylonitrile and methacrylonitrile Etc.
- fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate and vinyl laurate
- halogens such as vinyl chloride and vinyl bromide Vinyl halides
- vinylidene halides such as vinylidene chloride
- nitrogen-containing aromatic vinyls such as vinyl
- Examples of the monomer (a5-7) having a plurality of (meth) acryloyl groups in the molecule include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1 , 9-nonanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, etc.
- the (meth) acrylic resin (A) is a methacrylic monomer such as methacrylate (methacrylic acid ester) (a5-3) or methacrylamide monomer (a5-4). It is preferable that the proportion (or content) of the structural unit derived from the monomer is small. That is, the proportion of the structural unit is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, with respect to 100 parts by weight of all the structural units constituting the (meth) acrylic resin (A). In particular, it may be 1 part by weight or less.
- the proportion of the structural unit derived from the other monomer (a5) is, for example, 0 to 20 parts by weight, preferably 0 with respect to 100 parts by weight of all the structural units constituting the (meth) acrylic resin (A). It may be about 10 to 10 parts by weight (for example, 0.001 to 10 parts by weight), more preferably about 0 to 5 parts by weight (for example, 0.01 to 3 parts by weight).
- the (meth) acrylic resin (A) has a weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography GPC, for example, 6.0 ⁇ 10 5 to 2.5 ⁇ 10 6 (for example, 8. 0 ⁇ 10 5 to 2.5 ⁇ 10 6 ), preferably 1.0 ⁇ 10 6 to 2.0 ⁇ 10 6 , more preferably 1.2 ⁇ 10 6 to 1.8 ⁇ 10 6 (eg 1.3 ⁇ 10 6 to 1.6 ⁇ 10 6 ).
- Mw weight average molecular weight in terms of standard polystyrene by gel permeation chromatography GPC
- Mw weight average molecular weight in terms of standard polystyrene by gel permeation chromatography GPC
- the molecular weight distribution represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / Mn) is usually 2 to 10, preferably 3 to 8, and more preferably 4 to 6.
- the (meth) acrylic resin (A) preferably has a single peak in the range of 1.0 ⁇ 10 3 to 2.5 ⁇ 10 6 on the discharge curve in GPC.
- Use of the (meth) acrylic resin (A) having a peak number of 1 is advantageous for improving the durability of the pressure-sensitive adhesive layer.
- “Having a single peak” in the above range of the obtained discharge curve means having only one maximum value in the range of Mw 1.0 ⁇ 10 3 to 2.5 ⁇ 10 6 .
- a peak having an S / N ratio of 30 or more in the GPC emission curve is defined.
- the number of peaks in the GPC discharge curve and the Mw and Mn of the (meth) acrylic resin (A) can be determined according to the GPC measurement conditions described in the Examples section.
- the viscosity at 25 ° C. is preferably 20 Pa ⁇ s or less, preferably 0.1 to 7 Pa ⁇ s. It is more preferable that When the viscosity is within this range, it is advantageous from the viewpoint of coatability when the pressure-sensitive adhesive composition is applied to a substrate.
- the viscosity can be measured with a Brookfield viscometer.
- the glass transition temperature (Tg) of the (meth) acrylic resin (A) is, for example, ⁇ 60 to 0 ° C. (eg, ⁇ 50 to ⁇ 10 ° C.), preferably ⁇ 50 to ⁇ 20 ° C., more preferably ⁇ 40 to It may be ⁇ 20 ° C. (for example, ⁇ 40 to ⁇ 25 ° C.). Within this range, it is advantageous for improving the durability.
- the glass transition temperature can be measured with a differential scanning calorimeter (DSC).
- the (meth) acrylic resin (A) can be produced by a known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, or an emulsion polymerization method, and the solution polymerization method is particularly preferable.
- a solution polymerization method for example, a monomer and an organic solvent are mixed, a thermal polymerization initiator is added under a nitrogen atmosphere, and a temperature condition of about 40 to 90 ° C. (preferably 50 to 80 ° C.) is applied. The method of stirring for about 15 hours is raised.
- a monomer or a thermal polymerization initiator may be added continuously or intermittently during the polymerization.
- the monomer or thermal initiator may be added to an organic solvent.
- the polymerization initiator a thermal polymerization initiator, a photopolymerization initiator, or the like is used.
- the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone.
- thermal polymerization initiators examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2′-azobis (2-methylpropio) Azo) compounds such as 2,2′-azobis (2-hydroxymethylpropionitrile); lauryl peroxide, t-butyl hydroperoxide, benzoyl peroxide, t-butyl peroxybenzoate, cumene hydroperoxide , Diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, t-butyl peroxy Organic peroxides such as decanoate, t-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) per
- the ratio of the polymerization initiator is about 0.001 to 5 parts by weight with respect to 100 parts by weight of the total amount of monomers constituting the (meth) acrylic resin.
- a polymerization method using active energy rays for example, ultraviolet rays may be used.
- organic solvent examples include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propyl alcohol and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. And the like.
- Crosslinking agent (B) The pressure-sensitive adhesive composition contains a crosslinking agent (B).
- the crosslinking agent (B) reacts with a polar functional group containing a hydroxy group in the (meth) acrylic resin (A).
- the OH group (hydroxyl group) of a hydroxyalkyl group having a predetermined different carbon chain introduced into the side chain of the (meth) acrylic resin (A) reacts with the crosslinking agent (B), resulting in durability. And a cross-linked structure advantageous for reworkability is formed.
- crosslinking agent (B) examples include conventional crosslinking agents (for example, isocyanate compounds, epoxy compounds, aziridine compounds, metal chelate compounds, peroxides, etc.), and in particular, the pot life of the pressure-sensitive adhesive composition and the pressure-sensitive adhesive layer attached. From the viewpoint of the durability of the optical film, the crosslinking rate, etc., an isocyanate compound is preferable.
- the isocyanate compound is preferably a compound having at least two isocyanato groups (—NCO) in the molecule.
- an aliphatic isocyanate compound eg, hexamethylene diisocyanate
- an alicyclic isocyanate compound eg, isophorone diisocyanate.
- Aromatic isocyanate compounds for example, tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.).
- the crosslinking agent (B) is an adduct (adduct) of the isocyanate compound with a polyhydric alcohol compound [for example, an adduct with glycerol, trimethylolpropane or the like], an isocyanurate, a burette type compound, a polyether polyol, or a polyester. It may be a derivative such as a urethane prepolymer type isocyanate compound obtained by addition reaction with a polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol or the like.
- a crosslinking agent (B) can be used individually or in combination of 2 or more types.
- typically aromatic isocyanate compounds for example, tolylene diisocyanate, xylylene diisocyanate
- aliphatic isocyanate compounds for example, hexamethylene diisocyanate
- polyhydric alcohol compounds thereof glycerol, trimethylolpropane
- examples include adducts.
- the cross-linking agent (B) is an adduct of an aromatic isocyanate compound and / or these polyhydric alcohol compounds, it may be advantageous for the formation of an optimal cross-linking density (or cross-linked structure). Can be improved.
- durability for example, durability when an adhesive layer is applied to an ITO substrate
- durability for example, durability when an adhesive layer is applied to an ITO substrate
- the ratio of the crosslinking agent (B) is, for example, 0.01 to 10 parts by weight (eg 0.05 to 5 parts by weight), preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the (meth) acrylic resin (A). It may be 3 parts by weight (eg 0.1 to 2 parts by weight), more preferably 0.2 to 1 part by weight (eg 0.3 to 0.8 parts by weight). When it is at most the upper limit value, it is advantageous for improving followability (or peeling resistance), and when it is at least the lower limit value, it is advantageous for improving aggregation resistance (or foam resistance) and reworkability.
- the pressure-sensitive adhesive composition contains a silane compound (C).
- a silane compound (C) By including the silane compound (C), adhesion (or adhesiveness) between the pressure-sensitive adhesive layer and the metal layer, the transparent electrode, the glass substrate, or the like can be improved.
- the silane compound (C) may be any silane compound that can be bonded to the reactive group (for example, OH group of hydroxyl group) of the (meth) acrylic resin (A).
- the silane compound (C) may be a silicone oligomer type compound.
- the silicone oligomer is represented by a combination of monomers, for example, 3-mercaptopropyldi or trimethoxysilane-tetramethoxysilane oligomer, 3 -Mercaptoalkyl group-containing oligomers such as mercaptomethyldi or trimethoxysilane-tetraethoxysilane oligomer, 3-mercaptopropyldi or triethoxysilane-tetramethoxysilane oligomer, 3-mercaptomethyldi or triethoxysilane-tetraethoxysilane oligomer
- the mercaptoalkyl group of the mercaptoalkyl group-containing oligomer is substituted with other substituents [3-glycidoxypropyl group, (meth) acryloyloxypropyl group, vinyl group, amino group, etc.
- the silane compound (C) may be a silane compound represented by the following formula (c1).
- the pressure-sensitive adhesive composition contains a silane compound represented by the following formula (c1), the adhesiveness (or adhesiveness) can be further improved, so that a pressure-sensitive adhesive layer having excellent peeling resistance can be formed. Furthermore, the pressure-sensitive adhesive layer is excellent in reworkability. In particular, even when the pressure-sensitive adhesive layer is applied (or laminated) to a transparent electrode (for example, an ITO substrate) in a high-temperature environment, adhesion (or adhesiveness) can be maintained and high durability can be exhibited.
- a transparent electrode for example, an ITO substrate
- B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group.
- —CH 2 — may be substituted with —O— or —CO—
- R 1 represents an alkyl group having 1 to 5 carbon atoms
- R 2 , R 3 , R 4 , R 5 and R 6 are each Independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms
- B represents an alkanediyl group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group; a cyclobutylene group (for example, 1,2-cyclobutylene group), cyclopentylene group (for example, 1,2-cyclopentylene group), cyclohexylene group (for example, 1,2-cyclohexylene group), cyclooctylene group (for example, 1,2- A divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms such as a cyclooctylene group; or —CH 2 — constituting these alkanediyl groups and the alicyclic hydrocarbon group is —O— or A substituted group is represented by —CO—.
- Preferred B is an alkanediyl group having 1 to 10 carbon atoms.
- R 1 represents an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, a t-butyl group, or a pentyl group
- R 2 , R 3 , R 4 , R 5 and R 6 are each independently an alkyl group having 1 to 5 carbon atoms exemplified for R 1 ; or methoxy group, ethoxy group, propoxy group, i-propoxy group, butoxy group, s-butoxy group And an alkoxy group having 1 to 5 carbon atoms such as t-butoxy group.
- R 2 , R 3 , R 4 , R 5 and R 6 are alkoxy groups having 1 to 5 carbon atoms.
- silane compound (c1) examples include (trimethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,3-bis ( Trimethoxysilyl) propane, 1,3-bis (triethoxysilyl) propane, 1,4-bis (trimethoxysilyl) butane, 1,4-bis (triethoxysilyl) butane, 1,5-bis (trimethoxy) Silyl) pentane, 1,5-bis (triethoxysilyl) pentane, 1,6-bis (trimethoxysilyl) hexane, 1,6-bis (triethoxysilyl) hexane, 1,6-bis (tripropoxysilyl) Hexane, 1,8-bis (trimethoxysilyl) octane, 1,8-bis (triethoxysilyl) octane, 1,8-bis (
- 1,2-bis (trimethoxysilyl) ethane 1,3-bis (trimethoxysilyl) propane, 1,4-bis (trimethoxysilyl) butane, 1,5-bis (trimethoxysilyl) Bis (triC 1-3 alkoxysilyl) C 1-10 alkanes such as pentane, 1,6-bis (trimethoxysilyl) hexane, 1,8-bis (trimethoxysilyl) octane are preferred, especially 1,6 -Bis (trimethoxysilyl) hexane and 1,8-bis (trimethoxysilyl) octane are preferred.
- the proportion of the silane compound (C) is, for example, 0.01 to 10 parts by weight (eg 0.03 to 5 parts by weight), preferably 0.05 with respect to 100 parts by weight of the (meth) acrylic resin (A). -3 parts by weight, more preferably 0.1-1 part by weight (for example, 0.2-0.5 parts by weight). If it is below the upper limit, it is advantageous for suppressing bleeding out of the silane compound (C) from the pressure-sensitive adhesive layer, and if it is above the lower limit, the adhesiveness between the pressure-sensitive adhesive layer and the metal layer or glass substrate ( (Or adhesiveness) is easy to improve, which is advantageous in improving peeling resistance.
- the pressure-sensitive adhesive composition may further contain an antistatic agent.
- the antistatic agent By including the antistatic agent, the antistatic property of the pressure-sensitive adhesive can be improved (for example, a problem caused by static electricity generated when a release film, a protective film, or the like is peeled off) can be suppressed.
