WO2007138850A1 - 偏光子保護フィルム、偏光板、および画像表示装置 - Google Patents
偏光子保護フィルム、偏光板、および画像表示装置 Download PDFInfo
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- WO2007138850A1 WO2007138850A1 PCT/JP2007/059895 JP2007059895W WO2007138850A1 WO 2007138850 A1 WO2007138850 A1 WO 2007138850A1 JP 2007059895 W JP2007059895 W JP 2007059895W WO 2007138850 A1 WO2007138850 A1 WO 2007138850A1
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- weight
- polarizing plate
- polarizer
- cellulose
- resin layer
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Definitions
- Polarizer protective film polarizing plate, and image display device
- the present invention relates to a polarizer protective film, a polarizing plate using the same, and an image display device such as a liquid crystal display device, an organic EL display device, and a PDP including at least one polarizing plate. .
- a polarizing plate is formed by applying a polarizer protective film using a cellulose resin film such as triacetyl cellulose on both sides of a polarizer made of a polyvinyl alcohol film and a dichroic material such as iodine. Those bonded with a rivul alcohol-based adhesive are used.
- (meth) acrylic resin such as polymethyl methacrylate
- (meth) acrylic resin is brittle and easily broken, causing problems such as breakage during film transportation and poor productivity. For this reason, it is difficult to use (meth) acrylic resin as it is for the polarizer protective film.
- a polarizer protective film having a compositional strength composed of a graft copolymer or butyl-modified acetyl cellulose) has been proposed (see Patent Document 1).
- the high heat resistance, high transparency, and high optical properties inherent in acrylic resin (wax) are impaired.
- Patent Document 1 JP-A-5-119217
- Patent Document 2 Japanese Patent Laid-Open No. 2000-230016
- Patent Document 3 Japanese Patent Laid-Open No. 2001-151814
- Patent Document 4 Japanese Patent Laid-Open No. 2002-120326
- Patent Document 5 Japanese Patent Laid-Open No. 2002-254544
- the present invention has been made in order to solve the above-described conventional problems.
- the object of the present invention is (1) having high heat resistance, high transparency, high optical characteristics, and high mechanical strength. And providing a polarizer protective film having excellent adhesion to the polarizer, and (2) adhesion between the polarizer protective film and the polarizer using such a polarizer protective film and the polarizer.
- the present invention provides a polarizing plate having excellent optical characteristics, in particular, excellent viewing angle characteristics of transmittance, and (3) providing a high-quality image display device using such a polarizing plate. is there. Means for solving the problem
- the polarizer protective film of the present invention contains a (meth) acrylic resin having a rataton ring structure.
- a transparent resin layer having a thickness of 0.3 to 3 m on at least one side of the transparent resin layer.
- the cellulose-based resin layer strength The cellulose-based resin solution obtained by dissolving the cellulose-based resin in a solvent is applied to at least one surface of the transparent resin layer and dried. It is formed by letting.
- a polarizing plate is provided.
- the polarizing plate of the present invention is formed by laminating the cellulose-based resin layer side of the polarizer protective film of the present invention on at least one surface of a polarizer formed from polybulal alcohol-based resin.
- an adhesive layer is provided between the cellulose-based resin layer of the polarizer protective film and the polarizer.
- the adhesive layer is a layer formed from a polybutyl alcohol adhesive.
- an adhesive layer is further provided as at least one of the outermost layers.
- an image display apparatus includes at least one polarizing plate of the present invention.
- a polarizer protective film having high heat resistance, high transparency, high optical characteristics, high mechanical strength, and excellent adhesion to the polarizer. Furthermore, using such a polarizer protective film and a polarizer, the adhesive property between the polarizer protective film and the polarizer is excellent, and the optical characteristics are excellent.
- a plate can be provided, and a high-quality image display device using such a polarizing plate can be provided.
- Such an effect is obtained by providing a polarizer protective film by providing a cellulose-based resin layer having a specific thickness on at least one surface of a transparent resin layer containing a (meth) acrylic resin having a rataton ring structure. It can be expressed.
- a (meth) acrylic resin having a rataton ring structure it exhibits high heat resistance, high transparency, high optical properties, and high mechanical strength, and has a specific property on the transparent resin layer.
- the polarizing plate obtained by combining such a polarizer protective film with the polarizer has excellent optical properties, In particular, the viewing angle characteristics of transmittance are excellent.
- FIG. 1 is a cross-sectional view showing an example of a polarizing plate of the present invention.
- FIG. 2 is a schematic sectional view of a liquid crystal display device according to a preferred embodiment of the present invention.
- the polarizer protective film of the present invention has a cellulose-based resin layer on at least one surface of a transparent resin layer containing a (meth) acrylic resin having a rataton ring structure.
- the transparent resin layer in the present invention contains a (meth) acrylic resin having a rataton ring structure.
- the content of the (meth) acrylic resin having a rataton ring structure in the transparent protective layer in the present invention is preferably 60 to: LOO wt%, more preferably 60 to 99 wt%, and even more preferably. 70 to 97% by weight, particularly preferably 80 to 95% by weight.
- the content is less than 50% by weight, the high heat resistance, high transparency, and high mechanical strength inherently possessed by the (meth) acrylic resin having a rataton ring structure may not be sufficiently reflected.
- the (meth) acrylic resin having the Lataton ring structure is preferably one having high light transmittance, low in-plane retardation ⁇ nd and thickness direction retardation Rth.
- the (meth) acrylic resin having a rataton ring structure preferably has a rataton ring structure represented by the following general formula (1).
- R ⁇ R 2 and R 3 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
- the organic residue may contain an oxygen atom. Good.
- the content of the rataton ring structure represented by the general formula (1) in the structure of the (meth) acrylic resin having a rataton ring structure is preferably 5 to 90% by weight, more preferably 10 to 70% by weight. More preferably, it is 10 to 60% by weight, particularly preferably 10 to 50% by weight.
- Lataton environment If the content of the Rataton ring structure represented by the general formula (1) in the structure of the (meth) acrylic resin having a structure is less than 5% by weight, the heat resistance, solvent resistance and surface hardness are insufficient. There is a risk of becoming. If the content ratio of the rataton ring structure represented by the general formula (1) in the structure of the (meth) acrylic resin having a rataton ring structure is more than 90% by weight, the moldability may be poor.
- the (meth) acrylic resin having a latathone ring structure may have a structure other than the latathone ring structure represented by the general formula (1)! /.
- the structure other than the laton ring structure represented by the general formula (1) is not particularly limited, but (meth) acrylic acid as described later as a method for producing a (meth) acrylic resin having a rataton ring structure.
- Polymer structural units (repeating structural units) constructed by polymerizing at least one selected from an ester, a hydroxyl group-containing monomer, an unsaturated carboxylic acid, and a monomer force represented by the following general formula (2a) are preferred. Masashi.
- R 4 represents a hydrogen atom or a methyl group
- X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a —CN group, —CO—R 5 group, or —O—CO—
- R 6 represents a group
- R 5 and R 6 represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
- the content ratio of the structure other than the rataton ring structure represented by the general formula (1) in the structure of the (meth) acrylic resin having a rataton ring structure is determined by polymerizing (meth) acrylic acid ester.
- the polymer structural unit to be constructed it is preferably 10 to 95% by weight, more preferably 10 to 90% by weight, further preferably 40 to 90% by weight, particularly preferably 50 to 90% by weight.
- a polymer structural unit (repeating structural unit) constructed by polymerizing a hydroxyl group-containing main monomer it is preferably 0 to 30% by weight, more preferably 0 to 20% by weight, and even more preferably Is 0 to 15% by weight, particularly preferably 0 to 10% by weight.
- a polymer structural unit (repeating structural unit) constructed by polymerizing an unsaturated carboxylic acid it is preferably 0 to 30% by weight, more preferably 0 to 20% by weight, still more preferably 0 to 15% by weight. , Particularly preferably 0 ⁇ 10% by weight.
- a polymer structural unit constructed by polymerizing the monomer represented by the general formula (2a)
- it is preferably 0 to 30% by weight, more preferably 0 to 20% by weight, Preferably 0 to 15% by weight, particularly preferably 0 to: L0% by weight.
- the method for producing a (meth) acrylic resin having a rataton ring structure is not particularly limited.
- the (meth) acrylic resin having a rataton ring structure is obtained by polymerizing the following predetermined monomer to obtain a polymer (a) having a hydroxyl group and an ester group in the molecular chain.
- the obtained polymer (a) is heat-treated to carry out a rataton cyclocondensation that introduces a Raton ring structure into the polymer.
- a polymer having a hydroxyl group and an ester group in the molecular chain is obtained by performing a polymerization reaction of the monomer component including the monomer represented by the following general formula (la). obtain.
- R 7 and R 8 each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
- Examples of the monomer represented by the general formula (la) include methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, and 2- (hydroxymethyl) acrylate. Examples thereof include propyl, n-butyl 2- (hydroxymethyl) acrylate, and t-butyl 2- (hydroxymethyl) acrylate. Among these, 2- (hydroxymethyl) methyl acrylate and 2- (hydroxymethyl) ethyl acrylate are particularly preferable because 2- (hydroxymethyl) methyl acrylate is particularly preferable because of its high heat resistance improvement effect. As the monomer represented by the general formula (la), only one type may be used, or two or more types may be used in combination.
- the content ratio of the monomer represented by the general formula (la) in the monomer component used in the polymerization step is preferably 5 to 90% by weight, more preferably 10 to 70% by weight, and still more preferably. Is 10 to 60% by weight, particularly preferably 10 to 50% by weight.
- the content of the monomer represented by the general formula (la) in the monomer component used in the polymerization process is less than 5% by weight, Thermal properties, solvent resistance, and surface hardness may be insufficient. If the content of the monomer represented by the general formula (la) in the monomer component used in the polymerization process is more than 90% by weight, gelling may occur during polymerization or rataton cyclization. The molding processability of the polymer may be poor.
