Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
  • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
  • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements

Definitions

• the present invention relates to a polarizing plate having a novel coating cured film, a liquid crystal display device using the polarizing plate, and a method for producing the same.
• a polarizing element is produced by adsorbing and orienting a dichroic dye, iodine or a dichroic dye, onto a polyvinyl alcohol (hereinafter abbreviated as PVA) resin film and then uniaxially stretching it. Is done.
• PVA polyvinyl alcohol
• a film made of triacetyl cellulose (hereinafter abbreviated as TAC) and the like are provided on at least one surface of the polarizing element via an adhesive layer. Is used for liquid crystal display devices and the like.
• TAC is suitable for optical applications because of its high light transmittance and low birefringence, and also has an advantageous feature in processing that it can be easily bonded to PVA resin by alkali treatment. Yes. Therefore, TAC is widely used as a protective film for polarizing elements.
• TAC since TAC has high moisture permeability, there is a risk of quality deterioration when used under high temperature and high humidity conditions.
• the thickness of the TAC film is reduced, in the environmental deterioration test of the polarizing plate, particularly in the durability test under a high temperature and high humidity condition, the light transmittance change and the polarization degree change of the polarizing plate are large, and the adhesion is further improved. There were problems such as getting worse.
• olefin films cycloolefin films, polyolefin films such as polypropylene
• films made of acrylic resins and vinyl esters
• Patent Document 5 discloses a technique in which a silane coupling agent layer is formed on the adhesion side surface of a siloxane cross-linked acrylic silicone resin film and then adhered to a polarizing element using a PVA adhesive.
• a silane coupling agent layer is formed on the adhesion side surface of a siloxane cross-linked acrylic silicone resin film and then adhered to a polarizing element using a PVA adhesive.
• Patent Documents 6 to 9 an energy beam polymerizable compound such as a polyfunctional compound is not attached to one side of the polarizing element, for reasons such as making the polarizing plate thinner and improving the durability of the polarizing plate.
• a curable resin containing a (meth) acrylic monomer and a photocurable prepolymer Patent Document 6
• an energy ray polymerizable compound such as ethylene oxide-modified bisphenol A di (meth) acrylate
• silane coupling agent hydrolyzate By coating a curable resin (Patent Document 7) or a curable resin (Patent Document 8) containing an energy ray polymerizable compound having a cyclo ring such as dicyclopentanyl or dicyclopentenyl, and then curing,
• a technique for providing a protective layer is also disclosed.
• JP2007-316603 JP 2008-009414 A JP2007-240640 JP2008-058348 WO2008 / 066157A1 JP2007-334307 JP-A-2005-107238 JP2003-185842 JP-A-2004-77579
• the present invention improves the protective film of the polarizing element to achieve a thin protective film, and improves the adhesion between the polarizing element and the protective film, thereby improving the durability, particularly the wet heat durability. Is going to get.
• the present inventors use a coating cured film of a curable resin composition containing a silicone resin having a specific silsesquioxane skeleton as a protective film of a polarizing element or the like.
• a polarizing plate having good adhesiveness of a coated cured film and having stable optical properties such as light transmittance and degree of polarization can be obtained even when used for a long time under high temperature and high humidity conditions.
• the present invention (1) On one or both sides of the polarizing element, General formula (1) [RSiO 3/2 ] n (1) (Wherein R is an organic functional group having a (meth) acryloyl group, and n is 8, 10 or 12), A curable resin composition comprising 5 to 80% by weight of a silicone resin (A) mainly comprising a polyorganosilsesquioxane having a cage structure in a structural unit and 95 to 20% by weight of a radically polymerizable unsaturated compound A polarizing plate having a coating cured film, (2) The polarizing plate according to the above (1), wherein the content of the polyorganosilsesquioxane having a cage structure is 50 to 100% by weight with respect to the total amount of the silicone resin (A), (3) The curable resin composition includes (i) a silicone resin (A) and an oligomer (B) having a urethane bond capable of radical polymerization with the silicone resin (A) as a radical polymerizable unsatur
• the curable resin composition further includes an unsaturated compound (C) capable of radical copolymerization with the silicone resin (A) other than (iii) the oligomer (B) as a radical polymerizable unsaturated compound.
• the unsaturated compound (C) is represented by the following formula (2) (In the formula, Z represents any group represented by (2a) or (2b), and R ′ represents a hydrogen atom or a methyl group)
• the polarizing plate according to (4) which is an alicyclic di (meth) acrylate (C ′) represented by:
• the silicone resin (A), the oligomer (B) and the unsaturated compound (C) are contained in a weight ratio of 5 to 80: 1 to 50:10 to 80,
• the polarizing plate according to (8), wherein the silane coupling agent for the silane coupling treatment is a (meth) acrylic silane coupling agent,
• a liquid crystal display device comprising the polarizing plate according to any one of (1) to (12) above, (14) The two polarizing plates described in (11) above are disposed so that the cured film of the curable resin composition is on the outer side when viewed from the liquid crystalline cell on both sides of the liquid crystalline cell ( 13) a liquid crystal display device according to (15) (i) General formula (1) [RSiO 3/2 ] n (1) (Wherein R is an organic functional group having a (meth) acryloyl group, and n is 8, 10 or 12), Silicone resin (A) mainly comprising polyorganosilsesquioxane having a cage structure in the structural unit, (Ii) an oligomer (B) capable of radical polymerization with the silicone resin (A) and having a urethane bond having a number average molecular weight of 1000 to 10,000, (Iii) In addition to the oligomer (B), an unsaturated compound (C) capable of radical copolymerization with the silicone resin (A
• the unsaturated compound (C) at least 10% by weight of the following formula (2) with respect to the total amount of the unsaturated compound (C):
• Z represents any group represented by (2a) or (2b)
• R ′ represents a hydrogen atom or a methyl group
• the unsaturated compound (C) is the alicyclic di (meth) acrylate (C ′) alone represented by the formula (2) or the alicyclic di (meth) acrylate (C ′)
• the polarizing plate using the cured film as a protective film has excellent moisture and heat resistance even if the cured film is a thin coated film.
• the adhesion between the protective film and the polarizing element is also good. Therefore, even when the polarizing plate is used for a long time under high-humidity heat conditions, there is little physical change such as shrinkage, light transmittance change and polarization degree change are small, and there is no problem in adhesion. Accordingly, the optical properties of the polarizing plate are stable even in long-term use under severe conditions, and the polarizing plate is particularly excellent in durability under severe conditions.
• the protective film bonding process can be omitted in the manufacturing process compared to a conventional bonded protective film, no adhesive is required, and thinning is realized.
• it has the effect that it can be easily wound into a roll when a long object is created. Therefore, the polarizing plate of the present invention is easy to produce, can cope with the thinning of the protective film, and is excellent in surface hardness, moist heat resistance, and display unevenness improvement effect.
• the polarizing plate of the present invention is particularly useful as a liquid crystal projector or in-vehicle polarizing plate that requires durability.
• the polarizing plate of the present invention is characterized in that a coating cured film of a curable resin composition containing a specific silicone resin (A) is used as a protective film (or support) for a polarizing element.
• the coating cured film refers to a film (or layer) obtained by curing the coating film (or coating layer).
• the resin composition is applied to both surfaces or one of the surfaces of the polarizing element, preferably a surface-treated surface, and after forming a coating film, the coating film is polymerized and cured. Can be obtained.