- the antistatic agent include conventional ones, and an ionic antistatic agent is preferable.
- the cation component constituting the ionic antistatic agent include organic cations and inorganic cations. Examples of the organic cation include a pyridinium cation, an imidazolium cation, an ammonium cation, a sulfonium cation, and a phosphonium cation.
- the inorganic cation examples include alkali metal cations such as lithium cation, potassium cation, sodium cation and cesium cation, and alkaline earth metal cations such as magnesium cation and calcium cation.
- the anionic component constituting the ionic antistatic agent may be either an inorganic anion or an organic anion, but an anionic component containing a fluorine atom is preferred from the viewpoint of excellent antistatic performance.
- anion component containing a fluorine atom examples include a hexafluorophosphate anion (PF 6- ), a bis (trifluoromethanesulfonyl) imide anion [(CF 3 SO 2 ) 2 N-], a bis (fluorosulfonyl) imide anion [(FSO 2 ) 2 N—], tetra (pentafluorophenyl) borate anion [(C 6 F 5 ) 4 B—] and the like.
- PF 6- hexafluorophosphate anion
- PF 6- bis (trifluoromethanesulfonyl) imide anion
- FSO 2 ) 2 N— bis (fluorosulfonyl) imide anion
- tetra (pentafluorophenyl) borate anion tetra (pentafluorophenyl) borate anion
- bis (trifluoromethanesulfonyl) imide anion [(CF 3 SO 2 ) 2 N—], bis (fluorosulfonyl) imide anion [(FSO 2 ) 2 N—], tetra (pentafluorophenyl) borate anion [(C 6 F5) 4 B-] is preferred.
- An ionic antistatic agent that is solid at room temperature is preferable in that the antistatic performance of the pressure-sensitive adhesive composition is excellent over time.
- the ratio of the antistatic agent is, for example, 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the (meth) acrylic resin (A). It may be.
- the pressure-sensitive adhesive composition includes a solvent, a crosslinking catalyst, an ultraviolet absorber, a weathering stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, light scattering fine particles, and the like.
- An agent can be contained alone or in combination of two or more. It is also useful to blend an ultraviolet curable compound into the pressure-sensitive adhesive composition and form a pressure-sensitive adhesive layer and then cure it by irradiating with ultraviolet rays to form a harder pressure-sensitive adhesive layer.
- crosslinking catalyst examples include amine compounds such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resin, and melamine resin.
- the pressure-sensitive adhesive composition can contain a rust preventive agent from the viewpoint of enhancing the metal corrosion resistance of the pressure-sensitive adhesive layer.
- a rust preventive agent examples include triazole compounds such as benzotriazole compounds; thiazole compounds such as benzothiazole compounds; imidazole compounds such as benzylimidazole compounds; imidazoline compounds; quinoline compounds; pyridine compounds; Examples include pyrimidine compounds; indole compounds; amine compounds; urea compounds; sodium benzoates; benzyl mercapto compounds; di-sec-butyl sulfide; and diphenyl sulfoxide.
- FIG. 1 is a schematic cross-sectional view showing an example of an optical film with an adhesive layer formed from the adhesive composition according to the present invention.
- the optical film 1 with an adhesive layer shown in FIG. 1 is an optical film having an optical film 10 and an adhesive layer 20 laminated on one side of the optical film.
- the pressure-sensitive adhesive layer 20 is usually laminated directly on the surface of the optical film 10.
- the pressure-sensitive adhesive layer 20 may be laminated on both surfaces of the optical film 10.
- a primer layer is formed on the bonding surface of the optical film 10 and / or the bonding surface of the pressure-sensitive adhesive layer 20, or the surface activation treatment (for example, plasma treatment, corona treatment and the like are preferably performed, and corona treatment is particularly preferable.
- the pressure-sensitive adhesive layer 20 is usually laminated on the polarizer surface, that is, the surface of the polarizer 2 opposite to the first resin film 3. (Preferably directly laminated).
- the pressure-sensitive adhesive layer 20 may be laminated on the outer surface of either the first or second resin film 3 or 4, and both outer surfaces May be laminated.
- a separate antistatic layer may be provided between the optical film 10 and the pressure-sensitive adhesive layer 20.
- silicon materials such as polysiloxane, inorganic metal materials such as tin-doped indium oxide and tin-doped antimony oxide, and organic polymer materials such as polythiophene, polystyrene sulfonic acid, and polyaniline can be used.
- the optical film 1 with an adhesive layer may include a separate film (release film) laminated on the outer surface of the adhesive layer 20.
- This separate film is usually peeled and removed when the pressure-sensitive adhesive layer 20 is used (for example, when laminated on a transparent conductive electrode or a glass substrate).
- the separate film is obtained by, for example, performing a release treatment such as a silicone treatment on the surface on which the adhesive layer 20 of a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyarate is formed. Also good.
- the optical film 1 with the pressure-sensitive adhesive layer is obtained by dissolving or dispersing each component constituting the pressure-sensitive adhesive composition in a solvent to obtain a solvent-containing pressure-sensitive adhesive composition, and then applying and drying this onto the surface of the optical film 10. And can be obtained by forming the pressure-sensitive adhesive layer 20. Moreover, the optical film 1 with an adhesive layer forms the adhesive layer 20 on the mold release process surface of a separate film similarly to the above, and laminates
- the thickness of the pressure-sensitive adhesive layer is usually 2 to 40 ⁇ m, and preferably 5 to 30 ⁇ m, more preferably 10 from the viewpoints of durability of the optical film with the pressure-sensitive adhesive layer and reworkability of the optical film with the pressure-sensitive adhesive layer. ⁇ 25 ⁇ m.
- the amount is not more than the upper limit value, the followability (or followability) of the pressure-sensitive adhesive layer with respect to the dimensional change of the optical film becomes good, and when it is not less than the lower limit value, the reworkability becomes good.
- the adhesive layer preferably exhibits a storage elastic modulus of 0.1 to 5 MPa in a temperature range of 23 to 80 ° C. Thereby, durability of the optical film with an adhesive layer can be improved more effectively.
- “Shows a storage elastic modulus of 0.1 to 5 MPa in a temperature range of 23 to 80 ° C.” means that the storage elastic modulus is a value within the above range at any temperature within this range. Since the storage elastic modulus usually decreases gradually as the temperature rises, if both the storage elastic modulus at 23 ° C. and 80 ° C. are within the above range, the storage elastic modulus within the above range is exhibited at the temperature in this range. Can be assumed.
- the storage elastic modulus of the pressure-sensitive adhesive layer can be measured using a commercially available viscoelasticity measuring device, for example, a viscoelasticity measuring device “DYNAMIC ANALYZER RDA II” manufactured by REOMETRIC.
- Gel fraction can be used as an index of crosslinking density. Since the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention has a predetermined cross-linking density, it exhibits a predetermined gel fraction. That is, the gel fraction of the pressure-sensitive adhesive layer is, for example, 50 to 95% by weight (eg 55 to 93% by weight), preferably 60 to 90% by weight (eg 65 to 90% by weight), and more preferably 70 to 85%. % By weight (for example, 80 to 85% by weight) may be used. When the gel fraction is at least the lower limit, it is advantageous for foaming resistance (cohesive fracture resistance) and reworkability of the pressure-sensitive adhesive layer, and when the gel fraction is at most the upper limit, it is advantageous for peeling resistance. . The gel fraction can be measured by the method described in the Examples section.
- the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention has a predetermined pressure-sensitive adhesive force. That is, the pressure-sensitive adhesive layer is bonded to a glass substrate, and the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer after 24 hours under the conditions of a temperature of 23 ° C. and a relative humidity of 50% is, for example, 0. It may be 5 to 25N (for example, 0.5 to 20N), preferably 0.5 to 10N (for example, 1 to 10N), and more preferably 1 to 8N.
- the adhesive strength is at least the lower limit, the adhesiveness (or adhesiveness) is improved, which is advantageous for peeling resistance, and when the adhesive strength is at most the upper limit, it is advantageous for reworkability.
- the adhesive strength can be measured by the method described in the Examples section.
- the optical film 10 constituting the optical film 1 with the pressure-sensitive adhesive layer may be various optical films (films having optical characteristics) that can be incorporated in an image display device such as a liquid crystal display device.
- the optical film 10 may have a single layer structure (for example, an optical functional film such as a polarizer, a retardation film, a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, a light collecting film, etc.)
- a multilayer structure for example, a polarizing plate, a phase difference plate, etc. may be used.
- the optical film 10 is preferably a polarizing plate, a polarizer, a retardation plate or a retardation film, and particularly preferably a polarizing plate or a polarizer.
- the optical film means a film that functions for image display (display screen or the like) (for example, a film that functions for improving the visibility of an image).
- the polarizing plate means that a resin film or a resin layer is laminated on at least one surface of a polarizer
- the retardation plate means a resin film on at least one surface of the retardation film. Or the thing on which the resin layer was laminated
- FIGS. 2 and 3 are schematic cross-sectional views showing examples of the layer structure of the polarizing plate.
- the polarizing plate 10a shown in FIG. 2 is a single-sided protective polarizing plate in which the first resin film 3 is laminated (or laminated) on one surface of the polarizer 2, and the polarizing plate 10b shown in FIG. This is a double-sided protective polarizing plate in which the second resin film 4 is further laminated (or laminated) on the other surface of the polarizer 2.
- the first and second resin films 3 and 4 can be bonded to the polarizer 2 via an adhesive layer and an adhesive layer (not shown).
- the polarizing plates 10a and 10b may include other films and layers other than the first and second resin films 3 and 4.
- the polarizer 2 is a film having a property of absorbing linearly polarized light having a vibration surface parallel to the absorption axis and transmitting linearly polarized light having a vibration surface orthogonal to the absorption axis (parallel to the transmission axis).
- a film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin film can be used.
- the dichroic dye include iodine and dichroic organic dyes.
- the polyvinyl alcohol resin can be obtained by saponifying a polyvinyl acetate resin.
- the polyvinyl acetate resin include polyvinyl acetate which is a homopolymer of vinyl acetate, and a monomer copolymerizable with vinyl acetate (for example, unsaturated carboxylic acid, olefin, vinyl ether, unsaturated sulfonic acid, ammonium group). (Meth) acrylamide etc.) and vinyl acetate.
- the saponification degree of the polyvinyl alcohol resin is usually 85 to 100 mol%, preferably 98 mol% or more.
- the polyvinyl alcohol-based resin may be modified, for example, polyvinyl formal or polyvinyl acetal modified with aldehydes.
- the average degree of polymerization of the polyvinyl alcohol-based resin is usually 1000 to 10000, preferably 1500 to 5000.
- the average degree of polymerization of the polyvinyl alcohol resin can be determined according to JIS K 6726.
- a film made of a polyvinyl alcohol resin is used as the original film of the polarizer 2.
- a polyvinyl alcohol-type resin can be formed into a film by a well-known method.
- the thickness of the raw film is usually 1 to 150 ⁇ m, and is preferably 10 ⁇ m or more in consideration of easiness of stretching.
- the polarizer 2 is, for example, a step of uniaxially stretching the original film, a step of dyeing the film with a dichroic dye and adsorbing the dichroic dye, a step of treating the film with an aqueous boric acid solution, and The film is washed with water and finally dried.
- the thickness of the polarizer 2 is usually 1 to 30 ⁇ m, and preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and particularly 10 ⁇ m or less from the viewpoint of thinning the optical film 1 with an adhesive layer.
- a polarizer 2 formed by adsorbing and orienting a dichroic dye on a polyvinyl alcohol-based resin film is as follows: 1) A single film of a polyvinyl alcohol-based resin film is used as a raw film, and this film is uniaxially stretched and dichroic. In addition to the method of dyeing dyes, 2) A base film having a polyvinyl alcohol resin layer was obtained by applying a coating liquid (such as an aqueous solution) containing a polyvinyl alcohol resin to the base film and drying it. Thereafter, this can also be obtained by uniaxially stretching the whole base film, subjecting the stretched polyvinyl alcohol resin layer to a dichroic dye dyeing process, and then peeling and removing the base film.
- a coating liquid such as an aqueous solution
- a film made of a thermoplastic resin similar to the thermoplastic resin that can constitute the first and second resin films 3 and 4 described later can be used, and preferably a polyester-based resin such as polyethylene terephthalate.
- a polyester-based resin such as polyethylene terephthalate.
- the method 2 is used, the thin film polarizer 2 can be easily manufactured.
- the polarizer 2 having a thickness of 7 ⁇ m or less can be easily manufactured.
- the first and second resin films 3 and 4 are each independently a light-transmitting, preferably optically transparent thermoplastic resin such as a chain polyolefin resin (polyethylene resin, polypropylene resin, etc.).