- the monomer component used in the polymerization step may contain a monomer other than the monomer represented by the general formula (la).
- a monomer is not particularly limited.
- a (meth) acrylic acid ester, a hydroxyl group-containing monomer, an unsaturated carboxylic acid, and a monomer represented by the following general formula (2a) are preferable.
- Only one type of monomer other than the monomer represented by formula (la) may be used, or two or more types may be used in combination.
- R 4 represents a hydrogen atom or a methyl group
- X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a —CN group, —CO—R 5 group, or —O—CO—
- R 6 represents a group
- R 5 and R 6 represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
- the (meth) acrylic acid ester is not particularly limited as long as it is a (meth) acrylic acid ester other than the monomer represented by the general formula (la), and examples thereof include methyl acrylate and acrylic acid ester.
- Acrylic esters such as chill, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, benzyl acrylate, etc .; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate
- Methacrylic acid esters such as isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate; these may be used alone or in combination of two or more. Also good. Among these, methyl methacrylate is particularly preferable from the viewpoint of excellent heat resistance and transparency.
- the content ratio in the monomer component used in the polymerization step sufficiently exhibits the effects of the present invention.
- it is preferably 10 to 95% by weight, more preferably 10 to 90% by weight, further preferably 40 to 90% by weight, particularly preferably 50 to 90% by weight.
- the hydroxyl group-containing monomer is not particularly limited as long as it is a hydroxyl group-containing monomer other than the monomer represented by the general formula (la).
- ⁇ -hydroxymethylstyrene, ⁇ -hydroxy 2- (hydroxyalkyl) acrylic acid esters such as shetylstyrene, 2- (hydroxyethyl) acrylic acid methyl; 2- (hydroxyalkyl) acrylic acid such as 2- (hydroxyethyl) acrylic acid;
- ⁇ -hydroxymethylstyrene ⁇ -hydroxy 2- (hydroxyalkyl) acrylic acid esters such as shetylstyrene, 2- (hydroxyethyl) acrylic acid methyl
- 2- (hydroxyalkyl) acrylic acid such as 2- (hydroxyethyl) acrylic acid
- the content ratio in the monomer component to be subjected to the polymerization step sufficiently exhibits the effects of the present invention.
- Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, a-substituted acrylic acid, and ⁇ -substituted methacrylic acid. These may be used alone or in combination of two or more. May be used in combination. Among these, acrylic acid and methacrylic acid are preferable in that the effects of the present invention are sufficiently exhibited.
- an unsaturated carboxylic acid when used, its content in the monomer component to be subjected to the polymerization step is preferably 0 to 30% by weight, more preferably, in order to sufficiently exhibit the effects of the present invention. It is 0 to 20% by weight, more preferably 0 to 15% by weight, particularly preferably 0 to 10% by weight.
- Examples of the monomer represented by the general formula (2a) include styrene, butyltoluene, ⁇ - methylstyrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, and vinyl acetate. May be used alone or in combination of two or more. Among these, styrene and a-methylstyrene are preferable because the effects of the present invention are sufficiently exhibited.
- the content ratio in the monomer component to be subjected to the polymerization step is preferably 0 to sufficiently exhibit the effects of the present invention. 30% by weight, more preferably 0-20% by weight, still more preferably 0-15% by weight, particularly preferably 0-1 0% by weight.
- the preferred form of the polymerization reaction for polymerizing the monomer components to obtain a polymer having a hydroxyl group and an ester group in the molecular chain is a polymerized form using a solvent. Polymerization is particularly preferred.
- the polymerization temperature and the polymerization time vary depending on the type of monomer used, the use ratio, and the like, but preferably the polymerization temperature is 0 to 150 ° C and the polymerization time is 0.5 to 20 hours. Preferably, the polymerization temperature is 80 to 140 ° C., and the polymerization time is 1 to 10 hours.
- the polymerization solvent is not particularly limited.
- an aromatic hydrocarbon solvent such as toluene, xylene, or ethylbenzene
- a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone
- ether solvents such as tetrahydrofuran, and the like.
- a polymerization initiator may be added! ⁇ .
- the polymerization initiator is not particularly limited. Organic peroxides such as mirmilperoxy 2-ethylhexanoate; 2, 2'-azobis (isobutyoroxy-tolyl), 1, ⁇ -azobis (cyclohexanecarbo-tolyl), 2, 2'-azobis ( 2, 4 dimethyl valerine-tolyl) and the like; these may be used alone or in combination of two or more.
- the amount of the polymerization initiator used is not particularly limited as long as it is appropriately set according to the combination of monomers to be used and reaction conditions.
- the concentration of the produced polymer in the polymerization reaction mixture is 50% by weight or less in order to suppress gelation of the reaction solution.
- concentration of the produced polymer in the polymerization reaction mixture exceeds 50% by weight, it is preferable to add a polymerization solvent to the polymerization reaction mixture and control it to be 50% by weight or less.
- the concentration of the produced polymer in the polymerization reaction mixture is more preferably 45% by weight or less, and still more preferably 40% by weight or less. It should be noted that if the concentration of the polymer in the polymerization reaction mixture is too low, the productivity is lowered. Therefore, the concentration of the produced polymer in the polymerization reaction mixture is preferably 10% by weight or more. % Or more is more preferable.
- the form in which the polymerization solvent is appropriately added to the polymerization reaction mixture is not particularly limited, and the polymerization solvent may be added continuously or intermittently.
- the concentration of the produced polymer in the polymerization reaction mixture in this way, the gelation of the reaction solution can be more sufficiently suppressed, and in particular, the heat resistance is improved by increasing the content ratio of the rataton ring. Therefore, gelation can be sufficiently suppressed even when the ratio of hydroxyl groups to ester groups in the molecular chain is increased.
- the polymerization solvent to be added it may be the same type of solvent as used in the initial stage of the polymerization reaction, or it may be a different type of solvent, but it may be used in the initial stage of the polymerization reaction. It is preferable to use the same type of solvent as the existing solvent. Further, the polymerization solvent to be added may be only one type of solvent or a mixed solvent of two or more types.
- the polymerization reaction mixture obtained upon completion of the above polymerization step usually contains a solvent in addition to the obtained polymer, but the solvent is completely removed to remove the polymer in a solid state. It is preferable to introduce it into the subsequent cyclone cyclization condensation step in the state of containing the solvent which need not be taken out in step (b). If necessary, a solvent suitable for the subsequent Rataton cyclization condensation process may be added again after taking out in a solid state!
- the polymer obtained in the polymerization step is a polymer having a hydroxyl group and an ester group in the molecular chain.
- the weight average molecular weight of the polymer (a) is preferably 1000-2000000, more preferably ⁇ 5,000 to 500,000, more preferably ⁇ 10000 or 500,000, particularly preferred. ⁇ is 5000 0 ⁇ 500000.
- the polymer (a) obtained in the polymerization step is subjected to heat treatment in the subsequent rataton cyclization condensation step, whereby the rataton ring structure is introduced into the polymer, and has a (meth) acrylic structure having a rataton ring structure. It becomes greaves.
- the reaction for introducing the polymer (a) heratatone ring structure is carried out by heating, whereby the hydroxyl group and the ester group present in the molecular chain of the polymer (a) are cyclized and condensed to produce a rataton ring structure.
- This is a reaction, and alcohol is produced as a by-product by the cyclization condensation.
- Lataton ring structure is a polymer component High heat resistance is imparted by being formed in the child chain (in the main skeleton of the polymer).
- the (meth) acrylic resin having a rataton ring structure obtained in the rataton cyclization condensation step preferably has a rataton ring structure represented by the following general formula (1).
- R 2 and R 3 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
- the organic residue may contain an oxygen atom.
- the method for heat-treating the polymer (a) is not particularly limited, and a known method can be used.
- the polymerization reaction mixture containing a solvent obtained by the polymerization step may be heat-treated as it is.
- the heat treatment can also be performed using a vacuum furnace for removing volatile components or a heating furnace having a devolatilizer, an extruder having a devolatilizer, or the like.
- thermoplastic resin in addition to the polymer (a), another thermoplastic resin may coexist.
- an ester catalyst such as P-toluenesulfonic acid or a transesterification catalyst generally used as a catalyst for the cyclization condensation reaction may be used, if necessary, acetic acid, Organic carboxylic acids such as propionic acid, benzoic acid, acrylic acid, and methacrylic acid may be used as a catalyst.
- JP-A-61-254608 and JP-A-6 As disclosed in JP-A-261303, basic compounds, organic carboxylates, carbonates and the like may be used.
- an organic phosphorus compound as a catalyst as disclosed in JP-A-2001-151814.
- an organophosphorus compound as a catalyst, the cyclization condensation reaction rate can be improved, and the coloring of the resulting latathone ring-containing polymer can be greatly reduced.
- an organophosphorus compound as a catalyst, it is possible to suppress a decrease in molecular weight that can occur when a devolatilization step described later is used in combination, and to impart excellent mechanical strength.
- the amount of the catalyst used in the cyclocondensation reaction is not particularly limited, but is preferably 0.001 to 5% by weight, more preferably 0.01-2. It is 5% by weight, more preferably 0.01 to 1% by weight, particularly preferably 0.05 to 0.5% by weight. If the amount of the catalyst used is less than 0.001% by weight, the reaction rate of the cyclization condensation reaction may not be improved sufficiently. On the other hand, if it exceeds 5% by weight, coloring may occur. There is a risk of melt molding due to cross-linking of the polymer.
- the timing of addition of the catalyst is not particularly limited, and it may be added at the beginning of the reaction, during the reaction, or both.
- the cyclization condensation reaction it is preferable to carry out the cyclization condensation reaction in the presence of a solvent and to use a devolatilization step in combination with the cyclization condensation reaction.
- a devolatilization step there are a form in which the devolatilization step is used together throughout the cyclization condensation reaction, and a form in which the devolatilization step is not used throughout the entire cyclization condensation reaction, but is used only in a part of the process.