• the coated and cured film is usually directly attached to the surface of the polarizing element without interposition of an adhesive layer and other resin layers between the surface of the polarizing element.
• “directly attached to the surface of the polarizing element” means that the adhesive layer and the other resin layer are not interposed between the coating cured film and the surface of the polarizing element. This includes the case where the coating cured film is directly attached to the surface of the polarizing element that has been surface-modified.
• the coating cured film in the present invention may have another resin layer or the like interposed between it and the surface of the polarizing element, but it usually adheres directly to the surface of the polarizing element without any interposition. It is preferable.
• a silicone resin (A) used in the present invention which is represented by the following formula (1) and has a polyorganosilsesquioxane having a cage structure in a structural unit as a main component, is disclosed in WO2004 / 085501A1 and the like. And can be easily obtained by those skilled in the art.
• the curable resin composition used for the polarizing plate of the present invention is a radical polymerization with the above silicone resin (A) mainly composed of polyorganosilsesquioxane having a cage structure in the structural unit. And an unsaturated compound.
• Silicone resin (A) (hereinafter also referred to as silicone resin (A)) 5 to 80% by weight of a polyorganosilsesquioxane having a cage structure in the structural unit as a main component, and a radically polymerizable unsaturated compound A curable resin composition containing 95 to 20% by weight.
• the radically polymerizable unsaturated compound may be one kind or a plurality of combined use. Usually, two or more combined use is preferable.
• One preferred radical-polymerizable unsaturated compound is an oligomer (B) having a urethane bond having a number average molecular weight of 1000 or more capable of radical copolymerization with the silicone resin (A) (hereinafter referred to as oligomer (B) or urethane). Oligomer (B)).
• the urethane oligomer (B) is usually contained in the range of 1 to 50% by weight.
• the curable resin composition is used as a balance with the silicone resin (A) other than the urethane oligomer (B).
• An unsaturated compound (C) capable of radical copolymerization (hereinafter also referred to as an unsaturated compound (C)) is included.
• the silicone resin (A), the oligomer (B) and the unsaturated compound (C) are preferably added in an amount of 5 to 80: 1 to 50:10. Contained in a weight ratio of ⁇ 80.
• a polarizing plate having a coating cured film of the curable resin composition including these three is more preferable.
• the curable resin composition used in the present invention can further contain any additive. Usually, those having the above three components as main components are preferred.
• the curable resin composition is applied to the surface of the polarizing element, irradiated with energy rays such as light (for example, ultraviolet rays), and cured by radical copolymerization, and a coating cured film (layer). Can be obtained.
• the coating is preferably performed directly on the surface of the polarizing element (including the silane coupling surface) so that the cured film (or cured layer) after curing is directly attached to the surface of the polarizing element.
• the “main component” preferably accounts for at least 50% by weight or more, more preferably 70% by weight or more based on the total amount. Further, unless otherwise specified, “%” represents wt%.
• the silicone resin (A) used in the present invention is represented by the general formula (1), and a polyorganosilsesquioxane (also referred to as a cage silsesquioxane) having a cage structure in the structural unit is a main component. In general, it contains 60 to 95% by weight of a cage silsesquioxane, and the balance is a non-silicone silicone resin component.
• R is an organic functional group having a (meth) acryloyl group, and preferred R includes a (meth) acryloyloxy C1-3 alkyl group represented by the following general formula (4). it can.
• m is an integer of 1 to 3
• R 1 is a hydrogen atom or a methyl group.
• R 1 is a hydrogen atom or a methyl group.
• R include a 3-methacryloxypropyl group, a methacryloxymethyl group, and a 3-acryloxypropyl group.
• the silicone resin (A) has the organic functional group on the silicon atom in the molecule.
• Specific structures of the cage polyorganosilsesquioxane in which n in the general formula (1) is 8, 10 or 12 are those represented by the following structural formulas (5), (6) and (7).
• Type structures also referred to as T8, T10, and T12, respectively.
• R in the following formula is the same as R in the general formula (1).
• the silicone resin (A) used in the present invention can be produced by the method described in WO2004 / 085501A1 and the like. That is, the silicone resin (A) has the following formula RSix 3 (In the formula, R represents an organic functional group having a (meth) acryloyl group, and X represents a hydrolyzable group)
• the silicon compound represented by the formula (1) is subjected to a hydrolysis reaction in a polar solvent in the presence of a basic catalyst and partially condensed, and the resulting hydrolysis condensation product is further obtained in a nonpolar solvent in the presence of a basic catalyst. It can be obtained by recondensing.
• the hydrolyzable group X is not particularly limited as long as it is a hydrolyzable group, and examples thereof include an alkoxy group, an acetoxy group, and a chlorine atom, and an alkoxyl group is preferable.
• the alkoxyl group include a methoxy group, an ethoxy group, an n- and i-propoxy group, and an n-, i- and t-butoxy group. Among these, a methoxy group is preferable because of its high reactivity.
• preferred compounds include methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxylane, 3-methacryloxypropyltrichlorosilane, 3-methacryloxypropyltrimethoxysilane, 3- Mention may be made of methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltrichlorosilane. Of these, 3-methacryloxypropyltrimethoxysilane, which is easily available, is preferable.
• Basic catalysts used in the hydrolysis reaction include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyl
• alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide
• tetramethylammonium hydroxide tetraethylammonium hydroxide
• tetrabutylammonium hydroxide benzyl
• ammonium hydroxide salts such as trimethylammonium hydroxide and benzyltriethylammonium hydroxide.
• tetramethylammonium hydroxide is preferably used because of its high catalytic activity.
• the basic catalyst is usually used as an aqueous solution.
• the reaction temperature is preferably 0 to 60 ° C, more preferably 20 to 40 ° C.
• the reaction rate becomes slow, and the hydrolyzable group remains in an unreacted state, resulting in a long reaction time.
• the temperature is higher than 60 ° C., the reaction rate is too high, so that a complex condensation reaction proceeds, and as a result, an increase in the molecular weight of the hydrolysis condensation product is promoted.
• the reaction time is preferably 2 hours or more. If the reaction time is less than 2 hours, the hydrolysis reaction does not proceed sufficiently and the hydrolyzable group remains in an unreacted state.
• water is not less than an amount sufficient to hydrolyze the hydrolyzable group, and is preferably 1.0 to 1.5 times the theoretical amount.
• an organic polar solvent such as methanol, ethanol or 2-propanol, or other organic polar solvents can be used. Preferred are lower alcohols having 1 to 6 carbon atoms that are soluble in water, and 2-propanol is more preferred.
• Use of a nonpolar solvent is not preferable because the reaction system is not uniform, the hydrolysis reaction does not proceed sufficiently, and unreacted alkoxyl groups remain.
• water or water-containing reaction solvent is separated. Separation of water or the water-containing reaction solvent can employ means such as evaporation under reduced pressure.
• a nonpolar solvent is added to dissolve the reaction product, and this solution is washed with brine or the like. Then, means such as drying with a drying agent such as anhydrous magnesium sulfate can be employed. If the nonpolar solvent is separated from the solution thus obtained by means such as evaporation, the target reaction product can be recovered. However, if the nonpolar solvent can be used as a solvent in the next reaction, it is not necessary to separate it.