- Polyolefin resins such as cyclic polyolefin resins (norbornene resins, etc.); cellulose resins (cellulose ester resins, etc.); polyester resins (polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, etc.); polycarbonate resins (for example, , Polycarbonates derived from bisphenols such as 2,2-bis (4-hydroxyphenyl) propane, etc.); (meth) acrylic resins; polystyrene resins; polyetheretherketone resins; polysulfone resins or mixtures thereof It may be a film made of copolymer.
- the first and second resin films 3 and 4 are films composed of a cyclic polyolefin resin, a polycarbonate resin, a cellulose resin, a polyester resin, a (meth) acrylic resin, and the like, respectively.
- a film composed of a cellulose resin and a cyclic polyolefin resin is preferable.
- chain polyolefin resin examples include a homopolymer of a chain olefin such as a polyethylene resin and a polypropylene resin, and a copolymer composed of two or more chain olefins.
- the cyclic polyolefin-based resin is a general term for resins containing, as polymerization units, cyclic olefins whose representative examples are norbornene, tetracyclododecene (also known as dimethanooctahydronaphthalene) or their derivatives.
- Cyclic polyolefin resins include ring-opening (co) polymers of cyclic olefins and hydrogenated products thereof, addition polymers of cyclic olefins, cyclic olefins and chain olefins such as ethylene and propylene, and aromatic compounds having a vinyl group And a modified (co) polymer obtained by modifying these with an unsaturated carboxylic acid or a derivative thereof.
- norbornene resins using norbornene monomers such as norbornene and polycyclic norbornene monomers as cyclic olefins are preferred.
- the cellulose resin is preferably a cellulose ester resin, that is, a cellulose partial or completely esterified product, and examples thereof include cellulose acetate ester, propionate ester, butyrate ester, and mixed ester thereof. Of these, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate and the like are preferable.
- the polyester-based resin is a resin other than the cellulose ester-based resin having an ester bond, and is generally made of a polycondensate of a polyvalent carboxylic acid or a derivative thereof and a polyhydric alcohol.
- the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexanedimethyl terephthalate, and polycyclohexanedimethyl naphthalate.
- Polycarbonate resin is a polyester formed from carbonic acid and glycol or bisphenol.
- an aromatic polycarbonate having a diphenylalkane in the molecular chain is preferable.
- the polycarbonate include 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, , 1-bis (4-hydroxyphenyl) isobutane, polycarbonates derived from bisphenols such as 1,1-bis (4-hydroxyphenyl) ethane and the like.
- the (meth) acrylic resin that can constitute the first and second resin films 3 and 4 can be a polymer mainly composed of a structural unit derived from a methacrylic ester (for example, containing 50% by weight or more).
- the copolymer is preferably a copolymer in which another copolymer component is copolymerized.
- the (meth) acrylic resin may contain two or more structural units derived from methacrylic acid esters. Examples of methacrylic acid esters include C 1 -C 4 alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like.
- Examples of the copolymer component that can be copolymerized with the methacrylic acid ester include acrylic acid esters.
- the acrylic acid ester is preferably a C 1 -C 8 alkyl ester of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like.
- Specific examples of other copolymerization components include unsaturated acids such as (meth) acrylic acid; aromatic vinyl compounds such as styrene, halogenated styrene, ⁇ -methylstyrene, and vinyl toluene; vinylcyan such as (meth) acrylonitrile.
- (Meth) acrylic resin may have a ring structure in the polymer main chain in that the durability of the film can be improved.
- the ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic imide structure, or a lactone ring structure.
- Specific examples of the cyclic acid anhydride structure include a glutaric anhydride structure and a succinic anhydride structure
- specific examples of the cyclic imide structure include a glutarimide structure and a succinimide structure. Examples include butyrolactone ring structure and valerolactone ring structure.
- the (meth) acrylic resin may contain acrylic rubber particles from the viewpoints of film-formability on the film and impact resistance of the film.
- Acrylic rubber particles are particles having an elastic polymer mainly composed of an acrylate ester as an essential component.
- the acrylic rubber particles have a single-layer structure consisting essentially of this elastic polymer, or an elastic polymer in one layer. And a multilayer structure having Examples of the elastic polymer include a cross-linked elastic copolymer obtained by copolymerizing an alkyl acrylate as a main component with another vinyl monomer and a cross-linkable monomer copolymerizable therewith.
- the number of carbon atoms of the alkyl group is preferably 4 or more.
- vinyl monomers that can be copolymerized with alkyl acrylate include compounds having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methacrylic acid such as methyl methacrylate.
- methacrylic acid such as methyl methacrylate.
- aromatic vinyl compounds such as esters and styrene, vinylcyan compounds such as (meth) acrylonitrile, and the like.
- crosslinkable monomer examples include a crosslinkable compound having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, ethylene glycol di (meth) acrylate, butanediol di ( Examples include (meth) acrylates of polyhydric alcohols such as (meth) acrylate, alkenyl esters of (meth) acrylic acid such as allyl (meth) acrylate, and divinylbenzene.
- the content of the acrylic rubber particles is preferably 5 parts by weight or more, more preferably 10 parts by weight or more with respect to 100 parts by weight of the (meth) acrylic resin.
- the content of the acrylic rubber particles is usually 80 parts by weight or less, preferably 60 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic resin.
- the first and second resin films 3 and 4 can contain usual additives in the technical field of the present invention.
- the additive include an ultraviolet absorber, an infrared absorber, an organic dye, a pigment, an inorganic dye, an antioxidant, an antistatic agent, a surfactant, a lubricant, a dispersant, and a heat stabilizer.
- the ultraviolet absorber include salicylic acid ester compounds, benzophenone compounds, benzotriazole compounds, triazine compounds, cyano (meth) acrylate compounds, nickel complex salts, and the like.
- Each of the first and second resin films 3 and 4 may be an unstretched film or a uniaxially or biaxially stretched film.
- the first resin film 3 and / or the second resin film 4 may be a protective film that plays a role of protecting the polarizer 2, or may be a protective film having an optical function such as a retardation film described later. Good.
- the first resin film 3 and the second resin film 4 may be the same or different films.
- the first resin film 3 and / or the second resin film 4 has a hard coat layer, an antiglare layer, an antireflection layer, a light diffusion layer, and an antistatic layer on the outer surface (the surface opposite to the polarizer 2). Further, a surface treatment layer (coating layer) such as an antifouling layer or a conductive layer may be provided.
- the thickness of each of the first resin film 3 and the second resin film 4 is usually 1 to 150 ⁇ m, preferably 5 to 100 ⁇ m (eg 5 to 60 ⁇ m), more preferably 50 ⁇ m or less (eg 1 to 40 ⁇ m), It may be 30 ⁇ m or less (for example, 5 to 25 ⁇ m).
- a polarizing plate for small and medium-sized devices such as smartphones and tablet terminals is often used as a thin film having a thickness of 30 ⁇ m or less as the first resin film 3 and / or the second resin film 4 because of the demand for thinning.
- Such a polarizing plate has a weak force to suppress the contraction force of the polarizer 2 and tends to have insufficient durability.
- the optical film 1 with the pressure-sensitive adhesive layer of the present invention has good durability.
- the first and second resin films 3 and 4 can be bonded to the polarizer 2 via an adhesive layer or an adhesive layer.
- an adhesive forming the adhesive layer a water-based adhesive or an active energy ray-curable adhesive can be used.
- a conventional water-based adhesive for example, an adhesive comprising a polyvinyl alcohol resin aqueous solution, an aqueous two-component urethane emulsion adhesive, an aldehyde compound, an epoxy compound, a melamine compound, a methylol compound, an isocyanate compound, And crosslinking agents such as amine compounds and polyvalent metal salts.
- a water-based adhesive made of a polyvinyl alcohol-based resin aqueous solution can be suitably used.
- a curing step for curing at a temperature of about 20 to 45 ° C. may be provided.
- the active energy ray-curable adhesive refers to an adhesive that cures when irradiated with active energy rays such as ultraviolet rays and electron beams.
- a curable composition containing a polymerizable compound and a photopolymerization initiator light Examples thereof include a curable composition containing a reactive resin, a curable composition containing a binder resin and a photoreactive cross-linking agent, and preferably an ultraviolet curable adhesive.
- an active energy ray-curable adhesive When an active energy ray-curable adhesive is used, after the polarizer 2 and the first and second resin films 3 and 4 are bonded, a drying process is performed as necessary, and then an active energy ray is irradiated. A curing step of curing the active energy ray-curable adhesive is performed.
- the light source of the active energy ray is not particularly limited, but ultraviolet light having a light emission distribution at a wavelength of 400 nm or less is preferable.
- the adhesive for bonding these resin films may be the same type of adhesive or a different type of adhesive.
- the polarizing plates 10a and 10b can further include other films or layers. Specific examples thereof include a retardation film, a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, a condensing film, an adhesive layer other than the adhesive layer 20, a coating layer, a protective film, and the like.
- the protective film is a film used for the purpose of protecting the surface of the optical film 10 such as a polarizing plate from scratches and dirt. After the optical film 1 with an adhesive layer is bonded onto, for example, a metal layer or a substrate, it is peeled off. It is customary to be removed.
- the base film is composed of a thermoplastic resin, for example, a polyolefin resin such as polyethylene resin or polypropylene resin; a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; a polycarbonate resin; a (meth) acrylic resin, or the like. be able to.
- a thermoplastic resin for example, a polyolefin resin such as polyethylene resin or polypropylene resin; a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; a polycarbonate resin; a (meth) acrylic resin, or the like.
- phase difference plate The phase difference film contained in the phase difference plate is an optical film exhibiting optical anisotropy as described above, and can be used for the first and second resin films 3 and 4.
- thermoplastic resins for example, polyvinyl alcohol resins, polyarylate resins, polyimide resins, polyether sulfone resins, polyvinylidene fluoride / polymethyl methacrylate resins, liquid crystal polyester resins, It can be a stretched film obtained by stretching a resin film made of an ethylene-vinyl acetate copolymer saponified product, a polyvinyl chloride resin or the like to about 1.01 to 6 times.
- a polycarbonate film, a cyclic olefin resin film, a (meth) acrylic resin film or a cellulose resin film is preferably a uniaxially stretched or biaxially stretched film.
- a zero retardation film is also included in the retardation film (however, it can also be used as a protective film).
- a film called a uniaxial retardation film, a wide viewing angle retardation film, a low photoelastic modulus retardation film, or the like is also applicable as the retardation film.
- the zero retardation film is a film having both an in-plane retardation value Re and a thickness direction retardation value Rth of ⁇ 15 to 15 nm.
- This retardation film is suitably used for an IPS mode liquid crystal display device.
- Both the in-plane retardation value Re and the thickness direction retardation value R th are preferably ⁇ 10 to 10 nm, more preferably ⁇ 5 to 5 nm.
- plane retardation value refers R e and the thickness direction retardation R th is a value at a wavelength of 590 nm.
- n x is a refractive index in a slow axis direction (x-axis direction) in the film plane
- n y is the fast axis direction in the film plane of the (y-axis direction orthogonal to the x-axis in a plane)
- nz is the refractive index in the film thickness direction (z-axis direction perpendicular to the film surface)
- d is the thickness of the film.
- a resin film made of a polyolefin resin such as a cellulose resin, a chain polyolefin resin, and a cyclic polyolefin resin, a polyethylene terephthalate resin, or a (meth) acrylic resin
- a cellulose resin, a polyolefin resin, or a (meth) acrylic resin is preferably used because the retardation value is easily controlled and easily available.
- a film that exhibits optical anisotropy by applying and orienting a liquid crystalline compound and a film that exhibits optical anisotropy by applying an inorganic layered compound can be used as the retardation film.
- a so-called temperature compensation type retardation film, and a rod-like liquid crystal sold under the trade name “NH film” from JX Nippon Mining & Energy Co., Ltd. are tilted.
- orientation type film examples include a biaxial orientation type film sold by Sumitomo Chemical Co., Ltd. under the trade name “new VAC film”.
- stacked on the at least one surface of retardation film can be the above-mentioned protective film, for example.
- FIGS. 4 to 8 are schematic cross-sectional views showing examples of an optical laminate including an optical film with an adhesive layer formed from the adhesive composition according to the present invention.
- the optical layered body 5 shown in FIG. 4 has a metal layer 30 (or a metal wiring layer 30) laminated on a substrate 40 and an adhesive film 1a (or a polarizing plate 1a with an adhesive layer). It is the optical laminated body laminated
- the optical film 1a with an adhesive layer is obtained by laminating an adhesive layer 20 on the surface of the polarizing plate 10a on the polarizer 2 side.
- the optical laminate 6 shown in FIG. 5 is obtained by laminating the metal layer 30 laminated on the substrate 40 on the surface on the pressure-sensitive adhesive layer side of the optical film 1b with pressure-sensitive adhesive layer (or the polarizing plate 1b with pressure-sensitive adhesive layer). It is an optical laminate.
