WO2020218061A1 - Curable composition, cured product layer, optical laminate, and image display device - Google Patents
Curable composition, cured product layer, optical laminate, and image display device Download PDFInfo
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- WO2020218061A1 WO2020218061A1 PCT/JP2020/016288 JP2020016288W WO2020218061A1 WO 2020218061 A1 WO2020218061 A1 WO 2020218061A1 JP 2020016288 W JP2020016288 W JP 2020016288W WO 2020218061 A1 WO2020218061 A1 WO 2020218061A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
Definitions
- the present invention relates to a curable composition.
- the present invention also relates to a cured product layer composed of a cured product of the curable composition, an optical laminate containing the cured product layer, and an image display device including the optical laminate.
- liquid crystal display devices have been developed for mobile device applications such as smartphones and tablet terminals and in-vehicle device applications such as car navigation systems.
- mobile device applications such as smartphones and tablet terminals
- in-vehicle device applications such as car navigation systems.
- the optical film incorporated in the 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 in which high temperature and low temperature are repeated. In these environments, However, it is required that the optical characteristics do not deteriorate.
- optical film examples include a polarizing plate in which a protective film is attached to one side or both sides of a polarizing element using an adhesive (Patent Document 1 and the like).
- An object of the present invention is to provide a curable composition containing a cured product layer composed of a cured product of the curable composition and capable of providing an optical laminate having good optical durability in a high temperature and high humidity environment.
- Another object of the present invention is to provide an optical laminate containing a cured product layer composed of a cured product of a curable composition and having good optical durability in a high temperature and high humidity environment, and an image display device including the same. To do.
- the present invention provides the curable composition, the cured product layer, the optical laminate, and the image display device shown below.
- the aqueous resin is a curable composition containing an oxazolyl group-containing polymer.
- the silane compound further comprises a group consisting of an amino group, a carboxyl group, an epoxy group, an acetoacetyl group, a hydroxyalkyl group, a mercapto group, an oxyalkylene group, and an alkenyl group which may have a substituent.
- the silane compound further contains a Si—O—Si bond and contains The curable composition according to [5] or [6], which has the functional group in the structure of the silane compound.
- [9] Includes an optical layer and a first cured product layer
- the first cured product layer is an optical laminate which is the cured product layer according to [8].
- it contains a first thermoplastic resin film, and contains The optical laminate according to [9], wherein the optical layer, the first cured product layer, and the first thermoplastic resin film are laminated in this order.
- a second cured product layer and a second thermoplastic resin film are included.
- curable composition containing a cured product layer composed of a cured product of the curable composition and capable of providing an optical laminate having good optical durability in a high temperature and high humidity environment. It is possible to provide an optical laminate containing a cured product layer composed of a cured product of a curable composition and having good optical durability in a high temperature and high humidity environment, and an image display device including the same.
- the curable composition according to the present invention contains an aqueous resin and a silane compound, and the aqueous resin contains an oxazolyl group-containing polymer.
- the curable composition according to the present invention is referred to as "curable composition (S)"
- the above-mentioned aqueous resin is referred to as “aqueous resin (A)”
- the above-mentioned oxazolyl group-containing polymer is referred to as "oxazolyl group-containing polymer (a)”.
- the silane compound having a silanol group may be referred to as "silane compound (B)”.
- the curable composition (S) can be used as a coating liquid for forming a coating film (coating layer) on the substrate.
- a coating film can be formed by applying the curable composition (S) onto a base material and curing the coating layer.
- the base material is preferably an optical layer.
- the optical layer will be described later.
- the optical laminate includes an optical layer and a first cured product layer composed of a cured product of the curable composition (S).
- the curable composition (S) can also be used as an adhesive composition.
- the curable composition (S) is an adhesive composition for adhering the optical layer and the first thermoplastic resin film.
- the optical laminate includes an optical layer, a first cured product layer (adhesive layer) composed of a cured product of the curable composition (S), and a first thermoplastic resin film in this order.
- the curable composition (S) is coated on at least one of the bonding surfaces of the optical layer and the first thermoplastic resin film, and the optical layer and the first thermoplastic are passed through the coating layer. It can be produced by laminating a resin film to obtain a laminated body and then curing the coating layer.
- the curable composition (S) is an aqueous composition containing the aqueous resin (A).
- the aqueous composition is a solution in which the compounding component is dissolved in a solvent containing water, or a dispersion (for example, an emulsion) in which the compounding component is dispersed in a solvent containing water.
- the viscosity of the curable composition (S) at 25 ° C. is preferably 50 mPa ⁇ sec or less, more preferably 1 mPa ⁇ sec or more and 30 mPa ⁇ sec or less, and 2 mPa ⁇ sec or more and 20 mPa ⁇ sec or less. Is even more preferable. If the viscosity at 25 ° C. exceeds 50 mPa ⁇ sec, it becomes difficult to apply the coating uniformly, which may cause uneven coating, and may cause problems such as clogging of piping.
- the viscosity of the curable composition (S) at 25 ° C. can be measured by an E-type viscometer.
- Water-based resin (A) contains at least one of a water-soluble polymer soluble in an aqueous solvent and an water-dispersible polymer dispersible in an aqueous solvent.
- the water-soluble polymer is not particularly limited as long as it is a polymer that can be dissolved in an aqueous solvent.
- the water-dispersible polymer is not particularly limited as long as it is a polymer that can be dispersed in an aqueous solvent.
- the aqueous solvent means water or a solvent containing water as a main component
- water as a main component means that 50% by mass or more of the total mass of the components constituting the solvent is water.
- the solvent other than water among the aqueous solvents is not particularly limited as long as it is a solvent that does not easily layer-separate in the coexistence with water, but is preferably a solvent that dissolves in water, for example, methanol, ethanol, or isopropyl alcohol.
- Alcohols such as n-propyl alcohol; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and diethylene glycol; glycol ethers such as N-methylpyrrolidone (NMP), tetrahydrofuran and butyl cellosolve and the like.
- NMP N-methylpyrrolidone
- the aqueous resin (A) contains at least the oxazolyl group-containing polymer (a).
- the aqueous resin (A) is one or 2 selected from a water-soluble polymer soluble in an aqueous solvent other than the oxazolyl group-containing polymer (a) and an aqueous-dispersible polymer dispersible in an aqueous solvent. It may contain more than a seed.
- the content of the aqueous resin (A) in the curable composition (S) is preferably 50% by mass or more and 95% by mass or less, more preferably, when the solid content concentration of the curable composition (S) is 100% by mass. Is 55% by mass or more and 90% by mass or less, more preferably 60% by mass or more and 85% by mass or less. Keeping the content of the aqueous resin (A) within the above range improves the optical durability of the optical laminate in a high temperature and high humidity environment, and between the optical layer and the first cured product layer in the optical laminate. It is preferable from the viewpoint of adhesion and adhesion between the first cured product layer and the first thermoplastic resin film.
- the solid content concentration refers to the total concentration of components other than the solvent contained in the curable composition (S).
- Oxazolyl group-containing polymer (a)
- the oxazolyl group-containing polymer (a) is a water-soluble polymer that can be dissolved in an aqueous solvent and an aqueous-dispersible polymer that can be dispersed in an aqueous solvent. From the viewpoint of the optical properties of the first cured product layer, the oxazolyl group-containing polymer (a) is preferably a water-soluble polymer.
- the oxazolyl group-containing polymer (a) is a polymer having an oxazolyl group in the molecule, and is preferably a polymer having an oxazolyl group in the side chain.
- the skeleton structure of the oxazolyl group-containing polymer (a) is not particularly limited, and may consist of, for example, one or more skeletons selected from (meth) acrylic skeleton, styrene skeleton, olefin skeleton, ester skeleton, carbonate skeleton and the like. it can.
- the term "(meth) acrylic” refers to at least one selected from the group consisting of acrylic and methacrylic. The same applies to the notations such as "(meth) acryloyl" and "(meth) acrylate”.
- the oxazolyl group-containing polymer (a) can have an oxazolyl group in the side chain of the skeletal structure.
- the oxazolyl group-containing polymer (a) may contain a structural unit having an oxazolyl group in the side chain (a structural unit derived from an oxazolyl group-containing monomer) and a structural unit having no oxazolyl group.
- a preferable example of the oxazolyl group-containing polymer (a) is a structural unit (derived from an oxazolyl group-containing monomer) having a skeleton structure composed of a (meth) acrylic skeleton as the main component of the structural unit and having an oxazolyl group in the side chain as a copolymerization component. It is an oxazolyl group-containing (meth) acrylic polymer into which the constituent unit of the above is introduced.
- the oxazolyl group-containing polymer (a) may be a copolymer of an oxazolyl group-containing monomer or a polymer containing an oxazolyl group by modifying the side chain functional group of the polymer.
- Examples of the oxazolyl group include a 2-oxazolyl group, a 3-oxazolyl group, a 4-oxazolyl group and the like.
- the oxazolyl group is preferably a 2-oxazolyl group or the like.
- Examples of the oxazoline group-containing monomer include 2-isopropenyl-2-oxazoline and vinyl-2-oxazoline.
- the weight average molecular weight of the oxazolyl group-containing polymer (a) is preferably 5,000 or more, and more preferably 10,000 or more.
- the fact that the weight average molecular weight is in the above range means that the optical durability of the optical laminate in a high temperature and high humidity environment is improved, the adhesion between the optical layer and the first cured product layer in the optical laminate, and the first cured product. It can be advantageous from the viewpoint of adhesion between the layer and the first thermoplastic resin film.
- the weight average molecular weight of the oxazolyl group-containing polymer (a) is usually 1,000,000 or less.
- the weight average molecular weight of the oxazolyl group-containing polymer (a) can be measured as a standard polystyrene-equivalent value by gel permeation chromatography (GPC).
- the amount of oxazolyl groups (the number of moles of oxazolyl groups per 1 g of solid content of the oxazolyl group-containing polymer (a)) of the oxazolyl group-containing polymer (a) is preferably 0.4 mmol / g ⁇ solid or more. If the amount of oxazolyl groups is smaller than the above range, the optical durability of the optical laminate in a high temperature and high humidity environment may be disadvantageous.
- the amount of oxazolyl groups in the oxazolyl group-containing polymer is more preferably 3 mmol / g ⁇ solid or more, still more preferably 5 mmol / g ⁇ solid or more and 9 mmol / g ⁇ solid or less.
- the upper limit of the amount of oxazolyl group is not particularly limited, but is usually 50 mmol / g ⁇ solid or less.
- a commercially available product may be used as the oxazolyl group-containing polymer (a).
- oxazolyl group-containing acrylic polymers such as Epocross WS-300, Epocross WS-500, and Epocross WS-700 (all trade names) manufactured by Nippon Shokubai Co., Ltd .; Epocross K-1000 series and Epocross manufactured by Nippon Shokubai Co., Ltd.
- examples thereof include oxazolyl group-containing acrylic / styrene polymers such as K-2000 series and Epocross RPS series (both are trade names).
- the oxazolyl group-containing polymer (a) can be used in combination of two or more.
- the oxazolyl group-containing polymer (a) is an oxazolyl group-containing acrylic polymer such as Epocross WS-300, Epocross WS-500, and Epocross WS-700. It is preferable to have.
- the content of the oxazolyl group-containing polymer (a) is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably, when the total amount of the aqueous resin (A) is 100% by mass. Is 70% by mass or more, may be 100% by mass, is usually 100% by mass or less, may be 99% by mass or less, or may be 95% by mass or less. Keeping the content of the oxazolyl group-containing polymer (a) within the above range improves the optical durability of the optical laminate in a high temperature and high humidity environment, and the optical layer and the first cured product layer in the optical laminate. It is preferable from the viewpoint of the adhesion between the first cured product layer and the first thermoplastic resin film.
- the water-based resin (A) is a water-soluble polymer soluble in an aqueous solvent other than the oxazolyl group-containing polymer (a) and a water-dispersible weight dispersible in an aqueous solvent. It may contain a coalescence (hereinafter, these may be collectively referred to as "other aqueous polymers").
- aqueous polymers examples include (meth) acrylic polymers; polyvinyl alcohol-based polymers; polyvinyl acetal-based polymers; ethylene-vinyl alcohol copolymers; polyvinylpyrrolidone-based polymers; polyamide-amine-based polymers; Epoxy-based polymer; Melamine-based polymer; Uria-based polymer; Polyamide-based polymer; Polyester-based polymer; Polyurethane-based polymer; Cellulous polymer such as methyl cellulose, hydroethyl cellulose, carboxymethyl cellulose; Sodium alginate, starch, etc. Examples include polymers.
- the content of the other aqueous polymer is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass, when the total amount of the aqueous resin (A) is 100% by mass. % Or less, 20% by mass or less, or 10% by mass or less.
- the silane compound (B) is preferably a compound in which an arbitrary functional group is bonded to a silicon atom.
- a functional group include a hydrolyzable group such as an alkoxy group, an organic group having a reactive functional group such as a vinyl group, an amino group, an epoxy group, a haloalkyl group, a (meth) acroyl group and a mercapto group.
- the silane compound (B) can be used alone or in combination of two or more.
- silane compound (B) examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2).
- the silane compound (B) may be of the silicone oligomer type.
- silicone oligomer is shown in the form of a (monomer) oligomer, for example, the following can be mentioned.
- 3-Mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer 3-Mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-Mercaptopropyltriethoxysilane-tetramethoxysilane copolymer, A mercaptopropyl group-containing copolymer such as 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer; Mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, Mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, Mercaptomethyltriethoxysilane-tetramethoxysilane copolymer, Mercaptomethyl group-containing copolymers such as mercaptomethyltriethoxysilane-tetraethoxysilane copolymer; 3-Glyd
- the silane compound (B) is preferably a compound having a silanol group (-SiOH).
- the silane compound (B) having a silanol group is not particularly limited as long as it has a silanol group. It may be a monomer having a silanol group. Further, even if a silanol group forms a dimer or a trimer by a condensation reaction or the like or a three-dimensional network structure is formed, if the formed body has a silanol group, a silanol group can be used. It can be included in the silane compound (B) having.
- the silane compound (B) is composed of an amino group, a carboxyl group, an epoxy group, an acetoacetyl group, a hydroxyalkyl group, a mercapto group, an oxyalkylene group, and an alkenyl group which may have a substituent in addition to the silanol group. It is preferable to have one or more functional groups selected from the group. Of these, the silane compound (B) more preferably has a functional group of at least one of an amino group and a carboxyl group which may have a substituent in addition to the silanol group, and has a carboxyl group. Is even more preferable.
- Amino groups that may have a substituent include an amino group that does not have a substituent (-NH 2 ), an alkylamino group in which one or two hydrogen atoms are substituted with an alkyl group, one or one.
- a (hydroxyalkyl) amino group in which two hydrogen atoms are substituted with a hydroxyalkyl group for example, -N (CH 2 HC (OH) CH 2 OH 2 ) 2
- an aminoalkyl amino group (-NHC 2 H 4 NH 2).
- the functional groups include -NH 2 , -NHC 2 H 4 NH 2 , -COOH, -CH (OH) CH 2 OH, and -N (CH 2 HC (OH) CH 2 OH 2 ) 2. , -CHCH 2 , -SH and the like.
- the functional groups may be the same or different from each other.
- the above-mentioned functional group which the silane compound (B) having a silanol group may have can react with the oxazolyl group of the oxazolyl group-containing polymer (a). Since the silane compound (B) has the above functional groups, the silane compound (B) and the oxazolyl group-containing polymer (a) can react with each other.
- the optical durability of the optical laminate in a high temperature and high humidity environment It is easy to improve the properties, the adhesion between the optical layer and the first cured product layer in the optical laminate, and the adhesion between the first cured product layer and the first thermoplastic resin film.
- the silane compound (B) preferably contains a Si—O—Si bond in addition to the silanol group and the above-mentioned functional group.
- the silanol group and the above-mentioned functional group may be present anywhere in the structure of the silane compound (B) containing a Si—O—Si bond, but the silane compound (B) containing a Si—O—Si bond). It is preferable to have the above-mentioned functional group at the end of.
- the content of the silane compound (B) is usually 0.01 part by mass or more with respect to 100 parts by mass of the aqueous resin (A) from the viewpoint of enhancing the optical durability of the optical laminate in a high temperature and high humidity environment. It is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and usually 60 parts by mass or less, preferably 45 parts by mass or less, and 30 parts by mass or less. Is more preferable.
- the content of the silane compound (B) in the curable composition (S) within the above range, the optical durability of the optical laminate in a high temperature and high humidity environment is improved, and the optical layer in the optical laminate is used.
- Acid compound (C) The acid compound (C) can promote the reaction between the oxazolyl group of the oxazolyl group-containing polymer (a) and the functional group of the silane compound (B), particularly the above-mentioned reactive functional group.
- the promotion referred to here includes the case of initiating the reaction.
- the silane compound (B) consists of an amino group, a carboxyl group, an epoxy group, an acetoacetyl group, a hydroxyalkyl group, a mercapto group, an oxyalkylene group, and an alkenyl group which may have a substituent in addition to the silanol group.
- the acid compound (C) can accelerate the reaction between this functional group and the oxazolyl group of the oxazolyl group-containing polymer (a).
- the acid compound (C) may be a compound that functions as a catalyst for the reaction between the oxazolyl group of the oxazolyl group-containing polymer (a) and the above-mentioned functional group of the silane compound (B).
- Examples of the acid compound (C) include inorganic acids such as sulfuric acid, hydrogen chloride, nitrate, phosphoric acid, phosphite, and boric acid; p-toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid, and benzenesulfon.
- examples thereof include organic acids such as acids, phenylphosphoric acids, sulfanic acids, phenylphosphonic acids, acetic acids and propionic acids.
- the acid compound (C) has the optical durability of the optical laminate in a high temperature and high humidity environment, the adhesion between the optical layer and the first cured product layer in the optical laminate, and the first cured product layer and the first cured product layer.
- a relatively strong acid is preferable, and examples of such an acid compound include sulfuric acid, hydrogen chloride (hydrochloric acid), nitric acid, p-toluenesulfonic acid and the like. Be done.
- the adhesion between the optical layer and the first cured product layer in the optical laminate and the adhesion between the first cured product layer and the first thermoplastic resin film are particularly high. There is a tendency to improve the adhesion between them.
- the curable composition (S) may contain one kind of acid compound (C) or may contain two or more kinds of acid compounds (C).
- the acid compound (C) may be blended in the curable composition (S) as a solution (for example, an aqueous solution) containing the acid compound (C).
- the content of the acid compound (C) is preferably 5 parts by mass or more and 80 parts by mass or less, more preferably 80 parts by mass, based on 100 parts by mass of the aqueous resin (A) (preferably the oxazolyl group-containing polymer (a)). It is 10 parts by mass or more and 70 parts by mass or less, and more preferably 15 parts by mass or more and 60 parts by mass or less.
- the content of the acid compound (C) is excessively small, the adhesion between the optical layer and the first cured product layer and between the first cured product layer and the first thermoplastic resin film in the optical laminate It is difficult to obtain at least one of.
- the content of the acid compound (C) is excessively large, it is between the optical layer and the first cured product layer in the optical laminate and between the first cured product layer and the first thermoplastic resin film. At least one of the adhesions tends to decrease.
- the curable composition (S) can contain other components other than the aqueous resin (A), the silane compound (B), and the acid compound (C).
- Other components include curable components such as polyvalent aldehydes such as glioxal and glioxal derivatives, melamine compounds, aziridine compounds, water-soluble epoxy resins, zirconium compounds, zinc compounds, titanium compounds, and metal compounds such as aluminum compounds, and cross-linking.
- Agents Modified polyvinyl alcohol-based polymers other than carboxyl group-modified polyvinyl alcohol-based polymers; Additives such as coupling agents, tackifiers, antioxidants, ultraviolet absorbers, heat stabilizers, and hydrolysis inhibitors. ..
- the curable composition (S) may contain one or more other components.
- the curable composition (S) preferably contains an aqueous solvent for dissolving or dispersing the aqueous resin (A).
- aqueous solvent those exemplified above can be used.
- 80% by mass or more of the total mass of the aqueous solvent is preferably water, more preferably 90% by mass or more is water, further preferably 95% by mass or more is water, and water. It may contain only.
- the solid content concentration of the curable composition (S) is usually 0.5% by mass or more and 20% by mass or less, preferably 1% by mass or more and 15% by mass or less.
- the optical laminate according to the present invention includes an optical layer and a first cured product layer (a cured product layer composed of a cured product of the curable composition (S)) laminated on at least one surface thereof.
- a first cured product layer a cured product layer composed of a cured product of the curable composition (S)
- the optical laminate since the cured product layer contained in the optical laminate is composed of the cured product of the curable composition (S), the optical laminate has good optical durability in a high temperature and high humidity environment. Can be.
- FIGS. 1 to 5 show examples of layer configurations of the optical laminates.
- the optical laminate shown in FIG. 1 includes an optical layer 30 and a first cured product layer 15 laminated on one surface of the optical layer 30.
- the first cured product layer 15 can function as an overcoat layer that coats and protects the surface of the optical layer 30, an optical functional layer that additionally imparts an optical function to the optical layer 30, and the like. It is preferable that the optical layer 30 and the first cured product layer 15 are in direct contact with each other.
- the optical laminate shown in FIG. 2 includes an optical layer 30 and a first thermoplastic resin film 10 laminated and bonded to one surface thereof via a first cured product layer 15.
- the first cured product layer 15 can function as an adhesive layer for adhering the optical layer 30 and the first thermoplastic resin film 10. It is preferable that the first cured product layer 15 and the first thermoplastic resin film 10 are in direct contact with each other. It is preferable that the optical layer 30 and the first cured product layer 15 are in direct contact with each other.
- the optical laminate shown in FIG. 3 includes an optical layer 30, a first thermoplastic resin film 10 laminated and bonded to one surface of the optical layer 30 via a first cured product layer 15, and the other surface of the optical layer 30.
- a second thermoplastic resin film 20 that is laminated and bonded via a second cured product layer 25. That is, the optical laminate according to the present invention includes the second thermoplastic resin film 20, the second cured product layer 25, the optical layer 30, the first cured product layer 15, and the first thermoplastic resin film 10 in this order. It may be.
- the first cured product layer 15 and the second cured product layer 25 each adhere an adhesive layer for adhering the optical layer 30 and the first thermoplastic resin film 10, and the optical layer 30 and the second thermoplastic resin film 20. It can function as an adhesive layer.
- the second cured product layer 25 and the second thermoplastic resin film 20 are in direct contact with each other.
- the optical layer 30 and the second cured product layer 25 are in direct contact with each other.
- the optical laminate shown in FIG. 4 is laminated and laminated on the optical layer 30, the first cured product layer 15 laminated on one surface thereof, and the other surface of the optical layer 30 via the second cured product layer 25.
- the first cured product layer 15 can function as an overcoat layer that coats and protects the surface of the optical layer 30, an optical functional layer that additionally imparts an optical function to the optical layer 30, and the like.
- the second cured product layer 25 can function as an adhesive layer for adhering the optical layer 30 and the second thermoplastic resin film 20. It is preferable that the optical layer 30 and the first cured product layer 15 are in direct contact with each other. It is preferable that the second cured product layer 25 and the second thermoplastic resin film 20 are in direct contact with each other. It is preferable that the optical layer 30 and the second cured product layer 25 are in direct contact with each other.
- the optical laminate shown in FIG. 5 includes an optical layer 30, a first cured product layer 15 laminated on one surface of the optical layer 30, and a second cured product layer 25 laminated on the other surface of the optical layer 30.
- the first cured product layer 15 and the second cured product layer 25 function as an overcoat layer that coats and protects the surface of the optical layer 30, an optical functional layer that additionally imparts an optical function to the optical layer 30, and the like. Can be done.
- the optical layer 30 and the first cured product layer 15 are in direct contact with each other.
- the optical layer 30 and the second cured product layer 25 are in direct contact with each other.
- the optical layer 30 may be various optical films (films having optical characteristics) that can be incorporated into an image display device such as a liquid crystal display device.
- Examples of the optical layer 30 include a polarizer, a retardation film, a brightness improving film, an antiglare film, an antireflection film, a diffusion film, a light collecting film and the like.
- the optical laminate can include layers (or films) other than the above.
- the other layer include an adhesive laminated on the outer surface of the first thermoplastic resin film 10, the second thermoplastic resin film 20, the first cured product layer 15, the second cured product layer 25, and / or the optical layer 30.
- Agent layer Separate film laminated on the outer surface of the pressure-sensitive adhesive layer (also referred to as "release film”); 1st thermoplastic resin film 10, 2nd thermoplastic resin film 20, 1st cured product layer 15, 2nd A protective film (also referred to as a "surface protective film”) laminated on the outer surface of the cured product layer 25 and / or the optical layer 30; the first thermoplastic resin film 10, the second thermoplastic resin film 20, and the first cured product layer.
- Examples thereof include an optically functional film (or layer) laminated on the outer surface of the second cured product layer 25 and / or the optical layer 30 via an adhesive layer or an adhesive layer.
- the polarized light is a layer or film having a function of selectively transmitting linearly polarized light in a certain direction from natural light.
- the polarizer include a film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin film.
- the dichroic dye include iodine and a dichroic organic dye.
- the polarizing element may be a coating type polarizing film in which a dichroic dye in a Riotrovic liquid crystal state is coated on a base film and oriented and immobilized.
- the above-mentioned polarizer is called an absorption type polarizer because it selectively transmits linearly polarized light in one direction from natural light and absorbs linearly polarized light in the other direction.
- the polarizer is not limited to the absorption type polarizer, but is a reflection type polarizer that selectively transmits linearly polarized light in one direction from natural light and reflects the linearly polarized light in the other direction, or a linearly polarized light in the other direction.
- a scattering type polarizer may be used, but an absorption type polarizer is preferable from the viewpoint of excellent visibility.
- a polyvinyl alcohol-based polarizing film composed of a polyvinyl alcohol-based resin film is more preferable, and a polyvinyl alcohol-based polarizing film in which a bicolor dye such as iodine or a bicolor dye is adsorbed and oriented on the polyvinyl alcohol-based resin film is preferable. More preferably, a polyvinyl alcohol-based polarizing film in which iodine is adsorbed and oriented on the polyvinyl alcohol-based resin film is particularly preferable.
- polyvinyl alcohol-based resin a saponified polyvinyl acetate-based resin
- examples of the polyvinyl acetate-based resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and a copolymer of vinyl acetate and another monomer copolymerizable with the vinyl acetate.
- examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth) acrylamides having an ammonium group.
- the degree of saponification of the polyvinyl alcohol-based resin is usually 85 mol% or more and 100 mol% or less, preferably 98 mol% or more.
- the polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can be used.
- the average degree of polymerization of the polyvinyl alcohol-based resin is usually 1000 or more and 10000 or less, preferably 1500 or more and 5000 or less.
- the average degree of polymerization of the polyvinyl alcohol-based resin can be determined in accordance with JIS K 6726: 1994.
- a film formed of such a polyvinyl alcohol-based resin is used as a raw film for a polarizing film composed of a polyvinyl alcohol-based resin film.
- the method for forming a film of the polyvinyl alcohol-based resin is not particularly limited, and a known method is adopted.
- the thickness of the polyvinyl alcohol-based raw film is, for example, 150 ⁇ m or less, preferably 100 ⁇ m or less (for example, 50 ⁇ m or less), and 5 ⁇ m or more.
- a polarizing film composed of a polyvinyl alcohol-based resin film can be produced by a known method. Specifically, the step of uniaxially stretching the polyvinyl alcohol-based resin film; the step of adsorbing the dichroic dye by dyeing the polyvinyl alcohol-based resin film with the dichroic dye; the polyvinyl alcohol on which the dichroic dye is adsorbed. It can be produced by a method including a step of treating (cross-linking) the based resin film with an aqueous boric acid solution; and a step of washing with water after treatment with the aqueous boric acid solution.
- the thickness of the polarizer can be 40 ⁇ m or less, preferably 30 ⁇ m or less (for example, 20 ⁇ m or less, further 15 ⁇ m or less, and further 10 ⁇ m or less or 8 ⁇ m or less).
- a thin-film polarizer can be more easily produced, and the thickness of the polarizer can be increased to, for example, 20 ⁇ m or less, further 15 ⁇ m. Below, it becomes easier to make it 10 ⁇ m or less or 8 ⁇ m or less.
- the thickness of the polarizer is usually 2 ⁇ m or more.
- Reducing the thickness of the polarizer is advantageous for reducing the thickness of the optical laminate (polarizing plate) and the image display device including the optical laminate (polarizing plate).
- the thinner the polarizer the lower the optical durability tends to be.
- the curable composition of the present invention even such a thin-film polarizing plate can have good durability. ..
- the retardation film is a stretched film obtained by uniaxially stretching or biaxially stretching a translucent thermoplastic resin; a film in which a liquid crystal compound such as a discotic liquid crystal or a nematic liquid crystal is oriented and fixed; Examples thereof include those in which the above-mentioned liquid crystal layer is formed on a material film. Further, in the present specification, the zero retardation film is also included in the retardation film.
- the base film is usually a film made of a thermoplastic resin, and an example of the thermoplastic resin is a cellulosic ester-based resin such as triacetyl cellulose.
- the translucent thermoplastic resin include resins constituting the first thermoplastic resin film 10 described later.
- the zero retardation film refers to a film in which both the in-plane retardation value Re and the thickness direction retardation value Rth are -15 to 15 nm. This retardation film is suitably used for a liquid crystal display device in IPS mode.
- the in-plane retardation value Re and the thickness direction retardation value Rth are preferably ⁇ 10 to 10 nm, and more preferably both ⁇ 5 to 5 nm.
- the in-plane retardation value Re and the thickness direction retardation value Rth referred to here are values 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 (the z-axis direction perpendicular to the film surface)
- d is the film thickness.
- 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 can be used.
- a cellulosic resin, a polyolefin resin, or a (meth) acrylic resin is preferably used.
- First form a retardation film in which a rod-shaped liquid crystal compound is oriented horizontally with respect to a supporting substrate.
- Second form a retardation film in which the rod-shaped liquid crystal compound is oriented perpendicular to the supporting substrate
- Third form A retardation film in which the rod-shaped liquid crystal compound changes its orientation spirally in the plane.
- Fourth form a retardation film in which a disk-shaped liquid crystal compound is inclined or oriented
- Fifth form A biaxial retardation film in which a disk-shaped liquid crystal compound is oriented perpendicularly to a supporting substrate.
- the first form, the second form, and the fifth form are preferably used. Alternatively, these may be laminated and used.
- the retardation film When the retardation film is a layer made of a polymer in the oriented state of the polymerizable liquid crystal compound (hereinafter, may be referred to as an "opticallyotropic layer"), the retardation film may have anti-wavelength dispersibility. preferable.
- the inverse wavelength dispersibility is an optical characteristic in which the liquid crystal alignment in-plane retardation value at a short wavelength is smaller than the liquid crystal alignment in-plane retardation value at a long wavelength, and the retardation film is preferably expressed by the following formula. (1) and equation (2) are satisfied.
- Re ( ⁇ ) represents an in-plane retardation value with respect to light having a wavelength of ⁇ nm.
- the retardation film is in the first form and has anti-wavelength dispersibility, it is preferable because the coloring at the time of black display on the display device is reduced, and 0.82 ⁇ Re (450) / Re (550) in the formula (1). ) ⁇ 0.93 is more preferable. Further, 120 ⁇ Re (550) ⁇ 150 is preferable.
- the polymerizable liquid crystal compound is described in "3" of the Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editorial Committee, published on October 30, 2000 by Maruzen Co., Ltd.).
- Examples of the method for producing a retardation film from a polymer in the oriented state of a polymerizable liquid crystal compound include the method described in JP-A-2010-31223.
- the in-plane retardation value Re (550) may be adjusted in the range of 0 to 10 nm, preferably in the range of 0 to 5 nm, and the phase difference value Rth in the thickness direction is ⁇ 10 to ⁇ . It may be adjusted in the range of 300 nm, preferably in the range of ⁇ 20 to ⁇ 200 nm.
- the phase difference value Rth in the thickness direction which means the refractive index anisotropy in the thickness direction, is the phase difference value R50 and the in-plane phase difference value Re, which are measured by inclining 50 degrees with the in-plane phase advance axis as the inclination axis. Can be calculated from.
- the retardation value Rth in the thickness direction is the in-plane retardation value Re
- the thickness d of the retardation film is the retardation film.
- Rth [(n x + n y ) / 2- nz ] x d (3)
- Re (n x ⁇ n y ) ⁇ d (4)
- n y ' n y x n z / [ ny 2 x sin 2 ( ⁇ ) + n z 2 x cos 2 ( ⁇ )] 1/2
- the retardation film may be a multilayer film having two or more layers.
- a protective film is laminated on one side or both sides of a retardation film, and two or more retardation films are laminated via an adhesive or an adhesive.
- the first cured product layer 15 is a cured product layer composed of a cured product of the curable composition (S).
- the curable composition (S) is as described above.
- the curable composition (S) can be cured by heat, for example.
- Thermoplastic Resin Film The first thermoplastic resin film 10 and the second thermoplastic resin film 20 are each a translucent (preferably optically transparent) thermoplastic resin, for example, a chain polyolefin resin.
- Polypropylene-based resins such as (polypropylene-based resins, etc.), cyclic polyolefin-based resins (norbornen-based resins, etc.); Cellulosic ester-based resins such as triacetyl cellulose and diacetyl cellulose; polyester-based resins such as polyethylene terephthalate, polyethylene naphthalate, and thermoplastics.
- a film made of a resin; a polycarbonate-based resin; a (meth) acrylic-based resin; a polystyrene-based resin; or a mixture thereof, a copolymer, or the like can be used.
- the first thermoplastic resin film 10 and the second thermoplastic resin film 20 may be either an unstretched film or a uniaxially or biaxially stretched film, respectively.
- the biaxial stretching may be a simultaneous biaxial stretching that simultaneously stretches in two stretching directions, or may be a sequential biaxial stretching that stretches in a second direction different from this after stretching in the first direction.
- the first thermoplastic resin film 10 and / or the second thermoplastic resin film 20 may be a protective film that plays a role of protecting the optical layer 30, or is a protective film that also has an optical function such as a retardation film. You can also do it.
- the retardation film the description in [3] above is cited.
- chain polyolefin resin examples include homopolymers of chain olefins such as polyethylene resin and polypropylene resin, and copolymers composed of two or more kinds of chain olefins.
- the cyclic polyolefin-based resin is a general term for resins containing norbornene, tetracyclododecene (also known as dimethanooctahydronaphthalene), or a cyclic olefin typified by a derivative thereof as a polymerization unit.
- the cyclic polyolefin resin include a ring-opening (co) polymer of a cyclic olefin and a hydrogenated product thereof, an addition polymer of a cyclic olefin, a cyclic olefin and a chain olefin such as ethylene and propylene, or an aromatic compound having a vinyl group.
- Examples thereof include copolymers of the above, and modified (co) copolymers obtained by modifying these with unsaturated carboxylic acids or derivatives thereof.
- a norbornene-based resin using a norbornene-based monomer such as norbornene or a polycyclic norbornene-based monomer is preferably used as the cyclic olefin.
- the cellulose ester-based resin is a resin in which at least a part of the hydroxyl groups in cellulose is acetic acid esterified, and a mixed ester in which a part is acetic acid esterified and a part is esterified with another acid. May be good.
- the cellulosic ester resin is preferably an acetyl cellulosic resin. Examples of the acetyl cellulosic resin include triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, and cellulose acetate butyrate.
- the polyester-based resin is a resin other than the above-mentioned cellulose ester-based resin having an ester bond, and is generally composed of a polyvalent carboxylic acid or a polycondensate of a derivative thereof and a polyhydric alcohol.
- the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexanedimethylterephthalate, and polycyclohexanedimethylnaphthalate.
- polyethylene terephthalate is preferably used from the viewpoints of mechanical properties, solvent resistance, scratch resistance, cost and the like.
- Polyethylene terephthalate refers to a resin in which 80 mol% or more of the repeating unit is composed of ethylene terephthalate, and is a constituent unit derived from other copolymerization components (dicarboxylic acid component such as isophthalic acid; diol component such as propylene glycol). May include.
- the polycarbonate resin is a polyester formed from carbonic acid and glycol or bisphenol.
- aromatic polycarbonate having a diphenylalkane in the molecular chain is preferably used from the viewpoint of heat resistance, weather resistance and acid resistance.
- examples of 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, and 1, Examples thereof include polycarbonate derived from bisphenols such as 1-bis (4-hydroxyphenyl) isobutane and 1,1-bis (4-hydroxyphenyl) ethane.
- the (meth) acrylic resin is a polymer containing a structural unit derived from the (meth) acrylic monomer, and examples of the (meth) acrylic monomer include methacrylic acid ester and acrylic acid ester.
- methacrylic acid ester examples include methyl methacrylate, ethyl methacrylate, n-, i- or t-butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, and 2-hydroxyethyl methacrylate. And so on.