• the reaction product in the hydrolysis accompanied by a condensation reaction is usually a colorless viscous liquid having a number average molecular weight of 1400 to 5000.
• this hydrolysis condensation product varies depending on the reaction conditions, it becomes an oligomer having a number average molecular weight of 1400 to 3000, and most, preferably almost all, of the hydrolyzable group X is substituted with OH groups. Most, preferably 95% or more is condensed.
• the structure of the hydrolytic condensation product there are a plurality of types of cages, ladders, and random silsesquioxanes.
• the ratio of the complete cage structure is small, and an incomplete cage structure in which a part of the cage is open is mainly used. Therefore, the hydrolysis-condensation product obtained by this hydrolysis is further heated in an organic solvent in the presence of a basic catalyst to condense siloxane bonds (referred to as recondensation). Oxane can be selectively produced.
• the recondensation reaction is performed in the presence of a nonpolar solvent and a basic catalyst.
• the reaction temperature is preferably in the range of 100 to 200 ° C, more preferably 110 to 140 ° C.
• the reaction temperature is preferably in the range of 100 to 200 ° C, more preferably 110 to 140 ° C.
• the reaction temperature is too low, a sufficient driving force for causing the recondensation reaction cannot be obtained, and the reaction does not proceed.
• the reaction temperature is too high, the (meth) acryloyl group may cause a self-polymerization reaction, so it is necessary to suppress the reaction temperature or add a polymerization inhibitor or the like.
• the reaction time is preferably 2 to 12 hours.
• the amount of the nonpolar solvent used may be an amount sufficient to dissolve the hydrolysis reaction product.
• the amount of the basic catalyst used is in the range of 0.1 to 10% by weight based on the hydrolysis condensation product.
• nonpolar solvent Any nonpolar solvent may be used as long as it has no or almost no solubility in water.
• hydrocarbon solvents are preferred.
• the hydrocarbon solvent is preferably a nonpolar solvent having a low boiling point such as toluene, benzene and xylene, and more preferably toluene.
• the basic catalyst used for a hydrolysis reaction can be used.
• Basic catalysts include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide, or tetramerammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide and benzyl Examples thereof include ammonium hydroxide salts such as triethylammonium hydroxide.
• a catalyst that is soluble in a nonpolar solvent such as tetraalkylammonium is preferable.
• a hydrolyzed condensation product used for recondensation which is washed, dehydrated and concentrated, but can be used without being washed and dehydrated.
• water may be present, but it is not necessary to add it positively, and it is preferable that the water is brought to the extent of water brought from the basic catalyst solution.
• the hydrolysis condensation product is not sufficiently hydrolyzed, water of a theoretical amount or more necessary for hydrolyzing the remaining hydrolyzable group is necessary.
• the hydrolysis reaction is sufficiently performed with moisture brought from the solution. After the recondensation reaction, the catalyst is washed away with water and then concentrated to obtain the desired silsesquioxane mixture.
• the silsesquioxane thus obtained varies depending on the reaction conditions and the state of the hydrolysis-condensation product, but the constituent component is at least 50% or more of the entire cage silsesquioxane, usually 70 % And the balance is a non-condensed condensate.
• the constituent components of the plurality of cage silsesquioxanes are 20 to 40% T8 represented by the general formula (5), 40 to 50% T10 represented by the general formula (6), and the remainder It is other components, and is usually T12 represented by the general formula (7).
• T8 can be separated as a needle-like crystal by leaving the siloxane mixture at 20 ° C. or lower.
• the cage silsesquioxane in the silicone resin (A) used in the present invention may be a mixture of T8, T10 and T12, or may be one obtained by separating or concentrating one or two of them. .
• the silicone resin (A) used by this invention is not limited to the silicone resin obtained by the said manufacturing method.
• the radically polymerizable unsaturated compound used in the curable resin composition is not particularly limited as long as it is radically polymerized with the reactive functional group in the silicone resin (A). Usually, a compound having a photopolymerizable double bond is preferred. More preferred compounds include (meth) acrylate compounds.
• One preferred example of the radical polymerizable unsaturated compound is a radical polymerizable urethane oligomer (B).
• a preferable curable resin composition includes a curable resin composition containing the radical polymerizable urethane oligomer (B) as at least one component of the radical polymerizable unsaturated compound.
• the content of the urethane oligomer (B) with respect to the total amount of the radical polymerizable unsaturated compound is preferably 1% or more, usually 1% to 50%, preferably 2 to 40%, more preferably 3 to 40%, still more preferably. Is about 3 to 30%. In another embodiment, it is preferably 5 to 40%, more preferably 5 to 30%, still more preferably 5 to 20%.
• the urethane oligomer (B) contains at least one unsaturated group represented by —R 3 —CR 4 ⁇ CH 2 or —CR 4 ⁇ CH 2 in the molecule, and has a number average molecular weight of 1000 or more, preferably 2000 More preferably, an oligomer (urethane oligomer) having a urethane bond of 2500 or more and usually 10,000 or less can be mentioned.
• R 3 represents an aliphatic C1 to C6 bridging group or —OCO— group.
• the aliphatic C1-C6 crosslinking group a lower alkylene group having 1 to 6 carbon atoms and a lower alkylidene group having 1 to 6 carbon atoms are preferable.
• R 3 is an —OCO— group or a methylene group, and an —OCO— group is more preferable.
• R 4 represents a hydrogen atom or a C1-C6 alkyl group. Preferred examples of R 4 include hydrogen or a C1-C3 alkyl group (preferably a methyl group).
• Preferred unsaturated groups represented by the above formula include at least one group selected from the group consisting of (meth) acryloyloxy group (acryloyloxy group or methacryloyloxy group), allyl group and vinyl group, and more Preferably, it is an acryloyloxy group or a methacryloyloxy group.
• the urethane oligomer (B) is preferably a urethane (meth) acrylate having an acryloyloxy group or a methacryloyloxy group.
• the urethane oligomer (B) can be produced by a conventionally used method. Examples of such a method include a method of synthesizing from a polyol, a polyisocyanate, and a compound having a polymerizable unsaturated group and a hydroxyl group at the terminal. In that case, the urethane oligomer (B) used for the curable resin composition of this invention can be obtained by adjusting suitably the molecular weight of a raw material substance, or the molar ratio at the time of reaction.
• polystyrene resin examples include polyester polyols obtained by polycondensation of polybasic acids and polyhydric alcohols; polyester polyols obtained by ring-opening polymerization of lactones such as ⁇ -caprolactone and ⁇ -valerolactone; ethylene oxide, propylene oxide And an alkylene oxide such as butylene oxide, a polymer of a cyclic ether such as tetrahydrofuran and an alkyl-substituted tetrahydrofuran, or a polyether polyol which is a copolymer of two or more of these.
• polyisocyanate compound examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene.
• Examples of the compound having a polymerizable unsaturated group and a hydroxyl group at the terminal include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, pentaerythritol tri (meth) acrylate, 3-acryloyloxyglycerin mono (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-1- (Meth) acryloxy-3- (meth) acryloxypropane, glycerin di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, poly ⁇ -caprolactone mono (meta Acrylate, 4-hydroxybutyl (meth) acrylate, .epsilon.-caprolactone
• the urethane oligomer (B) is preferably a urethane (meth) acrylate oligomer.
• the urethane (meth) acrylate oligomer can be obtained by using the above-mentioned (meth) acrylate compound having a hydroxyl group as a compound having a polymerizable unsaturated group and a hydroxyl group at the terminal.
• the oligomer (B) commercially available ones can be used.
• urethane acrylate oligomer UF-8001 number average molecular weight: 2600
• UF-503 number average molecular weight: manufactured by Kyoeisha Chemical Co., Ltd.
• 3800 is preferably used.