- the optical film 1b with an adhesive layer is an optical film in which an adhesive layer 20 is laminated on the surface of the polarizing plate 10b on the second resin film 4 side.
- the optical laminates 5 and 6 can be obtained by laminating the optical film with adhesive layer (1a, 1b) via the adhesive layer 20 to the metal layer 30 laminated on the substrate 40.
- the substrate 40 may be a transparent substrate constituting a liquid crystal cell included in the touch input element, and is preferably a glass substrate.
- a glass substrate As the material of the glass substrate, soda lime glass, low alkali glass, non-alkali glass, or the like can be used.
- the metal layer 30 may be formed on the entire surface of the substrate 40 or may be formed on a part thereof.
- the metal layer 30 includes, for example, at least one metal element selected from aluminum, copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and an alloy containing two or more of these metals. It may be a layer containing. Among these, from the viewpoint of conductivity, it may be a layer containing at least one metal element selected from aluminum, copper, silver and gold, more preferably from the viewpoint of conductivity and cost. It may be a layer containing an element, more preferably a layer containing an aluminum element as a main component (50% by weight or more of all metal components constituting the metal layer 30).
- the metal layer 30 may be a transparent electrode layer such as ITO (tin-doped indium oxide), for example, and may have a transparent electrode layer made of a metal oxide such as ITO together with the metal layer 30.
- ITO in-doped indium oxide
- the method for preparing the metal layer 30 is not particularly limited, and may be a metal foil, which may be formed by a vacuum deposition method, a sputtering method, an ion plating method, an ink jet printing method, or a gravure printing method.
- the metal layer is preferably formed by a sputtering method, an ink jet printing method, or a gravure printing method, and more preferably a metal layer formed by sputtering.
- the thickness of the metal layer 30 is not particularly limited, but is usually 3 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.8 ⁇ m or less, and usually 0.01 ⁇ m or more.
- the line width of the metal wiring is usually 10 ⁇ m or less, preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and usually 0.5 ⁇ m or more. It is.
- the optical laminate 7 shown in FIG. 6 is an optical laminate in which the adhesive layer 20 of the optical film 1 with an adhesive layer is laminated on a substrate 40.
- the optical laminated body 8 shown in FIG. 7 has a resin layer 50 further laminated on the surface of the metal layer 30 laminated on the substrate 40 (on the surface opposite to the substrate 40). It is an optical laminate laminated on the surface of the optical film 1 on the pressure-sensitive adhesive layer 20 side.
- resin which forms the resin layer 50 resin etc. which comprise the 1st or 2nd resin film of the said illustration are mentioned, for example.
- a plurality of metal layers 30 are laminated on a substrate 40 at predetermined intervals in the vertical and horizontal directions, and between the metal layers 30 (or gaps) and between the metal layers 30. It is the same as the optical laminate 7 except that the resin layer 50 is formed (or laminated) on the surface (on the surface opposite to the substrate 40).
- the metal layer 30 is, for example, a metal wiring layer (that is, an electrode layer) of a touch input element included in the touch input type liquid crystal display device. ).
- the plurality of metal layers 30 may or may not be in contact with the pressure-sensitive adhesive layer 20 in whole or in part. Further, the metal layer 30 may be a continuous film containing the above metal or alloy. The resin layer 50 may be omitted.
- optical film (1, 1a, 1b) and the substrate 40 (glass substrate, transparent substrate, etc.) or the metal layer 30 (transparent electrode layer) were bonded to produce an optical laminate, some trouble occurred.
- a so-called rework operation is required in which the optical film with the pressure-sensitive adhesive layer is peeled off from the substrate 40 or the metal layer 30 and another optical film 1 with the pressure-sensitive adhesive layer is reattached to the substrate 40 or the metal layer 30. May be.
- the optical film 1 with the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to the present invention hardly causes fogging or adhesive residue on the surface of the glass substrate or the transparent electrode after peeling, and is excellent in reworkability.
- the liquid crystal display device according to the present invention includes the optical film 1 with the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to the present invention, and more typically the optical laminated body. Is included. For this reason, the liquid crystal display device according to the present invention has excellent durability.
- the liquid crystal display device may be a touch input type liquid crystal display device having a touch panel function.
- the touch input type liquid crystal display device includes a touch input element including a liquid crystal cell and a backlight.
- the configuration of the touch panel may be a known method (for example, an out-cell type, an on-cell type, an in-cell type, etc.), and the operation method of the touch panel may be a known method [for example, a resistive film type, a capacitance type (surface type static type). Capacitance method, projection type capacitance method, etc.).
- the optical film 1 with an adhesive layer according to the present invention may be disposed on the viewing side of the touch input element (liquid crystal cell), may be disposed on the backlight side, or may be disposed on both.
- the driving method of the liquid crystal cell may be any conventionally known method such as a TN method, a VA method, an IPS method, a multi-domain method, and an OCB method.
- the substrate 40 included in the optical laminate may be a substrate (typically a glass substrate) included in the liquid crystal cell.
- the weight average molecular weight Mw and the number average molecular weight Mn are 4 columns of “TSKgel XL” manufactured by Tosoh Corp. and “Shodex GPC KF-” manufactured by Showa Denko K.K. 802 "is connected in series, a total of five are connected in series, tetrahydrofuran is used as the eluent, sample concentration is 5mg / mL, sample introduction amount is 100 ⁇ L, temperature is 40 ° C, flow rate is 1mL / min. It was measured by. The conditions for obtaining the GPC discharge curve were also the same.
- the glass transition temperature Tg was measured using a differential scanning calorimeter (DSC) “EXSTAR DSC6000” manufactured by SII NanoTechnology Co., Ltd. under a nitrogen atmosphere, a measurement temperature range of ⁇ 80 to 50 ° C., and a temperature increase rate of 10 ° C./min. It measured on condition of this.
- DSC differential scanning calorimeter
- Table 1 shows the composition of the monomers in each production example (the numerical values in Table 1 are parts by weight).
- D-1 N-decylpyridinium bis (fluorosulfonyl) imide
- D-2 Potassium bis (fluorosulfonyl) imide
- D-3 Lithium bis (trifluoromethylsulfonyl) imide
- D-4 N-decyl Pyridinium tetra (pentafluorophenyl) borate.
- a transparent protective film [trade name “KC2UA” manufactured by Konica Minolta Opto Co., Ltd.] made of a 25 ⁇ m-thick triacetyl cellulose film is placed on one side of the obtained polarizer with an adhesive made of an aqueous solution of a polyvinyl alcohol resin. And pasted.
- a zero retardation film [trade name “ZEONOR” manufactured by Nippon Zeon Co., Ltd.] made of a cyclic polyolefin resin having a thickness of 23 ⁇ m is formed on the surface opposite to the triacetyl cellulose film in the polarizer.
- a bonded polarizing plate was produced through an adhesive made of an aqueous resin solution.
- the optical film with pressure-sensitive adhesive layer (P-1) produced in the above (3) is 300 mm ⁇ 220 mm so that the stretching axis direction of the polarizing plate is the long side. It cut
- the test piece (the optical film with the pressure-sensitive adhesive layer to which the glass substrate was attached) obtained by attaching the obtained glass substrate was placed in an autoclave at a temperature of 50 ° C. and a pressure of 5 kg / cm 2 (490.3 kPa) for 20 minutes. Pressurized.
- a non-alkali glass product name “Eagle XG” manufactured by Corning was used for the glass substrate.
- a non-alkali glass manufactured by Corning [trade name “Eagle XG”] having a 30 nm ITO layer formed by ITO deposition was used.
- the following 3 types of durability tests were implemented.
- the optical film with pressure-sensitive adhesive layer (P-1) produced in the above (3) was cut into a test piece having a size of 25 mm ⁇ 150 mm.
- the separator was peeled off from the test piece, and the pressure-sensitive adhesive surface was attached to a glass substrate.
- the test piece (the optical film with the pressure-sensitive adhesive layer to which the glass substrate was attached) obtained by attaching the obtained glass substrate was placed in an autoclave at a temperature of 50 ° C. and a pressure of 5 kg / cm 2 (490.3 kPa) for 20 minutes. Pressurized. After storing for 24 hours in an atmosphere having a temperature of 23 ° C.
- the optical film was peeled from the test piece together with the pressure-sensitive adhesive layer in the direction of 180 ° at a speed of 300 mm / min.
- Table 3 shows the average peeling force at the time of peeling as the adhesive strength. When the adhesive force is 10 N or less, the rework property is excellent, and when it is 0.5 N or more, peeling hardly occurs even when an impact is applied from the end of the polarizing plate.
- the surface resistance value of the pressure-sensitive adhesive is measured by a surface resistivity measuring device [“HIRESTA-up MCP-HT450” (trade name) manufactured by Mitsubishi Chemical Corporation]. It was measured by. The measurement was performed under the measurement conditions of an applied voltage of 250 V and an applied time of 10 seconds. If the surface resistance value is 1.0 ⁇ 10 12 ⁇ / ⁇ or less, good antistatic properties can be obtained.
- the gel fraction evaluation method of the adhesive sheet of this invention is shown.
- the gel fraction is a value measured according to the following (1) to (4).
- Gel fraction (% by weight) [ ⁇ Wa ⁇ (Wb ⁇ Ws) ⁇ Wm ⁇ / (Ws ⁇ Wm)] ⁇ 100
- SYMBOLS 1,1a, 1b Optical film with an adhesive layer, 2 ... Polarizer, 3 ... 1st resin film, 4 ... 2nd resin film, 5, 6, 7, 8, 9 ... Optical laminated body, 10 ... Optical film DESCRIPTION OF SYMBOLS 10a, 10b ... Polarizing plate, 20 ... Adhesive layer, 30 ... Metal layer, 40 ... Substrate, 50 ... Resin layer.
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Abstract
Description
すなわち、本発明には、以下のものが含まれる。
[1](メタ)アクリル系樹脂(A)、架橋剤(B)、及びシラン化合物(C)を含む粘着剤組成物であって、
前記(メタ)アクリル系樹脂(A)は、下記式(a1) As a result of intensive studies in order to solve the above problems, the present inventors have completed the present invention.
That is, the present invention includes the following.
[1] A pressure-sensitive adhesive composition comprising a (meth) acrylic resin (A), a crosslinking agent (B), and a silane compound (C),
The (meth) acrylic resin (A) is represented by the following formula (a1)
で表されるヒドロキシ基含有(メタ)アクリレート由来の構成単位と、5-ヒドロキシペンチルアクリレート由来の構成単位とを含む粘着剤組成物。
[2](メタ)アクリル系樹脂を構成する全構成単位100重量部に対して、式(a1)で表されるヒドロキシ基含有(メタ)アクリレート由来の構成単位の割合は1.5~4.5重量部であり、5-ヒドロキシペンチルアクリレート由来の構成単位の割合は0.25~1.0重量部である[1]に記載の粘着剤組成物。
[3](メタ)アクリル系樹脂は、ホモポリマーのガラス転移温度が0℃未満のアルキルアクリレート(a3-1)由来の構成単位と、ホモポリマーのガラス転移温度が0℃以上のアルキルアクリレート由来の構成単位(a3-2)とを含有するアルキルアクリレート(a3)由来の構成単位を含む[1]又は[2]に記載の粘着剤組成物。
[4]ホモポリマーのガラス転移温度が0℃未満のアルキルアクリレート(a3-1)由来の構成単位と、ホモポリマーのガラス転移温度が0℃以上のアルキルアクリレート(a3-2)由来の構成単位との割合(重量比)は、(a3-1)/(a3-2)=20/80~95/5である[3]に記載の粘着剤組成物。
[5](メタ)アクリル系樹脂の重量平均分子量は、ポリスチレン換算で、6.0×105~2.5×106である[1]~[4]のいずれかに記載の粘着剤組成物。
[6]架橋剤(B)は、芳香族イソシアネート化合物及び/又は該芳香族イソシアネート化合物の多価アルコール化合物による付加体である[1]~[5]のいずれかに記載の粘着剤組成物。
[7]架橋剤(B)の割合は、(メタ)アクリル系樹脂(A)100重量部に対して、0.01~10重量部である[1]~[6]のいずれかに記載の粘着剤組成物。
[8]シラン化合物(C)は、下記式(c1)
A pressure-sensitive adhesive composition comprising a structural unit derived from a hydroxy group-containing (meth) acrylate and a structural unit derived from 5-hydroxypentyl acrylate.
[2] The proportion of the structural unit derived from the hydroxy group-containing (meth) acrylate represented by the formula (a1) with respect to 100 parts by weight of all the structural units constituting the (meth) acrylic resin is 1.5 to 4. The pressure-sensitive adhesive composition according to [1], which is 5 parts by weight and the proportion of the structural unit derived from 5-hydroxypentyl acrylate is 0.25 to 1.0 part by weight.