- the alcohol produced as a by-product in the condensation cyclization reaction is forcibly devolatilized and removed, so the equilibrium of the reaction is advantageous for the production side.
- the devolatilization step is a step of removing a volatile component such as a solvent and a residual monomer and an alcohol by-produced by a cyclization condensation reaction leading to a rataton ring structure, if necessary under reduced pressure heating conditions. Say. If this removal treatment is inadequate, the residual volatiles in the produced resin increase, resulting in problems such as coloration due to alteration during molding, and molding defects such as bubbles and silver streaks. Arise.
- a devolatilizer and vented extruder comprising a heat exchanger and a devolatilization tank, and the devolatilizer and the extruder are arranged in series. It is more preferable to use a devolatilizer or vented extruder with a heat exchanger and a devolatilizing tank power that are preferable to use.
- the reaction treatment temperature is preferably in the range of 150 to 350 ° C, more preferably in the range of 200 to 300 ° C. If the reaction treatment temperature is lower than 150 ° C, the cyclization condensation reaction may be insufficient and the residual volatile matter may increase, and if it is higher than 350 ° C, coloring or decomposition may occur.
- the pressure during the reaction treatment is in the range of 931 to 1.33 hpa (700 to lmmHg), preferably 798 to 66.5 hpa. A range of (600 to 50 mmHg) is more preferable. If the pressure is higher than 931 hpa, there is a problem that volatile matter including alcohol tends to remain. 1. If the pressure is lower than 33 hpa, industrial implementation becomes difficult! /, Kuto! / is there.
- vents When the above extruder with a vent is used, one or a plurality of vents may be used, but it is preferable to have a plurality of vents.
- the reaction treatment temperature is preferably in the range of 150 to 350 ° C, more preferably in the range of 200 to 300 ° C. If the temperature is lower than 150 ° C, the cyclization condensation reaction may be insufficient and residual volatile components may increase. If the temperature is higher than 350 ° C, coloring or decomposition may occur.
- the pressure during the reaction treatment is preferably in the range of 931 to 1.33 hpa (700 to: LmmHg). The range of 798 to 13.3 hpa (600 to 10 mmHg). Is more preferable.
- the pressure is higher than 931 hpa, there is a problem that volatile matter including alcohol tends to remain, and when it is lower than 33 hpa, industrial implementation becomes difficult.
- the devolatilization step is used throughout the cyclization condensation reaction, the physical properties of the resulting (meth) acrylic resin having a rataton ring structure are poor under severe heat treatment conditions, as will be described later. It is preferable to use a catalyst for the dealcoholization reaction described above, and use a vented extruder or the like under the mildest conditions possible.
- the devolatilization step is used together throughout the cyclization condensation reaction, preferably, the polymer (a) obtained in the polymerization step is introduced into the cyclization condensation reaction apparatus system together with a solvent. In this case, if necessary, it may be passed through the reactor system such as a vented extruder once again.
- the devolatilization step may not be used together over the entire process of the cyclization condensation reaction, but may be used only in part of the process.
- the apparatus for producing the polymer (a) is further heated, and if necessary, a part of the devolatilization step is used in advance to allow the cyclization condensation reaction to proceed to some extent, followed by desorption. This is a form in which a cyclocondensation reaction is performed simultaneously with the volatilization process to complete the reaction.
- the polymer (a) is heated at a high temperature close to 250 ° C or higher using a twin-screw extruder.
- the partial decomposition or the like may occur before the cyclization condensation reaction occurs due to the difference in thermal history, and the physical properties of the resulting (meth) acrylic resin having a rataton ring structure may be deteriorated. Therefore, if the cyclization condensation reaction is allowed to proceed to some extent before the cyclization condensation reaction using the devolatilization step at the same time, the reaction conditions in the latter half can be relaxed and the resulting rataton ring structure can be obtained.
- a particularly preferred form is a form in which the devolatilization process starts with a certain time for the initiation of the cyclization condensation reaction, that is, present in the molecular chain of the polymer (a) obtained in the polymerization process.
- An example is a form in which a hydroxyl group and an ester group are subjected to a cyclization condensation reaction in advance to increase the cyclization condensation reaction rate to some extent, and then a cyclization condensation reaction is performed simultaneously using a devolatilization step.
- a cyclization condensation reaction is allowed to proceed to a certain reaction rate in the presence of a solvent in advance using a kettle reactor, and then a reactor equipped with a devolatilizer, for example, Preferred is a mode in which the cyclization condensation reaction is completed by a devolatilizer comprising a heat exchanger and a devolatilization tank, an extruder with a vent, or the like. Particularly in this form, it is more preferable that a catalyst for the cyclization condensation reaction is present.
- the hydroxyl group and ester group present in the molecular chain of the polymer (a) obtained in the polymerization step are subjected to a cyclization condensation reaction in advance to increase the cyclization condensation reaction rate to some extent.
- a cyclization condensation reaction simultaneously using the devolatilization step is preferred in the present invention for obtaining a (meth) acrylic resin having a rataton ring structure.
- the cyclization condensation reaction rate is higher with a higher glass transition temperature, and a (meth) acrylic resin having a latathone ring structure with excellent heat resistance can be obtained.
- the weight loss rate between 150-300 ° C in dynamic TG measurement described later is 2% or less, more preferably 1.5% or less. More preferably, it is 1% or less.
- the reactor that can be used in the cyclization condensation reaction that is carried out in advance before the cyclization condensation reaction in which the devolatilization process is simultaneously used, but preferably an autoclave, a kettle reactor, a heat exchanger And a devolatilizer comprising a devolatilization tank, and a vented extruder suitable for a cyclization condensation reaction using a devolatilization step at the same time can also be used. More preferred are an auto turret and a kettle reactor. However, even when a reactor such as an extruder with a vent is used, autoclave can be controlled by adjusting the temperature condition, barrel condition, screw shape, screw operating condition, etc. The same as the reaction state in a kettle reactor
- the mixture containing the polymer (a) obtained in the polymerization step and the solvent is heated (i) by adding a catalyst, (ii) a reaction without heating with a catalyst, and A method of performing the above (i) or (ii) under pressure is mentioned.
- the "mixture containing the polymer (a) and the solvent" to be introduced into the cyclization condensation reaction in the Rataton cyclization condensation process uses the polymerization reaction mixture obtained in the polymerization process as it is. It may also mean that a solvent suitable for the cyclization condensation reaction may be added again after removing the solvent.
- the solvent that can be re-added in the cyclization condensation reaction carried out in advance before the cyclization condensation reaction simultaneously used in the devolatilization step is not particularly limited, and for example, aromatics such as toluene, xylene, ethylbenzene, etc. Hydrocarbons; ketones such as methyl ethyl ketone and methyl impyl ketone; black form, DMSO, tetrahydrofuran and the like may be used. It is the same kind of solvent that can be used in the process.
- Examples of the catalyst to be added in the above method (i) include generally used ester catalysts such as p-toluenesulfonic acid or transesterification catalysts, basic compounds, organic carboxylates, and carbonates.
- the aforementioned organic phosphorus compound is preferably used.
- the addition timing of the catalyst is not particularly limited, and it may be added at the beginning of the reaction, during the reaction, or both.
- the amount of the catalyst to be added is not particularly limited, but is preferably 0.001 to 5% by weight, more preferably 0.01 to 2.5% by weight, and still more preferably 0, based on the weight of the polymer (a). 01 to 1% by weight, particularly preferably 0.05 to 0.5% by weight.
- the heating temperature and heating time of method (i) are not particularly limited, but the heating temperature is preferably room temperature or higher, more preferably 50 ° C or higher, and the heating time is preferably 1 to 20 hours, more preferably. Is 2 to 10 hours. If the heating temperature is low or the heating time is short, the cyclization condensation reaction rate may decrease. Also, if the heating time is too long, the resin may be colored or decomposed.
- Examples of the method (ii) include a method of heating the polymerization reaction mixture obtained in the polymerization step as it is using a pressure-resistant kettle or the like.
- the heating temperature is preferably 100 ° C or higher, more preferably 150 ° C or higher.
- the heating time is preferably 1 to 20 hours, more preferably 2 to 10 hours. If the heating temperature is low or the heating time is short, the cyclization condensation reaction rate may decrease. Also, if the heating time is too long, the resin may be colored or decomposed.
- the decrease rate is preferably 2% or less, more preferably 1.5% or less, and even more preferably 1% or less. If the weight reduction rate is higher than 2%, the cyclacondensation reaction rate will not rise to a sufficiently high level even if a cyclization condensation reaction is carried out simultaneously with the devolatilization step at the same time. There is a risk that the physical properties will deteriorate.
- the above ring In the polycondensation reaction other thermoplastic resin may be coexisted in addition to the polymer (a).
- the hydroxyl group and ester group present in the molecular chain of the polymer (a) obtained in the polymerization step are subjected to a cyclization condensation reaction in advance to increase the cyclization condensation reaction rate to some extent, and then the devolatilization step is performed.
- a polymer obtained by a previously performed cyclized condensation reaction (a polymer in which at least a part of hydroxyl groups and ester groups present in the molecular chain have undergone cyclized condensation reaction) and
- the solvent may be introduced into the cyclization condensation reaction using the devolatilization step at the same time, or if necessary, the polymer (at least a part of the hydroxyl group and ester group present in the molecular chain is cyclized and condensed). It may be introduced into a cyclization condensation reaction in which a devolatilization step is used at the same time through other treatments such as isolation of the reacted polymer) and re-addition of a strong solvent.
- the devolatilization step is not limited to being completed at the same time as the cyclization condensation reaction, and may be completed over time from the completion of the cyclization condensation reaction.
- the (meth) acrylic resin having a rataton ring structure has a mass average molecular weight (sometimes referred to as a weight average molecular weight) force, preferably 1000 to 2000000, more preferably 5000 to 1000 000, and more preferably Mas ⁇ ma 10000-50000, Specially ⁇ ma 50000-50000. If the mass average molecular weight is out of the above range, the effects of the present invention may not be sufficiently exhibited.