• Preferred urethane oligomers (B) include urethane (meth) acrylate oligomers having a number average molecular weight of about 1,000 to 10,000, preferably a number average molecular weight of about 2,000 to 10,000.
• a urethane (meth) acrylate oligomer having a number average molecular weight of about 2,500 to 6,000 is preferred, preferably 2,500 to 10,000.
• Examples of the radical polymerizable unsaturated compound other than the urethane oligomer (B) include unsaturated compounds (C) that are unsaturated compounds other than the oligomer (B) and copolymerizable with the silicone resin (A).
• the unsaturated compound (C) is not limited as long as it satisfies the above conditions. However, the unsaturated compound (C) has a low water absorption by containing at least 10 to 100% of the alicyclic unsaturated compound. Therefore, it is preferable.
• the alicyclic unsaturated compound the following general formula (2)
• Z represents any group represented by (2a) or (2b), and R ′ represents hydrogen or a methyl group
• examples of the component contained in the unsaturated compound (C) other than the alicyclic unsaturated compound include a chain unsaturated compound having a polymerizable unsaturated group and an aromatic compound having a polymerizable unsaturated group.
• the alicyclic unsaturated compound preferably a large amount of the alicyclic di (meth) acrylate (C ′) represented by the general formula (2), is contained in some cases.
• the alicyclic unsaturated compound is at least 50% or more, preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more with respect to the total amount of the unsaturated compound (C).
• the total amount of the unsaturated compound (C) may be the alicyclic unsaturated compound.
• a reactive oligomer other than the urethane oligomer (B) which is a polymer having about 2 to 20 repeating structural units. And low molecular weight and low viscosity reactive monomers.
• the component is roughly classified into a monofunctional unsaturated compound having only one unsaturated group and a polyfunctional unsaturated compound having two or more.
• the alicyclic unsaturated compound preferably the alicyclic di (meta) represented by the general formula (2) is optionally contained in the unsaturated compound (C).
• a polyfunctional unsaturated compound other than acrylate (C ′) may be further contained.
• the average number of polymerizable unsaturated bonding groups in the unsaturated compound (C) is 1.1 or more, preferably 1.5 or more, per molecule. More preferably, it is 1.6 or more and 5 or less.
• the average number of functional groups can be appropriately adjusted by using a monofunctional unsaturated compound and a polyfunctional unsaturated compound having 2 to 5 unsaturated groups, or a mixture of polyfunctional unsaturated compounds. .
• the average per polymerizable unsaturated bond group is 2.
• Examples of the reactive oligomer include epoxy acrylate, epoxidized oil acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl acrylate, polyene / thiol, silicone acrylate, polybutadiene, and polystyrylethyl methacrylate. Can do.
• the reactive monomer includes a monofunctional monomer and a polyfunctional monomer.
• the reactive monofunctional monomer include styrene, vinyl acetate, N-vinyl pyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, and dicyclopentenyl.
• Examples include roxyethyl acrylate, phenoxyethyl acrylate, and trifluoroethyl methacrylate.
• Examples of the reactive polyfunctional monomer include tripropylene glycol diacrylate and 1,6-hexanediol, which are unsaturated compounds other than the alicyclic di (meth) acrylate (C ′) of the general formula (2).
• Examples include polyfunctional (meth) acrylate compounds having 2 to 6 functional groups such as erythritol triacrylate and dipentaerythritol hexaacrylate.
• (meth) acrylate compounds having 2 to 3 functional groups such as trimethylolpropane di or tri (meth) acrylate, pentaerythritol di or tri (meth) acrylate, and dipentaerythritol di or tri (Meth) acrylate and the like can be mentioned.
• trimethylolpropane triacrylate or dipentaerythritol triacrylate is more preferable.
• the unsaturated compound (C) various reactive oligomers and monomers other than those exemplified above can be used.
• the reactive oligomer or monomer other than the alicyclic di (meth) acrylate (C ′) of the general formula (2) is an alicyclic unsaturated compound, preferably of the general formula (2). You may use together with a compound individually or in combination of 2 or more types, respectively.
• Preferred examples of the unsaturated compound (C) include the alicyclic di (meth) acrylate (C ′) of the above general formula (2) or a monofunctional or polyfunctional (meth) acrylate compound.
• it is an alicyclic di (meth) acrylate (C ′) or a polyfunctional (meth) acrylate compound of the general formula (2), and as a more preferable embodiment, the alicyclic di ( The meth) acrylate (C ′) can be used alone, or the alicyclic di (meth) acrylate (C ′) and the polyfunctional (meth) acrylate compound of the general formula (2) can be used in combination.
• the curable resin composition used in the present invention contains 5 to 80% of the silicone resin (A) and 95 to 20% of the radical polymerizable compound with respect to the entire composition, Additives can be included.
• the optional additive include various additives including a photopolymerization initiator described later. It is preferable to include a photopolymerization initiator.
• a radically polymerizable compound it is preferable to contain both a urethane oligomer (B) and the said unsaturated compound (C). Therefore, a preferable curable resin composition contains three of the silicone resin (A), the urethane oligomer (B), and the unsaturated compound (C), and the total of these is 60 with respect to the total amount of the curable resin composition.
• the curable resin composition preferably occupies about 97%, preferably 70 to 96% by weight, more preferably about 80 to 95% by weight, and the balance is a photopolymerization initiator and other optional components.
• the mixing ratio (weight ratio) of each component of the silicone resin (A), the urethane oligomer (B) and the unsaturated compound (C) is in the range of 5 to 80: 1 to 50:10 to 80, preferably 10 to The range is from 70: 5 to 30:30 to 70. If the ratio of the silicone resin (A) is less than 5%, physical properties such as heat resistance, transparency and water absorption of the coated film after curing are not preferable. On the other hand, when the ratio of the silicone resin (A) exceeds 80%, the viscosity of the composition is increased, which makes application difficult.
• the ratio of the urethane oligomer (B) is 1 to 50%, the winding property of the obtained polarizing plate is improved, and it can be wound into a roll after long processing.
• the ratio of the urethane oligomer (B) exceeds 50%, the compatibility with the silicone resin is deteriorated, and it becomes difficult to obtain a uniform resin composition. Therefore, the above range is preferable.
• the proportion of the urethane oligomer (B) is more preferably 3 to 30% as described above, still more preferably about 3 to 20%, and in some cases 5 to 30% or 5 to 20%.
• the ratio of the silicone resin is large, the obtained cured product has superior physical properties as a silicone resin.
• the obtained cured product has superior physical properties as a resin composed of the unsaturated compound (C), and some of the disadvantages that occur when the silicone resin is dominant are some. Improved.
• the ratio of the alicyclic unsaturated compound contained in the unsaturated compound (C) is large, the resulting cured product is excellent in low hygroscopicity and is a non-alicyclic polyfunctional unsaturated compound.
• the ratio is large, the obtained cured product is excellent in low linear expansion. Therefore, it is preferable to change the composition ratio as appropriate according to the purpose of use.
• the composition ratio of each component with respect to the total amount of the three components of the silicone resin (A), the urethane oligomer (B) and the unsaturated compound (C) is as follows.
• the urethane oligomer (B) is 3 to 30%
• the unsaturated compound (C) is 40 to 70%.
• the urethane oligomer (B) is 5 to 30%, further 5 to 20%.
• the unsaturated compound (C) is an alicyclic di (meth) acrylate (C ′) represented by the general formula (2) 10 to 100%, preferably 20 to 100% of the total amount of the unsaturated compound (C), and other components contained in the unsaturated compound (C) are mixed with the components of the unsaturated compound (C).
• An embodiment containing 0 to 90%, preferably 0 to 80% based on the total amount is a more preferred embodiment.
• an alicyclic di (meth) acrylate (C ′) represented by the general formula (2) May be 50 to 100% based on the total amount of the unsaturated compound (C).