[3] The (meth) acrylic resin is derived from a structural unit derived from an alkyl acrylate (a3-1) having a homopolymer glass transition temperature of less than 0 ° C. and an alkyl acrylate derived from a homopolymer having a glass transition temperature of 0 ° C. or higher. The pressure-sensitive adhesive composition according to [1] or [2], comprising a structural unit derived from an alkyl acrylate (a3) containing the structural unit (a3-2).
[4] A structural unit derived from an alkyl acrylate (a3-1) having a glass transition temperature of the homopolymer of less than 0 ° C., and a structural unit derived from an alkyl acrylate (a3-2) having a glass transition temperature of the homopolymer of 0 ° C. or higher. The ratio (weight ratio) of the pressure-sensitive adhesive composition according to [3], wherein (a3-1) / (a3-2) = 20/80 to 95/5.
[5] The pressure-sensitive adhesive composition according to any one of [1] to [4], wherein the (meth) acrylic resin has a weight average molecular weight of 6.0 × 10 5 to 2.5 × 10 6 in terms of polystyrene. object.
[6] The pressure-sensitive adhesive composition according to any one of [1] to [5], wherein the crosslinking agent (B) is an adduct of an aromatic isocyanate compound and / or a polyhydric alcohol compound of the aromatic isocyanate compound.
[7] The ratio of the crosslinking agent (B) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic resin (A). Adhesive composition.
[8] The silane compound (C) is represented by the following formula (c1)
(式中、Bは、炭素数1~20のアルカンジイル基又は炭素数3~20の二価の脂環式炭化水素基を示し、前記アルカンジイル基及び前記脂環式炭化水素基を構成する-CH2-は、-O-又は-CO-に置換されてもよく、R1は炭素数1~5のアルキル基を示し、R2、R3、R4、R5及びR6はそれぞれ独立して、炭素数1~5のアルキル基又は炭素数1~5のアルコキシ基を示す)
で表されるシラン化合物である[1]~[7]のいずれかに記載の粘着剤組成物。
[9]式(c1)のBは炭素数1~10のアルカンジイル基であり、R1は炭素数1~5のアルキル基であり、R2、R3、R4、R5及びR6はそれぞれ独立して、炭素数1~5のアルコキシ基である[8]に記載の粘着剤組成物。
[10]シラン化合物(C)の割合は、(メタ)アクリル系樹脂(A)100重量部に対して、0.01~10重量部である[1]~[9]のいずれかに記載の粘着剤組成物。
[11]粘着剤組成物から形成される粘着剤のゲル分率は、50~95%である[1]~[10]のいずれかに記載の粘着剤組成物。
[12]ガラス基板に、前記粘着剤組成物から形成される粘着剤層を貼合し、温度23℃、相対湿度50%の条件下24時間後の前記粘着剤層の粘着力は、剥離速度300mm/分において、0.5~10N/25mmである[1]~[11]のいずれかに記載の粘着剤組成物。
[13]光学フィルムに積層される粘着剤層の形成に用いられる、[1]~[12]のいずれかに記載の粘着剤組成物。
(In the formula, B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group. —CH 2 — may be substituted with —O— or —CO—, R 1 represents an alkyl group having 1 to 5 carbon atoms, and R 2 , R 3 , R 4 , R 5 and R 6 are each Independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms)
The pressure-sensitive adhesive composition according to any one of [1] to [7], which is a silane compound represented by the formula:
[9] B in the formula (c1) is an alkanediyl group having 1 to 10 carbon atoms, R 1 is an alkyl group having 1 to 5 carbon atoms, R 2 , R 3 , R 4 , R 5 and R 6 Are each independently an alkoxy group having 1 to 5 carbon atoms, [8].
[10] The ratio of the silane compound (C) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic resin (A), according to any one of [1] to [9] Adhesive composition.
[11] The pressure-sensitive adhesive composition according to any one of [1] to [10], wherein the pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition has a gel fraction of 50 to 95%.
[12] A pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is bonded to a glass substrate, and the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer after 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50% is determined by a peeling rate. The pressure-sensitive adhesive composition according to any one of [1] to [11], which is 0.5 to 10 N / 25 mm at 300 mm / min.
[13] The pressure-sensitive adhesive composition according to any one of [1] to [12], which is used for forming a pressure-sensitive adhesive layer laminated on an optical film.
本発明の粘着剤組成物は、(メタ)アクリル系樹脂(A)、架橋剤(B)、シラン化合物(C)を含む。 [1] Pressure-sensitive adhesive composition The pressure-sensitive adhesive composition of the present invention contains a (meth) acrylic resin (A), a crosslinking agent (B), and a silane compound (C).
(メタ)アクリル系樹脂(A)は、(メタ)アクリル系単量体由来の構成単位を主成分とする(好ましくは50重量%以上含む)重合体又は共重合体であり、下記式(a1)に示されるヒドロキシ基含有(メタ)アクリレート由来の構成単位と5-ヒドロキシペンチルアクリレート由来の構成単位とを含む。 [1-1] (Meth) acrylic resin (A)
The (meth) acrylic resin (A) is a polymer or copolymer having a structural unit derived from a (meth) acrylic monomer as a main component (preferably containing 50% by weight or more), and represented by the following formula (a1 And a structural unit derived from a hydroxy group-containing (meth) acrylate and a structural unit derived from 5-hydroxypentyl acrylate.
式(a1)において、nは1~4の整数を示し、好ましくは1~3の整数、さらに好ましくは2である。 A 1 represents a hydrogen atom or an alkyl group, and the alkyl group may be an alkyl group exemplified in X 1 (preferably a methyl group or the like).
In the formula (a1), n represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2.
一方、カルボキシ基を有する単量体由来の構成単位[カルボキシル基含有(メタ)アクリレート由来の構成単位]を含有すると耐久性をさらに向上できる。本発明では、カルボキシル基含有(メタ)アクリレート由来の構成単位の割合が少なくても有効に耐久性を向上できるため、ITOの腐食を抑制しつつ、耐久性を向上させることが可能である。 In the present invention, since it shows high durability even if it does not contain a structural unit derived from a monomer having a carboxy group that is considered to increase ITO corrosivity (a structural unit derived from a carboxyl group-containing (meth) acrylate). It is possible to achieve both durability and ITO corrosion resistance.
On the other hand, when a structural unit derived from a monomer having a carboxy group [a structural unit derived from a carboxyl group-containing (meth) acrylate] is contained, the durability can be further improved. In the present invention, since the durability can be effectively improved even if the proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate is small, it is possible to improve the durability while suppressing the corrosion of ITO.
また、他の単量体(a5)由来の構成単位の割合は、(メタ)アクリル系樹脂(A)を構成する全構成単位100重量部に対して、例えば0~20重量部、好ましくは0~10重量部(例えば0.001~10重量部)、さらに好ましくは0~5重量部(例えば0.01~3重量部)程度であってもよい。 From the viewpoint of the reworkability of the pressure-sensitive adhesive layer, the (meth) acrylic resin (A) is a methacrylic monomer such as methacrylate (methacrylic acid ester) (a5-3) or methacrylamide monomer (a5-4). It is preferable that the proportion (or content) of the structural unit derived from the monomer is small. That is, the proportion of the structural unit is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, with respect to 100 parts by weight of all the structural units constituting the (meth) acrylic resin (A). In particular, it may be 1 part by weight or less.
Further, the proportion of the structural unit derived from the other monomer (a5) is, for example, 0 to 20 parts by weight, preferably 0 with respect to 100 parts by weight of all the structural units constituting the (meth) acrylic resin (A). It may be about 10 to 10 parts by weight (for example, 0.001 to 10 parts by weight), more preferably about 0 to 5 parts by weight (for example, 0.01 to 3 parts by weight).
粘着剤組成物は、架橋剤(B)を含む。該架橋剤(B)は、(メタ)アクリル系樹脂(A)中のヒドロキシ基を含む極性官能基と反応する。本発明では、(メタ)アクリル系樹脂(A)の側鎖に導入された所定の異なる炭素鎖を有するヒドロキシアルキル基のOH基(ヒドロキシル基)と架橋剤(B)とが反応し、耐久性及びリワーク性に有利な架橋構造を形成する。 [1-2] Crosslinking agent (B)
The pressure-sensitive adhesive composition contains a crosslinking agent (B). The crosslinking agent (B) reacts with a polar functional group containing a hydroxy group in the (meth) acrylic resin (A). In the present invention, the OH group (hydroxyl group) of a hydroxyalkyl group having a predetermined different carbon chain introduced into the side chain of the (meth) acrylic resin (A) reacts with the crosslinking agent (B), resulting in durability. And a cross-linked structure advantageous for reworkability is formed.
粘着剤組成物は、シラン化合物(C)を含む。該シラン化合物(C)を含むことにより、粘着剤層と、金属層、透明電極、ガラス基板等との密着性(又は接着性)を向上できる。シラン化合物(C)としては、(メタ)アクリル系樹脂(A)の反応性基(例えばヒドロキシル基のOH基)と結合可能なシラン化合物であればよく、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス(2-メトキシエトキシ)シラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルエトキシジメチルシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-クロロプロピルメチルジメトキシシラン、3-クロロプロピルトリメトキシシラン、3-メタクリロイルオキシプロピルトリメトキシシラン、3-メルカプトプロピルトリメトキシシラン、1,3-ビス(3’-トリメトキシプロピル)ウレアなどが挙げられる。 [1-3] Silane compound (C)
The pressure-sensitive adhesive composition contains a silane compound (C). By including the silane compound (C), adhesion (or adhesiveness) between the pressure-sensitive adhesive layer and the metal layer, the transparent electrode, the glass substrate, or the like can be improved. The silane compound (C) may be any silane compound that can be bonded to the reactive group (for example, OH group of hydroxyl group) of the (meth) acrylic resin (A). For example, vinyltrimethoxysilane, vinyltriethoxy Silane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 1 , - bis (3'-trimethoxy propyl) urea and the like.
粘着剤組成物は、帯電防止剤をさらに含んでもよい。帯電防止剤を含むことで、粘着剤の帯電防止性を向上(例えば離形フィルム、保護フィルムなどを剥離した際に生じる静電気による不具合などを抑制)することができる。帯電防止剤としては、慣用のものが挙げられ、イオン性帯電防止剤が好適である。イオン性帯電防止剤を構成するカチオン成分としては、有機カチオン、無機カチオンなどが挙げられる。有機カチオンとしては、例えばピリジニウムカチオン、イミダゾリウムカチオン、アンモニウムカチオン、スルホニウムカチオン、ホスホニウムカチオンなどが挙げられる。無機カチオンとしては、例えばリチウムカチオン、カリウムカチオン、ナトリウムカチオン、セシウムカチオンなどのアルカリ金属カチオン、マグネシウムカチオン、カルシウムカチオンなどのアルカリ土類金属カチオンなどが挙げられる。イオン性帯電防止剤を構成するアニオン成分としては、無機アニオン及び有機アニオンのいずれでもよいが、帯電防止性能に優れるという点で、フッ素原子を含むアニオン成分が好ましい。フッ素原子を含むアニオン成分としては、例えばヘキサフルオロホスフェートアニオン(PF6-)、ビス(トリフルオロメタンスルホニル)イミドアニオン[(CF3SO2)2N-]、ビス(フルオロスルホニル)イミドアニオン[(FSO2)2N-]、テトラ(ペンタフルオロフェニル)ボレートアニオン[(C6F5)4B-]などが挙げられる。これらの帯電防止剤は単独又は二種以上組み合わせて使用できる。特に、ビス(トリフルオロメタンスルホニル)イミドアニオン[(CF3SO2)2N-]、ビス(フルオロスルホニル)イミドアニオン[(FSO2)2N-]、テトラ(ペンタフルオロフェニル)ボレートアニオン[(C6F5)4B-]が好ましい。
粘着剤組成物の帯電防止性能の経時安定性に優れるという点で、室温で固体であるイオン性帯電防止剤が好ましい。
帯電防止剤の割合は、(メタ)アクリル系樹脂(A)100重量部に対して、例えば、0.01~10重量部、好ましくは0.1~5重量部、さらに好ましくは1~3重量であってもよい。 [1-4] Antistatic Agent The pressure-sensitive adhesive composition may further contain an antistatic agent. By including the antistatic agent, the antistatic property of the pressure-sensitive adhesive can be improved (for example, a problem caused by static electricity generated when a release film, a protective film, or the like is peeled off) can be suppressed. Examples of the antistatic agent include conventional ones, and an ionic antistatic agent is preferable. Examples of the cation component constituting the ionic antistatic agent include organic cations and inorganic cations. Examples of the organic cation include a pyridinium cation, an imidazolium cation, an ammonium cation, a sulfonium cation, and a phosphonium cation. Examples of the inorganic cation include alkali metal cations such as lithium cation, potassium cation, sodium cation and cesium cation, and alkaline earth metal cations such as magnesium cation and calcium cation. The anionic component constituting the ionic antistatic agent may be either an inorganic anion or an organic anion, but an anionic component containing a fluorine atom is preferred from the viewpoint of excellent antistatic performance. Examples of the anion component containing a fluorine atom include a hexafluorophosphate anion (PF 6- ), a bis (trifluoromethanesulfonyl) imide anion [(CF 3 SO 2 ) 2 N-], a bis (fluorosulfonyl) imide anion [(FSO 2 ) 2 N—], tetra (pentafluorophenyl) borate anion [(C 6 F 5 ) 4 B—] and the like. These antistatic agents can be used alone or in combination of two or more. In particular, bis (trifluoromethanesulfonyl) imide anion [(CF 3 SO 2 ) 2 N—], bis (fluorosulfonyl) imide anion [(FSO 2 ) 2 N—], tetra (pentafluorophenyl) borate anion [(C 6 F5) 4 B-] is preferred.