- acrylic acid ester examples include ethyl acrylate, n-, i- or t-butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate and the like. ..
- the (meth) acrylic resin may be a polymer consisting of only structural units derived from the (meth) acrylic monomer, or may contain other structural units.
- the (meth) acrylic resin comprises methyl methacrylate as a copolymerization component, or comprises methyl methacrylate and methyl acrylate.
- the (meth) acrylic resin can be a polymer containing a methacrylic acid ester as a main monomer (containing 50% by mass or more), and the methacrylic acid ester and other copolymerization components. Is preferably a copolymer in which is copolymerized.
- the glass transition temperature of the (meth) acrylic resin is preferably 80 ° C. or higher and 160 ° C. or lower.
- the glass transition temperature is the polymerization ratio of the methacrylic acid ester-based monomer and the acrylic acid ester-based monomer, the carbon chain length of each ester group, the type of functional group having them, and the polyfunctional monomer for the entire monomer. It can be controlled by adjusting the polymerization ratio of the monomer.
- the ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic imide structure and a lactone structure.
- a cyclic acid anhydride structure such as a glutaric anhydride structure and a succinic anhydride structure
- a cyclic imide structure such as a glutarimide structure and a succinic anhydride structure
- a lactone ring structure such as butyrolactone and valerolactone.
- the cyclic acid anhydride structure and the cyclic imide structure are introduced by copolymerizing a monomer having a cyclic structure such as maleic anhydride and maleimide; the cyclic acid anhydride structure is formed by a dehydration / demethanol condensation reaction after polymerization. Method of introduction; It can be introduced by a method of reacting an amino compound to introduce a cyclic imide structure or the like.
- a resin (polymer) having a lactone ring structure After preparing a polymer having a hydroxyl group and an ester group in a polymer chain, the hydroxyl group and the ester group in the obtained polymer are required by heating. Therefore, it can be obtained by a method of forming a lactone ring structure by cyclization condensation in the presence of a catalyst such as an organic phosphorus compound.
- the (meth) acrylic resin and the thermoplastic resin film formed from the (meth) acrylic resin may contain additives, if necessary.
- the additive include a lubricant, an antiblocking agent, a heat stabilizer, an antioxidant, an antistatic agent, a lightproofing agent, an impact resistance improving agent, a surfactant and the like. These additives can also be used when a thermoplastic resin other than the (meth) acrylic resin is used as the thermoplastic resin constituting the thermoplastic resin film.
- the (meth) acrylic resin may contain acrylic rubber particles which are impact improving agents from the viewpoint of film forming property on the film, impact resistance of the film, and the like.
- Acrylic rubber particles are particles containing an elastic polymer mainly composed of an acrylic acid ester as an essential component, and have a single-layer structure substantially consisting of only this elastic polymer, or one elastic polymer. Examples thereof include a multi-layer structure having layers.
- the elastic polymer examples include a crosslinked elastic copolymer containing alkyl acrylate as a main component and copolymerizing another copolymerizable vinyl-based monomer and a crosslinkable monomer.
- alkyl acrylate examples include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like, which have an alkyl group having 1 or more and 8 or less carbon atoms.
- An alkyl acrylate having an alkyl group having 4 or more carbon atoms is preferably used.
- Examples of the other vinyl-based monomer copolymerizable with the alkyl acrylate include a compound having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methyl methacrylate.
- Methacrylic acid esters such as, aromatic vinyl compounds such as styrene; vinyl cyan compounds such as 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 and butane.
- examples thereof include (meth) acrylates of polyhydric alcohols such as diol di (meth) acrylate; alkenyl esters of (meth) acrylic acid such as allyl (meth) acrylate; and divinylbenzene.
- a laminate of a film made of a (meth) acrylic resin containing no rubber particles and a film made of a (meth) acrylic resin containing rubber particles is used as a thermoplastic resin film to be bonded to the optical layer 30.
- a (meth) acrylic resin layer is formed on one side or both sides of a retardation-developing layer made of a resin different from the (meth) acrylic resin, and the one in which the retardation is expressed is bonded to the optical layer 30. It can also be a thermoplastic resin film.
- the first thermoplastic resin film 10 and the second thermoplastic resin film 20 are each one or more thermoplastics selected from the group consisting of a cellulose ester resin, a polyester resin, a (meth) acrylic resin, and a cyclic polyolefin resin.
- a film containing a resin is preferable, and a cellulose ester-based resin film, a polyester-based resin film, a (meth) acrylic-based resin film, or a cyclic polyolefin-based resin film is more preferable.
- the first thermoplastic resin film 10 and / or the second thermoplastic resin film 20 contains an ultraviolet absorber, an infrared absorber, an organic dye, a pigment, an inorganic dye, an antioxidant, an antistatic agent, a surfactant, a lubricant, and the like. It may contain a dispersant, a heat stabilizer and the like.
- a thermoplastic resin film containing an ultraviolet absorber is placed on the visual side of an image display element (for example, a liquid crystal cell or an organic EL display element) to display the image. Deterioration due to ultraviolet rays can be suppressed.
- the ultraviolet absorber include salicylic acid ester compounds, benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, nickel complex salt compounds and the like.
- the first thermoplastic resin film 10 and the second thermoplastic resin film 20 may be films made of the same thermoplastic resin, or may be films made of different thermoplastic resins.
- the first thermoplastic resin film 10 and the second thermoplastic resin film 20 may be the same or different in terms of thickness, presence / absence of additives, their types, retardation characteristics, and the like.
- the first thermoplastic resin film 10 and / or the second thermoplastic resin film 20 has a hard coat layer, an antiglare layer, an antireflection layer, a light diffusion layer, and an antistatic layer on its outer surface (the surface opposite to the optical layer 30).
- a surface treatment layer (coating layer) such as an antifouling layer, an antifouling layer, and a conductive layer may be provided.
- the thickness of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 is usually 5 ⁇ m or more and 200 ⁇ m or less, preferably 10 ⁇ m or more and 120 ⁇ m or less, more preferably 10 ⁇ m or more and 85 ⁇ m or less, and further preferably 15 ⁇ m or more and 65 ⁇ m or less. Is.
- the thickness of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 may be 50 ⁇ m or less, or 40 ⁇ m or less, respectively. Reducing the thickness of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 is advantageous for reducing the thickness of the optical laminate (polarizing plate) and the image display device including the optical laminate (polarizing plate).
- thermoplastic resin film 10 and the second thermoplastic resin film 20 On the surface to which the curable composition of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 is applied, from the viewpoint of improving adhesion, surfaces such as saponification treatment, plasma treatment, corona treatment, and primer treatment are performed.
- the modification treatment may be performed, or the surface modification treatment may not be performed from the viewpoint of simplifying the process.
- the surface modification treatment may be performed on the bonding surface of the optical layer 30 instead of the bonding surface of the thermoplastic resin film or together with the bonding surface.
- the saponification treatment include a method of immersing in an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide.
- the curable composition forming the second cured layer 25 may be the above-mentioned curable composition (S), or may be another curable composition different from this. There may be.
- the second cured product layer 25 is preferably a cured product layer of the curable composition (S) from the viewpoint of optical durability of the optical laminate in a high temperature and high humidity environment.
- these curable compositions may have the same composition or different compositions. You may.
- curable compositions include known water-based compositions (including water-based adhesives) in which a curable resin component is dissolved or dispersed in water, and known active energy rays containing an active energy ray-curable compound. Examples thereof include a curable composition (including an active energy ray-curable adhesive) and the like.
- the resin component contained in the aqueous composition examples include polyvinyl alcohol-based resin and urethane resin.
- the aqueous composition containing a polyvinyl alcohol-based resin is a curable component such as a polyhydric aldehyde, a melamine-based compound, a zirconia compound, a zinc compound, glyoxal, a glyoxal derivative, and a water-soluble epoxy resin in order to improve adhesion and adhesiveness.
- a cross-linking agent can be further contained.
- the aqueous composition containing the urethane resin include an aqueous composition containing a polyester ionomer type urethane resin and a compound having a glycidyloxy group.
- the polyester-based ionomer type urethane resin is a urethane resin having a polyester skeleton, in which a small amount of an ionic component (hydrophilic component) is introduced.
- the active energy ray-curable composition is a composition that is cured by irradiation with active energy rays such as ultraviolet rays, visible light, electron beams, and X-rays.
- active energy rays such as ultraviolet rays, visible light, electron beams, and X-rays.
- the second cured product layer 25 is a cured product layer of the composition.
- the active energy ray-curable composition can be a composition containing an epoxy compound that is cured by cationic polymerization as a curable component, and preferably an ultraviolet curable composition containing such an epoxy compound as a curable component. It is a thing.
- the epoxy-based compound means a compound having an average of 1 or more, preferably 2 or more epoxy groups in the molecule. Only one type of epoxy compound may be used, or two or more types may be used in combination.
- a hydride epoxy compound (having an alicyclic ring) obtained by reacting epichlorohydrin with an alicyclic polyol obtained by hydrogenating the aromatic ring of an aromatic polyol.
- Polyglycidyl ether of polyol an aliphatic epoxy compound such as an aliphatic polyhydric alcohol or a polyglycidyl ether of an alkylene oxide adduct thereof; an epoxy compound having one or more epoxy groups bonded to an alicyclic ring in the molecule. Examples thereof include certain alicyclic epoxy compounds.
- the active energy ray-curable composition can contain, as a curable component, a (meth) acrylic compound which is radically polymerizable in place of or together with the epoxy compound.
- the (meth) acrylic compound is a (meth) acrylate monomer having one or more (meth) acryloyloxy groups in the molecule; obtained by reacting two or more kinds of functional group-containing compounds, and at least two in the molecule. Examples thereof include (meth) acryloyloxy group-containing compounds such as (meth) acrylate oligomers having a (meth) acryloyloxy group.
- the active energy ray-curable composition contains an epoxy-based compound that is cured by cationic polymerization as a curable component, it preferably contains a photocationic polymerization initiator.
- the photocationic polymerization initiator include aromatic diazonium salts; onium salts such as aromatic iodonium salts and aromatic sulfonium salts; and iron-allene complexes.
- the active energy ray-curable composition contains a radically polymerizable component such as a (meth) acrylic compound, it preferably contains a photoradical polymerization initiator.
- photoradical polymerization initiator examples include an acetophenone-based initiator, a benzophenone-based initiator, a benzoin ether-based initiator, a thioxanthone-based initiator, xanthone, fluorenone, camphorquinone, benzaldehyde, anthraquinone and the like.
- the optical laminate may include an adhesive layer instead of the second cured product layer 25. That is, the second thermoplastic resin film 20 may be attached to the optical layer 30 via the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer the description of the pressure-sensitive adhesive layer described later is cited.
- the optical laminate having the configuration shown in FIG. 2 is obtained by laminating and adhering the first thermoplastic resin film 10 to one surface of the optical layer 30 via the first cured product layer 15. It can be obtained, and by further laminating and adhering the second thermoplastic resin film 20 to the other surface of the optical layer 30 via the second cured product layer 25, an optical laminate having the configuration shown in FIG. 3 can be obtained. Can be done. When producing an optical laminate having both the first thermoplastic resin film 10 and the second thermoplastic resin film 20, these films may be laminated and bonded one side at a time step by step, or the films on both sides may be laminated and bonded at the same time. It may be laminated and bonded.
- the curable composition (S) As a method of adhering the optical layer 30 and the first thermoplastic resin film 10 to one or both of the bonding surfaces of the optical layer 30 and the first thermoplastic resin film 10, the curable composition (S) is applied. Examples thereof include a method of coating, laminating the other laminating surface on the laminating surface, and pressing from above and below using a laminating roll or the like for laminating.
- various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used. Further, even in a method in which the optical layer 30 and the first thermoplastic resin film 10 are continuously supplied so that the bonding surfaces of both are on the inside, and the curable composition (S) is cast between them. Good.
- a heat treatment is performed on the laminate containing the optical layer 30, the first cured product layer 15, and the first thermoplastic resin film 10.
- the temperature of the heat treatment is, for example, 40 ° C. or higher and 100 ° C. or lower, preferably 50 ° C. or higher and 90 ° C. or lower.
- the solvent contained in the curable composition layer can be removed by heat treatment.
- the heat treatment can allow the curing / crosslinking reaction of the curable composition to proceed.
- the above bonding method can also be applied to bonding the optical layer 30 and the second thermoplastic resin film 20.
- the curable composition layer is dried as necessary and then irradiated with active energy rays to form the curable composition. Harden the material layer.
- the light source used for irradiating the active energy beam may be any light source capable of generating ultraviolet rays, electron beams, X-rays and the like.
- low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, and the like having an emission distribution having a wavelength of 400 nm or less are preferably used.
- an optical laminate having no first thermoplastic resin film on the first cured product layer 15 was obtained by coating the surface of the optical layer 30 with the curable composition (S).
- the laminate can be produced, for example, by subjecting the laminate to heat treatment at 80 ° C. for 300 seconds with a hot air dryer. Further, the optical laminate shown in FIG. 1 is also produced by producing a laminate composed of a separate film / curable composition (S) / optical layer 30, peeling off the separate film, and then performing heat treatment. be able to.
- the thickness of the first cured product layer 15 and the second cured product layer 25 formed from the curable composition (S) is, for example, 1 nm or more and 20 ⁇ m or less, preferably 5 nm or more and 10 ⁇ m or less, and more preferably 10 nm or more. It is 5 ⁇ m or less, more preferably 20 nm or more and 2 ⁇ m or less.
- the cured product layer formed from the above-mentioned known aqueous composition can also have the same thickness.
- the thickness of the cured product layer formed from the active energy ray-curable composition is, for example, 10 nm or more and 20 ⁇ m or less, preferably 100 nm or more and 10 ⁇ m or less, and more preferably 500 nm or more and 5 ⁇ m or less.
- the first cured product layer 15 and the second cured product layer 25 may have the same thickness or may be different in thickness.
- the optical laminate has optical functionality other than the optical layer 30 (for example, a polarizer) for imparting a desired optical function.
- a film can be provided, a preferred example thereof being a retardation film.
- the first thermoplastic resin film 10 and / or the second thermoplastic resin film 20 can also serve as a retardation film, but a retardation film can also be laminated separately from these films.
- the retardation film is the first thermoplastic resin film 10, the second thermoplastic resin film 20, the first cured product layer 15 and / or the second cured product layer 25 via the adhesive layer and the adhesive layer.
- the retardation film the description in [3] above is cited.
- optical functional films optical members
- optical laminate such as a polarizing plate
- examples of other optical functional films (optical members) that can be included in an optical laminate such as a polarizing plate include a condenser plate, a brightness improving film, a reflective layer (reflective film), a semi-transmissive reflective layer (semi-transmissive reflective film), A light diffusing layer (light diffusing film) or the like.
- the condensing plate is used for the purpose of controlling the optical path, and can be a prism array sheet, a lens array sheet, a sheet with dots, or the like.
- the brightness improving film is used for the purpose of improving the brightness in an image display device to which an optical laminate such as a polarizing plate is applied.
- a reflective polarizing separation sheet designed to generate anisotropy in reflectance by laminating a plurality of thin films having different refractive index anisotropy, an alignment film of cholesteric liquid crystal polymer, and its orientation. Examples thereof include a circularly polarized light separation sheet in which a liquid crystal layer is supported on a base film.
- the reflective layer, the semi-transmissive reflective layer, and the light diffusing layer are provided to make the polarizing plate a reflective, semi-transmissive, and diffuse optical member, respectively.
- the reflective polarizing plate is used in a liquid crystal display device of a type that reflects and displays incident light from the viewing side, and since a light source such as a backlight can be omitted, the liquid crystal display device can be easily made thinner.
- the transflective polarizing plate is used in a liquid crystal display device of a type that displays light from a backlight in a dark place as a reflective type in a bright place.
- the diffusion type polarizing plate is used for a liquid crystal display device that imparts light diffusivity and suppresses display defects such as moire.
- the reflective layer, the transflective reflective layer and the light diffusing layer can be formed by a known method.
- the optical laminate can include an adhesive layer.
- the pressure-sensitive adhesive layer include a pressure-sensitive adhesive layer for bonding an optical laminate to an image display element such as a liquid crystal cell or an organic EL display element, or another optical member.
- the pressure-sensitive adhesive layer is the outer surface of the optical layer 30 in the optical laminate having the configuration shown in FIGS. 1 and 2, and the first thermoplastic resin film 10 or the second thermoplastic in the optical laminate having the configuration shown in FIG.
- FIG. 6 shows an example in which the pressure-sensitive adhesive layer 40 is laminated on the outer surface of the second thermoplastic resin film 20 of the optical laminate having the configuration shown in FIG.
- a (meth) acrylic resin, a silicone-based resin, a polyester-based resin, a polyurethane-based resin, a polyether-based resin, or the like as a base polymer can be used.
- a (meth) acrylic pressure-sensitive adhesive is preferable from the viewpoints of transparency, adhesive strength, reliability, weather resistance, heat resistance, reworkability and the like.
- the (meth) acrylic pressure-sensitive adhesive includes a (meth) acrylic acid alkyl ester having an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group, an n-, i- or t-butyl group, and (meth).
- a (meth) acrylic resin having a value of 100,000 or more is useful as a base polymer.
- the pressure-sensitive adhesive composition is dissolved or dispersed in an organic solvent such as toluene or ethyl acetate to prepare a pressure-sensitive adhesive liquid, which is directly applied to the target surface of the optical laminate.
- an organic solvent such as toluene or ethyl acetate
- a method of forming an adhesive layer by coating, a method of forming an adhesive layer in a sheet shape on a separate film that has been subjected to a mold release treatment, and a method of transferring it to a target surface of an optical laminate, etc. Can be done by
- the thickness of the pressure-sensitive adhesive layer is determined according to the adhesive strength and the like, but a range of 1 ⁇ m or more and 50 ⁇ m or less is appropriate, and preferably 2 ⁇ m or more and 40 ⁇ m or less.
- the optical laminate may include the above separate film.
- the separate film can be a film made of a polyethylene resin such as polyethylene, a polypropylene resin such as polypropylene, a polyester resin such as polyethylene terephthalate, or the like. Of these, a polyethylene terephthalate stretched film is preferable.
- the pressure-sensitive adhesive layer contains, if necessary, a filler made of glass fiber, glass beads, resin beads, metal powder or other inorganic powder, a pigment, a colorant, an antioxidant, an ultraviolet absorber, an antistatic agent and the like. be able to.
- Protect film The surface of the optical laminate (typically, the first thermoplastic resin film 10, the second thermoplastic resin film 20, the first cured product layer 15 and / or the second cured product layer) A protective film for protecting the surface of 25) can be included. After the optical laminate is attached to, for example, an image display element or another optical member, the protective film is peeled off and removed together with the adhesive layer contained therein.
- the protective film is composed of, for example, a base film and an adhesive layer laminated on the base film.
- the above description is cited for the pressure-sensitive adhesive layer.
- the resin constituting the base film is, for example, a polyethylene resin such as polyethylene, a polypropylene resin such as polypropylene, a polyester resin such as polyethylene terephthalate or polyethylene naphthalate, or a thermoplastic resin such as a polycarbonate resin. be able to.
- a polyester resin such as polyethylene terephthalate is preferable.
- the optical laminate according to the present invention can be applied to an image display device such as a liquid crystal display device or an organic electroluminescence (EL) display device.
- the image display device includes an optical laminate and an image display element.
- the image display element include a liquid crystal cell and an organic EL display element.
- these image display elements conventionally known ones can be used.
- the optical laminate which is a polarizing plate When the optical laminate which is a polarizing plate is applied to a liquid crystal display device, the optical laminate may be arranged on the backlight side (back side) of the liquid crystal cell, or may be arranged on the visual side. It may be placed in both of them.
- the optical laminate, which is a polarizing plate is applied to an organic EL display device, the optical laminate is usually arranged on the visual side of the organic EL display element.
- a polarizer having a thickness of 23 ⁇ m in which iodine was adsorbed and oriented on a polyvinyl alcohol film.
- the stretching was mainly carried out in the steps of iodine staining and boric acid treatment, and the total stretching ratio was 5.5 times.
- curable composition (adhesive aqueous solution) was prepared by mixing the components shown in Table 1 with pure water as an aqueous solvent in the blending amount shown in Table 1.
- the unit of the blending amount of each component shown in Table 1 is a mass part, and the blending amount of each component is the amount in terms of solid content.
- the concentration of the aqueous resin (A) in the obtained curable composition was 5.0% by mass.
- a triacetyl cellulose (TAC) film [trade name "KC4UAW” manufactured by Konica Minolta Opto Co., Ltd., thickness: 40 ⁇ m] is saponified on one side and then on the saponified surface.
- the curable composition prepared in (1) above is coated with a bar coater, and a zero retardation film made of a cyclic polyolefin resin [trade name "ZEONOR” manufactured by Nippon Zeon Co., Ltd., thickness: 23 ⁇ m] is used.
- One surface was corona-treated, and the curable composition prepared in (1) above was coated on the corona-treated surface using a bar coater.
- a saponified TAC film is laminated on one surface of the polarizer and a corona-treated zero retardation film is laminated on the other surface so that the curable composition layer is on the polarizer side, so that the zero retardation is achieved.
- a laminate having a layer structure of a film / curable composition layer / polarizer / curable composition layer / TAC film was obtained.
- a polarizing plate having a layer structure of zero retardation film / cured product layer / polarizer / cured product layer / TAC film can be obtained.
- the thickness of the cured product layer in the produced polarizing plate was 20 to 60 nm per layer.
- the layer structure of the measurement sample is a glass substrate / (meth) acrylic pressure-sensitive adhesive layer / zero retardation film / cured product layer / polarizer / cured product layer / TAC film.
- a non-alkali glass substrate [trade name "Eagle XG" manufactured by Corning Inc.] was used as the glass substrate.
- the obtained measurement sample was measured for MD transmittance and TD transmittance in the wavelength range of 380 to 780 nm using a spectrophotometer with an integrating sphere [product name "V7100" manufactured by JASCO Corporation], and each wavelength was measured.
- the degree of polarization in was calculated.
- the calculated degree of polarization is corrected for luminosity factor by the 2 degree field (C light source) of JIS Z 8701: 1999 "Color display method-XYZ color system and X10Y10Z10 color system”, and the luminosity factor is corrected before the durability test.
- the degree of polarization Py was determined.
- the measurement sample was set in a spectrophotometer with an integrating sphere so that the TAC film side of the polarizing plate was the detector side and the light entered from the glass substrate side.
- Tp ( ⁇ ) is the transmittance (%) of the measurement sample measured in relation to the linearly polarized light of the incident wavelength ⁇ (nm) and the parallel Nicol.
- Tc ( ⁇ ) is the transmittance (%) of the measurement sample measured in relation to the linearly polarized light of the incident wavelength ⁇ (nm) and the cross Nicol.
- this measurement sample was placed in a high temperature and high humidity environment with a temperature of 85 ° C. and a relative humidity of 85% RH for 500 hours, and then subjected to a durability test in which the measurement sample was placed in an environment with a temperature of 23 ° C. and a relative humidity of 50% RH for 24 hours. ..
- the luminosity factor correction polarization degree Py was determined by the same method as before the durability test.
- ) of the difference between the luminosity factor correction polarization Py after the durability test and the luminosity factor correction polarization Py before the durability test was calculated.
- are shown in Table 1.
- the obtained polarizing plate was bonded to a glass substrate on the zero retardation film side via a (meth) acrylic pressure-sensitive adhesive to prepare a polarizing plate with a pressure-sensitive adhesive layer.
- a test piece having a width of 25 mm and a length of about 200 mm was cut from the obtained polarizing plate with an adhesive layer, and the pressure-sensitive adhesive layer surface was bonded to soda glass.
- a cutter blade is inserted between the polarizer and the TAC film, and the peeled portion is peeled 30 mm from the end in the length direction, and the peeled portion is peeled off by a universal tensile tester [“AG-1” manufactured by Shimadzu Corporation]. I grabbed it with the grip.
- test piece in this state is subjected to JIS K 6854-2: 1999 "Adhesive-Peeling Adhesive Strength Test Method-Part 2: 180 ° Peeling" in an atmosphere at a temperature of 23 ° C. and a relative humidity of 55%.
- a 180-degree peeling test was performed at a gripping movement speed of 300 mm / min, and adhesion over a length of 170 mm excluding 30 mm of the gripped portion was determined. The results are shown in Table 1.
- thermoplastic resin film 10 1st thermoplastic resin film, 15 1st cured product layer, 20 2nd thermoplastic resin film, 25 2nd cured product layer, 30 optical layer, 40 adhesive layer.
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Abstract
This curable composition includes an aqueous resin and a silane compound. The aqueous resin includes an oxazolyl group-containing polymer. This curable composition also ideally includes an acid compound and the oxazolyl group-containing polymer ideally is an oxazolyl group-containing (meth) acrylic polymer. This optical laminate includes an optical layer and a first cured product layer comprising a cured product of the curable composition.
Description
本発明は、硬化性組成物に関する。また、本発明は、この硬化性組成物の硬化物から構成される硬化物層、該硬化物層を含む光学積層体、及び、該光学積層体を含む画像表示装置に関する。
The present invention relates to a curable composition. The present invention also relates to a cured product layer composed of a cured product of the curable composition, an optical laminate containing the cured product layer, and an image display device including the optical laminate.
近年、液晶表示装置は、スマートフォンやタブレット型端末に代表されるモバイル機器用途やカーナビゲーションシステムに代表される車載用機器用途に展開されている。このような用途においては、従来の屋内用TV用途に比べて苛酷な環境にさらされる可能性があることから、装置の耐久性向上が課題となっている。
In recent years, liquid crystal display devices have been developed for mobile device applications such as smartphones and tablet terminals and in-vehicle device applications such as car navigation systems. In such an application, since there is a possibility of being exposed to a harsher environment as compared with the conventional indoor TV application, it is an issue to improve the durability of the device.
液晶表示装置等を構成する光学フィルムにおいても同様に耐久性が求められている。すなわち、液晶表示装置等に組み込まれた光学フィルムは、高温又は高温高湿環境下に置かれたり、高温と低温とが繰り返される環境下に置かれたりすることがあるが、これらの環境下においても、光学特性が劣化しないことが求められる。
Durability is also required for optical films that make up liquid crystal display devices and the like. That is, the optical film incorporated in the 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 in which high temperature and low temperature are repeated. In these environments, However, it is required that the optical characteristics do not deteriorate.
光学フィルムとしては、偏光子の片面又は両面に、接着剤を用いて保護フィルムを貼合した偏光板が挙げられる(特許文献1等)。
Examples of the optical film include a polarizing plate in which a protective film is attached to one side or both sides of a polarizing element using an adhesive (Patent Document 1 and the like).
本発明の目的は、硬化性組成物の硬化物から構成される硬化物層を含み、高温高湿環境下における光学耐久性が良好な光学積層体を与えることができる硬化性組成物を提供することにある。
本発明の他の目的は、硬化性組成物の硬化物から構成される硬化物層を含み、高温高湿環境下における光学耐久性が良好な光学積層体、及びこれを含む画像表示装置を提供することにある。 An object of the present invention is to provide a curable composition containing a cured product layer composed of a cured product of the curable composition and capable of providing an optical laminate having good optical durability in a high temperature and high humidity environment. There is.
Another object of the present invention is to provide an optical laminate containing a cured product layer composed of a cured product of a curable composition and having good optical durability in a high temperature and high humidity environment, and an image display device including the same. To do.
本発明の他の目的は、硬化性組成物の硬化物から構成される硬化物層を含み、高温高湿環境下における光学耐久性が良好な光学積層体、及びこれを含む画像表示装置を提供することにある。 An object of the present invention is to provide a curable composition containing a cured product layer composed of a cured product of the curable composition and capable of providing an optical laminate having good optical durability in a high temperature and high humidity environment. There is.
Another object of the present invention is to provide an optical laminate containing a cured product layer composed of a cured product of a curable composition and having good optical durability in a high temperature and high humidity environment, and an image display device including the same. To do.
本発明は、以下に示す硬化性組成物、硬化物層、光学積層体、及び画像表示装置を提供する。
〔1〕 水系樹脂とシラン化合物とを含み、
前記水系樹脂は、オキサゾリル基含有重合体を含む、硬化性組成物。
〔2〕 オキサゾリル基含有重合体は、オキサゾリル基含有(メタ)アクリル系重合体である、〔1〕に記載の硬化性組成物。
〔3〕 さらに、酸化合物を含む、〔1〕又は〔2〕に記載の硬化性組成物。
〔4〕 前記シラン化合物は、シラノール基を有する、〔1〕~〔3〕のいずれかに記載の硬化性組成物。
〔5〕 前記シラン化合物は、さらに、置換基を有していてもよいアミノ基、カルボキシル基、エポキシ基、アセトアセチル基、ヒドロキシアルキル基、メルカプト基、オキシアルキレン基、及びアルケニル基からなる群より選択される1以上の官能基を有する、〔4〕に記載の硬化性組成物。
〔6〕 前記シラン化合物は、さらに、置換基を有していてもよいアミノ基及びカルボキシル基のうちの少なくとも一方の官能基を有する官能基を有する、〔4〕又は〔5〕に記載の硬化性組成物。
〔7〕 前記シラン化合物は、さらにSi-O-Si結合を含み、
前記シラン化合物の構造中に前記官能基を有する、〔5〕又は〔6〕に記載の硬化性組成物。
〔8〕 〔1〕~〔7〕のいずれかに記載の硬化性組成物を硬化させてなる、硬化物層。
〔9〕 光学層及び第1硬化物層を含み、
前記第1硬化物層は、〔8〕に記載の硬化物層である、光学積層体。
〔10〕 さらに、第1熱可塑性樹脂フィルムを含み、
前記光学層、前記第1硬化物層、及び前記第1熱可塑性樹脂フィルムがこの順に積層されている、〔9〕に記載の光学積層体。
〔11〕 さらに、第2硬化物層及び第2熱可塑性樹脂フィルムを含み、
前記光学層の前記第1硬化物層側とは反対側に、前記第2硬化物層及び前記第2熱可塑性樹脂フィルムがこの順に積層されている、〔9〕又は〔10〕に記載の光学積層体。
〔12〕 前記第2硬化物層は、〔8〕に記載の硬化性組成物の硬化物である、〔11〕に記載の光学積層体。
〔13〕 〔1〕~〔13〕のいずれかに記載の光学積層体、及び、画像表示素子を含む、画像表示装置。 The present invention provides the curable composition, the cured product layer, the optical laminate, and the image display device shown below.
[1] Containing an aqueous resin and a silane compound,
The aqueous resin is a curable composition containing an oxazolyl group-containing polymer.
[2] The curable composition according to [1], wherein the oxazolyl group-containing polymer is an oxazolyl group-containing (meth) acrylic polymer.
[3] The curable composition according to [1] or [2], which further contains an acid compound.
[4] The curable composition according to any one of [1] to [3], wherein the silane compound has a silanol group.
[5] The silane compound further comprises a group consisting of an amino group, a carboxyl group, an epoxy group, an acetoacetyl group, a hydroxyalkyl group, a mercapto group, an oxyalkylene group, and an alkenyl group which may have a substituent. The curable composition according to [4], which has one or more functional groups of choice.
[6] The curing according to [4] or [5], wherein the silane compound further has a functional group having at least one functional group of an amino group and a carboxyl group which may have a substituent. Sex composition.
[7] The silane compound further contains a Si—O—Si bond and contains
The curable composition according to [5] or [6], which has the functional group in the structure of the silane compound.
[8] A cured product layer obtained by curing the curable composition according to any one of [1] to [7].
[9] Includes an optical layer and a first cured product layer
The first cured product layer is an optical laminate which is the cured product layer according to [8].
[10] Further, it contains a first thermoplastic resin film, and contains
The optical laminate according to [9], wherein the optical layer, the first cured product layer, and the first thermoplastic resin film are laminated in this order.
[11] Further, a second cured product layer and a second thermoplastic resin film are included.
The optical according to [9] or [10], wherein the second cured product layer and the second thermoplastic resin film are laminated in this order on the side of the optical layer opposite to the first cured product layer side. Laminated body.
[12] The optical laminate according to [11], wherein the second cured product layer is a cured product of the curable composition according to [8].
[13] An image display device including the optical laminate according to any one of [1] to [13] and an image display element.
〔1〕 水系樹脂とシラン化合物とを含み、
前記水系樹脂は、オキサゾリル基含有重合体を含む、硬化性組成物。
〔2〕 オキサゾリル基含有重合体は、オキサゾリル基含有(メタ)アクリル系重合体である、〔1〕に記載の硬化性組成物。
〔3〕 さらに、酸化合物を含む、〔1〕又は〔2〕に記載の硬化性組成物。
〔4〕 前記シラン化合物は、シラノール基を有する、〔1〕~〔3〕のいずれかに記載の硬化性組成物。
〔5〕 前記シラン化合物は、さらに、置換基を有していてもよいアミノ基、カルボキシル基、エポキシ基、アセトアセチル基、ヒドロキシアルキル基、メルカプト基、オキシアルキレン基、及びアルケニル基からなる群より選択される1以上の官能基を有する、〔4〕に記載の硬化性組成物。
〔6〕 前記シラン化合物は、さらに、置換基を有していてもよいアミノ基及びカルボキシル基のうちの少なくとも一方の官能基を有する官能基を有する、〔4〕又は〔5〕に記載の硬化性組成物。
〔7〕 前記シラン化合物は、さらにSi-O-Si結合を含み、
前記シラン化合物の構造中に前記官能基を有する、〔5〕又は〔6〕に記載の硬化性組成物。
〔8〕 〔1〕~〔7〕のいずれかに記載の硬化性組成物を硬化させてなる、硬化物層。
〔9〕 光学層及び第1硬化物層を含み、
前記第1硬化物層は、〔8〕に記載の硬化物層である、光学積層体。
〔10〕 さらに、第1熱可塑性樹脂フィルムを含み、
前記光学層、前記第1硬化物層、及び前記第1熱可塑性樹脂フィルムがこの順に積層されている、〔9〕に記載の光学積層体。
〔11〕 さらに、第2硬化物層及び第2熱可塑性樹脂フィルムを含み、
前記光学層の前記第1硬化物層側とは反対側に、前記第2硬化物層及び前記第2熱可塑性樹脂フィルムがこの順に積層されている、〔9〕又は〔10〕に記載の光学積層体。
〔12〕 前記第2硬化物層は、〔8〕に記載の硬化性組成物の硬化物である、〔11〕に記載の光学積層体。
〔13〕 〔1〕~〔13〕のいずれかに記載の光学積層体、及び、画像表示素子を含む、画像表示装置。 The present invention provides the curable composition, the cured product layer, the optical laminate, and the image display device shown below.
[1] Containing an aqueous resin and a silane compound,
The aqueous resin is a curable composition containing an oxazolyl group-containing polymer.
[2] The curable composition according to [1], wherein the oxazolyl group-containing polymer is an oxazolyl group-containing (meth) acrylic polymer.
[3] The curable composition according to [1] or [2], which further contains an acid compound.
[4] The curable composition according to any one of [1] to [3], wherein the silane compound has a silanol group.
[5] The silane compound further comprises a group consisting of an amino group, a carboxyl group, an epoxy group, an acetoacetyl group, a hydroxyalkyl group, a mercapto group, an oxyalkylene group, and an alkenyl group which may have a substituent. The curable composition according to [4], which has one or more functional groups of choice.
[6] The curing according to [4] or [5], wherein the silane compound further has a functional group having at least one functional group of an amino group and a carboxyl group which may have a substituent. Sex composition.
[7] The silane compound further contains a Si—O—Si bond and contains
The curable composition according to [5] or [6], which has the functional group in the structure of the silane compound.
[8] A cured product layer obtained by curing the curable composition according to any one of [1] to [7].
[9] Includes an optical layer and a first cured product layer
The first cured product layer is an optical laminate which is the cured product layer according to [8].
[10] Further, it contains a first thermoplastic resin film, and contains
The optical laminate according to [9], wherein the optical layer, the first cured product layer, and the first thermoplastic resin film are laminated in this order.
[11] Further, a second cured product layer and a second thermoplastic resin film are included.
The optical according to [9] or [10], wherein the second cured product layer and the second thermoplastic resin film are laminated in this order on the side of the optical layer opposite to the first cured product layer side. Laminated body.
[12] The optical laminate according to [11], wherein the second cured product layer is a cured product of the curable composition according to [8].
[13] An image display device including the optical laminate according to any one of [1] to [13] and an image display element.
硬化性組成物の硬化物から構成される硬化物層を含み、高温高湿環境下における光学耐久性が良好な光学積層体を与えることができる硬化性組成物を提供することができる。
硬化性組成物の硬化物から構成される硬化物層を含み、高温高湿環境下における光学耐久性が良好な光学積層体、及びこれを含む画像表示装置を提供することができる。 It is possible to provide a curable composition containing a cured product layer composed of a cured product of the curable composition and capable of providing an optical laminate having good optical durability in a high temperature and high humidity environment.