- the (meth) acrylic resin having a rataton ring structure has a weight loss rate of 150% to 300 ° C in dynamic TG measurement of 1% or less, more preferably 0.5. % Or less, more preferably 0.3% or less.
- the (meth) acrylic resin having a latatotone ring structure has a high cyclization condensation reaction rate, it is possible to avoid the disadvantage that bubbles and silver streaks enter the molded product after the molding. Further, since the rataton ring structure is sufficiently introduced into the polymer due to the high cyclization condensation reaction rate, the resulting (meth) acrylic resin having the rataton ring structure has sufficiently high heat resistance. Speak
- the (meth) acrylic resin having a rataton ring structure preferably has a coloring degree (YI) of 6 or less in a 15% by weight Kuroguchi form solution, more preferably 3 or less, and further Preferably 2 Below, most preferably 1 or less. If the coloring degree (YI) exceeds 6, transparency may be impaired due to coloring, and it may not be used for the intended purpose.
- YI coloring degree
- the (meth) acrylic resin having a rataton ring structure preferably has a 5% weight reduction temperature of 280 ° C or higher in thermogravimetric analysis (TG), more preferably 290 ° C or higher. More preferably, it is 300 ° C or higher.
- TG thermogravimetric analysis
- the 5% weight loss temperature in thermogravimetric analysis (TG) is an index of thermostability (heat resistance), and if it is less than 280 ° C, sufficient thermal stability (heat resistance) may not be exhibited. There is.
- the (meth) acrylic resin having a rataton ring structure has a glass transition temperature (Tg) of preferably 115 ° C or higher, more preferably 125 ° C or higher, still more preferably 130 ° C or higher, and still more preferably. It is preferably 135 ° C or higher, most preferably 140 ° C or higher.
- Tg glass transition temperature
- the upper limit value of Tg of the (meth) acrylic resin having a rataton ring structure is not particularly limited, but is preferably 150 ° C. or lower in order to further exert the effects of the present invention.
- the (meth) acrylic resin having a rataton ring structure has a total amount of residual volatile components contained therein of preferably 5000 ppm or less, more preferably 2000 ppm or less. If the total amount of residual volatiles exceeds 5000 ppm, it may cause molding defects such as coloration, foaming, silver streak, etc. due to deterioration during molding.
- the (meth) acrylic resin having a rataton ring structure is a total light transmittance force measured by a method according to ASTM-D-1003, preferably 85% or more, of a molded product obtained by injection molding. More preferably it is 88% or more, and still more preferably 90% or more.
- the total light transmittance is a measure of transparency, and if it is less than 85%, the transparency is lowered and there is a fear that it cannot be used for the intended purpose.
- the transparent resin layer in the present invention may contain other thermoplastic resin other than the (meth) acrylic resin having the above-described rataton ring structure.
- the other thermoplastic resin according to the present invention has a glass transition temperature of 120 ° C. or higher and a surface direction of 100 when blended with a (meth) acrylic resin having the above-mentioned rataton ring structure to form a film.
- the phase difference force per / zm is 20 nm or less and the total light transmittance is 85% or more
- the type is not particularly limited, but the thermodynamically compatible thermoplastic resin is better.
- Transparency and mechanical strength I like it in terms of improvement.
- thermoplastic resins examples include olefin-based polymers such as polyethylene, polypropylene, ethylene propylene copolymer, poly (4-methyl-1 pentene); Halogen-containing polymers such as fats; Acrylic polymers such as polymethyl methacrylate; Styrene such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer Polymers: Polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; Polyamides such as nylon 6, nylon 66 and nylon 610; Polyacetanol; Polycarbonate; Polyphenol-lenoxide; Polyether sulfone; Polyether sulfone; Polyoxybenzylene; Polyamideimide; ABS polymer blended with polybutadiene rubber and acrylic rubber; Rubber polymer such as
- the rubbery polymer preferably has on its surface a graph collar having a composition that is compatible with the Lataton ring polymer of the present invention.
- the average particle diameter of the rubbery polymer is transparent when formed into a film. From the viewpoint of improving the properties, it is preferably 1 OO nm or less, more preferably 70 nm or less.
- the thermoplastic resin that is thermodynamically compatible with the (meth) acrylic resin having a rataton ring structure includes cyan vinyl monomer units and aromatic vinyl monomer units.
- a copolymer containing acrylonitrile specifically, a polymer containing 50% by weight or more of acrylonitrile styrene-based copolymer, poly (vinyl chloride) resin, and methacrylic acid esters may be used.
- the glass transition temperature is 120 ° C or more
- the phase difference per 100 ⁇ m in the plane direction is 20 nm or less
- the total light transmittance is 85% or more.
- a fat layer can be easily obtained.
- the content ratio of the (meth) acrylic resin having the above-mentioned rataton ring structure and the other heatable resin is: 60 to 99: 1 to 40% by weight, preferably 70 to 97: 3 to 30% by weight, more preferably 80 to 95: 5 to 20% by weight.
- the content ratio of the (meth) acrylic resin having the laton ring structure in the transparent resin layer is less than 60% by weight, the effects of the present invention may not be sufficiently exhibited.
- the transparent resin layer in the present invention may contain other additives.
- additives include, for example, hindered phenol-based, phosphorous-based, and io-based acid-and-acid inhibitors; light stabilizers, weather-resistant stabilizers, heat stabilizers, and other stabilizers; glass fibers, carbon fibers Reinforcing materials such as: phenyl salicylate, ultraviolet absorbers such as (2, 2'-hydroxy-5-methylphenol) benzotriazole, 2-hydroxybenzophenone; near infrared absorbers; tris (dibromopropyl) phosphate, triallyl Flame retardants such as phosphate and acid antimony; Anti-static agents such as cation-based, cationic and non-ionic surfactants; Coloring agents such as inorganic pigments, organic pigments and dyes; Organic fillers and inorganic fillers A resin modifier, an organic filler, an inorganic filler, a plasticizer, a lubricant, an antistatic agent, a flame retardant, and the like.
- the content of other additives in the transparent resin layer in the present invention is preferably 0 to 5% by weight, more preferably 0 to 2% by weight, and still more preferably 0 to 0.5% by weight. .
- the transparent resin layer in the present invention can function as an optical film that can sufficiently exhibit characteristics according to various optical uses.
- the glass transition temperature of the transparent resin layer in the present invention is preferably 120 ° C or higher, more preferably 125 ° C or higher, and further preferably 130 ° C or higher.
- the film thickness of the transparent resin layer in the present invention is preferably 1 ⁇ m or more and less than 500 ⁇ m, more preferably 10 m or more and less than 300 m.
- a transparent resin layer having a film thickness of less than 1 ⁇ m may have insufficient strength, and is likely to break when stretched.
- the transparent resin layer in the present invention has a tensile strength measured based on ASTM-D-882-61T of preferably 1 OMPa or more and less than lOOMPa, more preferably 30 MPa or more and less than lOOMPa. If it is less than lOMPa, sufficient mechanical strength may not be achieved. If it exceeds lOOMPa, workability may be deteriorated.
- the transparent resin layer in the present invention has an elongation measured based on ASTM-D-882-61T of preferably 1% or more, and more preferably 3% or more.
- the upper limit is not particularly limited, but is usually preferably 100% or less. If it is less than 1%, the toughness may be lacking.
- the transparent resin layer in the present invention preferably has a tensile elastic modulus measured based on ASTM-D-882-61T of 0.5 GPa or more, more preferably lGPa or more, and even more preferably. It is more than 2GPa.
- the upper limit is not particularly limited, but usually it is preferably 20 GPa or less. If it is less than 5 GPa, sufficient mechanical strength may not be achieved.
- the transparent resin layer in the present invention preferably has an in-plane retardation And of 3. Onm or less, a thickness direction retardation Rth of 10. Onm or less, and a tear strength of 2. ONZmm or more. In-plane retardation And, thickness direction retardation Rth, tear strength force By being in these ranges, it is possible to achieve both excellent optical properties and excellent mechanical strength.
- the in-plane retardation And is preferably as small as possible, preferably 2. Onm or less, more preferably 1.5 nm or less, and even more preferably 1. Onm. It is as follows. If the in-plane phase difference And exceeds 3. Onm, the effects of the present invention, in particular, excellent optical characteristics may not be exhibited.
- the thickness direction retardation Rth is preferably as small as possible, preferably 7. Onm or less, more preferably 5. Onm or less, and further preferably 3. Onm or less. When the thickness direction retardation Rth exceeds 10. Onm, the effects of the present invention, in particular, excellent optical characteristics may not be exhibited.
- the transparent resin layer in the present invention preferably has excellent mechanical strength.
- the tear strength is preferably 2. INZ mm or more, more preferably 2.2 NZ mm or more, further preferably 2.3 NZ mm or more, particularly preferably 2.4 NZ mm or more, and most preferably 2.5 NZ mm or more.
- the upper limit of the tear strength is not particularly limited, but is preferably 5. ONZ mm or less from the viewpoint of formability. If the tear strength is out of the above range, excellent mechanical strength may not be exhibited!
- the lower Yogu preferably Ku is 100gZm 2 '24hr or less, more preferably 60gZm 2' is 24hr or less. If the moisture permeability exceeds Sl00g / m 2 '24hr, the moisture resistance may be inferior.
- the lower the haze representing optical transparency the lower it is, preferably 5% or less, more preferably 3% or less, more preferably 1.5% or less, particularly Preferably it is 1% or less.
- the haze is 5% or less, a good tally feeling can be visually given to the film.
- the haze is 1.5% or less, even when used as a daylighting member such as a window, visibility and daylighting performance are improved.
- the transparent resin layer in the present invention is preferably 85% or more, more preferably 88% or more, as the total light transmittance measured by a method according to ASTM-D-1003 is higher. More preferably, it is 90% or more. If the total light transmittance is less than 85%, the transparency is lowered and there is a possibility that it cannot be used for the intended purpose.