An ionic antistatic agent that is solid at room temperature is preferable in that the antistatic performance of the pressure-sensitive adhesive composition is excellent over time.
The ratio of the antistatic agent is, for example, 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the (meth) acrylic resin (A). It may be.
粘着剤組成物は、溶剤、架橋触媒、紫外線吸収剤、耐候安定剤、タッキファイヤー、可塑剤、軟化剤、染料、顔料、無機フィラー、光散乱性微粒子等の添加剤を単独又は2種以上含むことができる。また、粘着剤組成物に紫外線硬化性化合物を配合し、粘着剤層を形成した後に紫外線を照射して硬化させ、より硬い粘着剤層とすることも有用である。架橋触媒としては、例えばヘキサメチレンジアミン、エチレンジアミン、ポリエチレンイミン、ヘキサメチレンテトラミン、ジエチレントリアミン、トリエチレンテトラミン、イソホロンジアミン、トリメチレンジアミン、ポリアミノ樹脂及びメラミン樹脂等のアミン系化合物などが挙げられる。 [1-5] Other components The pressure-sensitive adhesive composition includes a solvent, a crosslinking catalyst, an ultraviolet absorber, a weathering stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, light scattering fine particles, and the like. An agent can be contained alone or in combination of two or more. It is also useful to blend an ultraviolet curable compound into the pressure-sensitive adhesive composition and form a pressure-sensitive adhesive layer and then cure it by irradiating with ultraviolet rays to form a harder pressure-sensitive adhesive layer. Examples of the crosslinking catalyst include amine compounds such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resin, and melamine resin.
本発明の粘着剤組成物は、表面活性化処理(例えばプラズマ処理、コロナ処理等)などを施すことにより粘着剤層を形成できる。通常、該粘着剤層は光学フィルムの少なくとも一方の面に積層される。
図1は、本発明に係る粘着剤組成物から形成された粘着剤層付光学フィルムの一例を示す概略断面図である。図1に示される粘着剤層付光学フィルム1は、光学フィルム10と、該光学フィルムの片面に粘着剤層20が積層された光学フィルムである。該粘着剤層20は、通常、光学フィルム10の表面に直接積層される。なお、粘着剤層20は、光学フィルム10の両面に積層されてもよい。
粘着剤層20を光学フィルム10の表面に積層する際には、光学フィルム10の貼合面及び/又は粘着剤層20の貼合面にプライマー層を形成させること、又は前記表面活性化処理(例えばプラズマ処理、コロナ処理など)を施すことが好ましく、特にコロナ処理を施すことが好ましい。 [2] Structure and production method of pressure-sensitive adhesive layer and optical film with pressure-sensitive adhesive layer The pressure-sensitive adhesive composition of the present invention forms a pressure-sensitive adhesive layer by performing surface activation treatment (for example, plasma treatment, corona treatment, etc.). it can. Usually, the pressure-sensitive adhesive layer is laminated on at least one surface of the optical film.
FIG. 1 is a schematic cross-sectional view showing an example of an optical film with an adhesive layer formed from the adhesive composition according to the present invention. The
When laminating the pressure-
粘着剤層付光学フィルム1を構成する光学フィルム10は、液晶表示装置等の画像表示装置に組み込まれ得る各種の光学フィルム(光学特性を有するフィルム)であってもよい。該光学フィルム10は、単層構造(例えば偏光子、位相差フィルム、輝度向上フィルム、防眩フィルム、反射防止フィルム、拡散フィルム、集光フィルム等の光学機能性フィルムなど)であってもよく、多層構造(例えば偏光板、位相差板など)であってもよい。光学フィルム10は、偏光板、偏光子、位相差板又は位相差フィルムが好ましく、特に偏光板又は偏光子が好ましい。なお、本明細書において、光学フィルムとは、画像表示(表示画面等)のために機能するフィルム(例えば、画像の見やすさの向上のために機能するフィルム)を意味する。また、本明細書において偏光板とは、偏光子の少なくとも一方の面に樹脂フィルム又は樹脂層が積層されたものを意味し、位相差板とは、位相差フィルムの少なくとも一方の面に樹脂フィルム又は樹脂層が積層されたものを意味する。 [2-1] Optical Film The
図2及び図3は、偏光板の層構成の例を示す概略断面図である。図2に示される偏光板10aは、偏光子2の一方の面に第1樹脂フィルム3が積層(又は積層貼合)された片面保護偏光板であり、図3に示される偏光板10bは、偏光子2の他方の面にさらに第2樹脂フィルム4が積層(又は積層貼合)された両面保護偏光板である。第1,第2樹脂フィルム3,4は、図示しない接着剤層や粘着剤層を介して偏光子2に貼合することができる。なお、偏光板10a,10bは、第1,第2樹脂フィルム3,4以外の他のフィルムや層を含んでいてもよい。 [2-2] Polarizing Plate FIGS. 2 and 3 are schematic cross-sectional views showing examples of the layer structure of the polarizing plate. The
(メタ)アクリル系樹脂は、メタクリル酸エステル由来の構成単位を2種以上含んでいてもよい。メタクリル酸エステルとしては、メチルメタクリレート、エチルメタクリレート、ブチルメタクリレート等のメタクリル酸のC1~C4アルキルエステルが挙げられる。 The (meth) acrylic resin that can constitute the first and
The (meth) acrylic resin may contain two or more structural units derived from methacrylic acid esters. Examples of methacrylic acid esters include C 1 -C 4 alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like.
性接着剤を用いることができる。 The first and
位相差板に含まれる位相差フィルムは、上述のとおり、光学異方性を示す光学フィルムであり、第1,第2樹脂フィルム3,4に用いることができるものとして上で例示した熱可塑性樹脂のほか、例えば、ポリビニルアルコール系樹脂、ポリアリレート系樹脂、ポリイミド系樹脂、ポリエーテルサルホン系樹脂、ポリビニリデンフルオライド/ポリメチルメタクリレート系樹脂、液晶ポリエステル系樹脂、エチレン-酢酸ビニル共重合体ケン化物、ポリ塩化ビニル系樹脂等からなる樹脂フィルムを1.01~6倍程度に延伸することにより得られる延伸フィルムであることができる。これらのうち、ポリカーボネート系樹脂フィルムや環状オレフィン系樹脂フィルム、(メタ)アクリル系樹脂フィルム又はセルロース系樹脂フィルムを一軸延伸又は二軸延伸した延伸フィルムが好ましい。また本明細書においては、ゼロレタデーションフィルムも位相差フィルムに含まれる(ただし、保護フィルムとして用いることもできる。)。そのほか、一軸性位相差フィルム、広視野角位相差フィルム、低光弾性率位相差フィルム等と称されるフィルムも位相差フィルムとして適用可能である。 [2-3] Phase difference plate The phase difference film contained in the phase difference plate is an optical film exhibiting optical anisotropy as described above, and can be used for the first and
Re=(nx-ny)×d
Rth=〔(nx+ny)/2-nz〕×d
で定義される。式中、nxはフィルム面内の遅相軸方向(x軸方向)の屈折率であり、nyはフィルム面内の進相軸方向(面内でx軸に直交するy軸方向)の屈折率であり、nzはフィルム厚み方向(フィルム面に垂直なz軸方向)の屈折率であり、dはフィルムの厚みである。 The in-plane retardation value Re and the thickness direction retardation value R th are respectively expressed by the following formulas:
R e = (n x −n y ) × d
R th = [(n x + ny ) / 2−n z ] × d
Defined by Wherein, n x is a refractive index in a slow axis direction (x-axis direction) in the film plane, n y is the fast axis direction in the film plane of the (y-axis direction orthogonal to the x-axis in a plane) It is a refractive index, nz is the refractive index in the film thickness direction (z-axis direction perpendicular to the film surface), and d is the thickness of the film.
図4~図8は、本発明に係る粘着剤組成物から形成された粘着剤層付光学フィルムを含む光学積層体の例を示す概略断面図である。
図4に示される光学積層体5は、基板40上に積層された金属層30(又は金属配線層30)を、前記粘着剤層付光学フィルム1a(又は粘着剤層付偏光板1a)の粘着剤層側の面に積層した光学積層体である。前記粘着剤層付光学フィルム1aは、前記偏光板10aの偏光子2側の面に粘着剤層20を積層したものである。 [3] Optical Laminate FIGS. 4 to 8 are schematic cross-sectional views showing examples of an optical laminate including an optical film with an adhesive layer formed from the adhesive composition according to the present invention.
The optical
本発明に係る液晶表示装置は、上記本発明に係る粘着剤組成物から形成された粘着剤層付光学フィルム1を含むものであり、より典型的には上記光学積層体を含むものである。
このため、本発明に係る液晶表示装置は、優れた耐久性を有する。 [4] Liquid crystal display device The liquid crystal display device according to the present invention includes the
For this reason, the liquid crystal display device according to the present invention has excellent durability.
冷却管、窒素導入管、温度計及び攪拌機を備えた反応容器に、表1に示す組成(表1の数値は重量部である。)の単量体を酢酸エチル81.8部と混合して得られた溶液を仕込んだ。反応容器内の空気を窒素ガスで置換した後、内温を60℃にした。その後、アゾビスイソブチロニトリル0.12部を酢酸エチル10部に溶解させた溶液を添加した。1時間同温で保持した後、内温を54~56℃に保ちながら、添加速度17.3部/Hrで酢酸エチルを、重合体の濃度がほぼ35%となるように反応容器内へ連続的に加えた。酢酸エチルの添加開始から12時間経過するまで内温を54~56℃に保持した後、酢酸エ
チルをさらに加えて重合体の濃度が20%となるように調整し、(メタ)アクリル系樹脂(A-1)の酢酸エチル溶液を得た。得られた(メタ)アクリル系樹脂(A-1)の重量平均分子量Mwは139万、重量平均分子量Mwと数平均分子量Mnとの比(Mw/Mn)は5.32であった。 <Production Example 1: Production of (meth) acrylic resin (A-1) for pressure-sensitive adhesive layer>
In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirrer, a monomer having the composition shown in Table 1 (the numerical values in Table 1 are parts by weight) was mixed with 81.8 parts of ethyl acetate. The resulting solution was charged. After the air in the reaction vessel was replaced with nitrogen gas, the internal temperature was set to 60 ° C. Thereafter, a solution in which 0.12 part of azobisisobutyronitrile was dissolved in 10 parts of ethyl acetate was added. After maintaining at the same temperature for 1 hour, while maintaining the internal temperature at 54 to 56 ° C., ethyl acetate was continuously fed into the reaction vessel at an addition rate of 17.3 parts / hr so that the polymer concentration was approximately 35%. Added. After maintaining the internal temperature at 54 to 56 ° C. until 12 hours have passed since the start of the addition of ethyl acetate, ethyl acetate was further added to adjust the polymer concentration to 20%, and a (meth) acrylic resin ( An ethyl acetate solution of A-1) was obtained. The obtained (meth) acrylic resin (A-1) had a weight average molecular weight Mw of 1.39 million and a ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn of 5.32.
単量体の組成を、表1に示す組成にしたこと以外は、製造例1と同様にして、(メタ)アクリル系樹脂(A-2~12)の酢酸エチル溶液を得た(樹脂濃度:20%)。得られた(メタ)アクリル系樹脂(A-2~12)の重量平均分子量Mwはいずれも130万~150万の範囲であり、Mw/Mnは4~6の範囲であった。 <Production Example 2-12: Production of (meth) acrylic resin (A-2 to 12) for pressure-sensitive adhesive layer>
An ethyl acetate solution of (meth) acrylic resin (A-2 to 12) was obtained in the same manner as in Production Example 1 except that the monomer composition was changed to the composition shown in Table 1 (resin concentration: 20%). The obtained (meth) acrylic resins (A-2 to 12) each had a weight average molecular weight Mw in the range of 1.3 million to 1.5 million, and Mw / Mn in the range of 4 to 6.