It is possible to provide an optical laminate containing a cured product layer composed of a cured product of a curable composition and having good optical durability in a high temperature and high humidity environment, and an image display device including the same.
硬化性組成物の硬化物から構成される硬化物層を含み、高温高湿環境下における光学耐久性が良好な光学積層体、及びこれを含む画像表示装置を提供することができる。 It is possible to provide a curable composition containing a cured product layer composed of a cured product of the curable composition and capable of providing an optical laminate having good optical durability in a high temperature and high humidity environment.
It is possible to provide an optical laminate containing a cured product layer composed of a cured product of a curable composition and having good optical durability in a high temperature and high humidity environment, and an image display device including the same.
<硬化性組成物>
本発明に係る硬化性組成物は、水系樹脂とシラン化合物とを含み、水系樹脂がオキサゾリル基含有重合体を含む。以下、本発明に係る硬化性組成物を「硬化性組成物(S)」、上記の水系樹脂を「水系樹脂(A)」、上記オキサゾリル基含有重合体を「オキサゾリル基含有重合体(a)」、シラノール基を有するシラン化合物を「シラン化合物(B)」ということがある。 <Curable composition>
The curable composition according to the present invention contains an aqueous resin and a silane compound, and the aqueous resin contains an oxazolyl group-containing polymer. Hereinafter, the curable composition according to the present invention is referred to as "curable composition (S)", the above-mentioned aqueous resin is referred to as "aqueous resin (A)", and the above-mentioned oxazolyl group-containing polymer is referred to as "oxazolyl group-containing polymer (a)". , The silane compound having a silanol group may be referred to as "silane compound (B)".
本発明に係る硬化性組成物は、水系樹脂とシラン化合物とを含み、水系樹脂がオキサゾリル基含有重合体を含む。以下、本発明に係る硬化性組成物を「硬化性組成物(S)」、上記の水系樹脂を「水系樹脂(A)」、上記オキサゾリル基含有重合体を「オキサゾリル基含有重合体(a)」、シラノール基を有するシラン化合物を「シラン化合物(B)」ということがある。 <Curable composition>
The curable composition according to the present invention contains an aqueous resin and a silane compound, and the aqueous resin contains an oxazolyl group-containing polymer. Hereinafter, the curable composition according to the present invention is referred to as "curable composition (S)", the above-mentioned aqueous resin is referred to as "aqueous resin (A)", and the above-mentioned oxazolyl group-containing polymer is referred to as "oxazolyl group-containing polymer (a)". , The silane compound having a silanol group may be referred to as "silane compound (B)".
硬化性組成物(S)は、基材上に塗膜(コーティング層)を形成するための塗工液として用いることができる。例えば、硬化性組成物(S)を基材上に塗工し、塗工層を硬化させることによって塗膜を形成することができる。基材は、好ましくは光学層である。光学層については後述する。この場合、光学積層体は、光学層と、硬化性組成物(S)の硬化物から構成される第1硬化物層とを含む。
The curable composition (S) can be used as a coating liquid for forming a coating film (coating layer) on the substrate. For example, a coating film can be formed by applying the curable composition (S) onto a base material and curing the coating layer. The base material is preferably an optical layer. The optical layer will be described later. In this case, the optical laminate includes an optical layer and a first cured product layer composed of a cured product of the curable composition (S).
硬化性組成物(S)は、接着剤組成物として用いることもできる。1つの実施形態において硬化性組成物(S)は、光学層と第1熱可塑性樹脂フィルムとを貼合するための接着剤組成物である。この場合、光学積層体は、光学層と、硬化性組成物(S)の硬化物から構成される第1硬化物層(接着剤層)と、第1熱可塑性樹脂フィルムとをこの順に含む。
この光学積層体は、光学層及び第1熱可塑性樹脂フィルムの少なくともいずれか一方の貼合面に硬化性組成物(S)を塗工し、塗工層を介して光学層と第1熱可塑性樹脂フィルムとを積層させて積層体を得た後、塗工層を硬化させることによって作製することができる。 The curable composition (S) can also be used as an adhesive composition. In one embodiment, the curable composition (S) is an adhesive composition for adhering the optical layer and the first thermoplastic resin film. In this case, the optical laminate includes an optical layer, a first cured product layer (adhesive layer) composed of a cured product of the curable composition (S), and a first thermoplastic resin film in this order.
In this optical laminate, the curable composition (S) is coated on at least one of the bonding surfaces of the optical layer and the first thermoplastic resin film, and the optical layer and the first thermoplastic are passed through the coating layer. It can be produced by laminating a resin film to obtain a laminated body and then curing the coating layer.
この光学積層体は、光学層及び第1熱可塑性樹脂フィルムの少なくともいずれか一方の貼合面に硬化性組成物(S)を塗工し、塗工層を介して光学層と第1熱可塑性樹脂フィルムとを積層させて積層体を得た後、塗工層を硬化させることによって作製することができる。 The curable composition (S) can also be used as an adhesive composition. In one embodiment, the curable composition (S) is an adhesive composition for adhering the optical layer and the first thermoplastic resin film. In this case, the optical laminate includes an optical layer, a first cured product layer (adhesive layer) composed of a cured product of the curable composition (S), and a first thermoplastic resin film in this order.
In this optical laminate, the curable composition (S) is coated on at least one of the bonding surfaces of the optical layer and the first thermoplastic resin film, and the optical layer and the first thermoplastic are passed through the coating layer. It can be produced by laminating a resin film to obtain a laminated body and then curing the coating layer.
硬化性組成物(S)は、水系樹脂(A)を含む水系組成物である。水系組成物とは、水を含む溶媒に配合成分を溶解させた溶液であるか、水を含む溶媒に配合成分を分散させた分散体(例えばエマルション)である。
The curable composition (S) is an aqueous composition containing the aqueous resin (A). The aqueous composition is a solution in which the compounding component is dissolved in a solvent containing water, or a dispersion (for example, an emulsion) in which the compounding component is dispersed in a solvent containing water.
硬化性組成物(S)の25℃における粘度は、50mPa・sec以下であることが好ましく、1mPa・sec以上30mPa・sec以下であることがより好ましく、2mPa・sec以上20mPa・sec以下であることがさらに好ましい。25℃における粘度が50mPa・secを超えると、均一に塗工することが難しくなって塗工ムラを生じる可能性があり、また、配管の目詰まり等の不具合が発生する可能性がある。
硬化性組成物(S)の25℃における粘度は、E型粘度計によって測定することができる。 The viscosity of the curable composition (S) at 25 ° C. is preferably 50 mPa · sec or less, more preferably 1 mPa · sec or more and 30 mPa · sec or less, and 2 mPa · sec or more and 20 mPa · sec or less. Is even more preferable. If the viscosity at 25 ° C. exceeds 50 mPa · sec, it becomes difficult to apply the coating uniformly, which may cause uneven coating, and may cause problems such as clogging of piping.
The viscosity of the curable composition (S) at 25 ° C. can be measured by an E-type viscometer.
硬化性組成物(S)の25℃における粘度は、E型粘度計によって測定することができる。 The viscosity of the curable composition (S) at 25 ° C. is preferably 50 mPa · sec or less, more preferably 1 mPa · sec or more and 30 mPa · sec or less, and 2 mPa · sec or more and 20 mPa · sec or less. Is even more preferable. If the viscosity at 25 ° C. exceeds 50 mPa · sec, it becomes difficult to apply the coating uniformly, which may cause uneven coating, and may cause problems such as clogging of piping.
The viscosity of the curable composition (S) at 25 ° C. can be measured by an E-type viscometer.
〔1〕水系樹脂(A)
水系樹脂(A)は、水系溶媒に溶解可能な水溶性の重合体、及び、水系溶媒に分散可能な水分散性の重合体のうちの少なくとも一方を含む。水溶性の重合体としては、水系溶媒に溶解可能な重合体であれば特に限定されない。また、水分散性の重合体としては、水系溶媒に分散可能な重合体であれば特に限定されない。 [1] Water-based resin (A)
The water-based resin (A) contains at least one of a water-soluble polymer soluble in an aqueous solvent and an water-dispersible polymer dispersible in an aqueous solvent. The water-soluble polymer is not particularly limited as long as it is a polymer that can be dissolved in an aqueous solvent. The water-dispersible polymer is not particularly limited as long as it is a polymer that can be dispersed in an aqueous solvent.
水系樹脂(A)は、水系溶媒に溶解可能な水溶性の重合体、及び、水系溶媒に分散可能な水分散性の重合体のうちの少なくとも一方を含む。水溶性の重合体としては、水系溶媒に溶解可能な重合体であれば特に限定されない。また、水分散性の重合体としては、水系溶媒に分散可能な重合体であれば特に限定されない。 [1] Water-based resin (A)
The water-based resin (A) contains at least one of a water-soluble polymer soluble in an aqueous solvent and an water-dispersible polymer dispersible in an aqueous solvent. The water-soluble polymer is not particularly limited as long as it is a polymer that can be dissolved in an aqueous solvent. The water-dispersible polymer is not particularly limited as long as it is a polymer that can be dispersed in an aqueous solvent.
本明細書において、水系溶媒とは、水又は水を主成分とする溶媒をいい、水を主成分とするとは、溶媒をなす成分の合計質量の50質量%以上が水であることをいう。水系溶媒のうち水以外の溶媒としては、水との共存下で容易に層分離しない溶媒であれば特に限定されないが、水に溶解する溶媒であることが好ましく、例えば、メタノールやエタノール、イソプロピルアルコール、n-プロピルアルコール等のアルコール類;アセトンやメチルエチルケトン等のケトン類;エチレングリコール、ジエチレングリコール等のグリコール類;N-メチルピロリドン(NMP)、テトラヒドロフラン、ブチルセロソルブ等のグリコールエーテル類等が挙げられる。
In the present specification, the aqueous solvent means water or a solvent containing water as a main component, and the term "water as a main component" means that 50% by mass or more of the total mass of the components constituting the solvent is water. The solvent other than water among the aqueous solvents is not particularly limited as long as it is a solvent that does not easily layer-separate in the coexistence with water, but is preferably a solvent that dissolves in water, for example, methanol, ethanol, or isopropyl alcohol. , Alcohols such as n-propyl alcohol; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and diethylene glycol; glycol ethers such as N-methylpyrrolidone (NMP), tetrahydrofuran and butyl cellosolve and the like.
水系樹脂(A)は、少なくともオキサゾリル基含有重合体(a)を含む。
水系樹脂(A)は、オキサゾリル基含有重合体(a)以外の水系溶媒に溶解可能な水溶性の重合体、及び、水系溶媒に分散可能な水分散性の重合体から選ばれる1種又は2種以上を含んでいてもよい。 The aqueous resin (A) contains at least the oxazolyl group-containing polymer (a).
The aqueous resin (A) is one or 2 selected from a water-soluble polymer soluble in an aqueous solvent other than the oxazolyl group-containing polymer (a) and an aqueous-dispersible polymer dispersible in an aqueous solvent. It may contain more than a seed.
水系樹脂(A)は、オキサゾリル基含有重合体(a)以外の水系溶媒に溶解可能な水溶性の重合体、及び、水系溶媒に分散可能な水分散性の重合体から選ばれる1種又は2種以上を含んでいてもよい。 The aqueous resin (A) contains at least the oxazolyl group-containing polymer (a).
The aqueous resin (A) is one or 2 selected from a water-soluble polymer soluble in an aqueous solvent other than the oxazolyl group-containing polymer (a) and an aqueous-dispersible polymer dispersible in an aqueous solvent. It may contain more than a seed.
硬化性組成物(S)における水系樹脂(A)の含有量は、硬化性組成物(S)の固形分濃度を100質量%とするとき、好ましくは50質量%以上95質量%以下、より好ましくは55質量%以上90質量%以下、さらに好ましくは60質量%以上85質量%以下である。水系樹脂(A)の含有量を上記の範囲内にすることは、光学積層体の高温高湿環境下における光学耐久性の向上、光学積層体における光学層と第1硬化物層との間の密着性、第1硬化物層と第1熱可塑性樹脂フィルムとの間の密着性の観点から好ましい。
固形分濃度とは、硬化性組成物(S)に含まれる溶剤以外の成分の合計濃度をいう。 The content of the aqueous resin (A) in the curable composition (S) is preferably 50% by mass or more and 95% by mass or less, more preferably, when the solid content concentration of the curable composition (S) is 100% by mass. Is 55% by mass or more and 90% by mass or less, more preferably 60% by mass or more and 85% by mass or less. Keeping the content of the aqueous resin (A) within the above range improves the optical durability of the optical laminate in a high temperature and high humidity environment, and between the optical layer and the first cured product layer in the optical laminate. It is preferable from the viewpoint of adhesion and adhesion between the first cured product layer and the first thermoplastic resin film.
The solid content concentration refers to the total concentration of components other than the solvent contained in the curable composition (S).
固形分濃度とは、硬化性組成物(S)に含まれる溶剤以外の成分の合計濃度をいう。 The content of the aqueous resin (A) in the curable composition (S) is preferably 50% by mass or more and 95% by mass or less, more preferably, when the solid content concentration of the curable composition (S) is 100% by mass. Is 55% by mass or more and 90% by mass or less, more preferably 60% by mass or more and 85% by mass or less. Keeping the content of the aqueous resin (A) within the above range improves the optical durability of the optical laminate in a high temperature and high humidity environment, and between the optical layer and the first cured product layer in the optical laminate. It is preferable from the viewpoint of adhesion and adhesion between the first cured product layer and the first thermoplastic resin film.
The solid content concentration refers to the total concentration of components other than the solvent contained in the curable composition (S).
〔1-1〕オキサゾリル基含有重合体(a)
オキサゾリル基含有重合体(a)は、水系溶媒に溶解可能な水溶性の重合体、及び、水系溶媒に分散可能な水分散性の重合体である。第1硬化物層の光学特性の観点から、オキサゾリル基含有重合体(a)は、好ましくは水溶性の重合体である。 [1-1] Oxazolyl group-containing polymer (a)
The oxazolyl group-containing polymer (a) is a water-soluble polymer that can be dissolved in an aqueous solvent and an aqueous-dispersible polymer that can be dispersed in an aqueous solvent. From the viewpoint of the optical properties of the first cured product layer, the oxazolyl group-containing polymer (a) is preferably a water-soluble polymer.
オキサゾリル基含有重合体(a)は、水系溶媒に溶解可能な水溶性の重合体、及び、水系溶媒に分散可能な水分散性の重合体である。第1硬化物層の光学特性の観点から、オキサゾリル基含有重合体(a)は、好ましくは水溶性の重合体である。 [1-1] Oxazolyl group-containing polymer (a)
The oxazolyl group-containing polymer (a) is a water-soluble polymer that can be dissolved in an aqueous solvent and an aqueous-dispersible polymer that can be dispersed in an aqueous solvent. From the viewpoint of the optical properties of the first cured product layer, the oxazolyl group-containing polymer (a) is preferably a water-soluble polymer.
オキサゾリル基含有重合体(a)は、分子内にオキサゾリル基を有する重合体であり、側鎖にオキサゾリル基を有する重合体であることが好ましい。
オキサゾリル基含有重合体(a)の骨格構造は特に制限されないが、例えば、(メタ)アクリル骨格、スチレン骨格、オレフィン骨格、エステル骨格、カーボネート骨格等から選択される1種以上の骨格からなることができる。
本明細書において「(メタ)アクリル」とは、アクリル及びメタクリルからなる群より選択される少なくとも1種を表す。「(メタ)アクリロイル」及び「(メタ)アクリレート」等の表記についても同様である。 The oxazolyl group-containing polymer (a) is a polymer having an oxazolyl group in the molecule, and is preferably a polymer having an oxazolyl group in the side chain.
The skeleton structure of the oxazolyl group-containing polymer (a) is not particularly limited, and may consist of, for example, one or more skeletons selected from (meth) acrylic skeleton, styrene skeleton, olefin skeleton, ester skeleton, carbonate skeleton and the like. it can.
As used herein, the term "(meth) acrylic" refers to at least one selected from the group consisting of acrylic and methacrylic. The same applies to the notations such as "(meth) acryloyl" and "(meth) acrylate".
オキサゾリル基含有重合体(a)の骨格構造は特に制限されないが、例えば、(メタ)アクリル骨格、スチレン骨格、オレフィン骨格、エステル骨格、カーボネート骨格等から選択される1種以上の骨格からなることができる。
本明細書において「(メタ)アクリル」とは、アクリル及びメタクリルからなる群より選択される少なくとも1種を表す。「(メタ)アクリロイル」及び「(メタ)アクリレート」等の表記についても同様である。 The oxazolyl group-containing polymer (a) is a polymer having an oxazolyl group in the molecule, and is preferably a polymer having an oxazolyl group in the side chain.
The skeleton structure of the oxazolyl group-containing polymer (a) is not particularly limited, and may consist of, for example, one or more skeletons selected from (meth) acrylic skeleton, styrene skeleton, olefin skeleton, ester skeleton, carbonate skeleton and the like. it can.
As used herein, the term "(meth) acrylic" refers to at least one selected from the group consisting of acrylic and methacrylic. The same applies to the notations such as "(meth) acryloyl" and "(meth) acrylate".
オキサゾリル基含有重合体(a)は、上記骨格構造の側鎖にオキサゾリル基を有することができる。
オキサゾリル基含有重合体(a)は、側鎖にオキサゾリル基を有する構成単位(オキサゾリル基含有モノマー由来の構成単位)と、オキサゾリル基を有しない構成単位とを含むものであってよい。
オキサゾリル基含有重合体(a)の好ましい一例は、構成単位の主成分として(メタ)アクリル骨格からなる骨格構造を含み、共重合成分として側鎖にオキサゾリル基を有する構成単位(オキサゾリル基含有モノマー由来の構成単位)を導入したオキサゾリル基含有(メタ)アクリル系重合体である。
オキサゾリル基含有重合体(a)としては、オキサゾリル基含有モノマーを共重合したもののほか、重合体の側鎖官能基を変性することでオキサゾリル基を含有させたものであってもよい。 The oxazolyl group-containing polymer (a) can have an oxazolyl group in the side chain of the skeletal structure.
The oxazolyl group-containing polymer (a) may contain a structural unit having an oxazolyl group in the side chain (a structural unit derived from an oxazolyl group-containing monomer) and a structural unit having no oxazolyl group.
A preferable example of the oxazolyl group-containing polymer (a) is a structural unit (derived from an oxazolyl group-containing monomer) having a skeleton structure composed of a (meth) acrylic skeleton as the main component of the structural unit and having an oxazolyl group in the side chain as a copolymerization component. It is an oxazolyl group-containing (meth) acrylic polymer into which the constituent unit of the above is introduced.
The oxazolyl group-containing polymer (a) may be a copolymer of an oxazolyl group-containing monomer or a polymer containing an oxazolyl group by modifying the side chain functional group of the polymer.
オキサゾリル基含有重合体(a)は、側鎖にオキサゾリル基を有する構成単位(オキサゾリル基含有モノマー由来の構成単位)と、オキサゾリル基を有しない構成単位とを含むものであってよい。
オキサゾリル基含有重合体(a)の好ましい一例は、構成単位の主成分として(メタ)アクリル骨格からなる骨格構造を含み、共重合成分として側鎖にオキサゾリル基を有する構成単位(オキサゾリル基含有モノマー由来の構成単位)を導入したオキサゾリル基含有(メタ)アクリル系重合体である。
オキサゾリル基含有重合体(a)としては、オキサゾリル基含有モノマーを共重合したもののほか、重合体の側鎖官能基を変性することでオキサゾリル基を含有させたものであってもよい。 The oxazolyl group-containing polymer (a) can have an oxazolyl group in the side chain of the skeletal structure.
The oxazolyl group-containing polymer (a) may contain a structural unit having an oxazolyl group in the side chain (a structural unit derived from an oxazolyl group-containing monomer) and a structural unit having no oxazolyl group.
A preferable example of the oxazolyl group-containing polymer (a) is a structural unit (derived from an oxazolyl group-containing monomer) having a skeleton structure composed of a (meth) acrylic skeleton as the main component of the structural unit and having an oxazolyl group in the side chain as a copolymerization component. It is an oxazolyl group-containing (meth) acrylic polymer into which the constituent unit of the above is introduced.
The oxazolyl group-containing polymer (a) may be a copolymer of an oxazolyl group-containing monomer or a polymer containing an oxazolyl group by modifying the side chain functional group of the polymer.
オキサゾリル基としては、例えば、2-オキサゾリル基、3-オキサゾリル基、4-オキサゾリル基等が挙げられる。オキサゾリル基は、好ましくは2-オキサゾリル基等である。
上記オキサゾリル基含有モノマーとしては、2-イソプロぺニル-2-オキサゾリン、ビニル-2-オキサゾリン等が挙げられる。 Examples of the oxazolyl group include a 2-oxazolyl group, a 3-oxazolyl group, a 4-oxazolyl group and the like. The oxazolyl group is preferably a 2-oxazolyl group or the like.
Examples of the oxazoline group-containing monomer include 2-isopropenyl-2-oxazoline and vinyl-2-oxazoline.
上記オキサゾリル基含有モノマーとしては、2-イソプロぺニル-2-オキサゾリン、ビニル-2-オキサゾリン等が挙げられる。 Examples of the oxazolyl group include a 2-oxazolyl group, a 3-oxazolyl group, a 4-oxazolyl group and the like. The oxazolyl group is preferably a 2-oxazolyl group or the like.
Examples of the oxazoline group-containing monomer include 2-isopropenyl-2-oxazoline and vinyl-2-oxazoline.
オキサゾリル基含有重合体(a)の重量平均分子量は、好ましくは5000以上であり、より好ましくは10000以上である。重量平均分子量が上記範囲であることは、光学積層体の高温高湿環境下における光学耐久性の向上、光学積層体における光学層と第1硬化物層との間の密着性、第1硬化物層と第1熱可塑性樹脂フィルムとの間の密着性の観点から有利となり得る。
オキサゾリル基含有重合体(a)の重量平均分子量は、通常1000000以下である。
オキサゾリル基含有重合体(a)の重量平均分子量は、ゲルパーミエーションクロマトグラフィ(GPC)による標準ポリスチレン換算値として測定することができる。 The weight average molecular weight of the oxazolyl group-containing polymer (a) is preferably 5,000 or more, and more preferably 10,000 or more. The fact that the weight average molecular weight is in the above range means that the optical durability of the optical laminate in a high temperature and high humidity environment is improved, the adhesion between the optical layer and the first cured product layer in the optical laminate, and the first cured product. It can be advantageous from the viewpoint of adhesion between the layer and the first thermoplastic resin film.
The weight average molecular weight of the oxazolyl group-containing polymer (a) is usually 1,000,000 or less.
The weight average molecular weight of the oxazolyl group-containing polymer (a) can be measured as a standard polystyrene-equivalent value by gel permeation chromatography (GPC).
オキサゾリル基含有重合体(a)の重量平均分子量は、通常1000000以下である。
オキサゾリル基含有重合体(a)の重量平均分子量は、ゲルパーミエーションクロマトグラフィ(GPC)による標準ポリスチレン換算値として測定することができる。 The weight average molecular weight of the oxazolyl group-containing polymer (a) is preferably 5,000 or more, and more preferably 10,000 or more. The fact that the weight average molecular weight is in the above range means that the optical durability of the optical laminate in a high temperature and high humidity environment is improved, the adhesion between the optical layer and the first cured product layer in the optical laminate, and the first cured product. It can be advantageous from the viewpoint of adhesion between the layer and the first thermoplastic resin film.
The weight average molecular weight of the oxazolyl group-containing polymer (a) is usually 1,000,000 or less.
The weight average molecular weight of the oxazolyl group-containing polymer (a) can be measured as a standard polystyrene-equivalent value by gel permeation chromatography (GPC).
オキサゾリル基含有重合体(a)のオキサゾリル基量(オキサゾリル基含有重合体(a)の固形分1gあたりのオキサゾリル基のモル数)は、好ましくは0.4mmol/g・solid以上である。オキサゾリル基量が上記の範囲より小さいと、光学積層体の高温高湿環境下における光学耐久性に不利となり得る。該観点から、オキサゾリル基含有重合体のオキサゾリル基量は、より好ましくは3mmol/g・solid以上、さらに好ましくは5mmol/g・solid以上9mmol/g・solid以下である。
オキサゾリル基量の上限は特に制限されないが、通常は50mmol/g・solid以下である。 The amount of oxazolyl groups (the number of moles of oxazolyl groups per 1 g of solid content of the oxazolyl group-containing polymer (a)) of the oxazolyl group-containing polymer (a) is preferably 0.4 mmol / g · solid or more. If the amount of oxazolyl groups is smaller than the above range, the optical durability of the optical laminate in a high temperature and high humidity environment may be disadvantageous. From this point of view, the amount of oxazolyl groups in the oxazolyl group-containing polymer is more preferably 3 mmol / g · solid or more, still more preferably 5 mmol / g · solid or more and 9 mmol / g · solid or less.
The upper limit of the amount of oxazolyl group is not particularly limited, but is usually 50 mmol / g · solid or less.
オキサゾリル基量の上限は特に制限されないが、通常は50mmol/g・solid以下である。 The amount of oxazolyl groups (the number of moles of oxazolyl groups per 1 g of solid content of the oxazolyl group-containing polymer (a)) of the oxazolyl group-containing polymer (a) is preferably 0.4 mmol / g · solid or more. If the amount of oxazolyl groups is smaller than the above range, the optical durability of the optical laminate in a high temperature and high humidity environment may be disadvantageous. From this point of view, the amount of oxazolyl groups in the oxazolyl group-containing polymer is more preferably 3 mmol / g · solid or more, still more preferably 5 mmol / g · solid or more and 9 mmol / g · solid or less.
The upper limit of the amount of oxazolyl group is not particularly limited, but is usually 50 mmol / g · solid or less.
オキサゾリル基含有重合体(a)として、市販品を用いてもよい。具体的には、株式会社日本触媒製 エポクロスWS-300、エポクロスWS-500、エポクロスWS-700(いずれも商品名)等のオキサゾリル基含有アクリルポリマー;株式会社日本触媒製 エポクロスK-1000シリーズ、エポクロスK-2000シリーズ、エポクロスRPSシリーズ(いずれも商品名)等のオキサゾリル基含有アクリル/スチレンポリマーが挙げられる。
オキサゾリル基含有重合体(a)は、2種以上を併用して使用することができる。
光学積層体の高温高湿環境下における光学耐久性や光学特性、光学積層体における光学層と第1硬化物層との間の密着性、第1硬化物層と第1熱可塑性樹脂フィルムとの間の密着性、並びに第1硬化物層の耐水性の観点から、オキサゾリル基含有重合体(a)は、エポクロスWS-300、エポクロスWS-500、エポクロスWS-700等のオキサゾリル基含有アクリルポリマーであることが好ましい。 A commercially available product may be used as the oxazolyl group-containing polymer (a). Specifically, oxazolyl group-containing acrylic polymers such as Epocross WS-300, Epocross WS-500, and Epocross WS-700 (all trade names) manufactured by Nippon Shokubai Co., Ltd .; Epocross K-1000 series and Epocross manufactured by Nippon Shokubai Co., Ltd. Examples thereof include oxazolyl group-containing acrylic / styrene polymers such as K-2000 series and Epocross RPS series (both are trade names).
The oxazolyl group-containing polymer (a) can be used in combination of two or more.
Optical durability and optical characteristics of the optical laminate in a high temperature and high humidity environment, adhesion between the optical layer and the first cured product layer in the optical laminate, and the first cured product layer and the first thermoplastic resin film. From the viewpoint of the adhesion between the layers and the water resistance of the first cured product layer, the oxazolyl group-containing polymer (a) is an oxazolyl group-containing acrylic polymer such as Epocross WS-300, Epocross WS-500, and Epocross WS-700. It is preferable to have.
オキサゾリル基含有重合体(a)は、2種以上を併用して使用することができる。
光学積層体の高温高湿環境下における光学耐久性や光学特性、光学積層体における光学層と第1硬化物層との間の密着性、第1硬化物層と第1熱可塑性樹脂フィルムとの間の密着性、並びに第1硬化物層の耐水性の観点から、オキサゾリル基含有重合体(a)は、エポクロスWS-300、エポクロスWS-500、エポクロスWS-700等のオキサゾリル基含有アクリルポリマーであることが好ましい。 A commercially available product may be used as the oxazolyl group-containing polymer (a). Specifically, oxazolyl group-containing acrylic polymers such as Epocross WS-300, Epocross WS-500, and Epocross WS-700 (all trade names) manufactured by Nippon Shokubai Co., Ltd .; Epocross K-1000 series and Epocross manufactured by Nippon Shokubai Co., Ltd. Examples thereof include oxazolyl group-containing acrylic / styrene polymers such as K-2000 series and Epocross RPS series (both are trade names).
The oxazolyl group-containing polymer (a) can be used in combination of two or more.
Optical durability and optical characteristics of the optical laminate in a high temperature and high humidity environment, adhesion between the optical layer and the first cured product layer in the optical laminate, and the first cured product layer and the first thermoplastic resin film. From the viewpoint of the adhesion between the layers and the water resistance of the first cured product layer, the oxazolyl group-containing polymer (a) is an oxazolyl group-containing acrylic polymer such as Epocross WS-300, Epocross WS-500, and Epocross WS-700. It is preferable to have.
オキサゾリル基含有重合体(a)の含有量は、水系樹脂(A)の合計量を100質量%とするとき、好ましくは50質量%以上であり、より好ましくは60質量%以上であり、さらに好ましくは70質量%以上であり、100質量%であってもよく、通常100質量%以下であり、99質量%以下であってもよく、95質量%以下であってもよい。オキサゾリル基含有重合体(a)の含有量を上記の範囲内にすることは、光学積層体の高温高湿環境下における光学耐久性の向上、光学積層体における光学層と第1硬化物層との間の密着性、第1硬化物層と第1熱可塑性樹脂フィルムとの間の密着性の観点から好ましい。
The content of the oxazolyl group-containing polymer (a) is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably, when the total amount of the aqueous resin (A) is 100% by mass. Is 70% by mass or more, may be 100% by mass, is usually 100% by mass or less, may be 99% by mass or less, or may be 95% by mass or less. Keeping the content of the oxazolyl group-containing polymer (a) within the above range improves the optical durability of the optical laminate in a high temperature and high humidity environment, and the optical layer and the first cured product layer in the optical laminate. It is preferable from the viewpoint of the adhesion between the first cured product layer and the first thermoplastic resin film.
〔1-2〕その他の水系樹脂
水系樹脂(A)は、オキサゾリル基含有重合体(a)以外の、水系溶媒に溶解可能な水溶性の重合体及び水系溶媒に分散可能な水分散性の重合体(以下、これらをまとめて「その他の水系重合体」ということがある。)を含んでいてもよい。
その他の水系重合体としては、例えば、(メタ)アクリル系重合体;ポリビニルアルコール系重合体;ポリビニルアセタール系重合体;エチレン-ビニルアルコール共重合体;ポリビニルピロリドン系重合体;ポリアミドアミン系重合体;エポキシ系重合体;メラミン系重合体;ユリア系重合体;ポリアミド系重合体;ポリエステル系重合体;ポリウレタン系重合体;メチルセルロース、ヒドロエチルセルロース、カルボキシメチルセルロース等のセルロース系重合体;アルギン酸ナトリウム、デンプン等の多糖類等が挙げられる。 [1-2] Other water-based resins The water-based resin (A) is a water-soluble polymer soluble in an aqueous solvent other than the oxazolyl group-containing polymer (a) and a water-dispersible weight dispersible in an aqueous solvent. It may contain a coalescence (hereinafter, these may be collectively referred to as "other aqueous polymers").
Examples of other aqueous polymers include (meth) acrylic polymers; polyvinyl alcohol-based polymers; polyvinyl acetal-based polymers; ethylene-vinyl alcohol copolymers; polyvinylpyrrolidone-based polymers; polyamide-amine-based polymers; Epoxy-based polymer; Melamine-based polymer; Uria-based polymer; Polyamide-based polymer; Polyester-based polymer; Polyurethane-based polymer; Cellulous polymer such as methyl cellulose, hydroethyl cellulose, carboxymethyl cellulose; Sodium alginate, starch, etc. Examples include polymers.
水系樹脂(A)は、オキサゾリル基含有重合体(a)以外の、水系溶媒に溶解可能な水溶性の重合体及び水系溶媒に分散可能な水分散性の重合体(以下、これらをまとめて「その他の水系重合体」ということがある。)を含んでいてもよい。
その他の水系重合体としては、例えば、(メタ)アクリル系重合体;ポリビニルアルコール系重合体;ポリビニルアセタール系重合体;エチレン-ビニルアルコール共重合体;ポリビニルピロリドン系重合体;ポリアミドアミン系重合体;エポキシ系重合体;メラミン系重合体;ユリア系重合体;ポリアミド系重合体;ポリエステル系重合体;ポリウレタン系重合体;メチルセルロース、ヒドロエチルセルロース、カルボキシメチルセルロース等のセルロース系重合体;アルギン酸ナトリウム、デンプン等の多糖類等が挙げられる。 [1-2] Other water-based resins The water-based resin (A) is a water-soluble polymer soluble in an aqueous solvent other than the oxazolyl group-containing polymer (a) and a water-dispersible weight dispersible in an aqueous solvent. It may contain a coalescence (hereinafter, these may be collectively referred to as "other aqueous polymers").
Examples of other aqueous polymers include (meth) acrylic polymers; polyvinyl alcohol-based polymers; polyvinyl acetal-based polymers; ethylene-vinyl alcohol copolymers; polyvinylpyrrolidone-based polymers; polyamide-amine-based polymers; Epoxy-based polymer; Melamine-based polymer; Uria-based polymer; Polyamide-based polymer; Polyester-based polymer; Polyurethane-based polymer; Cellulous polymer such as methyl cellulose, hydroethyl cellulose, carboxymethyl cellulose; Sodium alginate, starch, etc. Examples include polymers.
その他の水系重合体の含有量は、水系樹脂(A)の合計量を100質量%とするとき、好ましくは50質量%以下であり、より好ましくは40質量%以下であり、さらに好ましくは30質量%以下であり、20質量%以下であってもよく、10質量%以下であってもよい。
The content of the other aqueous polymer is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass, when the total amount of the aqueous resin (A) is 100% by mass. % Or less, 20% by mass or less, or 10% by mass or less.
〔2〕シラン化合物(B)
シラン化合物(B)は、ケイ素原子に任意の官能基が結合した化合物であることが好ましい。このような官能基としては、例えば、アルコキシ基等の加水分解性基、ビニル基、アミノ基、エポキシ基、ハロアルキル基、(メタ)アクロイル基、メルカプト基等の反応性官能基を有する有機基等を挙げることができる。
シラン化合物(B)は、1種又は2種以上を組み合わせて用いることができる。
硬化性組成物(S)にシラン化合物(B)を添加することにより、光学積層体の高温高湿環境下における光学耐久性を向上することができる。 [2] Silane compound (B)
The silane compound (B) is preferably a compound in which an arbitrary functional group is bonded to a silicon atom. Examples of such a functional group include a hydrolyzable group such as an alkoxy group, an organic group having a reactive functional group such as a vinyl group, an amino group, an epoxy group, a haloalkyl group, a (meth) acroyl group and a mercapto group. Can be mentioned.
The silane compound (B) can be used alone or in combination of two or more.
By adding the silane compound (B) to the curable composition (S), the optical durability of the optical laminate in a high temperature and high humidity environment can be improved.
シラン化合物(B)は、ケイ素原子に任意の官能基が結合した化合物であることが好ましい。このような官能基としては、例えば、アルコキシ基等の加水分解性基、ビニル基、アミノ基、エポキシ基、ハロアルキル基、(メタ)アクロイル基、メルカプト基等の反応性官能基を有する有機基等を挙げることができる。
シラン化合物(B)は、1種又は2種以上を組み合わせて用いることができる。
硬化性組成物(S)にシラン化合物(B)を添加することにより、光学積層体の高温高湿環境下における光学耐久性を向上することができる。 [2] Silane compound (B)
The silane compound (B) is preferably a compound in which an arbitrary functional group is bonded to a silicon atom. Examples of such a functional group include a hydrolyzable group such as an alkoxy group, an organic group having a reactive functional group such as a vinyl group, an amino group, an epoxy group, a haloalkyl group, a (meth) acroyl group and a mercapto group. Can be mentioned.
The silane compound (B) can be used alone or in combination of two or more.
By adding the silane compound (B) to the curable composition (S), the optical durability of the optical laminate in a high temperature and high humidity environment can be improved.
シラン化合物(B)としては、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、N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、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メチルジメトキシシラン、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、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ジメトキシメチルシラン、3-グリシドキシプロピルエトキシジメチルシラン等が挙げられる。
Examples of the silane compound (B) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2). -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glysidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropylethoxydimethylsilane and the like can be mentioned.