- the method for producing the transparent resin layer in the present invention is not particularly limited.
- a transparent resin layer can be produced after mixing by a conventionally known mixing method to obtain a thermoplastic resin composition in advance.
- a method for producing this thermoplastic resin composition for example, a method of pre-blending with a mixer such as an omni mixer and then extruding and kneading the obtained mixture can be employed.
- the kneader used for extrusion kneading is not particularly limited.
- a conventionally known kneader such as a single-screw extruder, a twin-screw extruder, or a pressure kneader can be used. .
- the film forming method examples include known film forming methods such as a solution casting method (solution casting method), a melt extrusion method, a calendar method, and a compression molding method.
- a solution casting method solution casting method
- the melt extrusion method melt extrusion method
- a thermoplastic resin composition that has been extruded and kneaded in advance as described above may be used, or a rataton ring-containing polymer and other thermoplastic resins and other additives may be separately dissolved in a solution. After making a uniform mixed solution, it can be used for the film forming process of solution casting method (solution casting method) and melt extrusion method.
- Solvents used in the solution casting method include, for example, chlorinated solvents such as black mouth form and dichloromethane; aromatics such as toluene, xylene, benzene, and mixed solvents thereof.
- Solvents Alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, 2-butanol, etc .; methyl cetosolve, ethylcetosolve solve, butyl cellosolve, dimethylformamide, dimethyl sulfoxide, dioxane, cyclohexanone, tetrahydrofuran, acetone , Methyl ethyl ketone (MEK), ethyl acetate, and ethyl ether. These solvents may be used alone or in combination of two or more.
- apparatuses for performing the solution casting method include a drum-type casting machine, a band-type casting machine, and a spin coater.
- melt extrusion method examples include a T-die method and an inflation method.
- the film forming temperature is preferably 150 to 350, more preferably 200 to 300. C.
- a T-die is attached to the leading end of a known single-screw extruder or twin-screw extruder to obtain a roll-shaped film from the film extruded in a film shape be able to.
- by adding a step of stretching the film in the direction perpendicular to the extrusion direction it is possible to cover processes such as sequential biaxial stretching and simultaneous biaxial stretching.
- the transparent resin layer in the present invention may be an unstretched film or a stretched film.
- a uniaxially stretched film or a biaxially stretched film may be used.
- a biaxially stretched film it may be biaxially stretched simultaneously or sequentially biaxially stretched.
- the mechanical strength is improved and the film performance is improved.
- the (meth) acrylic resin having a rataton ring structure in the present invention can suppress an increase in retardation even when stretched by mixing with other thermoplastic resin, and has optical isotropy. I can keep it.
- the stretching temperature is preferably about the glass transition temperature of the thermoplastic resin composition of the film raw material.
- the stretching temperature is (glass transition temperature 30) ° C to (glass transition temperature + 100 0). It is preferable to carry out at a temperature of (° C.), more preferably (glass transition temperature 20) ° C. to (glass transition temperature +80) ° C. (Glass transition temperature 30) If it is lower than ° C, a sufficient draw ratio may not be obtained. If the glass transition temperature is higher than (glass transition temperature +100) ° C, the resin flow may occur and stable stretching may not be possible.
- the draw ratio defined by the area ratio is preferably in the range of 1.1 to 25 times, more preferably in the range of 1.3 to: LO times. 1. If it is less than 1 time, the improvement of toughness accompanying drawing may be insufficient. If it is larger than 25 times, the effect of increasing the draw ratio is not recognized.
- the stretching speed (one direction) is preferably in the range of 10 to 20000% Z, more preferably in the range of 100 to LOOOO% Z. If it is slower than 10% Z, a sufficient draw ratio is obtained. Therefore, it may take time and the manufacturing cost may increase. If it is earlier than 20000% Z, the stretched film may be cut off.
- heat treatment annealing
- the like can be performed after the stretching treatment.
- the raw material (resin composition) for forming the film before stretching contains a retardation reducing agent.
- a retardation reducing agent for example, a styrene-containing polymer such as acrylonitrile-styrene copolymer is preferable.
- the addition amount of the retardation reducing agent is preferably 30% by weight or less, more preferably 25% by weight or less, and still more preferably 20% by weight or less with respect to the (meth) acrylic resin. If added beyond this range, visible light is scattered and transparency is impaired, so that the properties as a transparent resin layer may be lacking.
- the transparent resin layer in the present invention can be used by being laminated on another substrate.
- substrates such as glass, polyolefin resin, ethylene vinylidene copolymer that forms a hyaline rear layer, polyester, etc.
- multilayer extrusion molding including adhesive resin layer and multilayer inflation molding, Lamination molding is also possible. If the heat-fusibility is high, the adhesive layer may be omitted.
- the transparent resin layer in the present invention is used in addition to the use as a member of a polarizer protective film, for example, a daylighting member for buildings such as windows and carport roof materials, a daylighting member for vehicles such as windows, and a warm chamber. It can be used by being laminated on a lighting member for agriculture such as lighting, a display member such as a front filter, etc., and has been conventionally coated with a (meth) acrylic resin film. It can also be used by being laminated on interior members, interior building materials, wallpaper, decorative boards, entrance doors, window frames, baseboards, and the like.
- the cellulose-based resin layer in the present invention is provided on at least one surface of the transparent resin layer.
- the method for forming the cellulose-based resin layer in the present invention is not particularly limited.
- cellulosic resin is dissolved in a solvent.
- the cellulose-based resin solution is applied to at least one surface of the transparent resin layer and dried to form a cellulose-based resin layer.
- the cellulose-based resin is not particularly limited.
- cellulose ester-based resin is used.
- examples of the cellulose ester-based resin include a fatty acid ester of cellulose having hydrolyzability, and is preferably a lower fatty acid ester of cellulose.
- Lower fatty acid means a fatty acid having 6 or less carbon atoms.
- the lower fatty acid ester of cellulose include, for example, single fatty acid esters such as cellulose diacetate, cenorelose triacetate, cenorelose propionate, cenorelose butyrate, cellulose acetate propionate, and cellulose acetate.
- single fatty acid esters such as cellulose diacetate, cenorelose triacetate, cenorelose propionate, cenorelose butyrate, cellulose acetate propionate, and cellulose acetate.
- mixed fatty acid esters such as tobutyrate, and mixtures thereof.
- cellulose acetate propionate and cellulose acetate butyrate are preferred!
- the solvent used for obtaining the cellulosic resin solution is a solvent that can dissolve or disperse the cellulosic resin to produce a fluid, and can be cast on the transparent resin layer in the present invention. It is preferable to have affinity. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, toluene, xylene, methanol, ethanol, isopropanol, n -Propanol and the like can be mentioned. These may be used alone or in combination of two or more.
- the concentration of the cellulosic resin solution is not particularly limited, but is preferably 1 to 20% by weight, more preferably 5 to 15% by weight. When the concentration is less than 1% by weight, the adhesion between the polarizer protective film of the present invention and the polarizer may not be sufficiently exhibited. If the concentration exceeds 20% by weight, the polarizer protective film of the present invention may not be able to sufficiently exhibit high heat resistance, high transparency, high optical properties, and high mechanical strength.
- the drying temperature after applying the cellulose-based resin solution on the transparent resin layer is preferably 50. It is -130 degreeC, More preferably, it is 80-120 degreeC.
- the drying time is preferably 30 seconds to 5 minutes, more preferably 30 seconds to 2 minutes. By increasing the drying temperature or lengthening the drying time, the amount of residual solvent can be reduced, but it is preferable that these drying conditions do not reduce the production efficiency! /, .
- the dry thickness of the cellulosic resin layer in the present invention is preferably 0.3 to 3 m, and more preferably 0.5 to 2.5 m. Outside this range, the residual amount of the solvent in the cellulosic resin layer increases, and the Tg of the cellulosic resin layer immediately decreases, resulting in a decrease in the storage elastic modulus at high temperatures and the polarizing plate under heating. When exposed to light, the amount of change in the polarizer increases, and polarizer cracks are likely to occur. On the other hand, if it is out of the above range, the adhesiveness (reworkability) may be deteriorated or the viewing angle characteristics of transmittance may be deteriorated when the polarizing plate is constituted.
- a crosslinking agent for cellulosic resin in the present invention, the term "crosslinking agent” means that a covalent bond can be formed by reacting with a hydroxyl group of cellulose resin in a molecule or an intermolecular bond such as a hydrogen bond is formed. (Meaning a compound having a functional group that can be formed) is added to improve the cohesive strength of the cellulose resin layer, thereby further improving the adhesion to the polarizer.
- cross-linking agent examples include alkylenediamines having two alkylene groups and two amino groups such as ethylenediamine, triethylenediamine, hexaethylenediamine, etc .; tolylene diisocyanate, hydrogenated tolylene diisocyanate, Isocyanates such as trimethylolpropane tolylene diisocyanate adduct, triphenylmethane triisocyanate, methylene bis (4-phenolmethane triisocyanate), isophorone diisocyanate and their ketoxime block or phenol block Ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin di or tridaricidino dioleo ethere, 1,6-hexanediol diglycidyl ether, trimethylolpropane Epoxys such as triglycidyl ether, diglycidyl dilin, diglycidyl
- the amount of the crosslinking agent used is preferably the number of functional groups capable of reacting or interacting with the functional group of the cellulose-based resin relative to the number of functional groups such as hydroxyl group of the cellulose-based resin. 3 times or less, more preferably 2 times or less, and even more preferably 1.5 times or less. Specifically, 0.1 to 40 parts by weight is usually preferable to 1 to 35 parts by weight, and more preferably 10 to 30 parts by weight with respect to 100 parts by weight of cellulose-based resin. A polarizing plate having uniform polarization characteristics, excellent adhesiveness with a polarizer, and excellent durability can be obtained within a strong range.
- the polarizer protective film of the present invention in which the cellulose-based resin layer is provided on the transparent protective layer can be used for adhesion of the polarizer after hydrophilic treatment.