BA:ブチルアクリレート(ホモポリマーのガラス転移温度:-54℃)、
MA:メチルアクリレート(ホモポリマーのガラス転移温度:10℃)、
HEA:2-ヒドロキシエチルアクリレート。
4HBA:4-ヒドロキシブチルアクリレート
5HPA:5-ヒドロキシペンチルアクリレート
PEA:フェノキシエチルアクリレート
PEA2:フェノキシジエチレングリコールアクリレート
BMAA:ブトキシメチルアクリルアミド
AA:アクリル酸 Abbreviations in the column of “monomer composition” in Table 1 mean the following monomers.
BA: butyl acrylate (glass transition temperature of homopolymer: −54 ° C.),
MA: methyl acrylate (glass transition temperature of homopolymer: 10 ° C.),
HEA: 2-hydroxyethyl acrylate.
4HBA: 4-hydroxybutyl acrylate 5HPA: 5-hydroxypentyl acrylate PEA: Phenoxyethyl acrylate PEA2: Phenoxydiethylene glycol acrylate BMAA: Butoxymethylacrylamide AA: Acrylic acid
(1)粘着剤組成物の調製
上記製造例で得られた(メタ)アクリル系樹脂の酢酸エチル溶液(樹脂濃度:20%)に、該溶液の固形分100部に対して、表2に示す量(重量部)の架橋剤(B)、シラン化合物(C)、及びイオン性化合物(D)を混合し、さらに固形分濃度が14%となるように酢酸エチルを添加して粘着剤組成物を得た。表2に示す各配合成分の配合量は、使用した商品が溶剤等を含む場合は、そこに含まれる有効成分としての重量部数である。 <Examples 1 to 13, Comparative Examples 1 to 8>
(1) Preparation of pressure-sensitive adhesive composition The ethyl acetate solution (resin concentration: 20%) of the (meth) acrylic resin obtained in the above production example is shown in Table 2 with respect to 100 parts of the solid content of the solution. A pressure-sensitive adhesive composition obtained by mixing an amount (parts by weight) of a crosslinking agent (B), a silane compound (C), and an ionic compound (D), and further adding ethyl acetate so that the solid content concentration becomes 14%. Got. The compounding amount of each compounding component shown in Table 2 is the number of parts by weight as an active ingredient contained therein when the product used contains a solvent or the like.
(架橋剤)
B-1:トリレンジイソシアネートのトリメチロールプロパンアダクト体の酢酸エチル溶液(固形分濃度75%)、東ソー(株)から入手した商品名「コロネートL」。
B-2:キシリレンジイソシアネートのトリメチロールプロパンアダクト体の酢酸エチル溶液(固形分濃度75%)、三井化学(株)から入手した商品名「タケネート D-110N」。 The details of each compounding component shown in abbreviations in Table 2 are as follows.
(Crosslinking agent)
B-1: Trimethylolpropane adduct of tolylene diisocyanate in ethyl acetate solution (solid content concentration 75%), trade name “Coronate L” obtained from Tosoh Corporation.
B-2: Trimethylolpropane adduct of xylylene diisocyanate in ethyl acetate solution (solid content 75%), trade name “Takenate D-110N” obtained from Mitsui Chemicals, Inc.
C-1:1,6-ビス(トリメトキシシリル)ヘキサン、C-2:1,8-ビス(トリメトキシシリル)ヘキサン、C-3:メチル基/メトキシ基含有シリコーンオリゴマー、信越化学工業(株)から入手した商品名「X-40-9250」、C-4:1,3-ビス(3’-トリメトキシプロピル)ウレア。 (Silane compound)
C-1: 1,6-bis (trimethoxysilyl) hexane, C-2: 1,8-bis (trimethoxysilyl) hexane, C-3: methyl oligomer / methoxy group-containing silicone oligomer, Shin-Etsu Chemical Co., Ltd. Trade name “X-40-9250”, C-4: 1,3-bis (3′-trimethoxypropyl) urea obtained from
D-1:N-デシルピリジニウム ビス(フロオロスルホニル)イミド、D-2:カリウム ビス(フロオロスルホニル)イミド、 D-3:リチウム ビス(トリフルオロメチルスルホニル)イミド、D-4:N-デシルピリジニウム テトラ(ペンタフルオロフェニル)ボレート。 (Ionic compounds)
D-1: N-decylpyridinium bis (fluorosulfonyl) imide, D-2: Potassium bis (fluorosulfonyl) imide, D-3: Lithium bis (trifluoromethylsulfonyl) imide, D-4: N-decyl Pyridinium tetra (pentafluorophenyl) borate.
上記(1)で調製した各粘着剤組成物を、離型処理が施されたポリエチレンテレフタレートフィルムからなるセパレートフィルム〔リンテック(株)から入手した商品名「PLR-382051」〕の離型処理面に、アプリケーターを用いて乾燥後の厚みが20μmとなるように塗布し、100℃で1分間乾燥して粘着剤層(粘着剤シート)を作製した。 (2) Production of pressure-sensitive adhesive layer Each pressure-sensitive adhesive composition prepared in (1) above was separated from a polyethylene terephthalate film subjected to a release treatment [trade name “PLR-382051 obtained from Lintec Corporation]. ]] Was applied using an applicator so that the thickness after drying was 20 μm, and dried at 100 ° C. for 1 minute to prepare an adhesive layer (adhesive sheet).
平均重合度約2400、ケン化度99.9モル%、厚み60μmのポリビニルアルコールフィルム〔(株)クラレ製の商品名「クラレビニロン VF-PE♯6000」〕を、37℃の純水に浸漬した後、ヨウ素とヨウ化カリウムとを含む水溶液(ヨウ素/ヨウ化カリウム/水(重量比)=0.04/1.5/100)に30℃で浸漬した。その後、ヨウ化カリウムとホウ酸とを含む水溶液(ヨウ化カリウム/ホウ酸/水(重量比)=12/3.6/100)に56.5℃で浸漬した。フィルムを10℃の純水で洗浄した後、85℃で乾燥して、ポリビニルアルコールにヨウ素が吸着配向された厚み約23μmの偏光子を得た。延伸は、主に、ヨウ素染色及びホウ酸処理の工程で行い、トータルの延伸倍率は5.3倍であった。 (3) Production of optical film (P-1) with pressure-sensitive adhesive layer Polyvinyl alcohol film having an average degree of polymerization of about 2400, a saponification degree of 99.9 mol% and a thickness of 60 μm [trade name “Kuraray Vinylon VF manufactured by Kuraray Co., Ltd.” -PE # 6000 "] is immersed in pure water at 37 ° C, and then an aqueous solution containing iodine and potassium iodide (iodine / potassium iodide / water (weight ratio) = 0.04 / 1.5 / 100). Soaked at 30 ° C. Then, it was immersed at 56.5 ° C. in an aqueous solution containing potassium iodide and boric acid (potassium iodide / boric acid / water (weight ratio) = 12 / 3.6 / 100). The film was washed with pure water at 10 ° C. and then dried at 85 ° C. to obtain a polarizer having a thickness of about 23 μm in which iodine was adsorbed and oriented on polyvinyl alcohol. Stretching was mainly performed in the iodine staining and boric acid treatment steps, and the total stretching ratio was 5.3 times.
上記(3)で作製した粘着剤層付光学フィルム(P-1)を、偏光板の延伸軸方向が長辺となるように300mm×220mmの大きさに裁断してセパレートフィルムを剥離し、露出した粘着剤層面をガラス基板又はITO(錫ドープ酸化インジウム)付きガラス基盤に貼合した。得られたガラス基板が貼り付けられた試験片(ガラス基板が貼り付けられた粘着剤層付光学フィルム)を、オートクレーブ中、温度50℃、圧力5kg/cm2(490.3kPa)で、20分間加圧した。ガラス基板には、コーニング社製の無アルカリガラス 商品名「Eagle XG」を使用した。また、ITO付きガラス基板として、コーニング社製の無アルカリガラス[商品名「Eagle XG」]に、ITO蒸着によって30nmのITO層を形成したものを使用した。
得られた光学積層体について、次の3種の耐久性試験を実施した。 (4) Durability evaluation of optical film with pressure-sensitive adhesive layer The optical film with pressure-sensitive adhesive layer (P-1) produced in the above (3) is 300 mm × 220 mm so that the stretching axis direction of the polarizing plate is the long side. It cut | judged to a magnitude | size, the separate film was peeled, and the exposed adhesive layer surface was bonded to the glass substrate or the glass base | substrate with ITO (tin dope indium oxide). The test piece (the optical film with the pressure-sensitive adhesive layer to which the glass substrate was attached) obtained by attaching the obtained glass substrate was placed in an autoclave at a temperature of 50 ° C. and a pressure of 5 kg / cm 2 (490.3 kPa) for 20 minutes. Pressurized. A non-alkali glass product name “Eagle XG” manufactured by Corning was used for the glass substrate. In addition, as a glass substrate with ITO, a non-alkali glass manufactured by Corning [trade name “Eagle XG”] having a 30 nm ITO layer formed by ITO deposition was used.
About the obtained optical laminated body, the following 3 types of durability tests were implemented.
・温度95℃の乾燥条件下で1000時間保持する耐熱試験、(ガラス基板)
・温度95℃の乾燥条件下で1000時間保持する耐熱試験、(ITO付きガラス)
・温度60℃、相対湿度90%の環境下で1000時間保持する耐湿熱試験(ガラス基板)、
・温度85℃の乾燥条件下で30分保持し、次いで温度-40℃の乾燥条件下で30分保持する操作を1サイクルとし、これを1000サイクル繰り返す耐ヒートショック(HS)試験(ガラス基板)。 [Durability test]
・ Heat resistance test held at a temperature of 95 ℃ for 1000 hours (glass substrate)
・ Heat resistance test held at a temperature of 95 ℃ for 1000 hours (Glass with ITO)
-Moisture and heat resistance test (glass substrate) held for 1000 hours in an environment of temperature 60 ° C and relative humidity 90%,
・ Heat shock (HS) test (glass substrate) that is held for 30 minutes under a drying condition at a temperature of 85 ° C. and then held for 30 minutes under a drying condition at a temperature of −40 ° C. for one cycle. .
4:浮き、剥れ、発泡等の外観変化がほとんどみられない、
3:浮き、剥れ、発泡等の外観変化がやや目立つ、
2:浮き、剥れ、発泡等の外観変化が目立つ、
1:浮き、剥れ、発泡等の外観変化が顕著に認められる。 5: No change in appearance such as floating, peeling, foaming, etc.
4: Almost no change in appearance such as floating, peeling, foaming, etc.
3: Appearance changes such as floating, peeling and foaming are slightly noticeable.
2: Appearance changes such as floating, peeling, foaming are conspicuous,
1: Appearance changes such as floating, peeling, foaming, etc. are noticeable.
上記(3)で作製した粘着剤層付光学フィルム(P-1)を、25mm×150mmの大きさの試験片に裁断した。試験片からセパレーターを剥がし、その粘着剤面をガラス基板に貼り付けた。得られたガラス基板が貼り付けられた試験片(ガラス基板が貼り付けられた粘着剤層付光学フィルム)を、オートクレーブ中、温度50℃、圧力5kg/cm2(490.3kPa)で、20分間加圧した。温度23℃、相対湿度50%の雰囲気中で24時間保管したのちに、試験片から光学フィルムを粘着剤層とともに300mm/分の速度で180°方向に剥離した。剥離時の平均剥離力を粘着力として表3に示す。粘着力が10N以下である場合にはリワーク性に優れ、また0.5N以上である場合には、偏光板端部から衝撃を受けた際にも剥がれが生じにくい。 (5) Evaluation of adhesive strength of optical film with pressure-sensitive adhesive layer The optical film with pressure-sensitive adhesive layer (P-1) produced in the above (3) was cut into a test piece having a size of 25 mm × 150 mm. The separator was peeled off from the test piece, and the pressure-sensitive adhesive surface was attached to a glass substrate. The test piece (the optical film with the pressure-sensitive adhesive layer to which the glass substrate was attached) obtained by attaching the obtained glass substrate was placed in an autoclave at a temperature of 50 ° C. and a pressure of 5 kg / cm 2 (490.3 kPa) for 20 minutes. Pressurized. After storing for 24 hours in an atmosphere having a temperature of 23 ° C. and a relative humidity of 50%, the optical film was peeled from the test piece together with the pressure-sensitive adhesive layer in the direction of 180 ° at a speed of 300 mm / min. Table 3 shows the average peeling force at the time of peeling as the adhesive strength. When the adhesive force is 10 N or less, the rework property is excellent, and when it is 0.5 N or more, peeling hardly occurs even when an impact is applied from the end of the polarizing plate.