シラン化合物(B)は、シリコーンオリゴマータイプのものであってもよい。シリコーンオリゴマーを(単量体)オリゴマーの形式で示すと、例えば、次のようなものを挙げることができる。
The silane compound (B) may be of the silicone oligomer type. When the silicone oligomer is shown in the form of a (monomer) oligomer, for example, the following can be mentioned.
3-メルカプトプロピルトリメトキシシラン-テトラメトキシシランコポリマー、
3-メルカプトプロピルトリメトキシシラン-テトラエトキシシランコポリマー、
3-メルカプトプロピルトリエトキシシラン-テトラメトキシシランコポリマー、
3-メルカプトプロピルトリエトキシシラン-テトラエトキシシランコポリマー
等のメルカプトプロピル基含有のコポリマー;
メルカプトメチルトリメトキシシラン-テトラメトキシシランコポリマー、
メルカプトメチルトリメトキシシラン-テトラエトキシシランコポリマー、
メルカプトメチルトリエトキシシラン-テトラメトキシシランコポリマー、
メルカプトメチルトリエトキシシラン-テトラエトキシシランコポリマー
等のメルカプトメチル基含有のコポリマー;
3-グリジドキシプロピルトリメトキシシラン-テトラメトキシシランコポリマー、
3-グリジドキシプロピルトリメトキシシラン-テトラエトキシシランコポリマー、
3-グリジドキシプロピルトリエトキシシラン-テトラメトキシシランコポリマー、
3-グリジドキシプロピルトリエトキシシラン-テトラエトキシシランコポリマー、
3-グリジドキシプロピルメチルジメトキシシラン-テトラメトキシシランコポリマー、
3-グリジドキシプロピルメチルジメトキシシラン-テトラエトキシシランコポリマー、
3-グリジドキシプロピルメチルジエトキシシラン-テトラメトキシシランコポリマー、
3-グリジドキシプロピルメチルジエトキシシラン-テトラエトキシシランコポリマー等の3-グリジドキシプロピル基含有のコポリマー;
3-メタクリロイルオキシプロピルトリメトキシシラン-テトラメトキシシランコポリマー、
3-メタクリロイルオキシプロピルトリメトキシシラン-テトラエトキシシランコポリマー、
3-メタクリロイルオキシプロピルトリエトキシシラン-テトラメトキシシランコポリマー、
3-メタクリロイルオキシプロピルトリエトキシシラン-テトラエトキシシランコポリマー、 3-メタクリロイルオキシプロピルメチルジメトキシシラン-テトラメトキシシランコポリマー、
3-メタクリロイルオキシプロピルメチルジメトキシシラン-テトラエトキシシランコポリマー、
3-メタクリロイルオキシプロピルメチルジエトキシシラン-テトラメトキシシランコポリマー、
3-メタクリロイルオキシプロピルメチルジエトキシシラン-テトラエトキシシランコポリマー
等のメタクリロイルオキシプロピル基含有のコポリマー;
3-アクリロイルオキシプロピルトリメトキシシラン-テトラメトキシシランコポリマー、
3-アクリロイルオキシプロピルトリメトキシシラン-テトラエトキシシランコポリマー、
3-アクリロイルオキシプロピルトリエトキシシラン-テトラメトキシシランコポリマー、
3-アクリロイルオキシプロピルトリエトキシシラン-テトラエトキシシランコポリマー、
3-アクリロイルオキシプロピルメチルジメトキシシラン-テトラメトキシシランコポリマー、
3-アクリロイルオキシプロピルメチルジメトキシシラン-テトラエトキシシランコポリマー、
3-アクリロイルオキシプロピルメチルジエトキシシラン-テトラメトキシシランコポリマー、
3-アクリロイルオキシプロピルメチルジエトキシシラン-テトラエトキシシランコポリマー
等のアクリロイルオキシプロピル基含有のコポリマー;
ビニルトリメトキシシラン-テトラメトキシシランコポリマー、
ビニルトリメトキシシラン-テトラエトキシシランコポリマー、
ビニルトリエトキシシラン-テトラメトキシシランコポリマー、
ビニルトリエトキシシラン-テトラエトキシシランコポリマー、
ビニルメチルジメトキシシラン-テトラメトキシシランコポリマー、
ビニルメチルジメトキシシラン-テトラエトキシシランコポリマー、
ビニルメチルジエトキシシラン-テトラメトキシシランコポリマー、
ビニルメチルジエトキシシラン-テトラエトキシシランコポリマー
等のビニル基含有のコポリマー;
3-アミノプロピルトリメトキシシラン-テトラメトキシシランコポリマー、
3-アミノプロピルトリメトキシシラン-テトラエトキシシランコポリマー、
3-アミノプロピルトリエトキシシラン-テトラメトキシシランコポリマー、
3-アミノプロピルトリエトキシシラン-テトラエトキシシランコポリマー、
3-アミノプロピルメチルジメトキシシラン-テトラメトキシシランコポリマー、
3-アミノプロピルメチルジメトキシシラン-テトラエトキシシランコポリマー、
3-アミノプロピルメチルジエトキシシラン-テトラメトキシシランコポリマー、
3-アミノプロピルメチルジエトキシシラン-テトラエトキシシランコポリマー
等のアミノ基含有のコポリマー等。 3-Mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer,
3-Mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer,
3-Mercaptopropyltriethoxysilane-tetramethoxysilane copolymer,
A mercaptopropyl group-containing copolymer such as 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer;
Mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer,
Mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer,
Mercaptomethyltriethoxysilane-tetramethoxysilane copolymer,
Mercaptomethyl group-containing copolymers such as mercaptomethyltriethoxysilane-tetraethoxysilane copolymer;
3-Glydoxypropyltrimethoxysilane-tetramethoxysilane copolymer,
3-Glydoxypropyltrimethoxysilane-tetraethoxysilane copolymer,
3-Glydoxypropyltriethoxysilane-tetramethoxysilane copolymer,
3-Glydoxypropyltriethoxysilane-tetraethoxysilane copolymer,
3-Glydoxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,
3-Glydoxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,
3-Glydoxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,
3-Glydoxypropyl group-containing copolymers such as 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymer;
3-Methoxyloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer,
3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer,
3-methacryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer,
3-Methacloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,
3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,
3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,
3-Methacloyloxypropyl methyldiethoxysilane-tetraethoxysilane copolymer or other copolymer containing a methacryloyloxypropyl group;
3-Acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer,
3-Acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer,
3-Acryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer,
3-Acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer,
3-Acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,
3-Acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,
3-Acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,
Acryloyloxypropyl group-containing copolymers such as 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer;
Vinyl Trimethoxysilane-Tetramethoxysilane Copolymer,
Vinyl Trimethoxysilane-Tetraethoxysilane Copolymer,
Vinyltriethoxysilane-tetramethoxysilane copolymer,
Vinyltriethoxysilane-tetraethoxysilane copolymer,
Vinylmethyldimethoxysilane-tetramethoxysilane copolymer,
Vinylmethyldimethoxysilane-tetraethoxysilane copolymer,
Vinyl methyldiethoxysilane-tetramethoxysilane copolymer,
Vinyl group-containing copolymers such as vinylmethyldiethoxysilane-tetraethoxysilane copolymer;
3-Aminopropyltrimethoxysilane-tetramethoxysilane copolymer,
3-Aminopropyltrimethoxysilane-tetraethoxysilane copolymer,
3-Aminopropyltriethoxysilane-tetramethoxysilane copolymer,
3-Aminopropyltriethoxysilane-tetraethoxysilane copolymer,
3-Aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer,
3-Aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer,
3-Aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer,
Amino group-containing copolymers such as 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer.
3-メルカプトプロピルトリメトキシシラン-テトラエトキシシランコポリマー、
3-メルカプトプロピルトリエトキシシラン-テトラメトキシシランコポリマー、
3-メルカプトプロピルトリエトキシシラン-テトラエトキシシランコポリマー
等のメルカプトプロピル基含有のコポリマー;
メルカプトメチルトリメトキシシラン-テトラメトキシシランコポリマー、
メルカプトメチルトリメトキシシラン-テトラエトキシシランコポリマー、
メルカプトメチルトリエトキシシラン-テトラメトキシシランコポリマー、
メルカプトメチルトリエトキシシラン-テトラエトキシシランコポリマー
等のメルカプトメチル基含有のコポリマー;
3-グリジドキシプロピルトリメトキシシラン-テトラメトキシシランコポリマー、
3-グリジドキシプロピルトリメトキシシラン-テトラエトキシシランコポリマー、
3-グリジドキシプロピルトリエトキシシラン-テトラメトキシシランコポリマー、
3-グリジドキシプロピルトリエトキシシラン-テトラエトキシシランコポリマー、
3-グリジドキシプロピルメチルジメトキシシラン-テトラメトキシシランコポリマー、
3-グリジドキシプロピルメチルジメトキシシラン-テトラエトキシシランコポリマー、
3-グリジドキシプロピルメチルジエトキシシラン-テトラメトキシシランコポリマー、
3-グリジドキシプロピルメチルジエトキシシラン-テトラエトキシシランコポリマー等の3-グリジドキシプロピル基含有のコポリマー;
3-メタクリロイルオキシプロピルトリメトキシシラン-テトラメトキシシランコポリマー、
3-メタクリロイルオキシプロピルトリメトキシシラン-テトラエトキシシランコポリマー、
3-メタクリロイルオキシプロピルトリエトキシシラン-テトラメトキシシランコポリマー、
3-メタクリロイルオキシプロピルトリエトキシシラン-テトラエトキシシランコポリマー、 3-メタクリロイルオキシプロピルメチルジメトキシシラン-テトラメトキシシランコポリマー、
3-メタクリロイルオキシプロピルメチルジメトキシシラン-テトラエトキシシランコポリマー、
3-メタクリロイルオキシプロピルメチルジエトキシシラン-テトラメトキシシランコポリマー、
3-メタクリロイルオキシプロピルメチルジエトキシシラン-テトラエトキシシランコポリマー
等のメタクリロイルオキシプロピル基含有のコポリマー;
3-アクリロイルオキシプロピルトリメトキシシラン-テトラメトキシシランコポリマー、
3-アクリロイルオキシプロピルトリメトキシシラン-テトラエトキシシランコポリマー、
3-アクリロイルオキシプロピルトリエトキシシラン-テトラメトキシシランコポリマー、
3-アクリロイルオキシプロピルトリエトキシシラン-テトラエトキシシランコポリマー、
3-アクリロイルオキシプロピルメチルジメトキシシラン-テトラメトキシシランコポリマー、
3-アクリロイルオキシプロピルメチルジメトキシシラン-テトラエトキシシランコポリマー、
3-アクリロイルオキシプロピルメチルジエトキシシラン-テトラメトキシシランコポリマー、
3-アクリロイルオキシプロピルメチルジエトキシシラン-テトラエトキシシランコポリマー
等のアクリロイルオキシプロピル基含有のコポリマー;
ビニルトリメトキシシラン-テトラメトキシシランコポリマー、
ビニルトリメトキシシラン-テトラエトキシシランコポリマー、
ビニルトリエトキシシラン-テトラメトキシシランコポリマー、
ビニルトリエトキシシラン-テトラエトキシシランコポリマー、
ビニルメチルジメトキシシラン-テトラメトキシシランコポリマー、
ビニルメチルジメトキシシラン-テトラエトキシシランコポリマー、
ビニルメチルジエトキシシラン-テトラメトキシシランコポリマー、
ビニルメチルジエトキシシラン-テトラエトキシシランコポリマー
等のビニル基含有のコポリマー;
3-アミノプロピルトリメトキシシラン-テトラメトキシシランコポリマー、
3-アミノプロピルトリメトキシシラン-テトラエトキシシランコポリマー、
3-アミノプロピルトリエトキシシラン-テトラメトキシシランコポリマー、
3-アミノプロピルトリエトキシシラン-テトラエトキシシランコポリマー、
3-アミノプロピルメチルジメトキシシラン-テトラメトキシシランコポリマー、
3-アミノプロピルメチルジメトキシシラン-テトラエトキシシランコポリマー、
3-アミノプロピルメチルジエトキシシラン-テトラメトキシシランコポリマー、
3-アミノプロピルメチルジエトキシシラン-テトラエトキシシランコポリマー
等のアミノ基含有のコポリマー等。 3-Mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer,
3-Mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer,
3-Mercaptopropyltriethoxysilane-tetramethoxysilane copolymer,
A mercaptopropyl group-containing copolymer such as 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer;
Mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer,
Mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer,
Mercaptomethyltriethoxysilane-tetramethoxysilane copolymer,
Mercaptomethyl group-containing copolymers such as mercaptomethyltriethoxysilane-tetraethoxysilane copolymer;
3-Glydoxypropyltrimethoxysilane-tetramethoxysilane copolymer,
3-Glydoxypropyltrimethoxysilane-tetraethoxysilane copolymer,
3-Glydoxypropyltriethoxysilane-tetramethoxysilane copolymer,
3-Glydoxypropyltriethoxysilane-tetraethoxysilane copolymer,
3-Glydoxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,
3-Glydoxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,
3-Glydoxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,
3-Glydoxypropyl group-containing copolymers such as 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymer;
3-Methoxyloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer,
3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer,
3-methacryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer,
3-Methacloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,
3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,
3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,
3-Methacloyloxypropyl methyldiethoxysilane-tetraethoxysilane copolymer or other copolymer containing a methacryloyloxypropyl group;
3-Acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer,
3-Acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer,
3-Acryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer,
3-Acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer,
3-Acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,
3-Acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,
3-Acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,
Acryloyloxypropyl group-containing copolymers such as 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer;
Vinyl Trimethoxysilane-Tetramethoxysilane Copolymer,
Vinyl Trimethoxysilane-Tetraethoxysilane Copolymer,
Vinyltriethoxysilane-tetramethoxysilane copolymer,
Vinyltriethoxysilane-tetraethoxysilane copolymer,
Vinylmethyldimethoxysilane-tetramethoxysilane copolymer,
Vinylmethyldimethoxysilane-tetraethoxysilane copolymer,
Vinyl methyldiethoxysilane-tetramethoxysilane copolymer,
Vinyl group-containing copolymers such as vinylmethyldiethoxysilane-tetraethoxysilane copolymer;
3-Aminopropyltrimethoxysilane-tetramethoxysilane copolymer,
3-Aminopropyltrimethoxysilane-tetraethoxysilane copolymer,
3-Aminopropyltriethoxysilane-tetramethoxysilane copolymer,
3-Aminopropyltriethoxysilane-tetraethoxysilane copolymer,
3-Aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer,
3-Aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer,
3-Aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer,
Amino group-containing copolymers such as 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer.
シラン化合物(B)は、シラノール基(-SiOH)を有する化合物であることが好ましい。
シラノール基を有するシラン化合物(B)は、シラノール基を有するものであれば特に限定されない。シラノール基を有する単量体であってもよい。また、シラノール基が縮合反応等により2量体や3量体を形成したもの、3次元ネットワーク構造を形成したものであっても、該形成体がシラノール基を有するものであれば、シラノール基を有するシラン化合物(B)に含むことができる。 The silane compound (B) is preferably a compound having a silanol group (-SiOH).
The silane compound (B) having a silanol group is not particularly limited as long as it has a silanol group. It may be a monomer having a silanol group. Further, even if a silanol group forms a dimer or a trimer by a condensation reaction or the like or a three-dimensional network structure is formed, if the formed body has a silanol group, a silanol group can be used. It can be included in the silane compound (B) having.
シラノール基を有するシラン化合物(B)は、シラノール基を有するものであれば特に限定されない。シラノール基を有する単量体であってもよい。また、シラノール基が縮合反応等により2量体や3量体を形成したもの、3次元ネットワーク構造を形成したものであっても、該形成体がシラノール基を有するものであれば、シラノール基を有するシラン化合物(B)に含むことができる。 The silane compound (B) is preferably a compound having a silanol group (-SiOH).
The silane compound (B) having a silanol group is not particularly limited as long as it has a silanol group. It may be a monomer having a silanol group. Further, even if a silanol group forms a dimer or a trimer by a condensation reaction or the like or a three-dimensional network structure is formed, if the formed body has a silanol group, a silanol group can be used. It can be included in the silane compound (B) having.
シラン化合物(B)は、シラノール基に加えて、置換基を有していてもよいアミノ基、カルボキシル基、エポキシ基、アセトアセチル基、ヒドロキシアルキル基、メルカプト基、オキシアルキレン基、及びアルケニル基からなる群より選択される1以上の官能基を有することが好ましい。このうち、シラン化合物(B)は、シラノール基に加えて、置換基を有していてもよいアミノ基及びカルボキシル基のうちの少なくとも一方の官能基を有することがより好ましく、カルボキシル基を有することがさらに好ましい。
置換基を有していてもよいアミノ基としては、置換基を有していないアミノ基(-NH2)、1つ又は2つの水素原子がアルキル基で置換されたアルキルアミノ基、1つ又は2つの水素原子がヒドロキシアルキル基で置換された(ヒドロキシアルキル)アミノ基(例えば、-N(CH2HC(OH)CH2OH2)2)、アミノアルキルアミノ基(-NHC2H4NH2)等を挙げることができる。
上記官能基としては、具体的には、-NH2、-NHC2H4NH2、-COOH、-CH(OH)CH2OH、-N(CH2HC(OH)CH2OH2)2、-CHCH2、-SH等を挙げることができる。 The silane compound (B) is composed of an amino group, a carboxyl group, an epoxy group, an acetoacetyl group, a hydroxyalkyl group, a mercapto group, an oxyalkylene group, and an alkenyl group which may have a substituent in addition to the silanol group. It is preferable to have one or more functional groups selected from the group. Of these, the silane compound (B) more preferably has a functional group of at least one of an amino group and a carboxyl group which may have a substituent in addition to the silanol group, and has a carboxyl group. Is even more preferable.
Amino groups that may have a substituent include an amino group that does not have a substituent (-NH 2 ), an alkylamino group in which one or two hydrogen atoms are substituted with an alkyl group, one or one. A (hydroxyalkyl) amino group in which two hydrogen atoms are substituted with a hydroxyalkyl group (for example, -N (CH 2 HC (OH) CH 2 OH 2 ) 2 ), an aminoalkyl amino group (-NHC 2 H 4 NH 2). ) Etc. can be mentioned.
Specific examples of the functional groups include -NH 2 , -NHC 2 H 4 NH 2 , -COOH, -CH (OH) CH 2 OH, and -N (CH 2 HC (OH) CH 2 OH 2 ) 2. , -CHCH 2 , -SH and the like.
置換基を有していてもよいアミノ基としては、置換基を有していないアミノ基(-NH2)、1つ又は2つの水素原子がアルキル基で置換されたアルキルアミノ基、1つ又は2つの水素原子がヒドロキシアルキル基で置換された(ヒドロキシアルキル)アミノ基(例えば、-N(CH2HC(OH)CH2OH2)2)、アミノアルキルアミノ基(-NHC2H4NH2)等を挙げることができる。
上記官能基としては、具体的には、-NH2、-NHC2H4NH2、-COOH、-CH(OH)CH2OH、-N(CH2HC(OH)CH2OH2)2、-CHCH2、-SH等を挙げることができる。 The silane compound (B) is composed of an amino group, a carboxyl group, an epoxy group, an acetoacetyl group, a hydroxyalkyl group, a mercapto group, an oxyalkylene group, and an alkenyl group which may have a substituent in addition to the silanol group. It is preferable to have one or more functional groups selected from the group. Of these, the silane compound (B) more preferably has a functional group of at least one of an amino group and a carboxyl group which may have a substituent in addition to the silanol group, and has a carboxyl group. Is even more preferable.
Amino groups that may have a substituent include an amino group that does not have a substituent (-NH 2 ), an alkylamino group in which one or two hydrogen atoms are substituted with an alkyl group, one or one. A (hydroxyalkyl) amino group in which two hydrogen atoms are substituted with a hydroxyalkyl group (for example, -N (CH 2 HC (OH) CH 2 OH 2 ) 2 ), an aminoalkyl amino group (-NHC 2 H 4 NH 2). ) Etc. can be mentioned.
Specific examples of the functional groups include -NH 2 , -NHC 2 H 4 NH 2 , -COOH, -CH (OH) CH 2 OH, and -N (CH 2 HC (OH) CH 2 OH 2 ) 2. , -CHCH 2 , -SH and the like.
シラン化合物(B)が上記官能基を2以上有する場合、官能基は互いに同じであってもよく、互いに異なっていてもよい。
シラノール基を有するシラン化合物(B)が有していてもよい上記の官能基は、オキサゾリル基含有重合体(a)のオキサゾリル基と反応することができる。シラン化合物(B)が上記の官能基を有することにより、シラン化合物(B)とオキサゾリル基含有重合体(a)とが反応することができるため、光学積層体の高温高湿環境下における光学耐久性や、光学積層体における光学層と第1硬化物層との間の密着性、第1硬化物層と第1熱可塑性樹脂フィルムとの間の密着性を向上させやすい。 When the silane compound (B) has two or more of the above functional groups, the functional groups may be the same or different from each other.
The above-mentioned functional group which the silane compound (B) having a silanol group may have can react with the oxazolyl group of the oxazolyl group-containing polymer (a). Since the silane compound (B) has the above functional groups, the silane compound (B) and the oxazolyl group-containing polymer (a) can react with each other. Therefore, the optical durability of the optical laminate in a high temperature and high humidity environment It is easy to improve the properties, the adhesion between the optical layer and the first cured product layer in the optical laminate, and the adhesion between the first cured product layer and the first thermoplastic resin film.
シラノール基を有するシラン化合物(B)が有していてもよい上記の官能基は、オキサゾリル基含有重合体(a)のオキサゾリル基と反応することができる。シラン化合物(B)が上記の官能基を有することにより、シラン化合物(B)とオキサゾリル基含有重合体(a)とが反応することができるため、光学積層体の高温高湿環境下における光学耐久性や、光学積層体における光学層と第1硬化物層との間の密着性、第1硬化物層と第1熱可塑性樹脂フィルムとの間の密着性を向上させやすい。 When the silane compound (B) has two or more of the above functional groups, the functional groups may be the same or different from each other.
The above-mentioned functional group which the silane compound (B) having a silanol group may have can react with the oxazolyl group of the oxazolyl group-containing polymer (a). Since the silane compound (B) has the above functional groups, the silane compound (B) and the oxazolyl group-containing polymer (a) can react with each other. Therefore, the optical durability of the optical laminate in a high temperature and high humidity environment It is easy to improve the properties, the adhesion between the optical layer and the first cured product layer in the optical laminate, and the adhesion between the first cured product layer and the first thermoplastic resin film.
シラン化合物(B)は、シラノール基及び上記した官能基に加えて、Si-O-Si結合を含むことが好ましい。シラノール基及び上記した官能基は、Si-O-Si結合を含むシラン化合物(B)の構造中であればどこに有していてもよいが、Si-O-Si結合を含むシラン化合物(B)の末端に、上記した官能基を有することが好ましい。
The silane compound (B) preferably contains a Si—O—Si bond in addition to the silanol group and the above-mentioned functional group. The silanol group and the above-mentioned functional group may be present anywhere in the structure of the silane compound (B) containing a Si—O—Si bond, but the silane compound (B) containing a Si—O—Si bond). It is preferable to have the above-mentioned functional group at the end of.
シラン化合物(B)の含有量は、光学積層体の高温高湿環境下における光学耐久性を高める観点から、水系樹脂(A)100質量部に対して、通常0.01質量部以上であり、0.1質量部以上であることが好ましく、1質量部以上であることがより好ましく、また、通常60質量部以下であり、45質量部以下であることが好ましく、30質量部以下であることがより好ましい。
硬化性組成物(S)におけるシラン化合物(B)の含有量を上記の範囲とすることにより、高温高湿環境下における光学積層体の光学耐久性を向上させつつ、光学積層体における光学層と第1硬化物層との間、及び、第1硬化物層と第1熱可塑性樹脂フィルムとの間で、良好な密着性を得ることができる。
シラン化合物(B)の含有量が過度に少ないと、高温高湿環境下における光学積層体の光学耐久性が得られにくい。また、シラン化合物(B)の含有量が過度に多いと、高温高湿環境下における光学積層体の光学耐久性が低下しやすい傾向にある。 The content of the silane compound (B) is usually 0.01 part by mass or more with respect to 100 parts by mass of the aqueous resin (A) from the viewpoint of enhancing the optical durability of the optical laminate in a high temperature and high humidity environment. It is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and usually 60 parts by mass or less, preferably 45 parts by mass or less, and 30 parts by mass or less. Is more preferable.
By setting the content of the silane compound (B) in the curable composition (S) within the above range, the optical durability of the optical laminate in a high temperature and high humidity environment is improved, and the optical layer in the optical laminate is used. Good adhesion can be obtained between the first cured product layer and between the first cured product layer and the first thermoplastic resin film.
If the content of the silane compound (B) is excessively small, it is difficult to obtain the optical durability of the optical laminate in a high temperature and high humidity environment. Further, if the content of the silane compound (B) is excessively large, the optical durability of the optical laminate in a high temperature and high humidity environment tends to decrease.
硬化性組成物(S)におけるシラン化合物(B)の含有量を上記の範囲とすることにより、高温高湿環境下における光学積層体の光学耐久性を向上させつつ、光学積層体における光学層と第1硬化物層との間、及び、第1硬化物層と第1熱可塑性樹脂フィルムとの間で、良好な密着性を得ることができる。
シラン化合物(B)の含有量が過度に少ないと、高温高湿環境下における光学積層体の光学耐久性が得られにくい。また、シラン化合物(B)の含有量が過度に多いと、高温高湿環境下における光学積層体の光学耐久性が低下しやすい傾向にある。 The content of the silane compound (B) is usually 0.01 part by mass or more with respect to 100 parts by mass of the aqueous resin (A) from the viewpoint of enhancing the optical durability of the optical laminate in a high temperature and high humidity environment. It is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and usually 60 parts by mass or less, preferably 45 parts by mass or less, and 30 parts by mass or less. Is more preferable.
By setting the content of the silane compound (B) in the curable composition (S) within the above range, the optical durability of the optical laminate in a high temperature and high humidity environment is improved, and the optical layer in the optical laminate is used. Good adhesion can be obtained between the first cured product layer and between the first cured product layer and the first thermoplastic resin film.
If the content of the silane compound (B) is excessively small, it is difficult to obtain the optical durability of the optical laminate in a high temperature and high humidity environment. Further, if the content of the silane compound (B) is excessively large, the optical durability of the optical laminate in a high temperature and high humidity environment tends to decrease.
〔3〕酸化合物(C)
酸化合物(C)は、オキサゾリル基含有重合体(a)のオキサゾリル基と、シラン化合物(B)が有する官能基、特に上記した反応性官能基との反応を促進させることができる。ここでいう促進には、該反応を開始させる場合も含まれる。 [3] Acid compound (C)
The acid compound (C) can promote the reaction between the oxazolyl group of the oxazolyl group-containing polymer (a) and the functional group of the silane compound (B), particularly the above-mentioned reactive functional group. The promotion referred to here includes the case of initiating the reaction.
酸化合物(C)は、オキサゾリル基含有重合体(a)のオキサゾリル基と、シラン化合物(B)が有する官能基、特に上記した反応性官能基との反応を促進させることができる。ここでいう促進には、該反応を開始させる場合も含まれる。 [3] Acid compound (C)
The acid compound (C) can promote the reaction between the oxazolyl group of the oxazolyl group-containing polymer (a) and the functional group of the silane compound (B), particularly the above-mentioned reactive functional group. The promotion referred to here includes the case of initiating the reaction.
シラン化合物(B)がシラノール基に加えて、置換基を有していてもよいアミノ基、カルボキシル基、エポキシ基、アセトアセチル基、ヒドロキシアルキル基、メルカプト基、オキシアルキレン基、及びアルケニル基からなる群より選択される1以上の官能基を有する場合、酸化合物(C)は、この官能基とオキサゾリル基含有重合体(a)のオキサゾリル基との反応を促進させることができる。酸化合物(C)は、オキサゾリル基含有重合体(a)のオキサゾリル基と、シラン化合物(B)の上記した官能基との反応の触媒として機能する化合物であってもよい。
The silane compound (B) consists of an amino group, a carboxyl group, an epoxy group, an acetoacetyl group, a hydroxyalkyl group, a mercapto group, an oxyalkylene group, and an alkenyl group which may have a substituent in addition to the silanol group. When having one or more functional groups selected from the group, the acid compound (C) can accelerate the reaction between this functional group and the oxazolyl group of the oxazolyl group-containing polymer (a). The acid compound (C) may be a compound that functions as a catalyst for the reaction between the oxazolyl group of the oxazolyl group-containing polymer (a) and the above-mentioned functional group of the silane compound (B).
酸化合物(C)としては、硫酸、塩化水素、硝酸、リン酸、亜リン酸、ホウ酸等の無機酸;p-トルエンスルホン酸、ドデシルベンゼンスルホン酸、ナフタレンスルホン酸、メタンスルホン酸、ベンゼンスルホン酸、フェニルリン酸、スルファニル酸、フェニルホスホン酸、酢酸、プロピオン酸等の有機酸が挙げられる。
中でも、酸化合物(C)は、光学積層体の高温高湿環境下における光学耐久性、光学積層体における光学層と第1硬化物層との間の密着性、第1硬化物層と第1熱可塑性樹脂フィルムとの間の密着性を高める観点から、比較的強い酸であることが好ましく、このような酸化合物として、硫酸、塩化水素(塩酸)、硝酸、p-トルエンスルホン酸等が挙げられる。
酸化合物(C)として上記のような強酸を用いると、とりわけ光学積層体における光学層と第1硬化物層との間の密着性や、第1硬化物層と第1熱可塑性樹脂フィルムとの間の密着性を向上させやすい傾向にある。 Examples of the acid compound (C) include inorganic acids such as sulfuric acid, hydrogen chloride, nitrate, phosphoric acid, phosphite, and boric acid; p-toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid, and benzenesulfon. Examples thereof include organic acids such as acids, phenylphosphoric acids, sulfanic acids, phenylphosphonic acids, acetic acids and propionic acids.
Among them, the acid compound (C) has the optical durability of the optical laminate in a high temperature and high humidity environment, the adhesion between the optical layer and the first cured product layer in the optical laminate, and the first cured product layer and the first cured product layer. From the viewpoint of enhancing the adhesion with the thermoplastic resin film, a relatively strong acid is preferable, and examples of such an acid compound include sulfuric acid, hydrogen chloride (hydrochloric acid), nitric acid, p-toluenesulfonic acid and the like. Be done.
When the above-mentioned strong acid is used as the acid compound (C), the adhesion between the optical layer and the first cured product layer in the optical laminate and the adhesion between the first cured product layer and the first thermoplastic resin film are particularly high. There is a tendency to improve the adhesion between them.
中でも、酸化合物(C)は、光学積層体の高温高湿環境下における光学耐久性、光学積層体における光学層と第1硬化物層との間の密着性、第1硬化物層と第1熱可塑性樹脂フィルムとの間の密着性を高める観点から、比較的強い酸であることが好ましく、このような酸化合物として、硫酸、塩化水素(塩酸)、硝酸、p-トルエンスルホン酸等が挙げられる。
酸化合物(C)として上記のような強酸を用いると、とりわけ光学積層体における光学層と第1硬化物層との間の密着性や、第1硬化物層と第1熱可塑性樹脂フィルムとの間の密着性を向上させやすい傾向にある。 Examples of the acid compound (C) include inorganic acids such as sulfuric acid, hydrogen chloride, nitrate, phosphoric acid, phosphite, and boric acid; p-toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid, and benzenesulfon. Examples thereof include organic acids such as acids, phenylphosphoric acids, sulfanic acids, phenylphosphonic acids, acetic acids and propionic acids.
Among them, the acid compound (C) has the optical durability of the optical laminate in a high temperature and high humidity environment, the adhesion between the optical layer and the first cured product layer in the optical laminate, and the first cured product layer and the first cured product layer. From the viewpoint of enhancing the adhesion with the thermoplastic resin film, a relatively strong acid is preferable, and examples of such an acid compound include sulfuric acid, hydrogen chloride (hydrochloric acid), nitric acid, p-toluenesulfonic acid and the like. Be done.
When the above-mentioned strong acid is used as the acid compound (C), the adhesion between the optical layer and the first cured product layer in the optical laminate and the adhesion between the first cured product layer and the first thermoplastic resin film are particularly high. There is a tendency to improve the adhesion between them.
硬化性組成物(S)は、1種の酸化合物(C)を含んでいてもよいし、2種以上の酸化合物(C)を含んでいてもよい。
酸化合物(C)は、酸化合物(C)を含む溶液(例えば水溶液)として硬化性組成物(S)に配合されてもよい。 The curable composition (S) may contain one kind of acid compound (C) or may contain two or more kinds of acid compounds (C).
The acid compound (C) may be blended in the curable composition (S) as a solution (for example, an aqueous solution) containing the acid compound (C).
酸化合物(C)は、酸化合物(C)を含む溶液(例えば水溶液)として硬化性組成物(S)に配合されてもよい。 The curable composition (S) may contain one kind of acid compound (C) or may contain two or more kinds of acid compounds (C).
The acid compound (C) may be blended in the curable composition (S) as a solution (for example, an aqueous solution) containing the acid compound (C).
酸化合物(C)の含有量は、水系樹脂(A)(好ましくはオキサゾリル基含有重合体(a))100質量部に対して、好ましくは5質量部以上80質量部以下であり、より好ましくは10質量部以上70質量部以下であり、さらに好ましくは15質量部以上60質量部以下である。
酸化合物(C)の含有量が過度に少ないと、光学積層体における光学層と第1硬化物層との間、及び、第1硬化物層と第1熱可塑性樹脂フィルムとの間の密着性の少なくともいずれかが得られにくい。また、酸化合物(C)の含有量が過度に多いと、光学積層体における光学層と第1硬化物層との間、及び、第1硬化物層と第1熱可塑性樹脂フィルムとの間の密着性の少なくともいずれかが低下しやすい傾向にある。 The content of the acid compound (C) is preferably 5 parts by mass or more and 80 parts by mass or less, more preferably 80 parts by mass, based on 100 parts by mass of the aqueous resin (A) (preferably the oxazolyl group-containing polymer (a)). It is 10 parts by mass or more and 70 parts by mass or less, and more preferably 15 parts by mass or more and 60 parts by mass or less.
When the content of the acid compound (C) is excessively small, the adhesion between the optical layer and the first cured product layer and between the first cured product layer and the first thermoplastic resin film in the optical laminate It is difficult to obtain at least one of. Further, when the content of the acid compound (C) is excessively large, it is between the optical layer and the first cured product layer in the optical laminate and between the first cured product layer and the first thermoplastic resin film. At least one of the adhesions tends to decrease.
酸化合物(C)の含有量が過度に少ないと、光学積層体における光学層と第1硬化物層との間、及び、第1硬化物層と第1熱可塑性樹脂フィルムとの間の密着性の少なくともいずれかが得られにくい。また、酸化合物(C)の含有量が過度に多いと、光学積層体における光学層と第1硬化物層との間、及び、第1硬化物層と第1熱可塑性樹脂フィルムとの間の密着性の少なくともいずれかが低下しやすい傾向にある。 The content of the acid compound (C) is preferably 5 parts by mass or more and 80 parts by mass or less, more preferably 80 parts by mass, based on 100 parts by mass of the aqueous resin (A) (preferably the oxazolyl group-containing polymer (a)). It is 10 parts by mass or more and 70 parts by mass or less, and more preferably 15 parts by mass or more and 60 parts by mass or less.
When the content of the acid compound (C) is excessively small, the adhesion between the optical layer and the first cured product layer and between the first cured product layer and the first thermoplastic resin film in the optical laminate It is difficult to obtain at least one of. Further, when the content of the acid compound (C) is excessively large, it is between the optical layer and the first cured product layer in the optical laminate and between the first cured product layer and the first thermoplastic resin film. At least one of the adhesions tends to decrease.
〔4〕その他の成分
硬化性組成物(S)は、水系樹脂(A)、シラン化合物(B)、及び酸化合物(C)以外のその他の成分を含むことができる。
その他の成分としては、グリオキザール、グリオキザール誘導体等の多価アルデヒド、メラミン系化合物、アジリジン化合物、水溶性エポキシ樹脂、ジルコニウム化合物、亜鉛化合物、チタン化合物、アルミニウム化合物等の金属化合物等の硬化性成分や架橋剤;カルボキシル基変性ポリビニルアルコール系重合体以外の変性ポリビニルアルコール系重合体;カップリング剤、粘着付与剤、酸化防止剤、紫外線吸収剤、熱安定剤、加水分解防止剤等の添加剤が挙げられる。
硬化性組成物(S)は、その他の成分を1種又は2種以上含むことができる。 [4] Other components The curable composition (S) can contain other components other than the aqueous resin (A), the silane compound (B), and the acid compound (C).