- hydrophilic treatment include dry treatment such as alkali treatment, plasma treatment, and corona treatment.
- alkali treatment is preferable.
- the alkali treatment is carried out for 10 seconds in a 1 to 20% by weight aqueous solution of sodium hydroxide and sodium hydroxide in which the transparent protective layer provided with the cellulose-based resin layer is adjusted to about 30 to 95 ° C. Do soaking for about 20 minutes and saponification. After the ken treatment, it is washed with pure water and dried.
- the polarizing plate of the present invention is formed by laminating the cellulose-based resin layer side of the polarizer protective film of the present invention on at least one side of a polarizer formed from a polyvinyl alcohol-based resin.
- One of the preferred embodiments of the polarizing plate of the present invention is that, as shown in FIG. 1, one surface of the polarizer 31 is transparent to the cellulose-based resin layer 33 via the adhesive layer 32. It is formed by adhering to the polarizer protective film 300 of the present invention comprising the resin layer 34, and the other surface of the polarizer 31 is bonded to the polarizer protective film 36 via the adhesive layer 35. .
- Polarizer protection The protective film 36 may be the polarizer protective film 300 of the present invention, or may be any other appropriate polarizer protective film.
- a polarizer formed from the polybulal alcohol-based resin has a polybulal alcohol-based resin film dyed with a dichroic substance (typically iodine, a dichroic dye). A stretched one is used.
- the degree of polymerization of the polybula alcoholic resin constituting the polybulal alcoholic resin film is preferably 100 to 5000, more preferably 1400 to 4000.
- the polybulualcohol-based resin film constituting the polarizer can be formed by any appropriate method (for example, casting method, casting method, extrusion method in which a solution in which the resin is dissolved in water or an organic solvent is cast). Can be molded.
- the thickness of the polarizer can be appropriately set according to the purpose and application of the LCD in which the polarizing plate is used, but is typically 5 to 80 / zm.
- any appropriate method can be adopted depending on the purpose, materials used, conditions and the like.
- a method is employed in which the polyvinyl alcohol-based resin film is subjected to a series of production steps including swelling, dyeing, crosslinking, stretching, washing, and drying.
- the treatment is performed by immersing the polyvinyl alcohol-based resin film in a bath containing the solution used in each step.
- the order, number of times, and the presence / absence of each treatment of swelling, dyeing, crosslinking, stretching, washing with water, and drying can be appropriately set according to the purpose, materials used, conditions and the like.
- the stretching process may be performed after the dyeing process or before the dyeing process, or may be performed simultaneously with the swelling process, the dyeing process, and the crosslinking process. Further, for example, it can be suitably employed to perform the crosslinking treatment before and after the stretching treatment. Further, for example, the water washing process may be performed only after a specific process that may be performed after all the processes.
- the swelling step is typically performed by immersing the polyvinyl alcohol-based resin film in a treatment bath (swelling bath) filled with water. This treatment cleans the surface of the poly (vinyl alcohol) resin film and the anti-blocking agent, and swells the polyvinyl alcohol resin film to prevent unevenness such as uneven dyeing.
- Glycerin, potassium iodide, or the like can be appropriately added to the swelling bath.
- the temperature of the swelling bath is typically about 20-60 ° C, and the immersion time in the swelling bath is typically 0.1-10. About minutes.
- the dyeing step is typically performed by immersing the polyvinyl alcohol-based resin film in a treatment bath (dye bath) containing a dichroic substance such as iodine.
- a dichroic substance such as iodine.
- water is generally used, but an appropriate amount of an organic solvent compatible with water may be added.
- the dichroic substance is typically used at a ratio of 0.1 to 1.0 part by weight with respect to 100 parts by weight of the solvent.
- the dye bath solution preferably further contains an auxiliary agent such as iodide. This is because the dyeing efficiency is improved.
- the auxiliary is used in a proportion of preferably 0.02 to 20 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the solvent.
- iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, An example is titanium iodide.
- the temperature of the dyeing bath is typically about 20 to 70 ° C, and the immersion time in the dyeing bath is typically about 1 to 20 minutes.
- the crosslinking step is typically performed by immersing the dyed polyvinyl alcohol resin film in a treatment bath (crosslinking bath) containing a crosslinking agent.
- a crosslinking agent can be adopted as the crosslinking agent.
- Specific examples of the crosslinking agent include boron compounds such as boric acid and borax, darioxal, dartalaldehyde and the like. These can be used alone or in combination.
- a solvent used for the solution of the crosslinking bath water is generally used, but an appropriate amount of an organic solvent having compatibility with water may be added.
- the crosslinking agent is typically used at a ratio of 1 to 10 parts by weight per 100 parts by weight of the solvent.
- the solution of the crosslinking bath preferably further contains an auxiliary agent such as iodide. This is because uniform characteristics are easily obtained in the surface.
- the concentration of the auxiliaries is preferably 0.05 to 15% by weight, more preferably 0.5 to 8% by weight. Specific examples of iodide are the same as those in the dyeing process.
- the temperature of the crosslinking bath is typically about 20 to 70 ° C, preferably 40 to 60 ° C.
- the immersion time in the crosslinking bath is typically about 1 second to 15 minutes, preferably 5 seconds to 10 minutes.
- the stretching step may be performed at any stage as described above. Specifically, it may be carried out after the crosslinking treatment, which may be carried out after the dyeing treatment or before the dyeing treatment, or may be carried out simultaneously with the swelling treatment, the dyeing treatment and the crosslinking treatment.
- the cumulative draw ratio of the polybulal alcohol-based resin film needs to be 5 times or more, preferably 5 to 7 times, more preferably 5 to 6.5 times. If the cumulative draw ratio is less than 5 times, it may be difficult to obtain a polarizing plate with a high degree of polarization.
- the polyvinyl alcohol-based resin film may be easily broken.
- Arbitrary appropriate methods may be employ
- the polyvinyl alcohol-based resin film is stretched at a predetermined magnification in a treatment bath (stretching bath).
- a solution obtained by adding various metal salts, iodine, boron or zinc compounds in a solvent such as water or an organic solvent (for example, ethanol) is preferably used.
- the water washing step is typically performed by immersing the polyvinyl alcohol-based resin film that has been subjected to the above-described various treatments in a treatment bath (water washing bath).
- a treatment bath water washing bath
- the washing bath may be an aqueous solution of iodide (eg, potassium iodide or sodium iodide) which may be pure water.
- concentration of the aqueous iodide solution is preferably 0.1 to 10% by mass.
- An auxiliary agent such as zinc sulfate or zinc chloride may be added to the iodide aqueous solution.
- the temperature of the washing bath is preferably 10 to 60 ° C, more preferably 30 to 40 ° C.
- the immersion time is typically 1 second to 1 minute.
- the water washing process may be performed only once or multiple times as necessary. In the case of carrying out a plurality of times, the kind and concentration of the additive contained in the washing bath used for each treatment can be appropriately adjusted.
- the water washing step includes a step of immersing the polymer film in a potassium iodide aqueous solution (0.1 to 10% by mass, 10 to 60 ° C.) for 1 second to 1 minute, and a step of rinsing with pure water.
- any appropriate drying method for example, natural drying, air drying, heat drying
- the drying temperature is typically 20 to 80 ° C.
- the drying time is typically 1 to: LO minutes.
- a polarizer is obtained.
- a force including the polarizer and the polarizer protective film of the present invention has an adhesive layer between the cellulose-based resin layer of the polarizer protective film and the polarizer. It is preferable.
- the adhesive layer is preferably a layer formed with a polybulal alcohol adhesive force.
- the polyalcohol-based adhesive contains a polybulualcohol-based resin and a cross-linking agent.
- the polyvinyl alcohol-based resin is not particularly limited, but for example, polybulal alcohol obtained by saponification of polyvinyl acetate; a derivative thereof; and a single copolymer having a co-polymerization property with vinyl acetate. Saponified products of copolymers with monomers; modified polyvinyl alcohols obtained by acetalization, urethanization, etherification, grafting, phosphoric esterification, etc.
- polyvinyl alcohol examples include unsaturated carboxylic acids such as (maleic anhydride), fumaric acid, crotonic acid, itaconic acid, (meth) acrylic acid and esters thereof; a -olefins such as ethylene and propylene, ( Examples include (meth) aryl sulfonic acid (soda), sulfonic acid soda (monoalkyl malate), disulfonic acid soda alkyl maleate, N-methylol acrylamide, acrylamide alkyl sulfonic acid alkali salt, N-bulylpyrrolidone, N-bulurpyrrolidone derivatives, etc. It is done.
- These polybulal alcoholic resins can be used for only one type, or two or more types can be used in combination.
- the polyvinyl alcohol-based resin preferably has an average degree of polymerization of 100 to 3000, more preferably 500 to 3000, and an average strength of elasticity S, preferably 85 to: LO 0 mole 0/0, more preferably 90: a LOO mol 0/0.
- a polybulal alcohol-based resin having a acetoacetyl group can be used as the polybula alcohol-based resin.
- the polybutyl alcohol-based resin having a acetoacetyl group is a highly reactive polyvinyl alcohol-based adhesive having a functional group, and is preferable in terms of improving the durability of the polarizing plate.
- the polybula alcohol-based resin containing a acetoacetyl group is obtained by reacting a polybulal alcohol-based resin with diketene by a known method.
- polyvinyl alcohol-based resin is dispersed in a solvent such as acetic acid, and diketene is added thereto.
- Polyvinyl alcohol-based resin is dissolved in a solvent such as dimethylformamide or dioxane in advance.
- a method of adding diketene to this is also mentioned.
- Polyvinyl Examples include a method in which diketene gas or liquid diketene is directly brought into contact with alcohol.
- the degree of modification of the acetoacetyl group of the polyvinyl alcohol-based resin having a acetoacetyl group is not particularly limited as long as it is 0.1 mol% or more. If it is less than 1 mol%, the adhesive layer has insufficient water resistance, which is inappropriate.