ITO層付きガラス基板のITO層の表面の表面抵抗(試験前表面抵抗値)を低抵抗率計〔三菱化学アナリテック(株)製の商品名「ロレスタ―AX」〕で測定した。次に、上記(3)で作製した粘着剤層が形成された偏光板を、20mm×40mmの大きさの試験片に裁断し、ガラス基板のITO層側に、粘着剤層を介して貼着した。得られた光学積層体を、温度60℃、相対湿度90%のオーブン中で500時間保管した後、温度23℃、相対湿度50%の雰囲気下で、ITO層と粘着剤層との間で剥離した。剥離後のITO層の表面抵抗(試験後表面抵抗値)を測定した。試験前後の抵抗変化率を、下記式により算出し、以下の基準で評価した。抵抗変化率が小さいほど、ITO腐食性が低い。結果を表3に示す。
抵抗変化率(%)=[(試験後表面抵抗値)-(試験前表面抵抗値)]/[試験前表面抵抗値]×100 [Evaluation of ITO corrosivity of optical laminates]
The surface resistance (surface resistance value before the test) of the ITO layer of the glass substrate with the ITO layer was measured with a low resistivity meter (trade name “Loresta-AX” manufactured by Mitsubishi Chemical Analytech Co., Ltd.). Next, the polarizing plate on which the pressure-sensitive adhesive layer prepared in the above (3) is formed is cut into a test piece having a size of 20 mm × 40 mm, and attached to the ITO layer side of the glass substrate via the pressure-sensitive adhesive layer. did. The obtained optical layered body was stored in an oven at a temperature of 60 ° C. and a relative humidity of 90% for 500 hours, and then peeled between the ITO layer and the adhesive layer in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50%. did. The surface resistance (surface resistance value after test) of the ITO layer after peeling was measured. The rate of change in resistance before and after the test was calculated by the following formula and evaluated according to the following criteria. The smaller the rate of resistance change, the lower the ITO corrosivity. The results are shown in Table 3.
Resistance change rate (%) = [(surface resistance value after test) − (surface resistance value before test)] / [surface resistance value before test] × 100
○:抵抗変化率が50%未満であり、ITO腐食性が良好な光学積層体である。
×:抵抗変化率が50%以上であり、光学積層体のITO腐食性は不良である。 <Evaluation criteria for ITO corrosivity>
◯: An optical laminate having a resistance change rate of less than 50% and good ITO corrosivity.
X: The resistance change rate is 50% or more, and the ITO corrosiveness of the optical laminate is poor.
得られた粘着剤層付き偏光フィルムのセパレーターを剥離したのちに、粘着剤の表面抵抗値を表面固有抵抗測定装置〔三菱化学(株)製の「ハイレスタ-up MCP-HT450」(商品名)〕により測定した。印加電圧250V、印加時間10秒の測定条件で実施した。表面抵抗値が1.0×1012Ω/□以下であれば、良好な帯電防止性が得られる。 (6) Evaluation of antistatic property of optical film with adhesive layer
After removing the separator of the obtained polarizing film with the pressure-sensitive adhesive layer, the surface resistance value of the pressure-sensitive adhesive is measured by a surface resistivity measuring device [“HIRESTA-up MCP-HT450” (trade name) manufactured by Mitsubishi Chemical Corporation]. It was measured by. The measurement was performed under the measurement conditions of an applied voltage of 250 V and an applied time of 10 seconds. If the surface resistance value is 1.0 × 10 12 Ω / □ or less, good antistatic properties can be obtained.
本発明の粘着剤シートのゲル分率評価方法を示す。ゲル分率が大きいほど粘着剤中で多くの架橋反応が進行していることになり、架橋密度の目安とすることができる。ゲル分率は、以下の(1)~(4)に従って測定される値である。 [Gel fraction of adhesive sheet]
The gel fraction evaluation method of the adhesive sheet of this invention is shown. The larger the gel fraction, the more cross-linking reactions are progressing in the pressure-sensitive adhesive, and this can be used as a measure of the cross-linking density. The gel fraction is a value measured according to the following (1) to (4).
(2)上記(1)で得られた貼合物を秤量して、その重量をWs とし、次に粘着剤シートを包み込むように4回折りたたんでホッチキス(ステープラー)で留めた後秤量し、その重量をWb とする。
(3)上記(2)でホッチキス留めしたメッシュをガラス容器に入れ、酢酸エチル60mLを加えて浸漬した後、このガラス容器を室温で3日間保管する。
(4)ガラス容器からメッシュを取り出し、120℃で24時間乾燥した後秤量し、その重量をWa とし、次式に基づいてゲル分率を計算する。
ゲル分率(重量%)=〔{Wa-(Wb-Ws)-Wm}/(Ws-Wm)〕×100 (1) An adhesive sheet having an area of about 8 cm × about 8 cm and a metal mesh made of SUS304 (about 10 cm × about 10 cm) (with a weight of Wm) are bonded.
(2) Weigh the bonded product obtained in (1) above, weigh it Ws, then fold it 4 times so as to wrap the adhesive sheet, weigh it with a stapler (stapler), weigh it, Let the weight be Wb.
(3) The mesh stapled in (2) above is placed in a glass container, and 60 mL of ethyl acetate is added and immersed, and then the glass container is stored at room temperature for 3 days.
(4) The mesh is taken out from the glass container, dried at 120 ° C. for 24 hours, weighed, the weight is taken as Wa, and the gel fraction is calculated based on the following formula.
Gel fraction (% by weight) = [{Wa− (Wb−Ws) −Wm} / (Ws−Wm)] × 100
Claims (13)
- (メタ)アクリル系樹脂(A)、架橋剤(B)、及びシラン化合物(C)を含む粘着剤組成物であって、
前記(メタ)アクリル系樹脂(A)は、下記式(a1)
で表されるヒドロキシ基含有(メタ)アクリレート由来の構成単位と、5-ヒドロキシペンチルアクリレート由来の構成単位とを含む粘着剤組成物。 A pressure-sensitive adhesive composition comprising a (meth) acrylic resin (A), a crosslinking agent (B), and a silane compound (C),
The (meth) acrylic resin (A) is represented by the following formula (a1)
A pressure-sensitive adhesive composition comprising a structural unit derived from a hydroxy group-containing (meth) acrylate and a structural unit derived from 5-hydroxypentyl acrylate. - (メタ)アクリル系樹脂を構成する全構成単位100重量部に対して、式(a1)で表されるヒドロキシ基含有(メタ)アクリレート由来の構成単位の割合は1.5~4.5重量部であり、5-ヒドロキシペンチルアクリレート由来の構成単位の割合は0.25~1.0重量部である請求項1に記載の粘着剤組成物。 The proportion of the structural unit derived from the hydroxy group-containing (meth) acrylate represented by the formula (a1) is 1.5 to 4.5 parts by weight with respect to 100 parts by weight of all the structural units constituting the (meth) acrylic resin. The pressure-sensitive adhesive composition according to claim 1, wherein the proportion of the structural unit derived from 5-hydroxypentyl acrylate is 0.25 to 1.0 part by weight.
- (メタ)アクリル系樹脂は、ホモポリマーのガラス転移温度が0℃未満のアルキルアクリレート(a3-1)由来の構成単位と、ホモポリマーのガラス転移温度が0℃以上のアルキルアクリレート由来の構成単位(a3-2)とを含有するアルキルアクリレート(a3)由来の構成単位を含む請求項1又は2に記載の粘着剤組成物。 The (meth) acrylic resin includes a structural unit derived from an alkyl acrylate (a3-1) having a glass transition temperature of the homopolymer of less than 0 ° C., and a structural unit derived from an alkyl acrylate having a glass transition temperature of the homopolymer of 0 ° C. or higher ( The pressure-sensitive adhesive composition according to claim 1 or 2, comprising a structural unit derived from an alkyl acrylate (a3) containing a3-2).
- ホモポリマーのガラス転移温度が0℃未満のアルキルアクリレート(a3-1)由来の構成単位と、ホモポリマーのガラス転移温度が0℃以上のアルキルアクリレート(a3-2)由来の構成単位との割合(重量比)は、(a3-1)/(a3-2)=20/80~95/5である請求項3に記載の粘着剤組成物。 Ratio of structural unit derived from alkyl acrylate (a3-1) having a glass transition temperature of the homopolymer of less than 0 ° C. and structural unit derived from alkyl acrylate (a3-2) having a glass transition temperature of the homopolymer of 0 ° C. or higher ( The pressure-sensitive adhesive composition according to claim 3, wherein (weight ratio) is (a3-1) / (a3-2) = 20/80 to 95/5.
- (メタ)アクリル系樹脂の重量平均分子量は、ポリスチレン換算で、6.0×105~2.5×106である請求項1~4のいずれかに記載の粘着剤組成物。 5. The pressure-sensitive adhesive composition according to claim 1, wherein the (meth) acrylic resin has a weight average molecular weight of 6.0 × 10 5 to 2.5 × 10 6 in terms of polystyrene.
- 架橋剤(B)は、芳香族イソシアネート化合物及び/又は該芳香族イソシアネート化合物の多価アルコール化合物による付加体である請求項1~5のいずれかに記載の粘着剤組成物。 6. The pressure-sensitive adhesive composition according to claim 1, wherein the crosslinking agent (B) is an adduct of an aromatic isocyanate compound and / or a polyhydric alcohol compound of the aromatic isocyanate compound.
- 架橋剤(B)の割合は、(メタ)アクリル系樹脂(A)100重量部に対して、0.01~10重量部である請求項1~6のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 6, wherein the ratio of the crosslinking agent (B) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic resin (A).
- シラン化合物(C)は、下記式(c1)
(式中、Bは、炭素数1~20のアルカンジイル基又は炭素数3~20の二価の脂環式炭化水素基を示し、前記アルカンジイル基及び前記脂環式炭化水素基を構成する-CH2-は、-O-又は-CO-に置換されてもよく、R1は炭素数1~5のアルキル基を示し、R2、R3、R4、R5及びR6はそれぞれ独立して、炭素数1~5のアルキル基又は炭素数1~5のアルコキシ基を示す)
で表されるシラン化合物である請求項1~7のいずれかに記載の粘着剤組成物。 The silane compound (C) is represented by the following formula (c1)
(In the formula, B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group. —CH 2 — may be substituted with —O— or —CO—, R 1 represents an alkyl group having 1 to 5 carbon atoms, and R 2 , R 3 , R 4 , R 5 and R 6 are each Independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms)
The pressure-sensitive adhesive composition according to any one of claims 1 to 7, which is a silane compound represented by the formula: - 式(c1)のBは炭素数1~10のアルカンジイル基であり、R1は炭素数1~5のアルキル基であり、R2、R3、R4、R5及びR6はそれぞれ独立して、炭素数1~5のアルコキシ基である請求項8に記載の粘着剤組成物。 B in the formula (c1) is an alkanediyl group having 1 to 10 carbon atoms, R 1 is an alkyl group having 1 to 5 carbon atoms, and R 2 , R 3 , R 4 , R 5 and R 6 are each independently The pressure-sensitive adhesive composition according to claim 8, which is an alkoxy group having 1 to 5 carbon atoms.
- シラン化合物(C)の割合は、(メタ)アクリル系樹脂(A)100重量部に対して、0.01~10重量部である請求項1~9のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 9, wherein the proportion of the silane compound (C) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic resin (A).
- 粘着剤組成物から形成される粘着剤のゲル分率は、50~95%である請求項1~10のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 10, wherein the pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition has a gel fraction of 50 to 95%.
- ガラス基板に、前記粘着剤組成物から形成される粘着剤層を貼合し、温度23℃、相対湿度50%の条件下24時間後の前記粘着剤層の粘着力は、剥離速度300mm/分において、0.5~10N/25mmである請求項1~11のいずれかに記載の粘着剤組成物。 A pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is bonded to a glass substrate, and the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer after 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50% is a peeling rate of 300 mm / min. The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive composition is 0.5 to 10 N / 25 mm.
- 光学フィルムに積層される粘着剤層の形成に用いられる、請求項1~12のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 12, which is used for forming a pressure-sensitive adhesive layer laminated on an optical film.
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JP2019031586A (en) * | 2017-08-04 | 2019-02-28 | 日本合成化学工業株式会社 | Adhesive composition, adhesive using the same, adhesive for polarizing plate, and image display device |
WO2024014394A1 (en) * | 2022-07-11 | 2024-01-18 | 綜研化学株式会社 | Adhesive layer-bearing polarizing film and image display device |
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JP7014879B2 (en) * | 2020-11-12 | 2022-02-01 | 藤森工業株式会社 | Adhesive composition and adhesive film |
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