Other components include curable components such as polyvalent aldehydes such as glioxal and glioxal derivatives, melamine compounds, aziridine compounds, water-soluble epoxy resins, zirconium compounds, zinc compounds, titanium compounds, and metal compounds such as aluminum compounds, and cross-linking. Agents: Modified polyvinyl alcohol-based polymers other than carboxyl group-modified polyvinyl alcohol-based polymers; Additives such as coupling agents, tackifiers, antioxidants, ultraviolet absorbers, heat stabilizers, and hydrolysis inhibitors. ..
The curable composition (S) may contain one or more other components.
硬化性組成物(S)は、水系樹脂(A)、シラン化合物(B)、及び酸化合物(C)以外のその他の成分を含むことができる。
その他の成分としては、グリオキザール、グリオキザール誘導体等の多価アルデヒド、メラミン系化合物、アジリジン化合物、水溶性エポキシ樹脂、ジルコニウム化合物、亜鉛化合物、チタン化合物、アルミニウム化合物等の金属化合物等の硬化性成分や架橋剤;カルボキシル基変性ポリビニルアルコール系重合体以外の変性ポリビニルアルコール系重合体;カップリング剤、粘着付与剤、酸化防止剤、紫外線吸収剤、熱安定剤、加水分解防止剤等の添加剤が挙げられる。
硬化性組成物(S)は、その他の成分を1種又は2種以上含むことができる。 [4] Other components The curable composition (S) can contain other components other than the aqueous resin (A), the silane compound (B), and the acid compound (C).
Other components include curable components such as polyvalent aldehydes such as glioxal and glioxal derivatives, melamine compounds, aziridine compounds, water-soluble epoxy resins, zirconium compounds, zinc compounds, titanium compounds, and metal compounds such as aluminum compounds, and cross-linking. Agents: Modified polyvinyl alcohol-based polymers other than carboxyl group-modified polyvinyl alcohol-based polymers; Additives such as coupling agents, tackifiers, antioxidants, ultraviolet absorbers, heat stabilizers, and hydrolysis inhibitors. ..
The curable composition (S) may contain one or more other components.
硬化性組成物(S)は、水系樹脂(A)を溶解又は分散させるための水系溶媒を含むことが好ましい。水系溶媒については、上記で例示したものを用いることができる。水系溶媒としては、水系溶媒の合計質量の80質量%以上が水であるものが好ましく、90質量%以上が水であるものがより好ましく、95質量%以上が水であるものがさらに好ましく、水のみを含むものであってもよい。
硬化性組成物(S)の固形分濃度は、通常0.5質量%以上20質量%以下であり、好ましくは1質量%以上15質量%以下である。 The curable composition (S) preferably contains an aqueous solvent for dissolving or dispersing the aqueous resin (A). As the aqueous solvent, those exemplified above can be used. As the aqueous solvent, 80% by mass or more of the total mass of the aqueous solvent is preferably water, more preferably 90% by mass or more is water, further preferably 95% by mass or more is water, and water. It may contain only.
The solid content concentration of the curable composition (S) is usually 0.5% by mass or more and 20% by mass or less, preferably 1% by mass or more and 15% by mass or less.
硬化性組成物(S)の固形分濃度は、通常0.5質量%以上20質量%以下であり、好ましくは1質量%以上15質量%以下である。 The curable composition (S) preferably contains an aqueous solvent for dissolving or dispersing the aqueous resin (A). As the aqueous solvent, those exemplified above can be used. As the aqueous solvent, 80% by mass or more of the total mass of the aqueous solvent is preferably water, more preferably 90% by mass or more is water, further preferably 95% by mass or more is water, and water. It may contain only.
The solid content concentration of the curable composition (S) is usually 0.5% by mass or more and 20% by mass or less, preferably 1% by mass or more and 15% by mass or less.
<光学積層体>
本発明に係る光学積層体は、光学層と、その少なくとも一方の面に積層される第1硬化物層(硬化性組成物(S)の硬化物から構成される硬化物層)とを含む。
本発明によれば、光学積層体に含まれる硬化物層が硬化性組成物(S)の硬化物から構成されているので、光学積層体の高温高湿環境下における光学耐久性を良好なものとすることができる。 <Optical laminate>
The optical laminate according to the present invention includes an optical layer and a first cured product layer (a cured product layer composed of a cured product of the curable composition (S)) laminated on at least one surface thereof.
According to the present invention, since the cured product layer contained in the optical laminate is composed of the cured product of the curable composition (S), the optical laminate has good optical durability in a high temperature and high humidity environment. Can be.
本発明に係る光学積層体は、光学層と、その少なくとも一方の面に積層される第1硬化物層(硬化性組成物(S)の硬化物から構成される硬化物層)とを含む。
本発明によれば、光学積層体に含まれる硬化物層が硬化性組成物(S)の硬化物から構成されているので、光学積層体の高温高湿環境下における光学耐久性を良好なものとすることができる。 <Optical laminate>
The optical laminate according to the present invention includes an optical layer and a first cured product layer (a cured product layer composed of a cured product of the curable composition (S)) laminated on at least one surface thereof.
According to the present invention, since the cured product layer contained in the optical laminate is composed of the cured product of the curable composition (S), the optical laminate has good optical durability in a high temperature and high humidity environment. Can be.
〔1〕光学積層体の構成
光学積層体の層構成の例を図1~図5に示す。
図1に示される光学積層体は、光学層30と、その一方の面に積層される第1硬化物層15とを含む。第1硬化物層15は、光学層30の表面を被覆して保護するオーバーコート層、光学層30に追加的に光学機能を付与する光学機能層等として機能することができる。
光学層30と第1硬化物層15とは直接接していることが好ましい。 [1] Configuration of Optical Laminates FIGS. 1 to 5 show examples of layer configurations of the optical laminates.
The optical laminate shown in FIG. 1 includes anoptical layer 30 and a first cured product layer 15 laminated on one surface of the optical layer 30. The first cured product layer 15 can function as an overcoat layer that coats and protects the surface of the optical layer 30, an optical functional layer that additionally imparts an optical function to the optical layer 30, and the like.
It is preferable that theoptical layer 30 and the first cured product layer 15 are in direct contact with each other.
光学積層体の層構成の例を図1~図5に示す。
図1に示される光学積層体は、光学層30と、その一方の面に積層される第1硬化物層15とを含む。第1硬化物層15は、光学層30の表面を被覆して保護するオーバーコート層、光学層30に追加的に光学機能を付与する光学機能層等として機能することができる。
光学層30と第1硬化物層15とは直接接していることが好ましい。 [1] Configuration of Optical Laminates FIGS. 1 to 5 show examples of layer configurations of the optical laminates.
The optical laminate shown in FIG. 1 includes an
It is preferable that the
図2に示される光学積層体は、光学層30と、その一方の面に第1硬化物層15を介して積層貼合される第1熱可塑性樹脂フィルム10とを含む。第1硬化物層15は、光学層30と第1熱可塑性樹脂フィルム10とを接着する接着剤層として機能することができる。
第1硬化物層15と第1熱可塑性樹脂フィルム10とは直接接していることが好ましい。
光学層30と第1硬化物層15とは直接接していることが好ましい。 The optical laminate shown in FIG. 2 includes anoptical layer 30 and a first thermoplastic resin film 10 laminated and bonded to one surface thereof via a first cured product layer 15. The first cured product layer 15 can function as an adhesive layer for adhering the optical layer 30 and the first thermoplastic resin film 10.
It is preferable that the first curedproduct layer 15 and the first thermoplastic resin film 10 are in direct contact with each other.
It is preferable that theoptical layer 30 and the first cured product layer 15 are in direct contact with each other.
第1硬化物層15と第1熱可塑性樹脂フィルム10とは直接接していることが好ましい。
光学層30と第1硬化物層15とは直接接していることが好ましい。 The optical laminate shown in FIG. 2 includes an
It is preferable that the first cured
It is preferable that the
図3に示される光学積層体は、光学層30と、その一方の面に第1硬化物層15を介して積層貼合される第1熱可塑性樹脂フィルム10と、光学層30の他方の面に第2硬化物層25を介して積層貼合される第2熱可塑性樹脂フィルム20とを含む。すなわち、本発明に係る光学積層体は、第2熱可塑性樹脂フィルム20と第2硬化物層25と光学層30と第1硬化物層15と第1熱可塑性樹脂フィルム10とをこの順に含むものであってもよい。第1硬化物層15及び第2硬化物層25はそれぞれ、光学層30と第1熱可塑性樹脂フィルム10とを接着する接着剤層、光学層30と第2熱可塑性樹脂フィルム20とを接着する接着剤層として機能することができる。
第2硬化物層25と第2熱可塑性樹脂フィルム20とは直接接していることが好ましい。
光学層30と第2硬化物層25とは直接接していることが好ましい。 The optical laminate shown in FIG. 3 includes anoptical layer 30, a first thermoplastic resin film 10 laminated and bonded to one surface of the optical layer 30 via a first cured product layer 15, and the other surface of the optical layer 30. Includes a second thermoplastic resin film 20 that is laminated and bonded via a second cured product layer 25. That is, the optical laminate according to the present invention includes the second thermoplastic resin film 20, the second cured product layer 25, the optical layer 30, the first cured product layer 15, and the first thermoplastic resin film 10 in this order. It may be. The first cured product layer 15 and the second cured product layer 25 each adhere an adhesive layer for adhering the optical layer 30 and the first thermoplastic resin film 10, and the optical layer 30 and the second thermoplastic resin film 20. It can function as an adhesive layer.
It is preferable that the second curedproduct layer 25 and the second thermoplastic resin film 20 are in direct contact with each other.
It is preferable that theoptical layer 30 and the second cured product layer 25 are in direct contact with each other.
第2硬化物層25と第2熱可塑性樹脂フィルム20とは直接接していることが好ましい。
光学層30と第2硬化物層25とは直接接していることが好ましい。 The optical laminate shown in FIG. 3 includes an
It is preferable that the second cured
It is preferable that the
図4に示される光学積層体は、光学層30と、その一方の面に積層される第1硬化物層15と、光学層30の他方の面に第2硬化物層25を介して積層貼合される第2熱可塑性樹脂フィルム20とを含む。第1硬化物層15は、光学層30の表面を被覆して保護するオーバーコート層、光学層30に追加的に光学機能を付与する光学機能層等として機能することができる。第2硬化物層25は、光学層30と第2熱可塑性樹脂フィルム20とを接着する接着剤層として機能することができる。
光学層30と第1硬化物層15とは直接接していることが好ましい。
第2硬化物層25と第2熱可塑性樹脂フィルム20とは直接接していることが好ましい。
光学層30と第2硬化物層25とは直接接していることが好ましい。 The optical laminate shown in FIG. 4 is laminated and laminated on theoptical layer 30, the first cured product layer 15 laminated on one surface thereof, and the other surface of the optical layer 30 via the second cured product layer 25. Includes a second thermoplastic resin film 20 to be combined. The first cured product layer 15 can function as an overcoat layer that coats and protects the surface of the optical layer 30, an optical functional layer that additionally imparts an optical function to the optical layer 30, and the like. The second cured product layer 25 can function as an adhesive layer for adhering the optical layer 30 and the second thermoplastic resin film 20.
It is preferable that theoptical layer 30 and the first cured product layer 15 are in direct contact with each other.
It is preferable that the second curedproduct layer 25 and the second thermoplastic resin film 20 are in direct contact with each other.
It is preferable that theoptical layer 30 and the second cured product layer 25 are in direct contact with each other.
光学層30と第1硬化物層15とは直接接していることが好ましい。
第2硬化物層25と第2熱可塑性樹脂フィルム20とは直接接していることが好ましい。
光学層30と第2硬化物層25とは直接接していることが好ましい。 The optical laminate shown in FIG. 4 is laminated and laminated on the
It is preferable that the
It is preferable that the second cured
It is preferable that the
図5に示される光学積層体は、光学層30と、その一方の面に積層される第1硬化物層15と、光学層30の他方の面に積層される第2硬化物層25とを含む。第1硬化物層15及び第2硬化物層25は、光学層30の表面を被覆して保護するオーバーコート層、光学層30に追加的に光学機能を付与する光学機能層等として機能することができる。
光学層30と第1硬化物層15とは直接接していることが好ましい。
光学層30と第2硬化物層25とは直接接していることが好ましい。 The optical laminate shown in FIG. 5 includes anoptical layer 30, a first cured product layer 15 laminated on one surface of the optical layer 30, and a second cured product layer 25 laminated on the other surface of the optical layer 30. Including. The first cured product layer 15 and the second cured product layer 25 function as an overcoat layer that coats and protects the surface of the optical layer 30, an optical functional layer that additionally imparts an optical function to the optical layer 30, and the like. Can be done.
It is preferable that theoptical layer 30 and the first cured product layer 15 are in direct contact with each other.
It is preferable that theoptical layer 30 and the second cured product layer 25 are in direct contact with each other.
光学層30と第1硬化物層15とは直接接していることが好ましい。
光学層30と第2硬化物層25とは直接接していることが好ましい。 The optical laminate shown in FIG. 5 includes an
It is preferable that the
It is preferable that the
光学層30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)であってよい。光学層30としては、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、集光フィルム等が挙げられる。
The optical layer 30 may be various optical films (films having optical characteristics) that can be incorporated into an image display device such as a liquid crystal display device. Examples of the optical layer 30 include a polarizer, a retardation film, a brightness improving film, an antiglare film, an antireflection film, a diffusion film, a light collecting film and the like.
光学積層体は、上記以外の他の層(又はフィルム)を含むことができる。他の層としては、例えば、第1熱可塑性樹脂フィルム10、第2熱可塑性樹脂フィルム20、第1硬化物層15、第2硬化物層25及び/又は光学層30の外面に積層される粘着剤層;該粘着剤層の外面に積層されるセパレートフィルム(「剥離フィルム」とも呼ばれる。);第1熱可塑性樹脂フィルム10、第2熱可塑性樹脂フィルム20、第1硬化物層15、第2硬化物層25及び/又は光学層30の外面に積層されるプロテクトフィルム(「表面保護フィルム」とも呼ばれる。);第1熱可塑性樹脂フィルム10、第2熱可塑性樹脂フィルム20、第1硬化物層15、第2硬化物層25及び/又は光学層30の外面に接着剤層や粘着剤層を介して積層される光学機能性フィルム(又は層)等が挙げられる。
The optical laminate can include layers (or films) other than the above. Examples of the other layer include an adhesive laminated on the outer surface of the first thermoplastic resin film 10, the second thermoplastic resin film 20, the first cured product layer 15, the second cured product layer 25, and / or the optical layer 30. Agent layer; Separate film laminated on the outer surface of the pressure-sensitive adhesive layer (also referred to as "release film"); 1st thermoplastic resin film 10, 2nd thermoplastic resin film 20, 1st cured product layer 15, 2nd A protective film (also referred to as a "surface protective film") laminated on the outer surface of the cured product layer 25 and / or the optical layer 30; the first thermoplastic resin film 10, the second thermoplastic resin film 20, and the first cured product layer. 15. Examples thereof include an optically functional film (or layer) laminated on the outer surface of the second cured product layer 25 and / or the optical layer 30 via an adhesive layer or an adhesive layer.
〔2〕偏光子
偏光子は、自然光からある一方向の直線偏光を選択的に透過する機能を有する層又はフィルムである。
偏光子としては、例えば、ポリビニルアルコール系樹脂フィルムに二色性色素を吸着・配向させたフィルムが挙げられる。二色性色素としては、ヨウ素、二色性有機染料等が挙げられる。
また、偏光子は、リオトロビック液晶状態の二色性染料を基材フィルムにコーティングし、配向・固定化した塗布型偏光フィルムであってもよい。
以上の偏光子は、自然光からある一方向の直線偏光を選択的に透過し、もう一方向の直線偏光を吸収するため吸収型偏光子と呼ばれている。 [2] Polarized light The polarized light is a layer or film having a function of selectively transmitting linearly polarized light in a certain direction from natural light.
Examples of the polarizer include a film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin film. Examples of the dichroic dye include iodine and a dichroic organic dye.
Further, the polarizing element may be a coating type polarizing film in which a dichroic dye in a Riotrovic liquid crystal state is coated on a base film and oriented and immobilized.
The above-mentioned polarizer is called an absorption type polarizer because it selectively transmits linearly polarized light in one direction from natural light and absorbs linearly polarized light in the other direction.
偏光子は、自然光からある一方向の直線偏光を選択的に透過する機能を有する層又はフィルムである。
偏光子としては、例えば、ポリビニルアルコール系樹脂フィルムに二色性色素を吸着・配向させたフィルムが挙げられる。二色性色素としては、ヨウ素、二色性有機染料等が挙げられる。
また、偏光子は、リオトロビック液晶状態の二色性染料を基材フィルムにコーティングし、配向・固定化した塗布型偏光フィルムであってもよい。
以上の偏光子は、自然光からある一方向の直線偏光を選択的に透過し、もう一方向の直線偏光を吸収するため吸収型偏光子と呼ばれている。 [2] Polarized light The polarized light is a layer or film having a function of selectively transmitting linearly polarized light in a certain direction from natural light.
Examples of the polarizer include a film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin film. Examples of the dichroic dye include iodine and a dichroic organic dye.
Further, the polarizing element may be a coating type polarizing film in which a dichroic dye in a Riotrovic liquid crystal state is coated on a base film and oriented and immobilized.
The above-mentioned polarizer is called an absorption type polarizer because it selectively transmits linearly polarized light in one direction from natural light and absorbs linearly polarized light in the other direction.
偏光子は、吸収型偏光子に限定されず、自然光からある一方向の直線偏光を選択的に透過し、もう一方向の直線偏光を反射する反射型偏光子、又はもう一方向の直線偏光を散乱する散乱型偏光子でも構わないが、視認性に優れる点から吸収型偏光子が好ましい。中でも、ポリビニルアルコール系樹脂フィルムで構成されるポリビニルアルコール系偏光フィルムがより好ましく、ポリビニルアルコール系樹脂フィルムにヨウ素や二色性染料等の二色性色素を吸着・配向させたポリビニルアルコール系偏光フィルムがさらに好ましく、ポリビニルアルコール系樹脂フィルムにヨウ素を吸着・配向させたポリビニルアルコール系偏光フィルムが特に好ましい。
The polarizer is not limited to the absorption type polarizer, but is a reflection type polarizer that selectively transmits linearly polarized light in one direction from natural light and reflects the linearly polarized light in the other direction, or a linearly polarized light in the other direction. A scattering type polarizer may be used, but an absorption type polarizer is preferable from the viewpoint of excellent visibility. Of these, a polyvinyl alcohol-based polarizing film composed of a polyvinyl alcohol-based resin film is more preferable, and a polyvinyl alcohol-based polarizing film in which a bicolor dye such as iodine or a bicolor dye is adsorbed and oriented on the polyvinyl alcohol-based resin film is preferable. More preferably, a polyvinyl alcohol-based polarizing film in which iodine is adsorbed and oriented on the polyvinyl alcohol-based resin film is particularly preferable.
ポリビニルアルコール系樹脂としては、ポリ酢酸ビニル系樹脂をケン化したものを用いることができる。ポリ酢酸ビニル系樹脂としては、酢酸ビニルの単独重合体であるポリ酢酸ビニルの他、酢酸ビニルと共重合可能な他の単量体との共重合体等が挙げられる。酢酸ビニルに共重合可能な他の単量体としては、不飽和カルボン酸類、オレフィン類、ビニルエーテル類、不飽和スルホン酸類、及びアンモニウム基を有する(メタ)アクリルアミド類等が挙げられる。
As the polyvinyl alcohol-based resin, a saponified polyvinyl acetate-based resin can be used. Examples of the polyvinyl acetate-based resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and a copolymer of vinyl acetate and another monomer copolymerizable with the vinyl acetate. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth) acrylamides having an ammonium group.
ポリビニルアルコール系樹脂のケン化度は通常、85モル%以上100モル%以下であり、98モル%以上が好ましい。ポリビニルアルコール系樹脂は変性されていてもよく、例えば、アルデヒド類で変性されたポリビニルホルマール又はポリビニルアセタール等を用いることもできる。ポリビニルアルコール系樹脂の平均重合度は、通常1000以上10000以下であり、1500以上5000以下が好ましい。
ポリビニルアルコール系樹脂の平均重合度は、JIS K 6726:1994に準拠して求めることができる。 The degree of saponification of the polyvinyl alcohol-based resin is usually 85 mol% or more and 100 mol% or less, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can be used. The average degree of polymerization of the polyvinyl alcohol-based resin is usually 1000 or more and 10000 or less, preferably 1500 or more and 5000 or less.
The average degree of polymerization of the polyvinyl alcohol-based resin can be determined in accordance with JIS K 6726: 1994.
ポリビニルアルコール系樹脂の平均重合度は、JIS K 6726:1994に準拠して求めることができる。 The degree of saponification of the polyvinyl alcohol-based resin is usually 85 mol% or more and 100 mol% or less, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can be used. The average degree of polymerization of the polyvinyl alcohol-based resin is usually 1000 or more and 10000 or less, preferably 1500 or more and 5000 or less.
The average degree of polymerization of the polyvinyl alcohol-based resin can be determined in accordance with JIS K 6726: 1994.
このようなポリビニルアルコール系樹脂を製膜したものが、ポリビニルアルコール系樹脂フィルムで構成された偏光フィルムの原反フィルムとして用いられる。ポリビニルアルコール系樹脂を製膜する方法は、特に限定されるものではなく、公知の方法が採用される。ポリビニルアルコール系原反フィルムの厚みは、例えば150μm以下であり、好ましくは100μm以下(例えば50μm以下)であり、5μm以上である。
A film formed of such a polyvinyl alcohol-based resin is used as a raw film for a polarizing film composed of a polyvinyl alcohol-based resin film. The method for forming a film of the polyvinyl alcohol-based resin is not particularly limited, and a known method is adopted. The thickness of the polyvinyl alcohol-based raw film is, for example, 150 μm or less, preferably 100 μm or less (for example, 50 μm or less), and 5 μm or more.
ポリビニルアルコール系樹脂フィルムで構成された偏光フィルムは、公知の方法によって製造できる。具体的には、ポリビニルアルコール系樹脂フィルムを一軸延伸する工程;ポリビニルアルコール系樹脂フィルムを二色性色素で染色することにより二色性色素を吸着させる工程;二色性色素が吸着されたポリビニルアルコール系樹脂フィルムをホウ酸水溶液で処理(架橋処理)する工程;及び、ホウ酸水溶液による処理後に水洗する工程を含む方法によって製造できる。
A polarizing film composed of a polyvinyl alcohol-based resin film can be produced by a known method. Specifically, the step of uniaxially stretching the polyvinyl alcohol-based resin film; the step of adsorbing the dichroic dye by dyeing the polyvinyl alcohol-based resin film with the dichroic dye; the polyvinyl alcohol on which the dichroic dye is adsorbed. It can be produced by a method including a step of treating (cross-linking) the based resin film with an aqueous boric acid solution; and a step of washing with water after treatment with the aqueous boric acid solution.
偏光子の厚みは、40μm以下とすることができ、好ましくは30μm以下(例えば20μm以下、さらには15μm以下、なおさらには10μm以下又は8μm以下)である。特開2000-338329号公報や特開2012-159778号公報に記載の方法によれば、薄膜の偏光子をより容易に製造することができ、偏光子の厚みを、例えば20μm以下、さらには15μm以下、なおさらには10μm以下又は8μm以下とすることがより容易になる。偏光子の厚みは、通常2μm以上である。偏光子の厚みを小さくすることは、光学積層体(偏光板)、及びこれを含む画像表示装置の薄型化に有利である。一般に、偏光子の厚みが薄いほど光学耐久性が劣る傾向にあるが、本発明の硬化性組成物を用いることで、そのような薄膜偏光板であっても良好な耐久性を有することができる。
The thickness of the polarizer can be 40 μm or less, preferably 30 μm or less (for example, 20 μm or less, further 15 μm or less, and further 10 μm or less or 8 μm or less). According to the methods described in JP-A-2000-338329 and JP-A-2012-159778, a thin-film polarizer can be more easily produced, and the thickness of the polarizer can be increased to, for example, 20 μm or less, further 15 μm. Below, it becomes easier to make it 10 μm or less or 8 μm or less. The thickness of the polarizer is usually 2 μm or more. Reducing the thickness of the polarizer is advantageous for reducing the thickness of the optical laminate (polarizing plate) and the image display device including the optical laminate (polarizing plate). In general, the thinner the polarizer, the lower the optical durability tends to be. However, by using the curable composition of the present invention, even such a thin-film polarizing plate can have good durability. ..
〔3〕位相差フィルム
位相差フィルムとしては、透光性を有する熱可塑性樹脂を一軸延伸又は二軸延伸した延伸フィルム;ディスコティック液晶又はネマチック液晶等の液晶性化合物が配向固定されたフィルム;基材フィルム上に上記の液晶層が形成されたもの等が挙げられる。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。
基材フィルムは通常、熱可塑性樹脂からなるフィルムであり、熱可塑性樹脂の一例は、トリアセチルセルロース等のセルロースエステル系樹脂である。
透光性を有する熱可塑性樹脂としては、後述する第1熱可塑性樹脂フィルム10を構成する樹脂等が挙げられる。 [3] Phase-difference film The retardation film is a stretched film obtained by uniaxially stretching or biaxially stretching a translucent thermoplastic resin; a film in which a liquid crystal compound such as a discotic liquid crystal or a nematic liquid crystal is oriented and fixed; Examples thereof include those in which the above-mentioned liquid crystal layer is formed on a material film. Further, in the present specification, the zero retardation film is also included in the retardation film.
The base film is usually a film made of a thermoplastic resin, and an example of the thermoplastic resin is a cellulosic ester-based resin such as triacetyl cellulose.
Examples of the translucent thermoplastic resin include resins constituting the firstthermoplastic resin film 10 described later.
位相差フィルムとしては、透光性を有する熱可塑性樹脂を一軸延伸又は二軸延伸した延伸フィルム;ディスコティック液晶又はネマチック液晶等の液晶性化合物が配向固定されたフィルム;基材フィルム上に上記の液晶層が形成されたもの等が挙げられる。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。
基材フィルムは通常、熱可塑性樹脂からなるフィルムであり、熱可塑性樹脂の一例は、トリアセチルセルロース等のセルロースエステル系樹脂である。
透光性を有する熱可塑性樹脂としては、後述する第1熱可塑性樹脂フィルム10を構成する樹脂等が挙げられる。 [3] Phase-difference film The retardation film is a stretched film obtained by uniaxially stretching or biaxially stretching a translucent thermoplastic resin; a film in which a liquid crystal compound such as a discotic liquid crystal or a nematic liquid crystal is oriented and fixed; Examples thereof include those in which the above-mentioned liquid crystal layer is formed on a material film. Further, in the present specification, the zero retardation film is also included in the retardation film.
The base film is usually a film made of a thermoplastic resin, and an example of the thermoplastic resin is a cellulosic ester-based resin such as triacetyl cellulose.
Examples of the translucent thermoplastic resin include resins constituting the first
ゼロレタデーションフィルムとは、面内位相差値Re及び厚み方向位相差値Rthがともに-15~15nmであるフィルムをいう。この位相差フィルムは、IPSモードの液晶表示装置に好適に用いられる。面内位相差値Re及び厚み方向位相差値Rthは、好ましくはともに-10~10nmであり、より好ましくはともに-5~5nmである。ここでいう面内位相差値Re及び厚み方向位相差値Rthは、波長590nmにおける値である。
The zero retardation film refers to a film in which both the in-plane retardation value Re and the thickness direction retardation value Rth are -15 to 15 nm. This retardation film is suitably used for a liquid crystal display device in IPS mode. The in-plane retardation value Re and the thickness direction retardation value Rth are preferably −10 to 10 nm, and more preferably both −5 to 5 nm. The in-plane retardation value Re and the thickness direction retardation value Rth referred to here are values at a wavelength of 590 nm.
面内位相差値Re及び厚み方向位相差値Rthは、それぞれ下記式:
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 Rth are expressed by the following equations, respectively:
Re = (n x − n y ) × d
Rth = [(n x + n y ) / 2-n z ] x d
Defined in. 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) The refractive index, nz is the refractive index in the film thickness direction (the z-axis direction perpendicular to the film surface), and d is the film thickness.
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 Rth are expressed by the following equations, respectively:
Re = (n x − n y ) × d
Rth = [(n x + n y ) / 2-n z ] x d
Defined in. 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) The refractive index, nz is the refractive index in the film thickness direction (the z-axis direction perpendicular to the film surface), and d is the film thickness.
ゼロレタデーションフィルムには、例えば、セルロース系樹脂、鎖状ポリオレフィン系樹脂及び環状ポリオレフィン系樹脂等のポリオレフィン系樹脂、ポリエチレンテレフタレート系樹脂又は(メタ)アクリル系樹脂からなる樹脂フィルムを用いることができる。特に、位相差値の制御が容易で、入手も容易であることから、セルロース系樹脂、ポリオレフィン系樹脂又は(メタ)アクリル系樹脂が好ましく用いられる。
As the zero retardation film, for example, 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 can be used. In particular, since the retardation value can be easily controlled and easily obtained, a cellulosic resin, a polyolefin resin, or a (meth) acrylic resin is preferably used.
液晶性化合物の塗布・配向によって光学異方性を発現させたフィルムとしては、
第一の形態:棒状液晶化合物が支持基材に対して水平方向に配向した位相差フィルム、
第二の形態:棒状液晶化合物が支持基材に対して垂直方向に配向した位相差フィルム、
第三の形態:棒状液晶化合物が面内で螺旋状に配向の方向が変化している位相差フィルム、
第四の形態:円盤状液晶化合物が傾斜配向している位相差フィルム、
第五の形態:円盤状液晶化合物が支持基材に対して垂直方向に配向した二軸性の位相差フィルムが挙げられる。 As a film that expresses optical anisotropy by coating and orientation of a liquid crystal compound,
First form: a retardation film in which a rod-shaped liquid crystal compound is oriented horizontally with respect to a supporting substrate.
Second form: a retardation film in which the rod-shaped liquid crystal compound is oriented perpendicular to the supporting substrate,
Third form: A retardation film in which the rod-shaped liquid crystal compound changes its orientation spirally in the plane.
Fourth form: a retardation film in which a disk-shaped liquid crystal compound is inclined or oriented,
Fifth form: A biaxial retardation film in which a disk-shaped liquid crystal compound is oriented perpendicularly to a supporting substrate.
第一の形態:棒状液晶化合物が支持基材に対して水平方向に配向した位相差フィルム、
第二の形態:棒状液晶化合物が支持基材に対して垂直方向に配向した位相差フィルム、
第三の形態:棒状液晶化合物が面内で螺旋状に配向の方向が変化している位相差フィルム、
第四の形態:円盤状液晶化合物が傾斜配向している位相差フィルム、
第五の形態:円盤状液晶化合物が支持基材に対して垂直方向に配向した二軸性の位相差フィルムが挙げられる。 As a film that expresses optical anisotropy by coating and orientation of a liquid crystal compound,
First form: a retardation film in which a rod-shaped liquid crystal compound is oriented horizontally with respect to a supporting substrate.
Second form: a retardation film in which the rod-shaped liquid crystal compound is oriented perpendicular to the supporting substrate,
Third form: A retardation film in which the rod-shaped liquid crystal compound changes its orientation spirally in the plane.
Fourth form: a retardation film in which a disk-shaped liquid crystal compound is inclined or oriented,
Fifth form: A biaxial retardation film in which a disk-shaped liquid crystal compound is oriented perpendicularly to a supporting substrate.
例えば、有機エレクトロルミネッセンスディスプレイに用いられる光学層としては、第一の形態、第二の形態、第五の形態が好適に用いられる。又は、これらを積層させて用いてもよい。
For example, as the optical layer used in the organic electroluminescence display, the first form, the second form, and the fifth form are preferably used. Alternatively, these may be laminated and used.
位相差フィルムが、重合性液晶化合物の配向状態における重合体からなる層(以下、「光学異方性層」と称する場合がある)である場合、位相差フィルムは逆波長分散性を有することが好ましい。逆波長分散性とは、短波長での液晶配向面内位相差値の方が長波長での液晶配向面内位相差値よりも小さくなる光学特性であり、好ましくは、位相差フィルムが下記式(1)及び式(2)を満たすことである。なお、Re(λ)は波長λnmの光に対する面内位相差値を表す。
Re(450)/Re(550)≦1 (1)
1≦Re(630)/Re(550) (2)
位相差フィルムが第一の形態でかつ逆波長分散性を有する場合、表示装置での黒表示時の着色が低減するため好ましく、式(1)において0.82≦Re(450)/Re(550)≦0.93であればより好ましい。さらに120≦Re(550)≦150が好ましい。 When the retardation film is a layer made of a polymer in the oriented state of the polymerizable liquid crystal compound (hereinafter, may be referred to as an "opticallyotropic layer"), the retardation film may have anti-wavelength dispersibility. preferable. The inverse wavelength dispersibility is an optical characteristic in which the liquid crystal alignment in-plane retardation value at a short wavelength is smaller than the liquid crystal alignment in-plane retardation value at a long wavelength, and the retardation film is preferably expressed by the following formula. (1) and equation (2) are satisfied. Re (λ) represents an in-plane retardation value with respect to light having a wavelength of λ nm.
Re (450) / Re (550) ≤ 1 (1)
1 ≦ Re (630) / Re (550) (2)
When the retardation film is in the first form and has anti-wavelength dispersibility, it is preferable because the coloring at the time of black display on the display device is reduced, and 0.82 ≦ Re (450) / Re (550) in the formula (1). ) ≤ 0.93 is more preferable. Further, 120 ≦ Re (550) ≦ 150 is preferable.
Re(450)/Re(550)≦1 (1)
1≦Re(630)/Re(550) (2)
位相差フィルムが第一の形態でかつ逆波長分散性を有する場合、表示装置での黒表示時の着色が低減するため好ましく、式(1)において0.82≦Re(450)/Re(550)≦0.93であればより好ましい。さらに120≦Re(550)≦150が好ましい。 When the retardation film is a layer made of a polymer in the oriented state of the polymerizable liquid crystal compound (hereinafter, may be referred to as an "opticallyotropic layer"), the retardation film may have anti-wavelength dispersibility. preferable. The inverse wavelength dispersibility is an optical characteristic in which the liquid crystal alignment in-plane retardation value at a short wavelength is smaller than the liquid crystal alignment in-plane retardation value at a long wavelength, and the retardation film is preferably expressed by the following formula. (1) and equation (2) are satisfied. Re (λ) represents an in-plane retardation value with respect to light having a wavelength of λ nm.
Re (450) / Re (550) ≤ 1 (1)
1 ≦ Re (630) / Re (550) (2)
When the retardation film is in the first form and has anti-wavelength dispersibility, it is preferable because the coloring at the time of black display on the display device is reduced, and 0.82 ≦ Re (450) / Re (550) in the formula (1). ) ≤ 0.93 is more preferable. Further, 120 ≦ Re (550) ≦ 150 is preferable.
位相差フィルムが、光学異方性層を有するフィルムである場合の重合性液晶化合物としては、液晶便覧(液晶便覧編集委員会編、丸善(株)平成12年10月30日発行)の「3.8.6 ネットワーク(完全架橋型)」、「6.5.1 液晶材料 b.重合性ネマチック液晶材料」に記載された化合物の中で重合性基を有する化合物、並びに、特開2010-31223号公報、特開2010-270108号公報、特開2011-6360号公報、特開2011-207765号公報、特開2016-81035号公報、国際公開第2017/043438号に記載の重合性液晶化合物が挙げられる。
When the retardation film is a film having an optically anisotropic layer, the polymerizable liquid crystal compound is described in "3" of the Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editorial Committee, published on October 30, 2000 by Maruzen Co., Ltd.). Among the compounds described in ".8.6 Network (completely crosslinked type)" and "6.5.1 Liquid crystal material b. Polymerizable nematic liquid crystal material", compounds having a polymerizable group, and Japanese Patent Application Laid-Open No. 2010-31223 The polymerizable liquid crystal compounds described in JP-A-2010-270108, JP-A-2011-6360, JP-A-2011-207765, JP-A-2016-81035, and International Publication No. 2017/043438 Can be mentioned.
重合性液晶化合物の配向状態における重合体から位相差フィルムを製造する方法は、例えば、特開2010-31223号公報に記載の方法が挙げられる。
Examples of the method for producing a retardation film from a polymer in the oriented state of a polymerizable liquid crystal compound include the method described in JP-A-2010-31223.
第二の形態の場合、面内位相差値Re(550)は0~10nmの範囲に、好ましくは0~5nmの範囲に調整すればよく、厚み方向の位相差値Rthは、-10~-300nmの範囲に、好ましくは-20~-200nmの範囲に調整すればよい。
厚み方向の屈折率異方性を意味する厚み方向の位相差値Rthは、面内の進相軸を傾斜軸として50度傾斜させて測定される位相差値R50と面内位相差値Reとから算出できる。すなわち、厚み方向の位相差値Rthは、面内の位相差値Re、進相軸を傾斜軸として50度傾斜させて測定した位相差値R50、位相差フィルムの厚みd、及び位相差フィルムの平均屈折率n0から、以下の式(4)~(6)によりnx、ny及びnzを求め、これらを式(3)に代入して、算出することができる。 In the case of the second embodiment, the in-plane retardation value Re (550) may be adjusted in the range of 0 to 10 nm, preferably in the range of 0 to 5 nm, and the phase difference value Rth in the thickness direction is −10 to −−. It may be adjusted in the range of 300 nm, preferably in the range of −20 to −200 nm.