- Asetasechiru group modification degree is preferably from 0.1 to 40 mole 0/0, more preferably 1 to 20 mol%.
- the degree of modification of the acetoacetyl group is a value measured by NMR.
- crosslinking agent those used for polyvinyl alcohol-based adhesives can be used without particular limitation.
- cross-linking agent a compound having at least two functional groups having reactivity with the polybulal alcohol-based resin can be used. For example, ethylenediamine, triethyleneamine, hexamethylenediamine, etc.
- alkylene diamines having two amino groups and an amino group hexamethylene diamine is particularly preferred
- isocyanate block such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin di or triglycidyl ether, 1, 6 monohexanediol diglycidyl ether, trimethyl Epoxys such as propane propane triglycidyl ether, diglycidyl dilin, diglycidyl amine; monoaldehydes such as formaldehyde, cetaldehyde, propionaldehyde, butyraldehyde; glyoxal
- the amount of the crosslinking agent is preferably 100 parts by weight of the polyvinyl alcohol-based resin. Or 0.1 to 35 parts by weight, more preferably 10 to 25 parts by weight.
- a crosslinking agent can be blended in a range of more than 30 parts by weight and 46 parts by weight or less with respect to 100 parts by weight of the polybulal alcohol-based resin.
- the polybutyl alcohol adhesive further includes coupling agents such as silane coupling agents and titanium coupling agents, various tackifiers, ultraviolet absorbers, antioxidants, heat stabilizers, Stabilizers such as decomposition stabilizers can also be blended.
- coupling agents such as silane coupling agents and titanium coupling agents, various tackifiers, ultraviolet absorbers, antioxidants, heat stabilizers, Stabilizers such as decomposition stabilizers can also be blended.
- the adhesive layer is formed by applying the adhesive on one side or both sides of the polarizer protective film and on either side or both sides of the polarizer. After laminating the polarizer protective film and the polarizer, a drying process is performed to form an adhesive layer composed of a coated and dried layer. This can also be bonded after forming the adhesive layer. Bonding of the polarizer and the polarizer protective film can be performed with a roll laminator or the like. The heating and drying temperature and drying time are appropriately determined according to the type of adhesive.
- the thickness of the adhesive layer becomes too thick after drying, there is a possibility that a problem may occur in the adhesive property of the polarizer protective film. Therefore, preferably 0.01 to 10 / ⁇ ⁇ , More preferably, it is 0.03 to 5 ⁇ .
- the polarizer protective film can be bonded to the polarizer by adhering to both sides of the polarizer on one side of the polarizer protective film.
- the polarizer protective film of the polarizer is bonded to one side of the polarizer by bonding on one side of the polarizer protective film, and the cellulosic resin film is bonded to the other side. It is out.
- the cellulose-based resin film is not particularly limited, but triacetyl cellulose is preferable in terms of transparency and adhesiveness.
- the thickness of the cellulosic resin film is preferably 30 to: L00 ⁇ m, more preferably 40 to 80 ⁇ m. If the thickness force is less than 30 ⁇ m, the Finolem strength decreases and the workability is inferior. If the thickness force is more than 100 m, the light transmittance decreases significantly in durability.
- the polarizing plate according to the present invention may have an adhesive layer as at least one of the outermost layers! (Such a polarizing plate may be referred to as an adhesive polarizing plate). Particularly preferably, a pressure-sensitive adhesive layer for adhering to another member such as another optical film or a liquid crystal cell can be provided on the side of the polarizer protective film where the polarizer is not adhered.
- the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited.
- an acrylic polymer, silicone-based polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based polymer is a base polymer.
- those having excellent optical transparency such as an acrylic pressure-sensitive adhesive, exhibiting appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and having excellent weather resistance, heat resistance and the like can be preferably used.
- an acrylic pressure-sensitive adhesive made of an acrylic polymer having a carbon number of ⁇ 12 is preferred.
- a liquid crystal display device that prevents foaming and peeling due to moisture absorption, prevents optical characteristics from being deteriorated due to a difference in thermal expansion, prevents warping of the liquid crystal cell, and is high quality and has excellent durability. From the point of formability, etc., an adhesive layer having a low moisture absorption rate and excellent heat resistance is preferred.
- the above-mentioned pressure-sensitive adhesive layer is, for example, a natural product or a synthetic resin, in particular, a tackifying resin, glass fiber, glass beads, metal powder, other fillers such as inorganic powders, It may contain additives that can be added to the adhesive layer, such as pigments, colorants, and antioxidants.
- It may also be a pressure-sensitive adhesive layer containing fine particles and exhibiting light diffusion properties!
- the above-mentioned pressure-sensitive adhesive layer can be attached by an appropriate method.
- an adhesive solution of about 10 to 40% by weight in which a base polymer or a composition thereof is dissolved or dispersed in a solvent composed of a single solvent or a mixture of appropriate solvents such as toluene and ethyl acetate is prepared.
- the pressure-sensitive adhesive layer may be provided on one or both sides of the polarizing plate as a superposed layer of different compositions or types. Moreover, when providing in both surfaces, it can also be set as adhesive layers with a different composition, a kind, thickness, etc. in the front and back of a polarizing plate.
- the thickness of the pressure-sensitive adhesive layer can be appropriately determined according to the purpose of use and adhesive force, and is preferably 1 to 40 ⁇ m, more preferably 5 to 30 ⁇ m, and particularly preferably 10. ⁇ 25 ⁇ m. If it is thinner than 1 ⁇ m, the durability will be poor, and if it is thicker than 40 m, it will be liable to float or peel off due to foaming, resulting in poor appearance.
- an anchor layer may be provided between the layers.
- an anchor layer selected from polyurethane, polyester, and a polymer having an amino group in the molecule is used, and a polymer having an amino group in the molecule is particularly preferably used. Is done. For polymers containing amino groups in the molecule, the amino group in the molecule reacts with the carboxyl group in the adhesive, the polar group in the conductive polymer, or interacts with the ionic interaction. Good adhesion is ensured.
- Polymers containing an amino group in the molecule include, for example, polyethyleneimine, polyallylamine, polybulamine, polybulurpyridine, polybulurpyrrolidine, and dimethylaminoethyl represented by a copolymerization monomer of the aforementioned acrylic adhesive.
- Examples thereof include a polymer of an amino group-containing monomer such as acrylate.
- An antistatic agent may be added to impart antistatic properties to the anchor layer.
- Antistatic agents for imparting antistatic properties include ionic surfactant systems, conductive polymer systems such as polyaniline, polythiophene, polypyrrole, and polyquinoxaline, and metal acids such as tin oxide, antimony antimony, and indium oxide.
- a conductive polymer system is preferably used.
- water-soluble conductive polymers such as polyarlin and polythiophene, or water-dispersible conductive polymers are particularly preferably used. This is because when a water-soluble conductive polymer or a water-dispersible conductive polymer is used as a material for forming the antistatic layer, it is possible to suppress deterioration of the optical film substrate due to the organic solvent during the coating process.
- each layer such as a polarizer, a polarizer protective film, and the like that form the polarizing plate described above, and a pressure-sensitive adhesive layer may include, for example, a salicylic acid ester-based compound or a benzophenol-based compound.
- Compounds, benzotriazole compounds, cyanoacrylate compounds, nickel It may be one that has been provided with UV absorbing ability by a method such as a method of treating with a UV absorber such as a complex salt compound.
- the polarizing plate of the present invention is not limited to be provided on either the viewing side or the knocklight side of the liquid crystal cell, or on both sides.
- the image display device of the present invention includes at least one polarizing plate of the present invention.
- a liquid crystal display device will be described as an example, but it goes without saying that the present invention can be applied to any display device that requires a polarizing plate.
- Specific examples of image display devices to which the polarizing plate of the present invention can be applied include self-luminous display such as an electroluminescence (EL) display, a plasma display (PD), and a field emission display (FED). Apparatus.
- FIG. 2 is a schematic cross-sectional view of a liquid crystal display device according to a preferred embodiment of the present invention. In the illustrated example, a transmissive liquid crystal display device will be described, but it goes without saying that the present invention is also applied to a reflective liquid crystal display device and the like!
- the liquid crystal display device 100 includes a liquid crystal cell 10, a retardation film 20 and 20 'disposed with the liquid crystal cell 10 interposed therebetween, and a polarizing plate 30 disposed on the outside of the retardation films 20 and 20'. 30 ′, a light guide plate 40, a light source 50, and a reflector 60.
- the polarizing plates 30 and 30 ′ are arranged so that their polarization axes are orthogonal to each other.
- the liquid crystal cell 10 includes a pair of glass substrates 11 and 11 ′ and a liquid crystal layer 12 as a display medium disposed between the substrates.
- One substrate 11 is provided with a switching element (typically a TFT) for controlling the electro-optical characteristics of the liquid crystal, a scanning line for supplying a gate signal to the switching element, and a signal line for supplying a source signal. (Both not shown).
- the other glass substrate 11 ′ is provided with a color layer constituting a color filter and a light shielding layer (black matrix layer) (both not shown) o
- the distance (cell gap) between the substrates 11 and 11 is It is controlled by the spacer 13.
- the polarizing plate of the present invention described above is employed as at least one of the polarizing plates 30 and 30 ′.
- the liquid crystal molecules of the liquid crystal layer 12 are arranged in a state in which the polarization axis is shifted by 90 degrees. Like that In this state, the incident light that is transmitted through only one direction of light by the polarizing plate is twisted 90 degrees by the liquid crystal molecule. As described above, since the polarizing plates are arranged so that their polarization axes are orthogonal to each other, the light (polarized light) that has reached the other polarizing plate is transmitted through the polarizing plate. Therefore, when no voltage is applied, the liquid crystal display device 100 performs white display (normally white method).
- the polymer is dissolved in tetrahydrofuran, poured into excess hexane, re-precipitated, and the precipitate removed by filtration is dried under reduced pressure (ImmHg d. 33 hPa, 3 hours or more).