• the alicyclic di (meth) acrylate (C ′) represented by the general formula (2) is The remaining amount can also be made into the component contained in another unsaturated compound (C) by making it less than 50% with respect to the whole quantity of this unsaturated compound (C).
• the component contained in the other unsaturated compound (C) is a polyfunctional acrylate compound, preferably an aliphatic polyfunctional (meth) acrylate.
• the curable resin composition is preferably a photocurable resin composition, and in the composition, a photopolymerization initiator, a photoinitiator auxiliary agent, a sharpener, and the like as an additive that accelerates the reaction by ultraviolet rays or the like. Can be blended.
• the composition preferably contains a photopolymerization initiator.
• the addition amount is usually 0.1 to 10 parts by weight with respect to 100 parts by weight in total of the silicone resin (A), the oligomer (B) and the unsaturated compound (C).
• the amount is preferably 0.1 to 4 parts by weight, more preferably 1 to 4 parts by weight. In some cases, 1 to 6 parts by weight is preferable with respect to the total of 100 parts by weight.
• this addition amount is less than 0.1 parts by weight, curing will be insufficient and the strength and rigidity of the resulting molded product will be reduced. On the other hand, if the addition amount is 5 parts by weight or less, there is no problem such as coloring, which is preferable.
• acetophenone series compounds such as acetophenone series, benzoin series, benzophenone series, thioxanthone series, and acylphosphine oxide series can be suitably used.
• the photoinitiator adjuvant and the sharpening agent which show an effect in combination with a photoinitiator can also be used together.
• a photoinitiator may be previously mix
• additives other than those described above can be added to the resin composition as long as the characteristics are not impaired.
• Various additives include antioxidants, light stabilizers, ultraviolet absorbers, organic / inorganic fillers, plasticizers, flame retardants, thermal stabilizers, lubricants, antistatic agents, mold release agents, foaming agents, nucleating agents, and coloring. Examples thereof include an agent, a cross-linking agent, a dispersion aid, and a resin component.
• a hindered amine compound or the like can be preferably used. Specifically, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (1,2, 2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate and bis (2,2,6,6 -Tetramethyl-4-piperidyl) sepacate and the like.
• UV absorber compounds such as benzotriazole compounds, triazine compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, nickel compounds, and the like can be suitably used.
• antioxidant compounds such as hindered phenols can be suitably used. Specifically, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,6-bis (octylthiomethyl) -o-cresol, and the like.
• the curable resin composition used in the present invention preferably contains at least one selected from the group consisting of an ultraviolet absorber, an antioxidant, and a light stabilizer, together with a photopolymerization initiator, rather than including all of these. preferable.
• the ultraviolet absorber is usually from 0 to 100 parts by weight with respect to a total of 100 parts by weight of the silicone resin (A), oligomer (B) and unsaturated compound (C). 8 parts by weight, preferably 0.1 to 6 parts by weight, more preferably 2 to 6 parts by weight.
• the antioxidant and the light stabilizer are each independently 0 to 4 parts by weight, preferably 0.1 -3 parts by weight, more preferably 0.5-2 parts by weight.
• the polarizing element (polarizer) used in the polarizing plate of the present invention is not particularly limited as long as it is an element having a function of polarizing light from a light source, and absorbs light in a specific direction to make polarized light.
• a polarizing element or a reflective polarizing element that reflects light in a specific direction into polarized light can be used.
• an absorptive polarizing element for example, a polarizing element obtained by uniaxially stretching a hydrophilic polymer film such as a PVA film containing a dichroic dye such as a dye or polyvalent iodine ion; the PVA film A polarizing element obtained by dehydrating with an acid before and after uniaxial stretching to form a polyene structure; and a dichroic dye that expresses a lyotropic liquid crystal state on an alignment film that has been treated to be aligned in a certain direction And a polarizing element obtained by applying a solution and then removing the solvent.
• the reflective polarizing element for example, a polarizing element comprising a large number of laminated bodies having different birefringences; a polarizing element comprising a combination of a cholesteric liquid crystal having a selective reflection region and a quarter-wave plate; And a polarizing element provided with a fine wire grid.
• a hydrophilic polymer film such as a PVA film containing a dichroic dye such as a dye or a polyvalent iodine ion, which has excellent polarization characteristics as a polarizing element. It is preferable to use a polarizing element obtained by uniaxial stretching or a polarizing element obtained by dehydrating with an acid before and after uniaxial stretching of the PVA film to form a polyene structure.
• the polarizing element can be manufactured by a conventional method. For example, in the case of a polarizing element comprising a PVA film containing a dichroic dye such as a dye and polyvalent iodine ions, first, the PVA film is first swollen with warm water and then the dichroic dye is dissolved.
• the polarizing element can be obtained by immersing the film in a film, dyeing the film, stretching the film uniaxially in a bath containing a crosslinking agent such as boric acid or borax, and drying the film.
• dyes used for dyeing include iodine-potassium iodide aqueous solutions, azo compounds described in “Application of functional dyes” (supervised by Masahiro Irie, CMC Publishing) pages 98-100, and C.I. Eye. direct. Yellow 12, sea. Eye. direct. Yellow 28, Sea. Eye. direct. Yellow 44, Sea. Eye. direct. Orange 26, Sea. Eye. direct. Orange 39, sea. Eye. direct. Orange 107, sea. Eye. direct. Red 2, sea. Eye. direct. Red 31, sea. Eye. direct. Red 79, Sea. Eye. direct. Red 81, Sea. Eye. direct. Red 247, Sea. Eye. direct. Green 80, Sea. Eye. direct.
• dichroic dyes include, in addition to free acids, alkali metal salts (for example, Na salts, K salts, and Li salts), ammonium salts, salts of amines, and complex salts (for example, Cu complexes, Ni complexes, and Co complexes). Etc.) can be used.
• alkali metal salts for example, Na salts, K salts, and Li salts
• ammonium salts for example, salts of amines
• complex salts for example, Cu complexes, Ni complexes, and Co complexes.
• Etc. can be used.
• the performance of the polarizing element can be adjusted by the dichroism possessed by the dichroic dye, the stretching ratio during stretching, and the like.
• the surface of the polarizing element may be subjected to any surface modification treatment in order to improve the adhesion with the curable resin composition layer.
• the surface of the polarizing element is preferably subjected to surface modification treatment.
• the surface modification treatment include silane coupling treatment, corona treatment, plasma treatment, glow discharge treatment, flame treatment, ozone treatment, UV ozone treatment, and ultraviolet treatment. These processes may be performed alone or in combination of two or more processes.
• silane coupling treatment is preferable from the viewpoint of adhesion.
• the silane coupling treatment is performed by a conventionally known method for treating the coupling agent with a hydrolyzate of the silane coupling agent. For example, it can be achieved by hydrolyzing the silane coupling agent in water or an organic solvent containing water, and then uniformly applying the solution onto the polarizing element and removing the solvent by heating or the like.
• the silane coupling treatment the adhesive strength between the cured coating film (layer) and the polarizing element is further enhanced by the action of the silane compound present on the surface of the polarizing element.
• silane coupling agent examples include (meth) acrylic, amino and isocyanate silane coupling agents.
• a (meth) acrylic silane coupling agent examples include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldimethoxy.
• Examples include silane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, methacryloxymethyltrimethoxysilane, and methacryloxymethyltriethoxysilane.