The phase difference value Rth in the thickness direction, which means the refractive index anisotropy in the thickness direction, is the phase difference value R50 and the in-plane phase difference value Re, which are measured by inclining 50 degrees with the in-plane phase advance axis as the inclination axis. Can be calculated from. That is, the retardation value Rth in the thickness direction is the in-plane retardation value Re, the retardation value R50 measured by inclining 50 degrees with the phase advance axis as the tilt axis, the thickness d of the retardation film, and the retardation film. From the average refractive index n 0 , n x , ny and n z can be obtained by the following equations (4) to (6), and these can be substituted into the equation (3) for calculation.
厚み方向の屈折率異方性を意味する厚み方向の位相差値Rthは、面内の進相軸を傾斜軸として50度傾斜させて測定される位相差値R50と面内位相差値Reとから算出できる。すなわち、厚み方向の位相差値Rthは、面内の位相差値Re、進相軸を傾斜軸として50度傾斜させて測定した位相差値R50、位相差フィルムの厚みd、及び位相差フィルムの平均屈折率n0から、以下の式(4)~(6)によりnx、ny及びnzを求め、これらを式(3)に代入して、算出することができる。 In the case of the second embodiment, the in-plane retardation value Re (550) may be adjusted in the range of 0 to 10 nm, preferably in the range of 0 to 5 nm, and the phase difference value Rth in the thickness direction is −10 to −−. It may be adjusted in the range of 300 nm, preferably in the range of −20 to −200 nm.
The phase difference value Rth in the thickness direction, which means the refractive index anisotropy in the thickness direction, is the phase difference value R50 and the in-plane phase difference value Re, which are measured by inclining 50 degrees with the in-plane phase advance axis as the inclination axis. Can be calculated from. That is, the retardation value Rth in the thickness direction is the in-plane retardation value Re, the retardation value R50 measured by inclining 50 degrees with the phase advance axis as the tilt axis, the thickness d of the retardation film, and the retardation film. From the average refractive index n 0 , n x , ny and n z can be obtained by the following equations (4) to (6), and these can be substituted into the equation (3) for calculation.
Rth=[(nx+ny)/2-nz]×d (3)
Re =(nx-ny)×d (4)
R50=(nx-ny')×d/cos(φ) (5)
(nx+ny+nz)/3=n0 (6)
ここで、
φ=sin-1〔sin(40°)/n0〕
ny'=ny×nz/〔ny 2×sin2(φ)+nz 2×cos2(φ)〕1/2 Rth = [(n x + n y ) / 2- nz ] x d (3)
Re = (n x − n y ) × d (4)
R50 = (n x − n y ') × d / cos (φ) (5)
(n x + n y + n z ) / 3 = n 0 (6)
here,
φ = sin -1 [sin (40 °) / n 0 ]
n y '= n y x n z / [ ny 2 x sin 2 (φ) + n z 2 x cos 2 (φ)] 1/2
Re =(nx-ny)×d (4)
R50=(nx-ny')×d/cos(φ) (5)
(nx+ny+nz)/3=n0 (6)
ここで、
φ=sin-1〔sin(40°)/n0〕
ny'=ny×nz/〔ny 2×sin2(φ)+nz 2×cos2(φ)〕1/2 Rth = [(n x + n y ) / 2- nz ] x d (3)
Re = (n x − n y ) × d (4)
R50 = (n x − n y ') × d / cos (φ) (5)
(n x + n y + n z ) / 3 = n 0 (6)
here,
φ = sin -1 [sin (40 °) / n 0 ]
n y '= n y x n z / [ ny 2 x sin 2 (φ) + n z 2 x cos 2 (φ)] 1/2
位相差フィルムは、二以上の層を有する多層フィルムであってもよい。例えば、位相差フィルムの片面又は両面に保護フィルムが積層されたものや、二以上の位相差フィルムが粘着剤又は接着剤を介して積層されたものが挙げられる。
The retardation film may be a multilayer film having two or more layers. For example, a protective film is laminated on one side or both sides of a retardation film, and two or more retardation films are laminated via an adhesive or an adhesive.
〔4〕第1硬化物層
第1硬化物層15は、硬化性組成物(S)の硬化物から構成される硬化物層である。硬化性組成物(S)については上述のとおりである。硬化性組成物(S)は、例えば、熱によって硬化させることができる。 [4] First Cured Product Layer The first curedproduct layer 15 is a cured product layer composed of a cured product of the curable composition (S). The curable composition (S) is as described above. The curable composition (S) can be cured by heat, for example.
第1硬化物層15は、硬化性組成物(S)の硬化物から構成される硬化物層である。硬化性組成物(S)については上述のとおりである。硬化性組成物(S)は、例えば、熱によって硬化させることができる。 [4] First Cured Product Layer The first cured
〔5〕熱可塑性樹脂フィルム
第1熱可塑性樹脂フィルム10及び第2熱可塑性樹脂フィルム20はそれぞれ、透光性を有する(好ましくは光学的に透明な)熱可塑性樹脂、例えば、鎖状ポリオレフィン系樹脂(ポリプロピレン系樹脂等)、環状ポリオレフィン系樹脂(ノルボルネン系樹脂等)等のポリオレフィン系樹脂;トリアセチルセルロース、ジアセチルセルロース等のセルロースエステル系樹脂;ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート等のポリエステル系樹脂;ポリカーボネート系樹脂;(メタ)アクリル系樹脂;ポリスチレン系樹脂;又はこれらの混合物、共重合物等からなるフィルムであることができる。 [5] Thermoplastic Resin Film The firstthermoplastic resin film 10 and the second thermoplastic resin film 20 are each a translucent (preferably optically transparent) thermoplastic resin, for example, a chain polyolefin resin. Polypropylene-based resins such as (polypropylene-based resins, etc.), cyclic polyolefin-based resins (norbornen-based resins, etc.); Cellulosic ester-based resins such as triacetyl cellulose and diacetyl cellulose; polyester-based resins such as polyethylene terephthalate, polyethylene naphthalate, and thermoplastics. A film made of a resin; a polycarbonate-based resin; a (meth) acrylic-based resin; a polystyrene-based resin; or a mixture thereof, a copolymer, or the like can be used.
第1熱可塑性樹脂フィルム10及び第2熱可塑性樹脂フィルム20はそれぞれ、透光性を有する(好ましくは光学的に透明な)熱可塑性樹脂、例えば、鎖状ポリオレフィン系樹脂(ポリプロピレン系樹脂等)、環状ポリオレフィン系樹脂(ノルボルネン系樹脂等)等のポリオレフィン系樹脂;トリアセチルセルロース、ジアセチルセルロース等のセルロースエステル系樹脂;ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート等のポリエステル系樹脂;ポリカーボネート系樹脂;(メタ)アクリル系樹脂;ポリスチレン系樹脂;又はこれらの混合物、共重合物等からなるフィルムであることができる。 [5] Thermoplastic Resin Film The first
第1熱可塑性樹脂フィルム10及び第2熱可塑性樹脂フィルム20はそれぞれ、延伸されていないフィルム、又は一軸若しくは二軸延伸されたフィルムのいずれであってもよい。二軸延伸は、2つの延伸方向に同時に延伸する同時二軸延伸でもよく、第1方向に延伸した後でこれとは異なる第2方向に延伸する逐次二軸延伸であってもよい。
第1熱可塑性樹脂フィルム10及び/又は第2熱可塑性樹脂フィルム20は、光学層30を保護する役割を担う保護フィルムであってもよいし、位相差フィルム等の光学機能を併せ持つ保護フィルムであることもできる。
位相差フィルムについては、上記〔3〕の記載が引用される。 The firstthermoplastic resin film 10 and the second thermoplastic resin film 20 may be either an unstretched film or a uniaxially or biaxially stretched film, respectively. The biaxial stretching may be a simultaneous biaxial stretching that simultaneously stretches in two stretching directions, or may be a sequential biaxial stretching that stretches in a second direction different from this after stretching in the first direction.
The firstthermoplastic resin film 10 and / or the second thermoplastic resin film 20 may be a protective film that plays a role of protecting the optical layer 30, or is a protective film that also has an optical function such as a retardation film. You can also do it.
For the retardation film, the description in [3] above is cited.
第1熱可塑性樹脂フィルム10及び/又は第2熱可塑性樹脂フィルム20は、光学層30を保護する役割を担う保護フィルムであってもよいし、位相差フィルム等の光学機能を併せ持つ保護フィルムであることもできる。
位相差フィルムについては、上記〔3〕の記載が引用される。 The first
The first
For the retardation film, the description in [3] above is cited.
鎖状ポリオレフィン系樹脂としては、ポリエチレン樹脂、ポリプロピレン樹脂等の鎖状オレフィンの単独重合体のほか、2種以上の鎖状オレフィンからなる共重合体を挙げることができる。
Examples of the chain polyolefin resin include homopolymers of chain olefins such as polyethylene resin and polypropylene resin, and copolymers composed of two or more kinds of chain olefins.
環状ポリオレフィン系樹脂は、ノルボルネンやテトラシクロドデセン(別名:ジメタノオクタヒドロナフタレン)又はそれらの誘導体を代表例とする環状オレフィンを重合単位として含む樹脂の総称である。環状ポリオレフィン系樹脂としては、環状オレフィンの開環(共)重合体及びその水素添加物、環状オレフィンの付加重合体、環状オレフィンとエチレン、プロピレン等の鎖状オレフィン又はビニル基を有する芳香族化合物との共重合体、並びにこれらを不飽和カルボン酸やその誘導体で変性した変性(共)重合体等が挙げられる。
中でも、環状オレフィンとしてノルボルネンや多環ノルボルネン系単量体等のノルボルネン系単量体を用いたノルボルネン系樹脂が好ましく用いられる。 The cyclic polyolefin-based resin is a general term for resins containing norbornene, tetracyclododecene (also known as dimethanooctahydronaphthalene), or a cyclic olefin typified by a derivative thereof as a polymerization unit. Examples of the cyclic polyolefin resin include a ring-opening (co) polymer of a cyclic olefin and a hydrogenated product thereof, an addition polymer of a cyclic olefin, a cyclic olefin and a chain olefin such as ethylene and propylene, or an aromatic compound having a vinyl group. Examples thereof include copolymers of the above, and modified (co) copolymers obtained by modifying these with unsaturated carboxylic acids or derivatives thereof.
Of these, a norbornene-based resin using a norbornene-based monomer such as norbornene or a polycyclic norbornene-based monomer is preferably used as the cyclic olefin.
中でも、環状オレフィンとしてノルボルネンや多環ノルボルネン系単量体等のノルボルネン系単量体を用いたノルボルネン系樹脂が好ましく用いられる。 The cyclic polyolefin-based resin is a general term for resins containing norbornene, tetracyclododecene (also known as dimethanooctahydronaphthalene), or a cyclic olefin typified by a derivative thereof as a polymerization unit. Examples of the cyclic polyolefin resin include a ring-opening (co) polymer of a cyclic olefin and a hydrogenated product thereof, an addition polymer of a cyclic olefin, a cyclic olefin and a chain olefin such as ethylene and propylene, or an aromatic compound having a vinyl group. Examples thereof include copolymers of the above, and modified (co) copolymers obtained by modifying these with unsaturated carboxylic acids or derivatives thereof.
Of these, a norbornene-based resin using a norbornene-based monomer such as norbornene or a polycyclic norbornene-based monomer is preferably used as the cyclic olefin.
セルロースエステル系樹脂は、セルロースにおけるヒドロキシル基の少なくとも一部が酢酸エステル化されている樹脂であり、一部が酢酸エステル化され、一部が他の酸でエステル化されている混合エステルであってもよい。セルロースエステル系樹脂は、好ましくはアセチルセルロース系樹脂である。
アセチルセルロース系樹脂としては、トリアセチルセルロース、ジアセチルセルロース、セルロースアセテートプロピオネート、セルロースアセテートブチレート等が挙げられる。 The cellulose ester-based resin is a resin in which at least a part of the hydroxyl groups in cellulose is acetic acid esterified, and a mixed ester in which a part is acetic acid esterified and a part is esterified with another acid. May be good. The cellulosic ester resin is preferably an acetyl cellulosic resin.
Examples of the acetyl cellulosic resin include triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, and cellulose acetate butyrate.
アセチルセルロース系樹脂としては、トリアセチルセルロース、ジアセチルセルロース、セルロースアセテートプロピオネート、セルロースアセテートブチレート等が挙げられる。 The cellulose ester-based resin is a resin in which at least a part of the hydroxyl groups in cellulose is acetic acid esterified, and a mixed ester in which a part is acetic acid esterified and a part is esterified with another acid. May be good. The cellulosic ester resin is preferably an acetyl cellulosic resin.
Examples of the acetyl cellulosic resin include triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, and cellulose acetate butyrate.
ポリエステル系樹脂は、エステル結合を有する、上記セルロースエステル系樹脂以外の樹脂であり、多価カルボン酸又はその誘導体と多価アルコールとの重縮合体からなるものが一般的である。
ポリエステル系樹脂としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリトリメチレンテレフタレート、ポリトリメチレンナフタレート、ポリシクロへキサンジメチルテレフタレート、ポリシクロヘキサンジメチルナフタレート等が挙げられる。
中でも、機械的性質、耐溶剤性、耐スクラッチ性、コスト等の観点からポリエチレンテレフタレートが好ましく用いられる。ポリエチレンテレフタレートとは、繰返し単位の80モル%以上がエチレンテレフタレートで構成される樹脂をいい、他の共重合成分(イソフタル酸等のジカルボン酸成分;プロピレングリコール等のジオール成分等)に由来する構成単位を含んでいてもよい。 The polyester-based resin is a resin other than the above-mentioned cellulose ester-based resin having an ester bond, and is generally composed of a polyvalent carboxylic acid or a polycondensate of a derivative thereof and a polyhydric alcohol.
Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexanedimethylterephthalate, and polycyclohexanedimethylnaphthalate.
Of these, polyethylene terephthalate is preferably used from the viewpoints of mechanical properties, solvent resistance, scratch resistance, cost and the like. Polyethylene terephthalate refers to a resin in which 80 mol% or more of the repeating unit is composed of ethylene terephthalate, and is a constituent unit derived from other copolymerization components (dicarboxylic acid component such as isophthalic acid; diol component such as propylene glycol). May include.
ポリエステル系樹脂としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリトリメチレンテレフタレート、ポリトリメチレンナフタレート、ポリシクロへキサンジメチルテレフタレート、ポリシクロヘキサンジメチルナフタレート等が挙げられる。
中でも、機械的性質、耐溶剤性、耐スクラッチ性、コスト等の観点からポリエチレンテレフタレートが好ましく用いられる。ポリエチレンテレフタレートとは、繰返し単位の80モル%以上がエチレンテレフタレートで構成される樹脂をいい、他の共重合成分(イソフタル酸等のジカルボン酸成分;プロピレングリコール等のジオール成分等)に由来する構成単位を含んでいてもよい。 The polyester-based resin is a resin other than the above-mentioned cellulose ester-based resin having an ester bond, and is generally composed of a polyvalent carboxylic acid or a polycondensate of a derivative thereof and a polyhydric alcohol.
Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexanedimethylterephthalate, and polycyclohexanedimethylnaphthalate.
Of these, polyethylene terephthalate is preferably used from the viewpoints of mechanical properties, solvent resistance, scratch resistance, cost and the like. Polyethylene terephthalate refers to a resin in which 80 mol% or more of the repeating unit is composed of ethylene terephthalate, and is a constituent unit derived from other copolymerization components (dicarboxylic acid component such as isophthalic acid; diol component such as propylene glycol). May include.
ポリカーボネート系樹脂は、炭酸とグリコール又はビスフェノールとから形成されるポリエステルである。中でも、分子鎖にジフェニルアルカンを有する芳香族ポリカーボネートは、耐熱性、耐候性及び耐酸性の観点から好ましく使用される。
ポリカーボネートとしては、2,2-ビス(4-ヒドロキシフェニル)プロパン(別名ビスフェノールA)、2,2-ビス(4-ヒドロキシフェニル)ブタン、1,1-ビス(4-ヒドロキシフェニル)シクロヘキサン、1,1-ビス(4-ヒドロキシフェニル)イソブタン、1,1-ビス(4-ヒドロキシフェニル)エタン等のビスフェノールから誘導されるポリカーボネートが挙げられる。 The polycarbonate resin is a polyester formed from carbonic acid and glycol or bisphenol. Among them, aromatic polycarbonate having a diphenylalkane in the molecular chain is preferably used from the viewpoint of heat resistance, weather resistance and acid resistance.
Examples of 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, and 1, Examples thereof include polycarbonate derived from bisphenols such as 1-bis (4-hydroxyphenyl) isobutane and 1,1-bis (4-hydroxyphenyl) ethane.
ポリカーボネートとしては、2,2-ビス(4-ヒドロキシフェニル)プロパン(別名ビスフェノールA)、2,2-ビス(4-ヒドロキシフェニル)ブタン、1,1-ビス(4-ヒドロキシフェニル)シクロヘキサン、1,1-ビス(4-ヒドロキシフェニル)イソブタン、1,1-ビス(4-ヒドロキシフェニル)エタン等のビスフェノールから誘導されるポリカーボネートが挙げられる。 The polycarbonate resin is a polyester formed from carbonic acid and glycol or bisphenol. Among them, aromatic polycarbonate having a diphenylalkane in the molecular chain is preferably used from the viewpoint of heat resistance, weather resistance and acid resistance.
Examples of 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, and 1, Examples thereof include polycarbonate derived from bisphenols such as 1-bis (4-hydroxyphenyl) isobutane and 1,1-bis (4-hydroxyphenyl) ethane.
(メタ)アクリル系樹脂は、(メタ)アクリル系単量体由来の構成単位を含む重合体であり、(メタ)アクリル系単量体としては、メタクリル酸エステル及びアクリル酸エステルが挙げられる。
The (meth) acrylic resin is a polymer containing a structural unit derived from the (meth) acrylic monomer, and examples of the (meth) acrylic monomer include methacrylic acid ester and acrylic acid ester.
メタクリル酸エステルとしては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸n-、i-又はt-ブチル、メタクリル酸シクロヘキシル、メタクリル酸フェニル、メタクリル酸ベンジル、メタクリル酸2-エチルヘキシル、メタクリル酸2-ヒドロキシエチル等が挙げられる。
Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-, i- or t-butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, and 2-hydroxyethyl methacrylate. And so on.
アクリル酸エステルとしては、アクリル酸エチル、アクリル酸n-、i-又はt-ブチル、アクリル酸シクロヘキシル、アクリル酸フェニル、アクリル酸ベンジル、アクリル酸2-エチルヘキシル、アクリル酸2-ヒドロキシエチル等が挙げられる。
Examples of the acrylic acid ester include ethyl acrylate, n-, i- or t-butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate and the like. ..
(メタ)アクリル系樹脂は、(メタ)アクリルモノマー由来の構成単位のみからなる重合体であってもよいし、その他の構成単位を含んでいてもよい。
The (meth) acrylic resin may be a polymer consisting of only structural units derived from the (meth) acrylic monomer, or may contain other structural units.
1つの好ましい実施形態において(メタ)アクリル系樹脂は、共重合成分としてメタクリル酸メチルを含むか、又はメタクリル酸メチルとアクリル酸メチルとを含む。
1つの好ましい実施形態において(メタ)アクリル系樹脂は、メタクリル酸エステルを主たる単量体とする(50質量%以上含有する)重合体であることができ、メタクリル酸エステルと他の共重合成分とが共重合されている共重合体であることが好ましい。 In one preferred embodiment, the (meth) acrylic resin comprises methyl methacrylate as a copolymerization component, or comprises methyl methacrylate and methyl acrylate.
In one preferred embodiment, the (meth) acrylic resin can be a polymer containing a methacrylic acid ester as a main monomer (containing 50% by mass or more), and the methacrylic acid ester and other copolymerization components. Is preferably a copolymer in which is copolymerized.
1つの好ましい実施形態において(メタ)アクリル系樹脂は、メタクリル酸エステルを主たる単量体とする(50質量%以上含有する)重合体であることができ、メタクリル酸エステルと他の共重合成分とが共重合されている共重合体であることが好ましい。 In one preferred embodiment, the (meth) acrylic resin comprises methyl methacrylate as a copolymerization component, or comprises methyl methacrylate and methyl acrylate.
In one preferred embodiment, the (meth) acrylic resin can be a polymer containing a methacrylic acid ester as a main monomer (containing 50% by mass or more), and the methacrylic acid ester and other copolymerization components. Is preferably a copolymer in which is copolymerized.
(メタ)アクリル系樹脂のガラス転移温度は、好ましくは80℃以上160℃以下である。ガラス転移温度は、メタクリル酸エステル系単量体とアクリル酸エステル系単量体との重合比、それぞれのエステル基の炭素鎖長及びそれら有する官能基の種類、並びに単量体全体に対する多官能単量体の重合比の調整によって制御可能である。
The glass transition temperature of the (meth) acrylic resin is preferably 80 ° C. or higher and 160 ° C. or lower. The glass transition temperature is the polymerization ratio of the methacrylic acid ester-based monomer and the acrylic acid ester-based monomer, the carbon chain length of each ester group, the type of functional group having them, and the polyfunctional monomer for the entire monomer. It can be controlled by adjusting the polymerization ratio of the monomer.
(メタ)アクリル系樹脂のガラス転移温度を高めるための手段として、高分子の主鎖に環構造を導入することも有効である。環構造は、環状酸無水物構造、環状イミド構造及びラクトン構造等の複素環構造であることが好ましい。具体的には、無水グルタル酸構造、無水コハク酸構造等の環状酸無水物構造;グルタルイミド構造、コハクイミド構造等の環状イミド構造;ブチロラクトン、バレロラクトン等のラクトン環構造が挙げられる。
主鎖中の環構造の含有量を大きくするほど(メタ)アクリル系樹脂のガラス転移温度を高くすることができる傾向にある。
環状酸無水物構造、環状イミド構造は、無水マレイン酸、マレイミド等の環状構造を有する単量体を共重合させることによって導入する方法;重合後脱水・脱メタノール縮合反応により環状酸無水物構造を導入する方法;アミノ化合物を反応させて環状イミド構造を導入する方法等によって導入することができる。
ラクトン環構造を有する樹脂(重合体)は、高分子鎖にヒドロキシル基とエステル基とを有する重合体を調製した後、得られた重合体におけるヒドロキシル基とエステル基とを、加熱により、必要に応じて有機リン化合物等の触媒の存在下に環化縮合させてラクトン環構造を形成する方法によって得ることができる。 It is also effective to introduce a ring structure into the main chain of the polymer as a means for raising the glass transition temperature of the (meth) acrylic resin. The ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic imide structure and a lactone structure. Specific examples thereof include a cyclic acid anhydride structure such as a glutaric anhydride structure and a succinic anhydride structure; a cyclic imide structure such as a glutarimide structure and a succinic anhydride structure; and a lactone ring structure such as butyrolactone and valerolactone.
As the content of the ring structure in the main chain is increased, the glass transition temperature of the (meth) acrylic resin tends to be increased.
The cyclic acid anhydride structure and the cyclic imide structure are introduced by copolymerizing a monomer having a cyclic structure such as maleic anhydride and maleimide; the cyclic acid anhydride structure is formed by a dehydration / demethanol condensation reaction after polymerization. Method of introduction; It can be introduced by a method of reacting an amino compound to introduce a cyclic imide structure or the like.
For a resin (polymer) having a lactone ring structure, after preparing a polymer having a hydroxyl group and an ester group in a polymer chain, the hydroxyl group and the ester group in the obtained polymer are required by heating. Therefore, it can be obtained by a method of forming a lactone ring structure by cyclization condensation in the presence of a catalyst such as an organic phosphorus compound.
主鎖中の環構造の含有量を大きくするほど(メタ)アクリル系樹脂のガラス転移温度を高くすることができる傾向にある。
環状酸無水物構造、環状イミド構造は、無水マレイン酸、マレイミド等の環状構造を有する単量体を共重合させることによって導入する方法;重合後脱水・脱メタノール縮合反応により環状酸無水物構造を導入する方法;アミノ化合物を反応させて環状イミド構造を導入する方法等によって導入することができる。
ラクトン環構造を有する樹脂(重合体)は、高分子鎖にヒドロキシル基とエステル基とを有する重合体を調製した後、得られた重合体におけるヒドロキシル基とエステル基とを、加熱により、必要に応じて有機リン化合物等の触媒の存在下に環化縮合させてラクトン環構造を形成する方法によって得ることができる。 It is also effective to introduce a ring structure into the main chain of the polymer as a means for raising the glass transition temperature of the (meth) acrylic resin. The ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic imide structure and a lactone structure. Specific examples thereof include a cyclic acid anhydride structure such as a glutaric anhydride structure and a succinic anhydride structure; a cyclic imide structure such as a glutarimide structure and a succinic anhydride structure; and a lactone ring structure such as butyrolactone and valerolactone.
As the content of the ring structure in the main chain is increased, the glass transition temperature of the (meth) acrylic resin tends to be increased.
The cyclic acid anhydride structure and the cyclic imide structure are introduced by copolymerizing a monomer having a cyclic structure such as maleic anhydride and maleimide; the cyclic acid anhydride structure is formed by a dehydration / demethanol condensation reaction after polymerization. Method of introduction; It can be introduced by a method of reacting an amino compound to introduce a cyclic imide structure or the like.
For a resin (polymer) having a lactone ring structure, after preparing a polymer having a hydroxyl group and an ester group in a polymer chain, the hydroxyl group and the ester group in the obtained polymer are required by heating. Therefore, it can be obtained by a method of forming a lactone ring structure by cyclization condensation in the presence of a catalyst such as an organic phosphorus compound.
(メタ)アクリル系樹脂及びそれから形成される熱可塑性樹脂フィルムは、必要に応じて添加剤を含有していてもよい。添加剤としては、例えば、滑剤、ブロッキング防止剤、熱安定剤、酸化防止剤、帯電防止剤、耐光剤、耐衝撃性改良剤、界面活性剤等を挙げることができる。
これらの添加剤は、熱可塑性樹脂フィルムを構成する熱可塑性樹脂として、(メタ)アクリル系樹脂以外の他の熱可塑性樹脂を用いる場合にも使用することができる。 The (meth) acrylic resin and the thermoplastic resin film formed from the (meth) acrylic resin may contain additives, if necessary. Examples of the additive include a lubricant, an antiblocking agent, a heat stabilizer, an antioxidant, an antistatic agent, a lightproofing agent, an impact resistance improving agent, a surfactant and the like.
These additives can also be used when a thermoplastic resin other than the (meth) acrylic resin is used as the thermoplastic resin constituting the thermoplastic resin film.
これらの添加剤は、熱可塑性樹脂フィルムを構成する熱可塑性樹脂として、(メタ)アクリル系樹脂以外の他の熱可塑性樹脂を用いる場合にも使用することができる。 The (meth) acrylic resin and the thermoplastic resin film formed from the (meth) acrylic resin may contain additives, if necessary. Examples of the additive include a lubricant, an antiblocking agent, a heat stabilizer, an antioxidant, an antistatic agent, a lightproofing agent, an impact resistance improving agent, a surfactant and the like.
These additives can also be used when a thermoplastic resin other than the (meth) acrylic resin is used as the thermoplastic resin constituting the thermoplastic resin film.
(メタ)アクリル系樹脂は、フィルムへの製膜性やフィルムの耐衝撃性等の観点から、衝撃性改良剤であるアクリル系ゴム粒子を含有していてもよい。アクリル系ゴム粒子とは、アクリル酸エステルを主体とする弾性重合体を必須成分とする粒子であり、実質的にこの弾性重合体のみからなる単層構造のものや、この弾性重合体を1つの層とする多層構造のものが挙げられる。
The (meth) acrylic resin may contain acrylic rubber particles which are impact improving agents from the viewpoint of film forming property on the film, impact resistance of the film, and the like. Acrylic rubber particles are particles containing an elastic polymer mainly composed of an acrylic acid ester as an essential component, and have a single-layer structure substantially consisting of only this elastic polymer, or one elastic polymer. Examples thereof include a multi-layer structure having layers.
上記弾性重合体の例として、アクリル酸アルキルを主成分とし、これに共重合可能な他のビニル系単量体及び架橋性単量体を共重合させた架橋弾性共重合体が挙げられる。
弾性重合体の主成分となるアクリル酸アルキルとしては、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸2-エチルへキシル等、アルキル基の炭素数が1以上8以下程度のものが挙げられ、炭素数4以上のアルキル基を有するアクリル酸アルキルが好ましく用いられる。 Examples of the elastic polymer include a crosslinked elastic copolymer containing alkyl acrylate as a main component and copolymerizing another copolymerizable vinyl-based monomer and a crosslinkable monomer.
Examples of the alkyl acrylate that is the main component of the elastic polymer include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like, which have an alkyl group having 1 or more and 8 or less carbon atoms. An alkyl acrylate having an alkyl group having 4 or more carbon atoms is preferably used.
弾性重合体の主成分となるアクリル酸アルキルとしては、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸2-エチルへキシル等、アルキル基の炭素数が1以上8以下程度のものが挙げられ、炭素数4以上のアルキル基を有するアクリル酸アルキルが好ましく用いられる。 Examples of the elastic polymer include a crosslinked elastic copolymer containing alkyl acrylate as a main component and copolymerizing another copolymerizable vinyl-based monomer and a crosslinkable monomer.
Examples of the alkyl acrylate that is the main component of the elastic polymer include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like, which have an alkyl group having 1 or more and 8 or less carbon atoms. An alkyl acrylate having an alkyl group having 4 or more carbon atoms is preferably used.
上記アクリル酸アルキルに共重合可能な他のビニル系単量体としては、分子内に重合性炭素-炭素二重結合を1個有する化合物を挙げることができ、より具体的には、メタクリル酸メチル等のメタクリル酸エステル;スチレン等の芳香族ビニル化合物;アクリロニトリル等のビニルシアン化合物等が挙げられる。
Examples of the other vinyl-based monomer copolymerizable with the alkyl acrylate include a compound having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methyl methacrylate. Methacrylic acid esters such as, aromatic vinyl compounds such as styrene; vinyl cyan compounds such as acrylonitrile, and the like.
上記架橋性単量体としては、分子内に重合性炭素-炭素二重結合を少なくとも2個有する架橋性の化合物を挙げることができ、より具体的には、エチレングリコールジ(メタ)アクリレート、ブタンジオールジ(メタ)アクリレート等の多価アルコールの(メタ)アクリレート類;アリル(メタ)アクリレート等の(メタ)アクリル酸のアルケニルエステル;ジビニルベンゼン等が挙げられる。
Examples of the crosslinkable monomer include a crosslinkable compound having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, ethylene glycol di (meth) acrylate and butane. Examples thereof include (meth) acrylates of polyhydric alcohols such as diol di (meth) acrylate; alkenyl esters of (meth) acrylic acid such as allyl (meth) acrylate; and divinylbenzene.
ゴム粒子を含まない(メタ)アクリル系樹脂からなるフィルムと、ゴム粒子を含む(メタ)アクリル系樹脂からなるフィルムとの積層体を、光学層30に貼合される熱可塑性樹脂フィルムとすることもできる。また、(メタ)アクリル樹脂とは異なる樹脂からなる位相差発現層の片面又は両面に、(メタ)アクリル系樹脂層が形成され、位相差が発現されたものを、光学層30に貼合される熱可塑性樹脂フィルムとすることもできる。
A laminate of a film made of a (meth) acrylic resin containing no rubber particles and a film made of a (meth) acrylic resin containing rubber particles is used as a thermoplastic resin film to be bonded to the optical layer 30. You can also. Further, a (meth) acrylic resin layer is formed on one side or both sides of a retardation-developing layer made of a resin different from the (meth) acrylic resin, and the one in which the retardation is expressed is bonded to the optical layer 30. It can also be a thermoplastic resin film.
第1熱可塑性樹脂フィルム10及び第2熱可塑性樹脂フィルム20はそれぞれ、セルロースエステル系樹脂、ポリエステル系樹脂、(メタ)アクリル系樹脂及び環状ポリオレフィン系樹脂からなる群より選択される1以上の熱可塑性樹脂を含むフィルムであることが好ましく、セルロースエステル系樹脂フィルム、ポリエステル系樹脂フィルム、(メタ)アクリル系樹脂フィルム、又は環状ポリオレフィン系樹脂フィルムであることがより好ましい。
The first thermoplastic resin film 10 and the second thermoplastic resin film 20 are each one or more thermoplastics selected from the group consisting of a cellulose ester resin, a polyester resin, a (meth) acrylic resin, and a cyclic polyolefin resin. A film containing a resin is preferable, and a cellulose ester-based resin film, a polyester-based resin film, a (meth) acrylic-based resin film, or a cyclic polyolefin-based resin film is more preferable.
第1熱可塑性樹脂フィルム10及び/又は第2熱可塑性樹脂フィルム20は、紫外線吸収剤、赤外線吸収剤、有機系染料、顔料、無機色素、酸化防止剤、帯電防止剤、界面活性剤、滑剤、分散剤、熱安定化剤等を含有していてもよい。光学積層体を画像表示装置に適用する場合、紫外線吸収剤を含有する熱可塑性樹脂フィルムを画像表示素子(例えば液晶セルや有機EL表示素子等)の視認側に配置することで、画像表示素子の紫外線による劣化を抑制することができる。
紫外線吸収剤としては、サリチル酸エステル系化合物、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物、シアノアクリレート系化合物、ニッケル錯塩系化合物等が挙げられる。 The firstthermoplastic resin film 10 and / or the second thermoplastic resin film 20 contains an ultraviolet absorber, an infrared absorber, an organic dye, a pigment, an inorganic dye, an antioxidant, an antistatic agent, a surfactant, a lubricant, and the like. It may contain a dispersant, a heat stabilizer and the like. When the optical laminate is applied to an image display device, a thermoplastic resin film containing an ultraviolet absorber is placed on the visual side of an image display element (for example, a liquid crystal cell or an organic EL display element) to display the image. Deterioration due to ultraviolet rays can be suppressed.
Examples of the ultraviolet absorber include salicylic acid ester compounds, benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, nickel complex salt compounds and the like.
紫外線吸収剤としては、サリチル酸エステル系化合物、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物、シアノアクリレート系化合物、ニッケル錯塩系化合物等が挙げられる。 The first
Examples of the ultraviolet absorber include salicylic acid ester compounds, benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, nickel complex salt compounds and the like.
第1熱可塑性樹脂フィルム10及び第2熱可塑性樹脂フィルム20は、同じ熱可塑性樹脂で構成されるフィルムであってもよいし、互いに異なる熱可塑性樹脂で構成されるフィルムであってもよい。第1熱可塑性樹脂フィルム10及び第2熱可塑性樹脂フィルム20は、厚み、添加剤の有無やその種類、位相差特性等において同じであってもよいし、異なっていてもよい。
The first thermoplastic resin film 10 and the second thermoplastic resin film 20 may be films made of the same thermoplastic resin, or may be films made of different thermoplastic resins. The first thermoplastic resin film 10 and the second thermoplastic resin film 20 may be the same or different in terms of thickness, presence / absence of additives, their types, retardation characteristics, and the like.
第1熱可塑性樹脂フィルム10及び/又は第2熱可塑性樹脂フィルム20は、その外面(光学層30とは反対側の表面)にハードコート層、防眩層、反射防止層、光拡散層、帯電防止層、防汚層、導電層等の表面処理層(コーティング層)を備えていてもよい。
The first thermoplastic resin film 10 and / or the second thermoplastic resin film 20 has a hard coat layer, an antiglare layer, an antireflection layer, a light diffusion layer, and an antistatic layer on its outer surface (the surface opposite to the optical layer 30). A surface treatment layer (coating layer) such as an antifouling layer, an antifouling layer, and a conductive layer may be provided.
第1熱可塑性樹脂フィルム10及び第2熱可塑性樹脂フィルム20の厚みはそれぞれ、通常5μm以上200μm以下であり、好ましくは10μm以上120μm以下、より好ましくは10μm以上85μm以下、さらに好ましくは15μm以上65μm以下である。第1熱可塑性樹脂フィルム10及び第2熱可塑性樹脂フィルム20の厚みはそれぞれ、50μm以下であってもよく、40μm以下であってもよい。第1熱可塑性樹脂フィルム10及び第2熱可塑性樹脂フィルム20の厚みを小さくすることは、光学積層体(偏光板)、及びこれを含む画像表示装置の薄型化に有利である。
The thickness of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 is usually 5 μm or more and 200 μm or less, preferably 10 μm or more and 120 μm or less, more preferably 10 μm or more and 85 μm or less, and further preferably 15 μm or more and 65 μm or less. Is. The thickness of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 may be 50 μm or less, or 40 μm or less, respectively. Reducing the thickness of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 is advantageous for reducing the thickness of the optical laminate (polarizing plate) and the image display device including the optical laminate (polarizing plate).