- the components were removed, and the obtained fat was measured using a DSC apparatus (DSC 8230, manufactured by Rigaku Corporation).
- the transparent resin layer or film was chopped in accordance with the measurement cell size and measured without performing the reprecipitation operation.
- the dealcoholization reaction rate is based on the weight loss that occurs when all hydroxyl groups are deallocated as methanol from the polymer composition obtained by polymerization, and the 150 ° C force before the weight loss starts in dynamic TG measurement It was determined from the weight loss due to the dealcoholization reaction up to 300 ° C before the polymer began to decompose.
- the melt flow rate was measured at a test temperature of 240 ° C and a load of 10 kg based on JIS-K6874.
- a sample (adhesive polarizing plate) was prepared by laminating the adhesive layer of the above adhesive sheet on the (meth) acrylic resin layer surface of the polarizing plate to remove the polyethylene terephthalate film. : Thickness 0.7mm, size 300mm X 220mm) roller Attach together. Next, after the obtained sample was put into an autoclave (50 ° C., 5 atm ⁇ 15 minutes), the glass power was slowly peeled off the adhesive polarizing plate to perform a rework test.
- the polarizing plate peels cleanly even when a sudden force is applied.
- a polarizer protective film remains on the glass.
- a 30-liter reactor equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introduction pipe is charged with 8000 g of methyl methacrylate (MMA), 2000 g of 2- (hydroxymethyl) methyl acrylate (MH MA), and lOOOOg of toluene.
- MMA methyl methacrylate
- MH MA 2- (hydroxymethyl) methyl acrylate
- lOOOOg toluene
- the temperature was raised to 105 ° C while refluxing nitrogen, and the mixture was refluxed.
- the initiator 10. Og of tertiary aminoleperoxy isononanoate (manufactured by Watofina Yoshitomi, trade name: rubazole 570) was added.
- 20. Og initiator and 100g of toluene solution were added dropwise over 4 hours, solution polymerization was performed under reflux (about 105 ⁇ : L 10 ° C), and aging was performed for further 4 hours. .
- the latatone cyclization rate of the latton ring-containing acrylic resin pellet was 97.0%, the mass average molecular weight was 147700, the melt flow rate was 11. OgZlO, and Tg (glass transition temperature) was 130 ° C.
- Polybutyl alcohol adhesive aqueous solution prepared by adjusting an aqueous solution containing 20 parts by weight of methylol melamine to 100 parts by weight of polyvinyl alcohol resin modified with acetoacetyl group (acetylene degree 13%) to a concentration of 0.5% by weight was prepared.
- a solution was prepared by diluting cellulose-based resin (manufactured by Eastman Chemical Co., Ltd., cellulose acetate propionate) in butyl acetate (solid content concentration 7.5% by weight). This solution was applied to one side of the Lataton ring-containing acrylic resin film produced in Production Example 3 and dried in an oven at 100 ° C for 3 minutes to obtain a polarizer protective film (1A) with a cellulose resin film. Obtained. The dry thickness of the cellulosic resin layer was 0.8 m.
- One side of the polarizer obtained in Production Example 1 has the cellulose-based resin layer surface of the above-mentioned polarizer protective film (1A), and the other side is saponified triacetyl cellulose (TAC )
- TAC triacetyl cellulose
- the film (Fuji Photo Film Co., Ltd., trade name: UZ-T40, thickness 40 m) was bonded using the polyvinyl alcohol adhesive aqueous solution prepared in Production Example 4.
- a polarizing plate (1) was obtained by drying at 70 ° C. for 10 minutes.
- the obtained polarizing plate (1) was evaluated for adhesiveness (rework test) and viewing angle characteristics of transmittance. The results are shown in Table 1.
- a polarizing plate (2) was obtained in the same manner as in Example 1 except that the dry thickness of the cellulosic resin layer was 2.1 m in Example 1.
- the obtained polarizing plate (2) was evaluated for adhesion (rework test) and viewing angle characteristics of transmittance. The results are shown in Table 1.
- Cellulose-based rosin (manufactured by Eastman Chemical Co., Ltd., cellulose acetate butyrate) is diluted in methylethylketone: methylisoptylketone (7: 3 (weight ratio)) mixed solvent (solid content concentration 4% by weight).
- a solution was prepared by adding 27 parts by weight of hexamethylene diisocyanate to 100 parts by weight of cellulosic resin. This solution was applied to one side of the Lataton ring-containing acrylic resin film produced in Production Example 3, dried in an oven at 75 ° C for 3 minutes, and a polarizer protective film (1B) with a cellulose resin layer. Got.
- the dry thickness of the cellulose-based resin layer was 0.8 ⁇ m.
- Example 1 it replaced with the polarizer protective film (1A) with a cellulosic resin layer, and it carried out similarly to Example 1 except having used the polarizer protective film (1B) with a cellulosic resin layer, A polarizing plate (3) was obtained.
- the obtained polarizing plate (3) was evaluated for adhesion (rework test) and viewing angle characteristics of transmittance. The results are shown in Table 1.
- Example 1 instead of the polarizer protective film (1A) with a cellulose-based resin layer, a saponified triacetyl cellulose (TAC) film (Fuji Photo Film Co., Ltd., trade name: UZ) having a thickness of 40 ⁇ m was used.
- TAC triacetyl cellulose
- UZ triacetyl cellulose
- a polarizing plate (C2) was obtained in the same manner as in Example 1, except that in Example 1, the cellulose-based resin layer was not provided with strength.
- the obtained polarizing plate (C2) was evaluated for adhesion (rework test) and viewing angle characteristics of transmittance. The results are shown in Table 1.
- a polarizing plate (C3) was obtained in the same manner as in Example 1 except that the dry thickness of the cellulose-based resin layer was set to 0.2 m in Example 1.
- the obtained polarizing plate (C3) was evaluated for adhesion (rework test) and viewing angle characteristics of transmittance. The results are shown in Table 1.
- a polarizing plate (C4) was obtained in the same manner as in Example 1 except that the dry thickness of the cellulose-based resin layer was 4.5 m in Example 1.
- the obtained polarizing plate (C4) was evaluated for adhesion (rework test) and viewing angle characteristics of transmittance. The results are shown in Table 1.
- Polarizing plates (1) to (3) using the polarizer protective film of the present invention are adhesive evaluation (rework It can be seen that the result of (Test) is good and the viewing angle characteristics of transmittance are also excellent. It can be seen that the polarizing plate (C1) obtained by using a TAC film instead of the latton ring-containing acrylic resin film with the cellulose resin layer is inferior in the viewing angle characteristics of transmittance. Instead of the latatone ring-containing acrylic resin film with a cellulose-based resin layer, a cell-mouthed resin resin layer is provided, and a polarizing plate obtained by using a latathone ring-containing acrylic resin film ( It can be seen that C2) is inferior to the result of adhesion evaluation (rework test).
- the polarizing plate (C3) with a cellulose resin layer thickness of 0.2 / zm in the Lataton ring-containing acrylic resin film with cellulosic resin layer is inferior to the results of adhesion evaluation (rework test). I understand that.
- a polarizing plate (C4) with a cellulose resin layer thickness of 4.5 ⁇ m in a Lataton ring-containing acrylic resin film with a cellulose resin layer may have poor viewing angle characteristics of transmittance. I understand.
- the polarizer protective film and polarizing plate of the present invention can be suitably used for various image display devices (liquid crystal display devices, organic EL display devices, PDPs, etc.).
Abstract
Description
Claims
Priority Applications (2)
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KR1020117030906A KR101251082B1 (ko) | 2006-05-26 | 2007-05-14 | 편광자 보호 필름, 편광판 및 화상 표시 장치 |
US12/301,664 US20090202822A1 (en) | 2006-05-26 | 2007-05-14 | Polarizer protective film, polarizing plate, and image display apparatus |
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JP2006-146273 | 2006-05-26 | ||
JP2006146273A JP2007316366A (ja) | 2006-05-26 | 2006-05-26 | 偏光子保護フィルム、偏光板、および画像表示装置 |
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US (1) | US20090202822A1 (ja) |
JP (1) | JP2007316366A (ja) |
KR (2) | KR20080114841A (ja) |
CN (1) | CN101454697A (ja) |
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WO (1) | WO2007138850A1 (ja) |
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US20100284072A1 (en) * | 2008-01-31 | 2010-11-11 | Nitto Denko Corporation | Polarizer protective film, polarizing plate, and image display apparatus |
US9493684B2 (en) * | 2008-01-31 | 2016-11-15 | Nitto Denko Corporation | Polarizer protective film, polarizing plate, and image display apparatus |
US20110128478A1 (en) * | 2008-06-18 | 2011-06-02 | Konica Minolta Opto, Inc. | Polarizing plate, liquid crystal display, and method of manufacturing protective film for polarizing plate |
WO2017086265A1 (ja) * | 2015-11-18 | 2017-05-26 | 日本ゼオン株式会社 | 光学フィルム及び偏光板 |
JPWO2017086265A1 (ja) * | 2015-11-18 | 2017-11-16 | 日本ゼオン株式会社 | 光学フィルム及び偏光板 |
JP2018045241A (ja) * | 2015-11-18 | 2018-03-22 | 日本ゼオン株式会社 | 光学フィルム及び偏光板 |
US10941236B2 (en) | 2015-11-18 | 2021-03-09 | Zeon Corporation | Optical film and polarizing plate |
Also Published As
Publication number | Publication date |
---|---|
KR20120023131A (ko) | 2012-03-12 |
KR20080114841A (ko) | 2008-12-31 |
JP2007316366A (ja) | 2007-12-06 |
KR101251082B1 (ko) | 2013-04-05 |
TWI369517B (ja) | 2012-08-01 |
CN101454697A (zh) | 2009-06-10 |
US20090202822A1 (en) | 2009-08-13 |
TW200809278A (en) | 2008-02-16 |
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