• Examples of the hydrolysis method of the silane coupling agent include, for example, a method in which the silane coupling agent is added all at once to water or an organic solvent containing water and stirred; the organic solvent containing water or water is stirred.
• Various methods such as a method of adding the silane coupling agent in several batches; and a method of continuously adding the silane coupling agent while stirring water or an organic solvent containing water; Can be adopted.
• dissolved the said silane coupling agent in the organic solvent previously, and adding the said solution to the organic solvent containing water or water according to said method is also employable.
• acidic catalysts such as hydrochloric acid, sulfuric acid, boric acid, oxalic acid, citric acid and acetic acid, or ammonia, urea, ethanolamine and tetramethylammonium hydroxide
• acidic catalysts such as hydrochloric acid, sulfuric acid, boric acid, oxalic acid, citric acid and acetic acid, or ammonia, urea, ethanolamine and tetramethylammonium hydroxide
• the silane coupling agent can be dissolved, and further, compatible with water and a catalyst used as necessary, or in the presence of a surfactant, Any compound may be used as long as it is uniformly dispersed in a state in which water and the catalyst are associated (micellar).
• organic solvent examples include, for example, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, pentyl alcohol, ethylene glycol, propylene glycol and 1,4-butanediol; Ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; paraffins or cycloparaffins such as isooctane and cyclohexane; (cyclic) ethers such as dioxane and diethyl ether; and aromatic hydrocarbons such as benzene and toluene And the like.
• alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, pentyl alcohol, ethylene glycol, propylene glycol and 1,4-butanediol
• Ketones such as ace
• organic solvents may be used alone, or two or more kinds thereof may be appropriately mixed and used.
• organic solvents exemplified above alcohols are particularly preferable.
• an organic solvent that is incompatible with water and the catalyst can be used, in this case, it is necessary to add a surfactant in order to uniformly disperse the water and the catalyst.
• the concentration of the silane coupling agent in the silane coupling agent-containing liquid for hydrolysis is preferably 0.05 mol / L or more, and 1.2 mol / L or less with respect to the total capacity of the silane coupling agent-containing liquid. preferable.
• the concentration of water used in combination with the organic solvent is preferably 0.1 mol / L or more, and more preferably 2 mol / L or more. Further, the concentration of the water is preferably 50 mol / L or less, and more preferably 25 mol / L or less.
• the silane coupling agent is preferably hydrolyzed only with water without using an organic solvent.
• the concentration of the catalyst (concentration relative to the total volume of the liquid) cannot be generally specified depending on the catalyst, but for example, 0.8 mol / L or more is preferable.
• the concentration of the catalyst is preferably 10 mol / L or less, more preferably 9.4 mol / L or less.
• the pH of the solution of the silane coupling agent is preferably adjusted appropriately within the range of pH 2 to 11 depending on the silane coupling agent used. For example, since an aqueous solution of an amino silane coupling agent is weakly alkaline and stable, a preferable pH is 8 to 11, and a more preferable range is 9 to 10.5.
• the (meth) acrylic silane coupling agent preferable in the present invention is generally weakly acidic or neutral and stable, it is usually about 2 to 8.
• the pH is more preferably 2.5 to 5.0, and most preferably 3.0 to 4.5.
• the reaction temperature when hydrolyzing the silane coupling agent is preferably 5 ° C or higher, more preferably 10 ° C or higher, and further preferably 20 ° C or higher.
• the reaction temperature is preferably 100 ° C. or lower, more preferably 70 ° C. or lower, and further preferably 50 ° C. or lower. If reaction temperature is 0 degreeC or more, a hydrolysis reaction will advance rapidly, and if it is 100 degrees C or less, control of a hydrolysis reaction will become easy.
• the reaction time for hydrolyzing the silane coupling agent can be appropriately set according to the silane coupling agent to be used, and is not limited. For example, it is preferably 15 minutes or more, more preferably 20 minutes or more. Preferably, 25 minutes or more is more preferable.
• the reaction time is preferably 100 hours or less, more preferably 20 hours or less, and even more preferably 10 hours or less. If the reaction time is 15 minutes or longer, the hydrolysis reaction proceeds sufficiently, and if it is 100 hours or shorter, the energy required for the heat treatment can be kept low, and productivity is improved.
• the most preferable reaction condition when hydrolyzing the silane coupling agent is that water is used as a solvent, and the concentration of the silane coupling agent is in the range of 0.05 mol / L to 1.2 mol / L.
• the catalyst concentration is in the range of 0.8 mol / L to 9.4 mol / L, the reaction temperature is in the range of 20 ° C. to 50 ° C., and the reaction time is 25 minutes to 10 hours. Is within the range.
• the method for applying the hydrolyzate of the silane coupling agent to the polarizing element is not particularly limited, and any known method may be used as long as the coating surface is smooth and the thickness is uniformly applied. Specifically, a coating method using a bar coater, a roll coater, a doctor blade, a slit coater, a spin coater, or the like can be given.
• the solvent of the applied hydrolyzate of the silane coupling agent is removed by heat treatment.
• the heat treatment may be performed according to a normal method, and the treatment temperature is preferably 0 ° C. or higher, more preferably 20 ° C. or higher, and further preferably 30 ° C. or higher.
• the treatment temperature is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 60 ° C. or lower. If the said process temperature is 0 degreeC or more, drying of a solvent will advance rapidly, and if it is 100 degrees C or less, the influence on the performance of a polarizing element with a heat
• the treatment time for the heat treatment is usually about 2 minutes to 5 hours, preferably about 10 minutes to 2 hours, although it depends on the treatment temperature.
• the said curable resin composition used by this invention is apply
• cured material of the said curable resin composition is formed,
• the polarizing plate of this invention Can be obtained.
• the resin composition is applied as it is or after dilution with a solvent as necessary, to one or both sides of the polarizing element.
• the polarizing plate of the present invention is obtained by performing treatment such as the above, and irradiating the coating film (resin layer) with ultraviolet rays to cure the resin layer.
• the method for applying the resin composition is not particularly limited as long as the smoothness and thickness uniformity can be maintained. Examples thereof include a method using a bar coater, a gravure coater, a slit coater, a roll coater, and a spin coater. .
• Irradiation of energy rays is performed in air or in a nitrogen atmosphere.
• the coating film can be cured by irradiating ultraviolet rays having a wavelength of 10 to 400 nm so that the integrated dose is in the range of 1000 to 20000 mJ / cm 2 .
• the wavelength of light to be used is not particularly limited as long as it is within the above range, and near ultraviolet light having a wavelength of 200 to 400 nm is particularly preferably used.
• a lamp used as an ultraviolet ray generation source a low-pressure mercury lamp (output: 0.4 to 4 W / cm), a high-pressure mercury lamp (40 to 160 W / cm), an ultra-high pressure mercury lamp (173 to 435 W / cm), a metal halide lamp (80 to 160 W / cm), pulse xenon lamp (80 to 120 W / cm), electrodeless discharge lamp (80 to 120 W / cm), and the like.
• Each of these ultraviolet lamps is characterized by its spectral distribution, and is therefore selected according to the type of photoinitiator used.
• the thickness of the coating cured film (layer) of the resin composition can be appropriately determined according to the purpose, and is usually selected in the range of about 0.5 ⁇ m to 500 ⁇ m.
• a preferred range for the protective film is about 3 ⁇ m to 200 ⁇ m.
• it can be about 4 to 40 ⁇ m, more preferably 4 to 35 ⁇ m, and even more preferably 4 to 25 ⁇ m.
• the cured product layer (coating film cured film layer) of the curable resin composition is formed (laminated) on at least one side of the surface of the polarizing element, but in order to protect the polarizing element or to make the effects of the present invention more manifest. Therefore, it may be formed (laminated) on both sides of the polarizing element.