第1熱可塑性樹脂フィルム10及び第2熱可塑性樹脂フィルム20の硬化性組成物が塗布される面においては、密着性向上の観点より、ケン化処理、プラズマ処理、コロナ処理、プライマー処理等の表面改質処理を行ってもよいし、工程の簡素化の観点より、表面改質処理を実施しなくてもよい。表面改質処理は、熱可塑性樹脂フィルムの貼合面の代わりに、あるいは該貼合面とともに、光学層30の貼合面に行ってもよい。
第1熱可塑性樹脂フィルム10又は第2熱可塑性樹脂フィルム20がセルロースエステル系樹脂フィルムである場合は、密着性向上の観点から、ケン化処理を行うことが好ましい。ケン化処理としては、水酸化ナトリウムや水酸化カリウムのようなアルカリの水溶液に浸漬する方法が挙げられる。 On the surface to which the curable composition of the firstthermoplastic resin film 10 and the second thermoplastic resin film 20 is applied, from the viewpoint of improving adhesion, surfaces such as saponification treatment, plasma treatment, corona treatment, and primer treatment are performed. The modification treatment may be performed, or the surface modification treatment may not be performed from the viewpoint of simplifying the process. The surface modification treatment may be performed on the bonding surface of the optical layer 30 instead of the bonding surface of the thermoplastic resin film or together with the bonding surface.
When the firstthermoplastic resin film 10 or the second thermoplastic resin film 20 is a cellulose ester-based resin film, it is preferable to carry out a saponification treatment from the viewpoint of improving adhesion. Examples of the saponification treatment include a method of immersing in an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide.
第1熱可塑性樹脂フィルム10又は第2熱可塑性樹脂フィルム20がセルロースエステル系樹脂フィルムである場合は、密着性向上の観点から、ケン化処理を行うことが好ましい。ケン化処理としては、水酸化ナトリウムや水酸化カリウムのようなアルカリの水溶液に浸漬する方法が挙げられる。 On the surface to which the curable composition of the first
When the first
〔6〕第2硬化物層
第2硬化物層25を形成する硬化性組成物は、上述の硬化性組成物(S)であってもよいし、これとは異なる他の硬化性組成物であってもよい。第2硬化物層25は、光学積層体の高温高湿環境下における光学耐久性等の観点から、硬化性組成物(S)の硬化物層であることが好ましい。
第1硬化物層15及び第2硬化物層25が硬化性組成物(S)から形成される場合において、これらの硬化性組成物は、同一の組成であってもよいし、異なる組成であってもよい。
他の硬化性組成物としては、硬化性の樹脂成分を水に溶解又は分散させた公知の水系組成物(水系接着剤を含む。)及び活性エネルギー線硬化性化合物を含有する公知の活性エネルギー線硬化性組成物(活性エネルギー線硬化性接着剤を含む。)等が挙げられる。 [6] Second Curable Layer The curable composition forming the second curedlayer 25 may be the above-mentioned curable composition (S), or may be another curable composition different from this. There may be. The second cured product layer 25 is preferably a cured product layer of the curable composition (S) from the viewpoint of optical durability of the optical laminate in a high temperature and high humidity environment.
When the first curedproduct layer 15 and the second cured product layer 25 are formed from the curable composition (S), these curable compositions may have the same composition or different compositions. You may.
Other curable compositions include known water-based compositions (including water-based adhesives) in which a curable resin component is dissolved or dispersed in water, and known active energy rays containing an active energy ray-curable compound. Examples thereof include a curable composition (including an active energy ray-curable adhesive) and the like.
第2硬化物層25を形成する硬化性組成物は、上述の硬化性組成物(S)であってもよいし、これとは異なる他の硬化性組成物であってもよい。第2硬化物層25は、光学積層体の高温高湿環境下における光学耐久性等の観点から、硬化性組成物(S)の硬化物層であることが好ましい。
第1硬化物層15及び第2硬化物層25が硬化性組成物(S)から形成される場合において、これらの硬化性組成物は、同一の組成であってもよいし、異なる組成であってもよい。
他の硬化性組成物としては、硬化性の樹脂成分を水に溶解又は分散させた公知の水系組成物(水系接着剤を含む。)及び活性エネルギー線硬化性化合物を含有する公知の活性エネルギー線硬化性組成物(活性エネルギー線硬化性接着剤を含む。)等が挙げられる。 [6] Second Curable Layer The curable composition forming the second cured
When the first cured
Other curable compositions include known water-based compositions (including water-based adhesives) in which a curable resin component is dissolved or dispersed in water, and known active energy rays containing an active energy ray-curable compound. Examples thereof include a curable composition (including an active energy ray-curable adhesive) and the like.
水系組成物に含有される樹脂成分としては、ポリビニルアルコール系樹脂やウレタン樹脂等が挙げられる。
ポリビニルアルコール系樹脂を含む水系組成物は、密着性や接着性を向上させるために、多価アルデヒド、メラミン系化合物、ジルコニア化合物、亜鉛化合物、グリオキザール、グリオキザール誘導体、水溶性エポキシ樹脂等の硬化性成分や架橋剤をさらに含有することができる。
ウレタン樹脂を含む水系組成物としては、ポリエステル系アイオノマー型ウレタン樹脂とグリシジルオキシ基を有する化合物とを含む水系組成物が挙げられる。ポリエステル系アイオノマー型ウレタン樹脂とは、ポリエステル骨格を有するウレタン樹脂であって、その中に少量のイオン性成分(親水成分)が導入されたものである。 Examples of the resin component contained in the aqueous composition include polyvinyl alcohol-based resin and urethane resin.
The aqueous composition containing a polyvinyl alcohol-based resin is a curable component such as a polyhydric aldehyde, a melamine-based compound, a zirconia compound, a zinc compound, glyoxal, a glyoxal derivative, and a water-soluble epoxy resin in order to improve adhesion and adhesiveness. And a cross-linking agent can be further contained.
Examples of the aqueous composition containing the urethane resin include an aqueous composition containing a polyester ionomer type urethane resin and a compound having a glycidyloxy group. The polyester-based ionomer type urethane resin is a urethane resin having a polyester skeleton, in which a small amount of an ionic component (hydrophilic component) is introduced.
ポリビニルアルコール系樹脂を含む水系組成物は、密着性や接着性を向上させるために、多価アルデヒド、メラミン系化合物、ジルコニア化合物、亜鉛化合物、グリオキザール、グリオキザール誘導体、水溶性エポキシ樹脂等の硬化性成分や架橋剤をさらに含有することができる。
ウレタン樹脂を含む水系組成物としては、ポリエステル系アイオノマー型ウレタン樹脂とグリシジルオキシ基を有する化合物とを含む水系組成物が挙げられる。ポリエステル系アイオノマー型ウレタン樹脂とは、ポリエステル骨格を有するウレタン樹脂であって、その中に少量のイオン性成分(親水成分)が導入されたものである。 Examples of the resin component contained in the aqueous composition include polyvinyl alcohol-based resin and urethane resin.
The aqueous composition containing a polyvinyl alcohol-based resin is a curable component such as a polyhydric aldehyde, a melamine-based compound, a zirconia compound, a zinc compound, glyoxal, a glyoxal derivative, and a water-soluble epoxy resin in order to improve adhesion and adhesiveness. And a cross-linking agent can be further contained.
Examples of the aqueous composition containing the urethane resin include an aqueous composition containing a polyester ionomer type urethane resin and a compound having a glycidyloxy group. The polyester-based ionomer type urethane resin is a urethane resin having a polyester skeleton, in which a small amount of an ionic component (hydrophilic component) is introduced.
活性エネルギー線硬化性組成物は、紫外線、可視光、電子線、X線等の活性エネルギー線の照射によって硬化する組成物である。活性エネルギー線硬化性組成物を用いる場合、第2硬化物層25は、当該組成物の硬化物層である。
The active energy ray-curable composition is a composition that is cured by irradiation with active energy rays such as ultraviolet rays, visible light, electron beams, and X-rays. When an active energy ray-curable composition is used, the second cured product layer 25 is a cured product layer of the composition.
活性エネルギー線硬化性組成物は、カチオン重合によって硬化するエポキシ系化合物を硬化性成分として含有する組成物であることができ、好ましくは、かかるエポキシ系化合物を硬化性成分として含有する紫外線硬化性組成物である。エポキシ系化合物とは、分子内に平均1個以上、好ましくは2個以上のエポキシ基を有する化合物を意味する。エポキシ系化合物は、1種のみを使用してもよいし、2種以上を併用してもよい。
The active energy ray-curable composition can be a composition containing an epoxy compound that is cured by cationic polymerization as a curable component, and preferably an ultraviolet curable composition containing such an epoxy compound as a curable component. It is a thing. The epoxy-based compound means a compound having an average of 1 or more, preferably 2 or more epoxy groups in the molecule. Only one type of epoxy compound may be used, or two or more types may be used in combination.
エポキシ系化合物としては、芳香族ポリオールの芳香環に水素化反応を行って得られる脂環式ポリオールに、エピクロロヒドリンを反応させることにより得られる水素化エポキシ系化合物(脂環式環を有するポリオールのグリシジルエーテル);脂肪族多価アルコール又はそのアルキレンオキサイド付加物のポリグリシジルエーテル等の脂肪族エポキシ系化合物;脂環式環に結合したエポキシ基を分子内に1個以上有するエポキシ系化合物である脂環式エポキシ系化合物等が挙げられる。
As the epoxy compound, a hydride epoxy compound (having an alicyclic ring) obtained by reacting epichlorohydrin with an alicyclic polyol obtained by hydrogenating the aromatic ring of an aromatic polyol. Polyglycidyl ether of polyol); an aliphatic epoxy compound such as an aliphatic polyhydric alcohol or a polyglycidyl ether of an alkylene oxide adduct thereof; an epoxy compound having one or more epoxy groups bonded to an alicyclic ring in the molecule. Examples thereof include certain alicyclic epoxy compounds.
活性エネルギー線硬化性組成物は、硬化性成分として、上記エポキシ系化合物の代わりに、又はこれとともにラジカル重合性である(メタ)アクリル系化合物を含有することができる。(メタ)アクリル系化合物としては、分子内に1個以上の(メタ)アクリロイルオキシ基を有する(メタ)アクリレートモノマー;官能基含有化合物を2種以上反応させて得られ、分子内に少なくとも2個の(メタ)アクリロイルオキシ基を有する(メタ)アクリレートオリゴマー等の(メタ)アクリロイルオキシ基含有化合物を挙げることができる。
The active energy ray-curable composition can contain, as a curable component, a (meth) acrylic compound which is radically polymerizable in place of or together with the epoxy compound. The (meth) acrylic compound is a (meth) acrylate monomer having one or more (meth) acryloyloxy groups in the molecule; obtained by reacting two or more kinds of functional group-containing compounds, and at least two in the molecule. Examples thereof include (meth) acryloyloxy group-containing compounds such as (meth) acrylate oligomers having a (meth) acryloyloxy group.
活性エネルギー線硬化性組成物は、カチオン重合によって硬化するエポキシ系化合物を硬化性成分として含む場合、光カチオン重合開始剤を含有することが好ましい。光カチオン重合開始剤としては、例えば、芳香族ジアゾニウム塩;芳香族ヨードニウム塩や芳香族スルホニウム塩等のオニウム塩;鉄-アレン錯体等を挙げることができる。
活性エネルギー線硬化性組成物は、(メタ)アクリル系化合物等のラジカル重合性成分を含む場合、光ラジカル重合開始剤を含有することが好ましい。光ラジカル重合開始剤としては、例えば、アセトフェノン系開始剤、ベンゾフェノン系開始剤、ベンゾインエーテル系開始剤、チオキサントン系開始剤、キサントン、フルオレノン、カンファーキノン、ベンズアルデヒド、アントラキノン等を挙げることができる。 When the active energy ray-curable composition contains an epoxy-based compound that is cured by cationic polymerization as a curable component, it preferably contains a photocationic polymerization initiator. Examples of the photocationic polymerization initiator include aromatic diazonium salts; onium salts such as aromatic iodonium salts and aromatic sulfonium salts; and iron-allene complexes.
When the active energy ray-curable composition contains a radically polymerizable component such as a (meth) acrylic compound, it preferably contains a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include an acetophenone-based initiator, a benzophenone-based initiator, a benzoin ether-based initiator, a thioxanthone-based initiator, xanthone, fluorenone, camphorquinone, benzaldehyde, anthraquinone and the like.
活性エネルギー線硬化性組成物は、(メタ)アクリル系化合物等のラジカル重合性成分を含む場合、光ラジカル重合開始剤を含有することが好ましい。光ラジカル重合開始剤としては、例えば、アセトフェノン系開始剤、ベンゾフェノン系開始剤、ベンゾインエーテル系開始剤、チオキサントン系開始剤、キサントン、フルオレノン、カンファーキノン、ベンズアルデヒド、アントラキノン等を挙げることができる。 When the active energy ray-curable composition contains an epoxy-based compound that is cured by cationic polymerization as a curable component, it preferably contains a photocationic polymerization initiator. Examples of the photocationic polymerization initiator include aromatic diazonium salts; onium salts such as aromatic iodonium salts and aromatic sulfonium salts; and iron-allene complexes.
When the active energy ray-curable composition contains a radically polymerizable component such as a (meth) acrylic compound, it preferably contains a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include an acetophenone-based initiator, a benzophenone-based initiator, a benzoin ether-based initiator, a thioxanthone-based initiator, xanthone, fluorenone, camphorquinone, benzaldehyde, anthraquinone and the like.
光学積層体は、第2硬化物層25の代わりに粘着剤層を含むものであってもよい。すなわち、第2熱可塑性樹脂フィルム20を粘着剤層を介して光学層30に貼合してもよい。
該粘着剤層については、後述する粘着剤層についての記載が引用される。 The optical laminate may include an adhesive layer instead of the second curedproduct layer 25. That is, the second thermoplastic resin film 20 may be attached to the optical layer 30 via the pressure-sensitive adhesive layer.
As for the pressure-sensitive adhesive layer, the description of the pressure-sensitive adhesive layer described later is cited.
該粘着剤層については、後述する粘着剤層についての記載が引用される。 The optical laminate may include an adhesive layer instead of the second cured
As for the pressure-sensitive adhesive layer, the description of the pressure-sensitive adhesive layer described later is cited.
〔7〕光学積層体の製造
光学層30の一方の面に第1硬化物層15を介して第1熱可塑性樹脂フィルム10を積層接着することにより、図2に示される構成の光学積層体を得ることができ、光学層30の他方の面に第2硬化物層25を介して第2熱可塑性樹脂フィルム20をさらに積層接着することにより、図3に示される構成の光学積層体を得ることができる。
第1熱可塑性樹脂フィルム10及び第2熱可塑性樹脂フィルム20の双方を有する光学積層体を製造する場合、これらのフィルムは、段階的に片面ずつ積層接着してもよいし、両面のフィルムを同時に積層接着してもよい。 [7] Manufacture of Optical Laminate The optical laminate having the configuration shown in FIG. 2 is obtained by laminating and adhering the firstthermoplastic resin film 10 to one surface of the optical layer 30 via the first cured product layer 15. It can be obtained, and by further laminating and adhering the second thermoplastic resin film 20 to the other surface of the optical layer 30 via the second cured product layer 25, an optical laminate having the configuration shown in FIG. 3 can be obtained. Can be done.
When producing an optical laminate having both the firstthermoplastic resin film 10 and the second thermoplastic resin film 20, these films may be laminated and bonded one side at a time step by step, or the films on both sides may be laminated and bonded at the same time. It may be laminated and bonded.
光学層30の一方の面に第1硬化物層15を介して第1熱可塑性樹脂フィルム10を積層接着することにより、図2に示される構成の光学積層体を得ることができ、光学層30の他方の面に第2硬化物層25を介して第2熱可塑性樹脂フィルム20をさらに積層接着することにより、図3に示される構成の光学積層体を得ることができる。
第1熱可塑性樹脂フィルム10及び第2熱可塑性樹脂フィルム20の双方を有する光学積層体を製造する場合、これらのフィルムは、段階的に片面ずつ積層接着してもよいし、両面のフィルムを同時に積層接着してもよい。 [7] Manufacture of Optical Laminate The optical laminate having the configuration shown in FIG. 2 is obtained by laminating and adhering the first
When producing an optical laminate having both the first
光学層30と第1熱可塑性樹脂フィルム10とを接着させる方法としては、硬化性組成物(S)を光学層30及び第1熱可塑性樹脂フィルム10の貼合面のいずれか一方又はその両方に塗工し、これにもう一方の貼合面を積層し、例えば貼合ロール等を用いて上下から押圧して貼合する方法が挙げられる。
硬化性組成物(S)の塗工には、例えば、ドクターブレード、ワイヤーバー、ダイコーター、カンマコーター、グラビアコーター等、種々の塗工方式が利用できる。また、光学層30及び第1熱可塑性樹脂フィルム10を両者の貼合面が内側となるように連続的に供給しながら、その間に硬化性組成物(S)を流延させる方式であってもよい。 As a method of adhering theoptical layer 30 and the first thermoplastic resin film 10 to one or both of the bonding surfaces of the optical layer 30 and the first thermoplastic resin film 10, the curable composition (S) is applied. Examples thereof include a method of coating, laminating the other laminating surface on the laminating surface, and pressing from above and below using a laminating roll or the like for laminating.
For coating the curable composition (S), for example, various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used. Further, even in a method in which theoptical layer 30 and the first thermoplastic resin film 10 are continuously supplied so that the bonding surfaces of both are on the inside, and the curable composition (S) is cast between them. Good.
硬化性組成物(S)の塗工には、例えば、ドクターブレード、ワイヤーバー、ダイコーター、カンマコーター、グラビアコーター等、種々の塗工方式が利用できる。また、光学層30及び第1熱可塑性樹脂フィルム10を両者の貼合面が内側となるように連続的に供給しながら、その間に硬化性組成物(S)を流延させる方式であってもよい。 As a method of adhering the
For coating the curable composition (S), for example, various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used. Further, even in a method in which the
光学層30と第1熱可塑性樹脂フィルム10とを貼合した後、光学層30と第1硬化物層15と第1熱可塑性樹脂フィルム10とを含む積層体に対して、加熱処理を施すことが好ましい。加熱処理の温度は、例えば40℃以上100℃以下であり、好ましくは50℃以上90℃以下である。加熱処理によって硬化性組成物層に含まれる溶剤を除去することができる。また、該加熱処理によって硬化性組成物の硬化・架橋反応を進行させることができる。
After the optical layer 30 and the first thermoplastic resin film 10 are bonded together, a heat treatment is performed on the laminate containing the optical layer 30, the first cured product layer 15, and the first thermoplastic resin film 10. Is preferable. The temperature of the heat treatment is, for example, 40 ° C. or higher and 100 ° C. or lower, preferably 50 ° C. or higher and 90 ° C. or lower. The solvent contained in the curable composition layer can be removed by heat treatment. In addition, the heat treatment can allow the curing / crosslinking reaction of the curable composition to proceed.
以上の接着方法は、光学層30と第2熱可塑性樹脂フィルム20との接着にも適用することができる。
The above bonding method can also be applied to bonding the optical layer 30 and the second thermoplastic resin film 20.
第2硬化物層を構成する硬化性組成物として活性エネルギー線硬化性組成物を用いる場合、必要に応じて硬化性組成物層の乾燥を行った後、活性エネルギー線を照射して硬化性組成物層を硬化させる。
活性エネルギー線を照射するために用いる光源は、紫外線、電子線、X線等を発生できるものであればよい。特に波長400nm以下に発光分布を有する、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯、メタルハライドランプ等が好適に用いられる。 When an active energy ray-curable composition is used as the curable composition constituting the second cured product layer, the curable composition layer is dried as necessary and then irradiated with active energy rays to form the curable composition. Harden the material layer.
The light source used for irradiating the active energy beam may be any light source capable of generating ultraviolet rays, electron beams, X-rays and the like. In particular, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, and the like having an emission distribution having a wavelength of 400 nm or less are preferably used.
活性エネルギー線を照射するために用いる光源は、紫外線、電子線、X線等を発生できるものであればよい。特に波長400nm以下に発光分布を有する、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯、メタルハライドランプ等が好適に用いられる。 When an active energy ray-curable composition is used as the curable composition constituting the second cured product layer, the curable composition layer is dried as necessary and then irradiated with active energy rays to form the curable composition. Harden the material layer.
The light source used for irradiating the active energy beam may be any light source capable of generating ultraviolet rays, electron beams, X-rays and the like. In particular, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, and the like having an emission distribution having a wavelength of 400 nm or less are preferably used.
図1に示すような、第1硬化物層15上に第1熱可塑性樹脂フィルムを有しない光学積層体は、光学層30の表面に硬化性組成物(S)を塗工し、得られた積層体に対して、例えば熱風乾燥機で80℃、300秒間の加熱処理を施すことによって製造することができる。また、セパレートフィルム/硬化性組成物(S)/光学層30からなる積層体を製造した後、セパレートフィルムを剥離し、その後、加熱処理を施すことによっても図1に示す光学積層体を製造することができる。
As shown in FIG. 1, an optical laminate having no first thermoplastic resin film on the first cured product layer 15 was obtained by coating the surface of the optical layer 30 with the curable composition (S). The laminate can be produced, for example, by subjecting the laminate to heat treatment at 80 ° C. for 300 seconds with a hot air dryer. Further, the optical laminate shown in FIG. 1 is also produced by producing a laminate composed of a separate film / curable composition (S) / optical layer 30, peeling off the separate film, and then performing heat treatment. be able to.
硬化性組成物(S)から形成される第1硬化物層15や第2硬化物層25の厚みは、例えば1nm以上20μm以下であり、好ましくは5nm以上10μm以下であり、より好ましくは10nm以上5μm以下であり、さらに好ましくは20nm以上2μm以下である。上述の公知の水系組成物から形成される硬化物層もこれと同程度の厚みを有することができる。
活性エネルギー線硬化性組成物から形成される硬化物層の厚みは、例えば10nm以上20μm以下、好ましくは100nm以上10μm以下、より好ましくは500nm以上5μm以下である。
第1硬化物層15と第2硬化物層25とは、厚みが同じであってもよいし、異なっていてもよい。 The thickness of the first curedproduct layer 15 and the second cured product layer 25 formed from the curable composition (S) is, for example, 1 nm or more and 20 μm or less, preferably 5 nm or more and 10 μm or less, and more preferably 10 nm or more. It is 5 μm or less, more preferably 20 nm or more and 2 μm or less. The cured product layer formed from the above-mentioned known aqueous composition can also have the same thickness.
The thickness of the cured product layer formed from the active energy ray-curable composition is, for example, 10 nm or more and 20 μm or less, preferably 100 nm or more and 10 μm or less, and more preferably 500 nm or more and 5 μm or less.
The first curedproduct layer 15 and the second cured product layer 25 may have the same thickness or may be different in thickness.
活性エネルギー線硬化性組成物から形成される硬化物層の厚みは、例えば10nm以上20μm以下、好ましくは100nm以上10μm以下、より好ましくは500nm以上5μm以下である。
第1硬化物層15と第2硬化物層25とは、厚みが同じであってもよいし、異なっていてもよい。 The thickness of the first cured
The thickness of the cured product layer formed from the active energy ray-curable composition is, for example, 10 nm or more and 20 μm or less, preferably 100 nm or more and 10 μm or less, and more preferably 500 nm or more and 5 μm or less.
The first cured
〔8〕光学積層体のその他の構成要素
〔8-1〕光学機能性フィルム
光学積層体は、所望の光学機能を付与するための、光学層30(例えば偏光子)以外の他の光学機能性フィルムを備えることができ、その好適な一例は位相差フィルムである。
上述のように、第1熱可塑性樹脂フィルム10及び/又は第2熱可塑性樹脂フィルム20が位相差フィルムを兼ねることもできるが、これらのフィルムとは別途に位相差フィルムを積層することもできる。後者の場合、位相差フィルムは、粘着剤層や接着剤層を介して第1熱可塑性樹脂フィルム10、第2熱可塑性樹脂フィルム20、第1硬化物層15及び/又は第2硬化物層25の外面に積層することができる。位相差フィルムについては、上記〔3〕の記載が引用される。 [8] Other Components of Optical Laminate [8-1] Optical Functional Film The optical laminate has optical functionality other than the optical layer 30 (for example, a polarizer) for imparting a desired optical function. A film can be provided, a preferred example thereof being a retardation film.
As described above, the firstthermoplastic resin film 10 and / or the second thermoplastic resin film 20 can also serve as a retardation film, but a retardation film can also be laminated separately from these films. In the latter case, the retardation film is the first thermoplastic resin film 10, the second thermoplastic resin film 20, the first cured product layer 15 and / or the second cured product layer 25 via the adhesive layer and the adhesive layer. Can be laminated on the outer surface of. For the retardation film, the description in [3] above is cited.
〔8-1〕光学機能性フィルム
光学積層体は、所望の光学機能を付与するための、光学層30(例えば偏光子)以外の他の光学機能性フィルムを備えることができ、その好適な一例は位相差フィルムである。
上述のように、第1熱可塑性樹脂フィルム10及び/又は第2熱可塑性樹脂フィルム20が位相差フィルムを兼ねることもできるが、これらのフィルムとは別途に位相差フィルムを積層することもできる。後者の場合、位相差フィルムは、粘着剤層や接着剤層を介して第1熱可塑性樹脂フィルム10、第2熱可塑性樹脂フィルム20、第1硬化物層15及び/又は第2硬化物層25の外面に積層することができる。位相差フィルムについては、上記〔3〕の記載が引用される。 [8] Other Components of Optical Laminate [8-1] Optical Functional Film The optical laminate has optical functionality other than the optical layer 30 (for example, a polarizer) for imparting a desired optical function. A film can be provided, a preferred example thereof being a retardation film.
As described above, the first
偏光板等の光学積層体に含まれ得る他の光学機能性フィルム(光学部材)の例は、集光板、輝度向上フィルム、反射層(反射フィルム)、半透過反射層(半透過反射フィルム)、光拡散層(光拡散フィルム)等である。
Examples of other optical functional films (optical members) that can be included in an optical laminate such as a polarizing plate include a condenser plate, a brightness improving film, a reflective layer (reflective film), a semi-transmissive reflective layer (semi-transmissive reflective film), A light diffusing layer (light diffusing film) or the like.
集光板は、光路制御等を目的に用いられるもので、プリズムアレイシートやレンズアレイシート、ドット付設シート等であることができる。
The condensing plate is used for the purpose of controlling the optical path, and can be a prism array sheet, a lens array sheet, a sheet with dots, or the like.
輝度向上フィルムは、偏光板等の光学積層体を適用した画像表示装置における輝度を向上させる目的で使用される。具体的には、屈折率の異方性が互いに異なる薄膜フィルムを複数枚積層して反射率に異方性が生じるように設計された反射型偏光分離シート、コレステリック液晶ポリマーの配向フィルムやその配向液晶層を基材フィルム上に支持した円偏光分離シート等が挙げられる。
The brightness improving film is used for the purpose of improving the brightness in an image display device to which an optical laminate such as a polarizing plate is applied. Specifically, a reflective polarizing separation sheet designed to generate anisotropy in reflectance by laminating a plurality of thin films having different refractive index anisotropy, an alignment film of cholesteric liquid crystal polymer, and its orientation. Examples thereof include a circularly polarized light separation sheet in which a liquid crystal layer is supported on a base film.
反射層、半透過反射層、光拡散層は、偏光板を反射型、半透過型、拡散型の光学部材とするためにそれぞれ設けられる。反射型の偏光板は、視認側からの入射光を反射させて表示するタイプの液晶表示装置に用いられ、バックライト等の光源を省略できるため、液晶表示装置を薄型化しやすい。半透過型の偏光板は、明所では反射型として、暗所ではバックライトからの光で表示するタイプの液晶表示装置に用いられる。また拡散型の偏光板は、光拡散性を付与してモアレ等の表示不良を抑制した液晶表示装置に用いられる。反射層、半透過反射層及び光拡散層は、公知の方法により形成することができる。
The reflective layer, the semi-transmissive reflective layer, and the light diffusing layer are provided to make the polarizing plate a reflective, semi-transmissive, and diffuse optical member, respectively. The reflective polarizing plate is used in a liquid crystal display device of a type that reflects and displays incident light from the viewing side, and since a light source such as a backlight can be omitted, the liquid crystal display device can be easily made thinner. The transflective polarizing plate is used in a liquid crystal display device of a type that displays light from a backlight in a dark place as a reflective type in a bright place. Further, the diffusion type polarizing plate is used for a liquid crystal display device that imparts light diffusivity and suppresses display defects such as moire. The reflective layer, the transflective reflective layer and the light diffusing layer can be formed by a known method.
〔8-2〕粘着剤層
光学積層体は、粘着剤層を含むことができる。粘着剤層としては、光学積層体を液晶セルや有機EL表示素子等の画像表示素子、又は他の光学部材に貼合するための粘着剤層が挙げられる。該粘着剤層は、図1及び2に示される構成の光学積層体においては光学層30の外面、図3に示される構成の光学積層体においては第1熱可塑性樹脂フィルム10又は第2熱可塑性樹脂フィルム20の外面、図4に示される構成の光学積層体においては第1硬化物層15又は第2熱可塑性樹脂フィルム20の外面、図5に示される構成の光学積層体においては第1硬化物層15又は第2硬化物層25の外面に積層することができる。
図3に示される構成の光学積層体の第2熱可塑性樹脂フィルム20の外面に粘着剤層40を積層した例を図6に示す。 [8-2] Adhesive Layer The optical laminate can include an adhesive layer. Examples of the pressure-sensitive adhesive layer include a pressure-sensitive adhesive layer for bonding an optical laminate to an image display element such as a liquid crystal cell or an organic EL display element, or another optical member. The pressure-sensitive adhesive layer is the outer surface of theoptical layer 30 in the optical laminate having the configuration shown in FIGS. 1 and 2, and the first thermoplastic resin film 10 or the second thermoplastic in the optical laminate having the configuration shown in FIG. The outer surface of the resin film 20, the outer surface of the first cured product layer 15 or the second thermoplastic resin film 20 in the optical laminate having the configuration shown in FIG. 4, and the first curing in the optical laminate having the configuration shown in FIG. It can be laminated on the outer surface of the material layer 15 or the second cured product layer 25.
FIG. 6 shows an example in which the pressure-sensitive adhesive layer 40 is laminated on the outer surface of the second thermoplastic resin film 20 of the optical laminate having the configuration shown in FIG.
光学積層体は、粘着剤層を含むことができる。粘着剤層としては、光学積層体を液晶セルや有機EL表示素子等の画像表示素子、又は他の光学部材に貼合するための粘着剤層が挙げられる。該粘着剤層は、図1及び2に示される構成の光学積層体においては光学層30の外面、図3に示される構成の光学積層体においては第1熱可塑性樹脂フィルム10又は第2熱可塑性樹脂フィルム20の外面、図4に示される構成の光学積層体においては第1硬化物層15又は第2熱可塑性樹脂フィルム20の外面、図5に示される構成の光学積層体においては第1硬化物層15又は第2硬化物層25の外面に積層することができる。
図3に示される構成の光学積層体の第2熱可塑性樹脂フィルム20の外面に粘着剤層40を積層した例を図6に示す。 [8-2] Adhesive Layer The optical laminate can include an adhesive layer. Examples of the pressure-sensitive adhesive layer include a pressure-sensitive adhesive layer for bonding an optical laminate to an image display element such as a liquid crystal cell or an organic EL display element, or another optical member. The pressure-sensitive adhesive layer is the outer surface of the
FIG. 6 shows an example in which the pressure-
粘着剤層に用いられる粘着剤としては、(メタ)アクリル系樹脂や、シリコーン系樹脂、ポリエステル系樹脂、ポリウレタン系樹脂、ポリエーテル系樹脂等をベースポリマーとするものを用いることができる。中でも、透明性、粘着力、信頼性、耐候性、耐熱性、リワーク性等の観点から、(メタ)アクリル系粘着剤が好ましい。
(メタ)アクリル系粘着剤には、メチル基やエチル基やn-、i-又はt-ブチル基等の炭素数が20以下のアルキル基を有する(メタ)アクリル酸アルキルエステルと、(メタ)アクリル酸や(メタ)アクリル酸ヒドロキシエチル等の官能基含有(メタ)アクリル系モノマーとを、ガラス転移温度が好ましくは25℃以下、より好ましくは0℃以下となるように配合した、重量平均分子量が10万以上の(メタ)アクリル系樹脂がベースポリマーとして有用である。 As the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer, a (meth) acrylic resin, a silicone-based resin, a polyester-based resin, a polyurethane-based resin, a polyether-based resin, or the like as a base polymer can be used. Among them, a (meth) acrylic pressure-sensitive adhesive is preferable from the viewpoints of transparency, adhesive strength, reliability, weather resistance, heat resistance, reworkability and the like.
The (meth) acrylic pressure-sensitive adhesive includes a (meth) acrylic acid alkyl ester having an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group, an n-, i- or t-butyl group, and (meth). A weight average molecular weight of a functional group-containing (meth) acrylic monomer such as acrylic acid or hydroxyethyl (meth) acrylic acid blended so that the glass transition temperature is preferably 25 ° C. or lower, more preferably 0 ° C. or lower. A (meth) acrylic resin having a value of 100,000 or more is useful as a base polymer.
(メタ)アクリル系粘着剤には、メチル基やエチル基やn-、i-又はt-ブチル基等の炭素数が20以下のアルキル基を有する(メタ)アクリル酸アルキルエステルと、(メタ)アクリル酸や(メタ)アクリル酸ヒドロキシエチル等の官能基含有(メタ)アクリル系モノマーとを、ガラス転移温度が好ましくは25℃以下、より好ましくは0℃以下となるように配合した、重量平均分子量が10万以上の(メタ)アクリル系樹脂がベースポリマーとして有用である。 As the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer, a (meth) acrylic resin, a silicone-based resin, a polyester-based resin, a polyurethane-based resin, a polyether-based resin, or the like as a base polymer can be used. Among them, a (meth) acrylic pressure-sensitive adhesive is preferable from the viewpoints of transparency, adhesive strength, reliability, weather resistance, heat resistance, reworkability and the like.
The (meth) acrylic pressure-sensitive adhesive includes a (meth) acrylic acid alkyl ester having an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group, an n-, i- or t-butyl group, and (meth). A weight average molecular weight of a functional group-containing (meth) acrylic monomer such as acrylic acid or hydroxyethyl (meth) acrylic acid blended so that the glass transition temperature is preferably 25 ° C. or lower, more preferably 0 ° C. or lower. A (meth) acrylic resin having a value of 100,000 or more is useful as a base polymer.
光学積層体への粘着剤層の形成は、例えば、トルエンや酢酸エチル等の有機溶剤に粘着剤組成物を溶解又は分散させて粘着剤液を調製し、これを光学積層体の対象面に直接塗工して粘着剤層を形成する方式や、離型処理が施されたセパレートフィルム上に粘着剤層をシート状に形成しておき、それを光学積層体の対象面に移着する方式等により行うことができる。
粘着剤層の厚みは、その接着力等に応じて決定されるが、1μm以上50μm以下の範囲が適当であり、好ましくは2μm以上40μm以下である。 For the formation of the pressure-sensitive adhesive layer on the optical laminate, for example, the pressure-sensitive adhesive composition is dissolved or dispersed in an organic solvent such as toluene or ethyl acetate to prepare a pressure-sensitive adhesive liquid, which is directly applied to the target surface of the optical laminate. A method of forming an adhesive layer by coating, a method of forming an adhesive layer in a sheet shape on a separate film that has been subjected to a mold release treatment, and a method of transferring it to a target surface of an optical laminate, etc. Can be done by
The thickness of the pressure-sensitive adhesive layer is determined according to the adhesive strength and the like, but a range of 1 μm or more and 50 μm or less is appropriate, and preferably 2 μm or more and 40 μm or less.
粘着剤層の厚みは、その接着力等に応じて決定されるが、1μm以上50μm以下の範囲が適当であり、好ましくは2μm以上40μm以下である。 For the formation of the pressure-sensitive adhesive layer on the optical laminate, for example, the pressure-sensitive adhesive composition is dissolved or dispersed in an organic solvent such as toluene or ethyl acetate to prepare a pressure-sensitive adhesive liquid, which is directly applied to the target surface of the optical laminate. A method of forming an adhesive layer by coating, a method of forming an adhesive layer in a sheet shape on a separate film that has been subjected to a mold release treatment, and a method of transferring it to a target surface of an optical laminate, etc. Can be done by
The thickness of the pressure-sensitive adhesive layer is determined according to the adhesive strength and the like, but a range of 1 μm or more and 50 μm or less is appropriate, and preferably 2 μm or more and 40 μm or less.