• the coating film cured film layer is provided on one side of the surface of the polarizing element, the other surface preferably has a support for the polarizing element or a protective film made of other resin (hereinafter also referred to as a support or the like).
• the support or the like on the other surface is not particularly limited as long as it functions as a support or a protective film, and is usually a layer or film made of a resin different from the curable resin composition.
• a resin layer or film include a layer made of a cured product of an ultraviolet curable resin different from the resin composition, or a film made of TAC or a cycloolefin polymer, preferably TAC or cycloolefin. It is a film made of a polymer.
• the polarizing plate of the present invention having the cured film layer on one side of the polarizing element and a film made of a cycloolefin polymer as a support for the polarizing element on the other side has improved image display spots and contrast. Since heat resistance and heat-and-moisture resistance are also improved, it is preferable.
• the film or the like is used as a support or the like, it is usually bonded with an adhesive to the other surface of the polarizing element that does not have the coating film cured film layer of the curable resin composition of the present invention.
• the polarizing plate of the present invention When the polarizing plate of the present invention has a film such as TAC or cycloolefin polymer as a support on the other surface, the polarizing plate is liquid crystal display in the direction in which the film side of the polarizing plate becomes the liquid crystal cell side. It is preferably arranged in the device.
• Antireflection treatment such as AR (anti-reflection) and AG (anti-glare) is applied to the polarizing plate surface of the present invention (coating film surface or other surface of the curable resin composition of the present invention) as necessary.
• Various surface treatments such as antifouling treatment such as water repellency and oil repellency, and fingerprint prevention treatment for making fingerprints difficult to be attached or difficult to see may be applied.
• the polarizing plate of the present invention thus obtained can suppress dimensional changes as a polarizing plate due to the effect of the cured product layer of the curable resin composition.
• the dimensional change of the polarizing plate of the present invention is within 0.5%, more preferably within 0.3% when left for 24 hours in an atmosphere of 100 ° C. with respect to the original film size. It is.
• the image display device of the present invention By disposing the polarizing plate of the present invention in the light path of the image display device, for example, on at least one side of the liquid crystal cell of the liquid crystal display device, the image display device of the present invention, for example, the liquid crystal display device can be obtained.
• the polarizing plate of this invention can be used in any case.
• various modes such as VA (vertical alignment), IPS (in-plane switching), OCB (optically compensated bend), TN (twisted nematic), and STN (super twisted nematic)
• VA vertical alignment
• IPS in-plane switching
• OCB optical compensated bend
• TN twisted nematic
• STN super twisted nematic
• a retardation film for improving viewing angle characteristics and contrast may be inserted between the polarizing plate of the present invention and the liquid crystal cell.
• the type of retardation film used varies depending on the type of liquid crystal cell.
• a negative-C-plate or a film in which A-plate and negative-C-plate are combined is used, and in the case of the IPS, a biaxial-plate or a positive-C-plate is used.
• a film in which a hybrid aligned discotic liquid crystal is fixed is used
• STN type a biaxial plate or the like is used.
• the polarizing plate of the present invention can be suitably used for a liquid crystal projector, and in that case, it is usually used as a color polarizing plate for a liquid crystal cell that performs switching with respect to light sources of red, green and blue.
• the liquid crystal display device of the present invention may be any one as long as it is disposed in the light path of the image display device, for example, at least one side of the liquid crystal cell of the liquid crystal display device as described above. Usually, it is preferable to arrange two polarizing plates of the present invention so as to sandwich the liquid crystal cell.
• the coating cured film (layer) of the curable resin composition on the polarizing plate is viewed from the liquid crystal cell. It is preferable to dispose the polarizing plate of the present invention so as to be in the direction toward the outside, for example, a coating cured film (layer) of the curable resin composition / polarizing element / support, etc./liquid crystal cell.
• a liquid crystal display element incorporating the polarizing element of the present invention may be disposed in the light path of the image display apparatus.
• a pressure-sensitive adhesive is applied to one side of the polarizing plate of the present invention, and the polarizing plate of the present invention is provided on at least one side, preferably both sides of the liquid crystal cell. It can be obtained by bonding in the above-mentioned direction.
• Any pressure-sensitive adhesive can be used without particular limitation as long as it is transparent and does not have optical anisotropy.
• a liquid crystal display device such as a liquid crystal projector
• the polarizing plate of the present invention when the polarizing plate of the present invention is disposed on both sides of the liquid crystal, the surface of the support or the like is on the light incident side, and the curable resin composition of the present invention is coated and cured on the light emission side It can also be arranged in the direction in which the film surface becomes.
• Synthesis example ⁇ Synthesis example of polyorganosilsesquioxane having a cage structure>
• a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer was charged with 40 ml of 2-propanol (IPA) as a solvent and 3 g of a 5% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) as a basic catalyst.
• IPA 2-propanol
• TMAH aqueous solution a 5% tetramethylammonium hydroxide aqueous solution
• MTMS 3-methacryloxypropyltrimethoxysilane
• Example 1 (1) Preparation of curable resin composition Vertically silylated polyphenylsilsesquioxane having a methacryloxy group obtained in Synthesis Example: 30 parts by weight, urethane acrylate oligomer (manufactured by Kyoeisha Chemical Co., Ltd., trade name: UF-503) ): 5 parts by weight, dicyclopentanyl diacrylate (tricyclo [5.2.1.0 2,6 ] decane dimethylol diacrylate): 65 parts by weight, 1-hydroxycyclohexyl phenyl ketone: 2 parts by weight, bis ( 2,4,6-trimethylbenzoyl) -phenylphosphine oxide: 1 part by weight, UV absorber (manufactured by Ciba Specialty Chemicals, trade name: Tinuvin 384-2): 4 parts by weight, bis (1,2,2) , 6,6-pentamethyl-4-piperidyl) sebacate: 1 part by weight and pentaerythrito
• Silane coupling treatment of polarizing element A TAC that has been subjected to alkali treatment is bonded to a glass plate via an acrylic pressure-sensitive adhesive (manufactured by Polatechno Co., Ltd., AD-ROC), and further on the TAC surface.
• a polarizing element obtained by stretching a PVA resin film on which a dye was adsorbed (PVA Techno Co., Ltd., PHC element for SHC) was laminated using a PVA adhesive.
• the non-stacked surface of the stacked polarizing element was subjected to silane coupling treatment.
• the silane coupling treatment was performed as follows.
• Example 2 In Example 1, the obtained curable resin composition was applied using a spin coater so that the film thickness after curing was 5 ⁇ m, to obtain a cured product layer made of the curable resin composition of the present invention. A polarizing plate of the present invention was produced in the same manner as in Example 1 except that.
• Example 3 As shown in Table 1 below, in Example 1, 50 parts by weight of caged silylated polyphenylsilsesquioxane having a methacryloxy group obtained in the synthesis example; urethane acrylate oligomer (manufactured by Kyoeisha Chemical Co., Ltd., trade name: UF) -503) 10 parts by weight of urethane acrylate oligomer (manufactured by Kyoeisha Chemical Co., Ltd., trade name: UF-8001) instead of 5 parts by weight; and dicyclopentanyl diacrylate (tricyclo [5.2.1.0 2, 6 ] decane dimethylol diacrylate) 20 parts by weight of dicyclopentanyl diacrylate (tricyclo [5.2.1.0 2,6 ] decane dimethylol diacrylate) instead of 65 parts by weight and trimethylol propane triacrylate 20 Except for obtaining the curable resin composition of the present invention using parts by weight, Examples 1 was used to prepare the polarizing plate
• Example 4 As shown in Table 1 below, in Example 1, 25 parts by weight of caged silylated polyphenylsilsesquioxane having a methacryloxy group obtained in the synthesis example; urethane acrylate oligomer (manufactured by Kyoeisha Chemical Co., Ltd., trade name: UF -503) 10 parts by weight of urethane acrylate oligomer (manufactured by Kyoeisha Chemical Co., Ltd., trade name: UF-8001) instead of 5 parts by weight; and dicyclopentanyl diacrylate (tricyclo [5.2.1.0 2, 6 ) decane dimethylol diacrylate) 15 parts by weight of dicyclopentanyl diacrylate (tricyclo [5.2.1.0 2,6 ] decane dimethylol diacrylate) instead of 65 parts by weight and 50 of dipentaerythritol triacrylate Except for obtaining the curable resin composition of the present invention using parts by weight, Examples 1 was used to prepare the
• Example 5 As shown in Table 1 below, in Example 1, 20 parts by weight of caged silylated polyphenylsilsesquioxane having a methacryloxy group obtained in the synthesis example; urethane acrylate oligomer (manufactured by Kyoeisha Chemical Co., Ltd., trade name: UF -503) 12 parts by weight; and dicyclopentanyl diacrylate (tricyclo [5.2.1.0 2,6 ] decane dimethylol diacrylate) instead of 65 parts by weight [5.2.1.0 2,6 ] decane dimethylol diacrylate) 32 parts by weight and 36 parts by weight of dipentaerythritol triacrylate were used except that the curable resin composition of the present invention was obtained.
• a polarizing plate of the present invention was produced in the same manner as in Example 1. Table 1 below shows the compositions of the curable resin compositions of the present invention obtained in Examples 1 to 5.
• Example 6 According to the same operation as in Example 1, except that a polarizing element (manufactured by Polatechno Co., Ltd., PVA element for SKN) obtained by stretching a PVA resin film adsorbed with iodine (iodine polyvalent ions) is used as the polarizing element. An inventive polarizing plate was obtained.
• a polarizing element manufactured by Polatechno Co., Ltd., PVA element for SKN
• iodine iodine polyvalent ions
• Example 7 The same operation as in Example 3 was performed except that a polarizing element (manufactured by Polatechno Co., Ltd., PVA element for SKN) formed by stretching a PVA resin film adsorbed with iodine (iodine polyvalent ions) was used as a polarizing element. An inventive polarizing plate was obtained.
• a polarizing element manufactured by Polatechno Co., Ltd., PVA element for SKN
• iodine iodine polyvalent ions
• Example 8 According to the same procedure as in Example 4, except that a polarizing element (manufactured by Polatechno Co., Ltd., SKN PVA element) obtained by stretching a PVA resin film adsorbed with iodine (iodine polyvalent ions) is used as the polarizing element. An inventive polarizing plate was obtained.
• a polarizing element manufactured by Polatechno Co., Ltd., SKN PVA element obtained by stretching a PVA resin film adsorbed with iodine (iodine polyvalent ions) is used as the polarizing element.
• iodine iodine polyvalent ions
• Example 9 The same operation as in Example 5 was performed except that a polarizing element obtained by stretching a PVA-based resin film adsorbed with iodine (iodine polyvalent ions) (Polatechno Co., Ltd., SKN PVA element) was used as the polarizing element. An inventive polarizing plate was obtained.
• a polarizing element obtained by stretching a PVA-based resin film adsorbed with iodine (iodine polyvalent ions) (Polatechno Co., Ltd., SKN PVA element) was used as the polarizing element.
• An inventive polarizing plate was obtained.
• Example 10 In Example 1, instead of the TAC film, a cycloolefin film (Zeonor RTM manufactured by Nippon Zeon Co., Ltd.) was used, and a polarizing element (stock) obtained by stretching a PVA resin film adsorbed with iodine (iodine polyvalent ions) A polarizing plate of the present invention was obtained in the same manner as in Example 1 except that Polatechno, Inc., PVA element for SKN) was used.
• a polarizing element stock
• a silane coupling agent (trade name: KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to the film so that the thickness after drying was 1.0 ⁇ m and dried to form a silane coupling agent layer.
• the protective film was bonded to a polarizing element comprising a PVA film with a PVA adhesive and dried to obtain a polarizing plate.
• Comparative Example 2 Instead of the curable resin composition obtained in Example 1, KAYARAD RTM -MANDA (manufactured by Nippon Kayaku Co., Ltd., hydroxypivalate neopentyl glycol diacrylate) 50 parts by weight, KAYARAD RTM -TMPTA (Nippon Kayaku Co., Ltd.) Except for using a resin composition in which 50 parts by weight, made by company, trimethylolpropane triacrylate) and 5 parts by weight of Darocur RTM 1173 (photopolymerization initiator, manufactured by Ciba Specialty Chemicals) are uniformly mixed, A polarizing plate was produced in the same manner as in Example 6.
• KAYARAD RTM -MANDA manufactured by Nippon Kayaku Co., Ltd., hydroxypivalate neopentyl glycol diacrylate
• KAYARAD RTM -TMPTA Nippon Kayaku Co., Ltd.
• Darocur RTM 1173 photopolymerization initiator, manufactured
• Test example 1 ⁇ Adhesion evaluation test>
• the peeling polarizing element and the protective film were 90 degrees. While pulling to the angle, a cutter was inserted into the adhesive surface while confirming the adhesive surface of both with an optical magnifying lens, and the presence or absence of peeling was confirmed.
• the cutter could not be inserted into the adhesive surface between the polarizing element and the cured coating film, and when the cutter was forcibly pushed, the cured coating film was broken and the coating film was cured. The film could not be peeled from the surface of the polarizing element.
• Comparative Example 1 the bonded cured film was easily peeled from the surface of the polarizing element by inserting the cutter into the bonding surface by the above method.
• Test example 2 ⁇ Moisture and heat resistance evaluation test> After measuring the initial transmittance and the initial polarization degree of the polarizing plates obtained in Examples 6 to 10 and Comparative Example 2, each polarizing plate was allowed to stand for 72 hours under the wet heat test conditions of 85 ° C. and 85% RH. The transmittance and degree of polarization after the wet heat test were measured. The obtained measurement results are shown in Table 2.
• the polarizing plate of the present invention having a film has good adhesion and high durability after a constant temperature and humidity test even when the protective layer made of the coating cured film is as thin as 5 ⁇ m.
• the polarizing plate of the present invention can cope with the thinning of the protective film and is excellent in wet heat durability. Further, even under severe conditions, the protective film (layer) is not peeled off, the contraction of the polarizing plate is small, and optical characteristics such as the degree of polarization are hardly deteriorated. Furthermore, the polarizing plate of the present invention has features such that the manufacturing process can be simplified and a long object can be easily wound. Accordingly, the polarizing plate of the present invention is suitable as a polarizing plate for liquid crystal display devices used under severe conditions, including liquid crystal display devices used under normal conditions.
• the durability improvement of the polarizing plate of this invention can be expected by using a cycloolefin-type film as a support body on the single side
• the curable resin composition of the present invention can exhibit the above-described excellent characteristics when used as a protective film for the polarizing film as a coating cured film, etc. It is useful for applications such as protective films for parts.

Landscapes

• Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Polarising Elements (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Silicon Polymers (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=42633699

Family Applications (1)

Country Status (5)

Cited By (6)

Families Citing this family (4)

Citations (5)

Family Cites Families (4)

• 2010
  • 2010-02-12 TW TW099104612A patent/TW201038681A/zh unknown
  • 2010-02-15 CN CN2010800081920A patent/CN102317822A/zh active Pending
  • 2010-02-15 WO PCT/JP2010/000902 patent/WO2010095409A1/ja active Application Filing
  • 2010-02-15 JP JP2011500499A patent/JPWO2010095409A1/ja not_active Withdrawn
  • 2010-02-15 KR KR1020117017710A patent/KR20110122818A/ko not_active Application Discontinuation

Patent Citations (5)

Also Published As

Similar Documents

Legal Events