光学積層体は、上記のセパレートフィルムを含み得る。セパレートフィルムは、ポリエチレン等のポリエチレン系樹脂、ポリプロピレン等のポリプロピレン系樹脂、ポリエチレンテレフタレート等のポリエステル系樹脂等からなるフィルムであることができる。中でも、ポリエチレンテレフタレートの延伸フィルムが好ましい。
The optical laminate may include the above separate film. The separate film can be a film made of a polyethylene resin such as polyethylene, a polypropylene resin such as polypropylene, a polyester resin such as polyethylene terephthalate, or the like. Of these, a polyethylene terephthalate stretched film is preferable.
粘着剤層は、必要に応じて、ガラス繊維、ガラスビーズ、樹脂ビーズ、金属粉や他の無機粉末からなる充填剤、顔料、着色剤、酸化防止剤、紫外線吸収剤、帯電防止剤等を含むことができる。
The pressure-sensitive adhesive layer contains, if necessary, a filler made of glass fiber, glass beads, resin beads, metal powder or other inorganic powder, a pigment, a colorant, an antioxidant, an ultraviolet absorber, an antistatic agent and the like. be able to.
〔8-3〕プロテクトフィルム
光学積層体は、その表面(典型的には、第1熱可塑性樹脂フィルム10、第2熱可塑性樹脂フィルム20、第1硬化物層15及び/又は第2硬化物層25の表面)を保護するためのプロテクトフィルムを含むことができる。プロテクトフィルムは、例えば画像表示素子や他の光学部材に光学積層体が貼合された後、それが有する粘着剤層ごと剥離除去される。 [8-3] Protect film The surface of the optical laminate (typically, the firstthermoplastic resin film 10, the second thermoplastic resin film 20, the first cured product layer 15 and / or the second cured product layer) A protective film for protecting the surface of 25) can be included. After the optical laminate is attached to, for example, an image display element or another optical member, the protective film is peeled off and removed together with the adhesive layer contained therein.
光学積層体は、その表面(典型的には、第1熱可塑性樹脂フィルム10、第2熱可塑性樹脂フィルム20、第1硬化物層15及び/又は第2硬化物層25の表面)を保護するためのプロテクトフィルムを含むことができる。プロテクトフィルムは、例えば画像表示素子や他の光学部材に光学積層体が貼合された後、それが有する粘着剤層ごと剥離除去される。 [8-3] Protect film The surface of the optical laminate (typically, the first
プロテクトフィルムは、例えば、基材フィルムとその上に積層される粘着剤層とで構成される。粘着剤層については上述の記述が引用される。
基材フィルムを構成する樹脂は、例えば、ポリエチレンのようなポリエチレン系樹脂、ポリプロピレンのようなポリプロピレン系樹脂、ポリエチレンテレフタレートやポリエチレンナフタレートのようなポリエステル系樹脂、ポリカーボネート系樹脂等の熱可塑性樹脂であることができる。好ましくは、ポリエチレンテレフタレート等のポリエステル系樹脂である。 The protective film is composed of, for example, a base film and an adhesive layer laminated on the base film. The above description is cited for the pressure-sensitive adhesive layer.
The resin constituting the base film is, for example, a polyethylene resin such as polyethylene, a polypropylene resin such as polypropylene, a polyester resin such as polyethylene terephthalate or polyethylene naphthalate, or a thermoplastic resin such as a polycarbonate resin. be able to. A polyester resin such as polyethylene terephthalate is preferable.
基材フィルムを構成する樹脂は、例えば、ポリエチレンのようなポリエチレン系樹脂、ポリプロピレンのようなポリプロピレン系樹脂、ポリエチレンテレフタレートやポリエチレンナフタレートのようなポリエステル系樹脂、ポリカーボネート系樹脂等の熱可塑性樹脂であることができる。好ましくは、ポリエチレンテレフタレート等のポリエステル系樹脂である。 The protective film is composed of, for example, a base film and an adhesive layer laminated on the base film. The above description is cited for the pressure-sensitive adhesive layer.
The resin constituting the base film is, for example, a polyethylene resin such as polyethylene, a polypropylene resin such as polypropylene, a polyester resin such as polyethylene terephthalate or polyethylene naphthalate, or a thermoplastic resin such as a polycarbonate resin. be able to. A polyester resin such as polyethylene terephthalate is preferable.
<画像表示装置>
本発明に係る光学積層体は、液晶表示装置や有機エレクトロルミネッセンス(EL)表示装置等の画像表示装置に適用することができる。この場合、画像表示装置は、光学積層体と、画像表示素子とを含む。画像表示素子としては、液晶セル、有機EL表示素子等が挙げられる。これらの画像表示素子としては、従来公知のものを使用することができる。 <Image display device>
The optical laminate according to the present invention can be applied to an image display device such as a liquid crystal display device or an organic electroluminescence (EL) display device. In this case, the image display device includes an optical laminate and an image display element. Examples of the image display element include a liquid crystal cell and an organic EL display element. As these image display elements, conventionally known ones can be used.
本発明に係る光学積層体は、液晶表示装置や有機エレクトロルミネッセンス(EL)表示装置等の画像表示装置に適用することができる。この場合、画像表示装置は、光学積層体と、画像表示素子とを含む。画像表示素子としては、液晶セル、有機EL表示素子等が挙げられる。これらの画像表示素子としては、従来公知のものを使用することができる。 <Image display device>
The optical laminate according to the present invention can be applied to an image display device such as a liquid crystal display device or an organic electroluminescence (EL) display device. In this case, the image display device includes an optical laminate and an image display element. Examples of the image display element include a liquid crystal cell and an organic EL display element. As these image display elements, conventionally known ones can be used.
偏光板である光学積層体が液晶表示装置に適用される場合、光学積層体は、液晶セルのバックライト側(背面側)に配置されてもよいし、視認側に配置されてもよいし、それらの両方に配置されてもよい。偏光板である光学積層体が有機EL表示装置に適用される場合、光学積層体は通常、有機EL表示素子の視認側に配置される。
When the optical laminate which is a polarizing plate is applied to a liquid crystal display device, the optical laminate may be arranged on the backlight side (back side) of the liquid crystal cell, or may be arranged on the visual side. It may be placed in both of them. When the optical laminate, which is a polarizing plate, is applied to an organic EL display device, the optical laminate is usually arranged on the visual side of the organic EL display element.
以下、実施例を示して本発明をさらに具体的に説明するが、本発明はこれらの例によって限定されるものではない。実施例、比較例中の「%」及び「部」は、特記しない限り、質量%及び質量部である。
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" and "part" in Examples and Comparative Examples are mass% and parts by mass.
[製造例:偏光子の作製]
厚さ60μmのポリビニルアルコールフィルム(平均重合度:約2,400、ケン化度:99.9モル%以上)を30℃の純水に浸漬した後、ヨウ素/ヨウ化カリウム/水の質量比が0.02/2/100である30℃の水溶液に浸漬した。その後、ヨウ化カリウム/ホウ酸/水の質量比が12/5/100である56.5℃の水溶液に浸漬した。引き続き、8℃の純水で洗浄した後、65℃で乾燥させて、ポリビニルアルコールフィルムにヨウ素が吸着配向された厚み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、トータル延伸倍率は5.5倍であった。 [Manufacturing example: Fabrication of polarizer]
After immersing a 60 μm-thick polyvinyl alcohol film (average degree of polymerization: about 2,400, saponification degree: 99.9 mol% or more) in pure water at 30 ° C., the mass ratio of iodine / potassium iodide / water is increased. It was immersed in an aqueous solution at 30 ° C. of 0.02 / 2/100. Then, it was immersed in an aqueous solution at 56.5 ° C. having a mass ratio of potassium iodide / boric acid / water of 12/5/100. Subsequently, the mixture was washed with pure water at 8 ° C. and then dried at 65 ° C. to obtain a polarizer having a thickness of 23 μm in which iodine was adsorbed and oriented on a polyvinyl alcohol film. The stretching was mainly carried out in the steps of iodine staining and boric acid treatment, and the total stretching ratio was 5.5 times.
厚さ60μmのポリビニルアルコールフィルム(平均重合度:約2,400、ケン化度:99.9モル%以上)を30℃の純水に浸漬した後、ヨウ素/ヨウ化カリウム/水の質量比が0.02/2/100である30℃の水溶液に浸漬した。その後、ヨウ化カリウム/ホウ酸/水の質量比が12/5/100である56.5℃の水溶液に浸漬した。引き続き、8℃の純水で洗浄した後、65℃で乾燥させて、ポリビニルアルコールフィルムにヨウ素が吸着配向された厚み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、トータル延伸倍率は5.5倍であった。 [Manufacturing example: Fabrication of polarizer]
After immersing a 60 μm-thick polyvinyl alcohol film (average degree of polymerization: about 2,400, saponification degree: 99.9 mol% or more) in pure water at 30 ° C., the mass ratio of iodine / potassium iodide / water is increased. It was immersed in an aqueous solution at 30 ° C. of 0.02 / 2/100. Then, it was immersed in an aqueous solution at 56.5 ° C. having a mass ratio of potassium iodide / boric acid / water of 12/5/100. Subsequently, the mixture was washed with pure water at 8 ° C. and then dried at 65 ° C. to obtain a polarizer having a thickness of 23 μm in which iodine was adsorbed and oriented on a polyvinyl alcohol film. The stretching was mainly carried out in the steps of iodine staining and boric acid treatment, and the total stretching ratio was 5.5 times.
〔実施例1~3、比較例1〕
(1)硬化性組成物の調製
表1に示される成分を表1に示される配合量で、水系溶媒としての純水とともに混合して、硬化性組成物(接着剤水溶液)を調製した。表1に示される各成分の配合量の単位は質量部であり、各成分の配合量は固形分換算での量である。実施例1~3、比較例1~3において、得られた硬化性組成物における水系樹脂(A)の濃度は5.0質量%とした。 [Examples 1 to 3, Comparative Example 1]
(1) Preparation of curable composition A curable composition (adhesive aqueous solution) was prepared by mixing the components shown in Table 1 with pure water as an aqueous solvent in the blending amount shown in Table 1. The unit of the blending amount of each component shown in Table 1 is a mass part, and the blending amount of each component is the amount in terms of solid content. In Examples 1 to 3 and Comparative Examples 1 to 3, the concentration of the aqueous resin (A) in the obtained curable composition was 5.0% by mass.
(1)硬化性組成物の調製
表1に示される成分を表1に示される配合量で、水系溶媒としての純水とともに混合して、硬化性組成物(接着剤水溶液)を調製した。表1に示される各成分の配合量の単位は質量部であり、各成分の配合量は固形分換算での量である。実施例1~3、比較例1~3において、得られた硬化性組成物における水系樹脂(A)の濃度は5.0質量%とした。 [Examples 1 to 3, Comparative Example 1]
(1) Preparation of curable composition A curable composition (adhesive aqueous solution) was prepared by mixing the components shown in Table 1 with pure water as an aqueous solvent in the blending amount shown in Table 1. The unit of the blending amount of each component shown in Table 1 is a mass part, and the blending amount of each component is the amount in terms of solid content. In Examples 1 to 3 and Comparative Examples 1 to 3, the concentration of the aqueous resin (A) in the obtained curable composition was 5.0% by mass.
(2)偏光板の作製
トリアセチルセルロース(TAC)フィルム〔コニカミノルタオプト(株)製の商品名「KC4UAW」、厚み:40μm〕の片面にケン化処理を施した後、そのケン化処理面に上記(1)で調製した硬化性組成物をバーコータを用いて塗工するとともに、環状ポリオレフィン系樹脂からなるゼロ位相差フィルム〔日本ゼオン(株)製の商品名「ZEONOR」、厚み:23μm〕の片面にコロナ処理を施し、そのコロナ処理面に上記(1)で調製した硬化性組成物をバーコータを用いて塗工した。硬化性組成物層が偏光子側となるように、偏光子の一方の面にケン化処理済みTACフィルムを積層し、他方の面にコロナ処理済みゼロ位相差フィルムを積層して、ゼロ位相差フィルム/硬化性組成物層/偏光子/硬化性組成物層/TACフィルムの層構成を有する積層体を得た。この積層体に対して、熱風乾燥機で80℃、300秒間の加熱処理を行うことにより、ゼロ位相差フィルム/硬化物層/偏光子/硬化物層/TACフィルムの層構成を有する偏光板を作製した。作製した偏光板中の硬化物層の厚みは、一層につき20~60nmであった。 (2) Preparation of Polarizing Plate A triacetyl cellulose (TAC) film [trade name "KC4UAW" manufactured by Konica Minolta Opto Co., Ltd., thickness: 40 μm] is saponified on one side and then on the saponified surface. The curable composition prepared in (1) above is coated with a bar coater, and a zero retardation film made of a cyclic polyolefin resin [trade name "ZEONOR" manufactured by Nippon Zeon Co., Ltd., thickness: 23 μm] is used. One surface was corona-treated, and the curable composition prepared in (1) above was coated on the corona-treated surface using a bar coater. A saponified TAC film is laminated on one surface of the polarizer and a corona-treated zero retardation film is laminated on the other surface so that the curable composition layer is on the polarizer side, so that the zero retardation is achieved. A laminate having a layer structure of a film / curable composition layer / polarizer / curable composition layer / TAC film was obtained. By heat-treating this laminate at 80 ° C. for 300 seconds with a hot air dryer, a polarizing plate having a layer structure of zero retardation film / cured product layer / polarizer / cured product layer / TAC film can be obtained. Made. The thickness of the cured product layer in the produced polarizing plate was 20 to 60 nm per layer.
トリアセチルセルロース(TAC)フィルム〔コニカミノルタオプト(株)製の商品名「KC4UAW」、厚み:40μm〕の片面にケン化処理を施した後、そのケン化処理面に上記(1)で調製した硬化性組成物をバーコータを用いて塗工するとともに、環状ポリオレフィン系樹脂からなるゼロ位相差フィルム〔日本ゼオン(株)製の商品名「ZEONOR」、厚み:23μm〕の片面にコロナ処理を施し、そのコロナ処理面に上記(1)で調製した硬化性組成物をバーコータを用いて塗工した。硬化性組成物層が偏光子側となるように、偏光子の一方の面にケン化処理済みTACフィルムを積層し、他方の面にコロナ処理済みゼロ位相差フィルムを積層して、ゼロ位相差フィルム/硬化性組成物層/偏光子/硬化性組成物層/TACフィルムの層構成を有する積層体を得た。この積層体に対して、熱風乾燥機で80℃、300秒間の加熱処理を行うことにより、ゼロ位相差フィルム/硬化物層/偏光子/硬化物層/TACフィルムの層構成を有する偏光板を作製した。作製した偏光板中の硬化物層の厚みは、一層につき20~60nmであった。 (2) Preparation of Polarizing Plate A triacetyl cellulose (TAC) film [trade name "KC4UAW" manufactured by Konica Minolta Opto Co., Ltd., thickness: 40 μm] is saponified on one side and then on the saponified surface. The curable composition prepared in (1) above is coated with a bar coater, and a zero retardation film made of a cyclic polyolefin resin [trade name "ZEONOR" manufactured by Nippon Zeon Co., Ltd., thickness: 23 μm] is used. One surface was corona-treated, and the curable composition prepared in (1) above was coated on the corona-treated surface using a bar coater. A saponified TAC film is laminated on one surface of the polarizer and a corona-treated zero retardation film is laminated on the other surface so that the curable composition layer is on the polarizer side, so that the zero retardation is achieved. A laminate having a layer structure of a film / curable composition layer / polarizer / curable composition layer / TAC film was obtained. By heat-treating this laminate at 80 ° C. for 300 seconds with a hot air dryer, a polarizing plate having a layer structure of zero retardation film / cured product layer / polarizer / cured product layer / TAC film can be obtained. Made. The thickness of the cured product layer in the produced polarizing plate was 20 to 60 nm per layer.
(3)光学耐久性の評価
得られた偏光板を30mm×30mmの大きさに裁断した後、ゼロ位相差フィルム側に(メタ)アクリル系粘着剤を介してガラス基板に貼合し、測定サンプルを得た。測定サンプルの層構成は、ガラス基板/(メタ)アクリル系粘着剤層/ゼロ位相差フィルム/硬化物層/偏光子/硬化物層/TACフィルムである。ガラス基板には、無アルカリガラス基板〔コーニング社製の商品名「Eagle XG」〕を使用した。
得られた測定サンプルについて、積分球付き分光光度計〔日本分光(株)製の製品名「V7100」〕を用いて波長380~780nmの範囲におけるMD透過率とTD透過率を測定し、各波長における偏光度を算出した。算出した偏光度について、JIS Z 8701:1999「色の表示方法-XYZ表色系及びX10Y10Z10表色系」の2度視野(C光源)により視感度補正を行い、耐久性試験前の視感度補正偏光度Pyを求めた。なお、測定サンプルは、偏光板のTACフィルム側をディテクター側とし、ガラス基板側から光が入光するように積分球付き分光光度計にセットした。 (3) Evaluation of Optical Durability After cutting the obtained polarizing plate into a size of 30 mm × 30 mm, it is attached to a glass substrate via a (meth) acrylic adhesive on the zero retardation film side to measure a sample. Got The layer structure of the measurement sample is a glass substrate / (meth) acrylic pressure-sensitive adhesive layer / zero retardation film / cured product layer / polarizer / cured product layer / TAC film. A non-alkali glass substrate [trade name "Eagle XG" manufactured by Corning Inc.] was used as the glass substrate.
The obtained measurement sample was measured for MD transmittance and TD transmittance in the wavelength range of 380 to 780 nm using a spectrophotometer with an integrating sphere [product name "V7100" manufactured by JASCO Corporation], and each wavelength was measured. The degree of polarization in was calculated. The calculated degree of polarization is corrected for luminosity factor by the 2 degree field (C light source) of JIS Z 8701: 1999 "Color display method-XYZ color system and X10Y10Z10 color system", and the luminosity factor is corrected before the durability test. The degree of polarization Py was determined. The measurement sample was set in a spectrophotometer with an integrating sphere so that the TAC film side of the polarizing plate was the detector side and the light entered from the glass substrate side.
得られた偏光板を30mm×30mmの大きさに裁断した後、ゼロ位相差フィルム側に(メタ)アクリル系粘着剤を介してガラス基板に貼合し、測定サンプルを得た。測定サンプルの層構成は、ガラス基板/(メタ)アクリル系粘着剤層/ゼロ位相差フィルム/硬化物層/偏光子/硬化物層/TACフィルムである。ガラス基板には、無アルカリガラス基板〔コーニング社製の商品名「Eagle XG」〕を使用した。
得られた測定サンプルについて、積分球付き分光光度計〔日本分光(株)製の製品名「V7100」〕を用いて波長380~780nmの範囲におけるMD透過率とTD透過率を測定し、各波長における偏光度を算出した。算出した偏光度について、JIS Z 8701:1999「色の表示方法-XYZ表色系及びX10Y10Z10表色系」の2度視野(C光源)により視感度補正を行い、耐久性試験前の視感度補正偏光度Pyを求めた。なお、測定サンプルは、偏光板のTACフィルム側をディテクター側とし、ガラス基板側から光が入光するように積分球付き分光光度計にセットした。 (3) Evaluation of Optical Durability After cutting the obtained polarizing plate into a size of 30 mm × 30 mm, it is attached to a glass substrate via a (meth) acrylic adhesive on the zero retardation film side to measure a sample. Got The layer structure of the measurement sample is a glass substrate / (meth) acrylic pressure-sensitive adhesive layer / zero retardation film / cured product layer / polarizer / cured product layer / TAC film. A non-alkali glass substrate [trade name "Eagle XG" manufactured by Corning Inc.] was used as the glass substrate.
The obtained measurement sample was measured for MD transmittance and TD transmittance in the wavelength range of 380 to 780 nm using a spectrophotometer with an integrating sphere [product name "V7100" manufactured by JASCO Corporation], and each wavelength was measured. The degree of polarization in was calculated. The calculated degree of polarization is corrected for luminosity factor by the 2 degree field (C light source) of JIS Z 8701: 1999 "Color display method-XYZ color system and X10Y10Z10 color system", and the luminosity factor is corrected before the durability test. The degree of polarization Py was determined. The measurement sample was set in a spectrophotometer with an integrating sphere so that the TAC film side of the polarizing plate was the detector side and the light entered from the glass substrate side.
偏光度(%)は、下記式:
偏光度(λ)=100×(Tp(λ)-Tc(λ))/(Tp(λ)+Tc(λ))
で定義される。
Tp(λ)は、入射する波長λ(nm)の直線偏光とパラレルニコルの関係で測定した測定サンプルの透過率(%)である。
Tc(λ)は、入射する波長λ(nm)の直線偏光とクロスニコルの関係で測定した測定サンプルの透過率(%)である。 The degree of polarization (%) is calculated by the following formula:
Polarization degree (λ) = 100 × (Tp (λ) -Tc (λ)) / (Tp (λ) + Tc (λ))
Defined in.
Tp (λ) is the transmittance (%) of the measurement sample measured in relation to the linearly polarized light of the incident wavelength λ (nm) and the parallel Nicol.
Tc (λ) is the transmittance (%) of the measurement sample measured in relation to the linearly polarized light of the incident wavelength λ (nm) and the cross Nicol.
偏光度(λ)=100×(Tp(λ)-Tc(λ))/(Tp(λ)+Tc(λ))
で定義される。
Tp(λ)は、入射する波長λ(nm)の直線偏光とパラレルニコルの関係で測定した測定サンプルの透過率(%)である。
Tc(λ)は、入射する波長λ(nm)の直線偏光とクロスニコルの関係で測定した測定サンプルの透過率(%)である。 The degree of polarization (%) is calculated by the following formula:
Polarization degree (λ) = 100 × (Tp (λ) -Tc (λ)) / (Tp (λ) + Tc (λ))
Defined in.
Tp (λ) is the transmittance (%) of the measurement sample measured in relation to the linearly polarized light of the incident wavelength λ (nm) and the parallel Nicol.
Tc (λ) is the transmittance (%) of the measurement sample measured in relation to the linearly polarized light of the incident wavelength λ (nm) and the cross Nicol.
次いで、この測定サンプルを温度85℃、相対湿度85%RHの高温高湿環境下に500時間置いた後、温度23℃、相対湿度50%RHの環境下に24時間置く耐久性試験に供した。耐久性試験後、耐久性試験前と同様の方法によって視感度補正偏光度Pyを求めた。
耐久性試験後の視感度補正偏光度Pyと耐久性試験前の視感度補正偏光度Pyとの差の絶対値(|ΔPy|)を算出した。|ΔPy|の算出値を表1に示す。
|ΔPy|の値が小さいほど、高温高湿環境下における光学耐久性に優れる。いずれの実施例及び比較例においても、耐久試験後の視感度補正偏光度Pyと耐久試験前の視感度補正偏光度Pyの差は、負の値を示した。 Next, this measurement sample was placed in a high temperature and high humidity environment with a temperature of 85 ° C. and a relative humidity of 85% RH for 500 hours, and then subjected to a durability test in which the measurement sample was placed in an environment with a temperature of 23 ° C. and a relative humidity of 50% RH for 24 hours. .. After the durability test, the luminosity factor correction polarization degree Py was determined by the same method as before the durability test.
The absolute value (| ΔPy |) of the difference between the luminosity factor correction polarization Py after the durability test and the luminosity factor correction polarization Py before the durability test was calculated. The calculated values of | ΔPy | are shown in Table 1.
The smaller the value of | ΔPy |, the better the optical durability in a high temperature and high humidity environment. In each of the Examples and Comparative Examples, the difference between the luminosity factor correction polarization Py after the durability test and the luminosity factor correction polarization Py before the durability test showed a negative value.
耐久性試験後の視感度補正偏光度Pyと耐久性試験前の視感度補正偏光度Pyとの差の絶対値(|ΔPy|)を算出した。|ΔPy|の算出値を表1に示す。
|ΔPy|の値が小さいほど、高温高湿環境下における光学耐久性に優れる。いずれの実施例及び比較例においても、耐久試験後の視感度補正偏光度Pyと耐久試験前の視感度補正偏光度Pyの差は、負の値を示した。 Next, this measurement sample was placed in a high temperature and high humidity environment with a temperature of 85 ° C. and a relative humidity of 85% RH for 500 hours, and then subjected to a durability test in which the measurement sample was placed in an environment with a temperature of 23 ° C. and a relative humidity of 50% RH for 24 hours. .. After the durability test, the luminosity factor correction polarization degree Py was determined by the same method as before the durability test.
The absolute value (| ΔPy |) of the difference between the luminosity factor correction polarization Py after the durability test and the luminosity factor correction polarization Py before the durability test was calculated. The calculated values of | ΔPy | are shown in Table 1.
The smaller the value of | ΔPy |, the better the optical durability in a high temperature and high humidity environment. In each of the Examples and Comparative Examples, the difference between the luminosity factor correction polarization Py after the durability test and the luminosity factor correction polarization Py before the durability test showed a negative value.
(4)密着性の評価
得られた偏光板をゼロ位相差フィルム側に(メタ)アクリル系粘着剤を介してガラス基板に貼合し、粘着剤層付偏光板とした。得られた粘着剤層付偏光板から、幅25mm、長さ約200mmの試験片を裁断し、その粘着剤層面をソーダガラスに貼合した。次いで、偏光子とTACフィルムとの間にカッターの刃を入れ、長さ方向に端から30mm剥離し、その剥離部分を万能引張試験機〔(株)島津製作所製の「AG-1」〕のつかみ部でつかんだ。この状態の試験片を、温度23℃及び相対湿度55%の雰囲気中にて、JIS K 6854-2:1999「接着剤-はく離接着強さ試験方法-第2部:180度はく離」に準じて、つかみ移動速度300mm/分で180度はく離試験を行い、つかみ部の30mmを除く170mmの長さにわたる密着性を求めた。結果を表1に示す。 (4) Evaluation of Adhesion The obtained polarizing plate was bonded to a glass substrate on the zero retardation film side via a (meth) acrylic pressure-sensitive adhesive to prepare a polarizing plate with a pressure-sensitive adhesive layer. A test piece having a width of 25 mm and a length of about 200 mm was cut from the obtained polarizing plate with an adhesive layer, and the pressure-sensitive adhesive layer surface was bonded to soda glass. Next, a cutter blade is inserted between the polarizer and the TAC film, and the peeled portion is peeled 30 mm from the end in the length direction, and the peeled portion is peeled off by a universal tensile tester [“AG-1” manufactured by Shimadzu Corporation]. I grabbed it with the grip. The test piece in this state is subjected to JIS K 6854-2: 1999 "Adhesive-Peeling Adhesive Strength Test Method-Part 2: 180 ° Peeling" in an atmosphere at a temperature of 23 ° C. and a relative humidity of 55%. A 180-degree peeling test was performed at a gripping movement speed of 300 mm / min, and adhesion over a length of 170 mm excluding 30 mm of the gripped portion was determined. The results are shown in Table 1.
得られた偏光板をゼロ位相差フィルム側に(メタ)アクリル系粘着剤を介してガラス基板に貼合し、粘着剤層付偏光板とした。得られた粘着剤層付偏光板から、幅25mm、長さ約200mmの試験片を裁断し、その粘着剤層面をソーダガラスに貼合した。次いで、偏光子とTACフィルムとの間にカッターの刃を入れ、長さ方向に端から30mm剥離し、その剥離部分を万能引張試験機〔(株)島津製作所製の「AG-1」〕のつかみ部でつかんだ。この状態の試験片を、温度23℃及び相対湿度55%の雰囲気中にて、JIS K 6854-2:1999「接着剤-はく離接着強さ試験方法-第2部:180度はく離」に準じて、つかみ移動速度300mm/分で180度はく離試験を行い、つかみ部の30mmを除く170mmの長さにわたる密着性を求めた。結果を表1に示す。 (4) Evaluation of Adhesion The obtained polarizing plate was bonded to a glass substrate on the zero retardation film side via a (meth) acrylic pressure-sensitive adhesive to prepare a polarizing plate with a pressure-sensitive adhesive layer. A test piece having a width of 25 mm and a length of about 200 mm was cut from the obtained polarizing plate with an adhesive layer, and the pressure-sensitive adhesive layer surface was bonded to soda glass. Next, a cutter blade is inserted between the polarizer and the TAC film, and the peeled portion is peeled 30 mm from the end in the length direction, and the peeled portion is peeled off by a universal tensile tester [“AG-1” manufactured by Shimadzu Corporation]. I grabbed it with the grip. The test piece in this state is subjected to JIS K 6854-2: 1999 "Adhesive-Peeling Adhesive Strength Test Method-Part 2: 180 ° Peeling" in an atmosphere at a temperature of 23 ° C. and a relative humidity of 55%. A 180-degree peeling test was performed at a gripping movement speed of 300 mm / min, and adhesion over a length of 170 mm excluding 30 mm of the gripped portion was determined. The results are shown in Table 1.
表1に示される各成分の詳細は次のとおりである。
水系樹脂(A)のA-1:株式会社日本触媒製の商品名「エポクロス WS-300」〔2-オキサゾリル基を側鎖として有するオキサゾリル基含有アクリル系重合体の水溶液、固形分濃度:10質量%、オキサゾリン価(理論値):130g solid/eq.、オキサゾリン基量(理論値):7.7mmol/g,solid、数平均分子量:4×104、重量平均分子量:12×104)〕
水系樹脂(A)のA-2:日本合成化学工業株式会社の商品名「ゴーセファイマー Z-200」〔アセトアセチル基で変性されたポリビニルアルコール、平均重合度:1100、ケン化度:98.5モル%以上〕
シラン化合物(B):信越化学工業株式会社製の商品名「X-12-1135」〔カルボキシル基及びシラノール基を有するシラン化合物〕
酸化合物(C):硫酸 Details of each component shown in Table 1 are as follows.
A-1 of aqueous resin (A): Trade name "Epocross WS-300" manufactured by Nippon Catalyst Co., Ltd. [Aqueous solution of oxazoline group-containing acrylic polymer having 2-oxazoline group as side chain, solid content concentration: 10 mass %, Oxazoline value (theoretical value): 130 g solid / eq. , Oxazoline group weight (theoretical value): 7.7 mmol / g, solid, number average molecular weight: 4 × 10 4 , weight average molecular weight: 12 × 10 4 )]
A-2 of water-based resin (A): Trade name "Gosefimer Z-200" of Nippon Synthetic Chemical Industry Co., Ltd. [Polyvinyl alcohol modified with acetoacetyl group, average degree of polymerization: 1100, degree of saponification: 98. 5 mol% or more]
Silane compound (B): Trade name "X-12-1135" manufactured by Shin-Etsu Chemical Co., Ltd. [Silane compound having a carboxyl group and a silanol group]
Acid compound (C): Sulfuric acid
水系樹脂(A)のA-1:株式会社日本触媒製の商品名「エポクロス WS-300」〔2-オキサゾリル基を側鎖として有するオキサゾリル基含有アクリル系重合体の水溶液、固形分濃度:10質量%、オキサゾリン価(理論値):130g solid/eq.、オキサゾリン基量(理論値):7.7mmol/g,solid、数平均分子量:4×104、重量平均分子量:12×104)〕
水系樹脂(A)のA-2:日本合成化学工業株式会社の商品名「ゴーセファイマー Z-200」〔アセトアセチル基で変性されたポリビニルアルコール、平均重合度:1100、ケン化度:98.5モル%以上〕
シラン化合物(B):信越化学工業株式会社製の商品名「X-12-1135」〔カルボキシル基及びシラノール基を有するシラン化合物〕
酸化合物(C):硫酸 Details of each component shown in Table 1 are as follows.
A-1 of aqueous resin (A): Trade name "Epocross WS-300" manufactured by Nippon Catalyst Co., Ltd. [Aqueous solution of oxazoline group-containing acrylic polymer having 2-oxazoline group as side chain, solid content concentration: 10 mass %, Oxazoline value (theoretical value): 130 g solid / eq. , Oxazoline group weight (theoretical value): 7.7 mmol / g, solid, number average molecular weight: 4 × 10 4 , weight average molecular weight: 12 × 10 4 )]
A-2 of water-based resin (A): Trade name "Gosefimer Z-200" of Nippon Synthetic Chemical Industry Co., Ltd. [Polyvinyl alcohol modified with acetoacetyl group, average degree of polymerization: 1100, degree of saponification: 98. 5 mol% or more]
Silane compound (B): Trade name "X-12-1135" manufactured by Shin-Etsu Chemical Co., Ltd. [Silane compound having a carboxyl group and a silanol group]
Acid compound (C): Sulfuric acid
10 第1熱可塑性樹脂フィルム、15 第1硬化物層、20 第2熱可塑性樹脂フィルム、25 第2硬化物層、30 光学層、40 粘着剤層。
10 1st thermoplastic resin film, 15 1st cured product layer, 20 2nd thermoplastic resin film, 25 2nd cured product layer, 30 optical layer, 40 adhesive layer.
Claims (14)
- 水系樹脂とシラン化合物とを含み、
前記水系樹脂は、オキサゾリル基含有重合体を含む、硬化性組成物。 Contains water-based resin and silane compound
The aqueous resin is a curable composition containing an oxazolyl group-containing polymer. - 前記オキサゾリル基含有重合体は、オキサゾリル基含有(メタ)アクリル系重合体である、請求項1に記載の硬化性組成物。 The curable composition according to claim 1, wherein the oxazolyl group-containing polymer is an oxazolyl group-containing (meth) acrylic polymer.
- さらに、酸化合物を含む、請求項1又は2に記載の硬化性組成物。 The curable composition according to claim 1 or 2, further comprising an acid compound.
- 前記シラン化合物は、シラノール基を有する、請求項1~3のいずれか1項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 3, wherein the silane compound has a silanol group.
- 前記シラン化合物は、さらに、置換基を有していてもよいアミノ基、カルボキシル基、エポキシ基、アセトアセチル基、ヒドロキシアルキル基、メルカプト基、オキシアルキレン基、及びアルケニル基からなる群より選択される1以上の官能基を有する、請求項4に記載の硬化性組成物。 The silane compound is further selected from the group consisting of an amino group, a carboxyl group, an epoxy group, an acetoacetyl group, a hydroxyalkyl group, a mercapto group, an oxyalkylene group, and an alkenyl group which may have a substituent. The curable composition according to claim 4, which has one or more functional groups.
- 前記シラン化合物は、さらに、置換基を有していてもよいアミノ基及びカルボキシル基のうちの少なくとも一方の官能基を有する、請求項4又は5に記載の硬化性組成物。 The curable composition according to claim 4 or 5, wherein the silane compound further has a functional group of at least one of an amino group and a carboxyl group which may have a substituent.
- 前記シラン化合物は、さらにSi-O-Si結合を含み、
前記シラン化合物の構造中に前記官能基を有する、請求項5又は6に記載の硬化性組成物。 The silane compound further contains a Si—O—Si bond and contains
The curable composition according to claim 5 or 6, which has the functional group in the structure of the silane compound. - 請求項1~7のいずれか1項に記載の硬化性組成物を硬化させてなる、硬化物層。 A cured product layer obtained by curing the curable composition according to any one of claims 1 to 7.
- 光学層及び第1硬化物層を含み、
前記第1硬化物層は、請求項8に記載の硬化物層である、光学積層体。 Includes optical layer and first cured product layer
The first cured product layer is an optical laminate which is the cured product layer according to claim 8. - さらに、第1熱可塑性樹脂フィルムを含み、
前記光学層、前記第1硬化物層、及び前記第1熱可塑性樹脂フィルムがこの順に積層されている、請求項9に記載の光学積層体。 In addition, it contains a first thermoplastic resin film.
The optical laminate according to claim 9, wherein the optical layer, the first cured product layer, and the first thermoplastic resin film are laminated in this order. - さらに、第2硬化物層及び第2熱可塑性樹脂フィルムを含み、
前記光学層の前記第1硬化物層側とは反対側に、前記第2硬化物層及び前記第2熱可塑性樹脂フィルムがこの順に積層されている、請求項9又は10に記載の光学積層体。 Further, it contains a second cured product layer and a second thermoplastic resin film.
The optical laminate according to claim 9 or 10, wherein the second cured product layer and the second thermoplastic resin film are laminated in this order on the side of the optical layer opposite to the first cured product layer side. .. - 前記第2硬化物層は、請求項8に記載の硬化性組成物の硬化物である、請求項11に記載の光学積層体。 The optical laminate according to claim 11, wherein the second cured product layer is a cured product of the curable composition according to claim 8.
- 前記光学層は、偏光子である、請求項9~12のいずれか1項に記載の光学積層体。 The optical laminate according to any one of claims 9 to 12, wherein the optical layer is a polarizing element.
- 請求項9~13のいずれか1項に記載の光学積層体、及び、画像表示素子を含む、画像表示装置。 An image display device including the optical laminate according to any one of claims 9 to 13 and an image display element.
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