JP2009075472A - Retardation film and polarizing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a retardation film having high axial accuracy and uniform retardation, and to provide a polarizing plate comprising the retardation film. <P>SOLUTION: The retardation film has at least one layer comprising a crystalline polyolefin-based resin and a retardation control additive. Further, the polarizing plate is constituted by laminating the retardation film on at least one side of a polarizer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a retardation film and a polarizing plate including the retardation film.

  Liquid crystal display devices are used in various display devices by taking advantage of low power consumption, operation at low voltage, light weight and thinness. The liquid crystal display device is composed of many materials such as a liquid crystal cell, a polarizing plate, a retardation film, a condensing sheet, a diffusion film, a light guide plate, and a light reflecting sheet.

As the retardation film, for example, a film made of polypropylene having an isotactic index of 95% or more, or a mixture of the polypropylene and a small amount of other polyolefin is known (for example, see Patent Document 1).
Japanese Patent Publication No.53-11228 (April 20, 1978)

  However, the configuration of Patent Document 1 has a problem that it is difficult to use as a retardation film for a liquid crystal display device used in recent large-sized televisions and mobile phones.

  Specifically, a retardation film used in a liquid crystal display device of a recent large television or mobile phone is required to have high axial accuracy and a uniform retardation. However, in the configuration of Patent Document 1, since the amount of change in retardation with respect to stress applied during stretching of the film is large, it is difficult to uniformly control the retardation of the film by stretching.

  This invention is made | formed in view of said problem, The objective is to implement | achieve the polarizing plate containing the retardation film which has a high axial precision and a uniform retardation, and the said retardation film.

  In order to solve the above-described problems, the retardation film according to the present invention is characterized by having at least one layer containing a crystalline polyolefin resin and a retardation control additive.

  According to the above configuration, when the original film of the retardation film is stretched, the retardation control additive acts to reduce the amount of change in retardation with respect to the stress applied during stretching, and the retardation of the film. Can be suppressed. Therefore, according to the said structure, there exists an effect that the phase difference film which has high axial accuracy and a uniform phase difference can be provided.

  In the retardation film according to the present invention, the additive for controlling retardation is derived from an aromatic hydrocarbon resin comprising a structural unit derived from an aromatic hydrocarbon monomer, and an alicyclic hydrocarbon monomer having 5 to 25 carbon atoms. It is preferably at least one resin selected from the group consisting of alicyclic hydrocarbon resins consisting of the following structural units.

  According to the said structure, the retardation film which has higher axial accuracy and a more uniform phase difference can be provided.

In the retardation film according to the present invention, the number of foreign matters having a diameter of 0.1 mm or more is preferably 0.1 pieces / m ² or less.

  According to the said structure, there exists the further effect that the retardation film excellent in transparency can be provided.

  In order to solve the above-mentioned problems, the polarizing plate according to the present invention is characterized in that the retardation film according to the present invention is laminated on at least one surface of a polarizer.

  According to the above configuration, since a retardation film having high axial accuracy and a uniform phase difference is laminated on the polarizer, a polarizing plate capable of realizing a liquid crystal display device having excellent viewing angle characteristics is provided. There is an effect that can be done.

  As described above, the retardation film according to the present invention is characterized by having at least one layer containing a crystalline polyolefin resin and a retardation control additive.

  For this reason, there exists an effect that the phase difference film which has high axial accuracy and a uniform phase difference can be provided.

  The polarizing plate according to the present invention is characterized in that the retardation film according to the present invention is laminated on at least one surface of a polarizer as described above.

  For this reason, there is an effect that a polarizing plate capable of realizing a liquid crystal display device having excellent viewing angle characteristics can be provided.

  Hereinafter, the present invention will be described in detail.

  In this specification, “weight” is treated as a synonym for “mass”, and “weight%” is treated as a synonym for “mass%”. Further, “A to B” indicating the range indicates that the range is A or more and B or less.

  Moreover, in this specification, the "main component" means containing 50 mass% or more.

  The retardation film according to the present embodiment has at least one layer containing a crystalline polyolefin resin and a retardation controlling additive.

(A) Retardation control additive The retardation control additive according to the present embodiment is a phase difference film obtained by stretching a film having at least one layer containing a crystalline polyolefin resin and an additive. In addition, it means an additive exhibiting an effect that the phase difference is significantly different compared to a film to which the additive is not added.

Specifically, a film having at least one layer composed of a crystalline polyolefin-based resin and an additive, and the same film as that except that the additive is not included, are stretched under the same conditions. The following formula (1)
Q = 100 × | A−B | / B / C (1)
(In the above formula (1), A is a difference in retardation (nm) before and after stretching in a film containing an additive, and B is a difference in retardation (nm) before and after stretching in a film not containing an additive. C is the blending amount of the retardation control additive per 100 parts by mass of the crystalline polyolefin resin (
Part by mass). )
An additive having a phase difference control index Q of 10 or more (more preferably 30 or more, still more preferably 50 or more, particularly preferably 100 or more). Further, A is preferably smaller than B from the viewpoint of suppressing the deviation of the retardation of the film by reducing the amount of change in retardation with respect to the stress applied during stretching.

  Further, A can be made larger than B while having the effect of eliminating the bias of the phase difference by selecting the additive for controlling the phase difference. Thereby, a retardation film having a higher retardation can be obtained, or a thinner film can be obtained in the case of the same retardation.

  In addition, although the value of the phase difference control index Q can take various values depending on conditions such as the drawing speed and the type of the crystalline polyolefin resin, in this specification, the phase difference control index Q is at least one condition. The additive which becomes 10 or more is assumed to be an additive for phase difference control.

  Further, the thickness of the film before stretching when determining the phase difference control index Q is preferably in the range of 20 to 300 μm, and the stretching ratio (= (length after stretching−length before stretching) ÷ The length before stretching) is preferably in the range of 1.2 to 6 times.

  Specific examples of the retardation control additive include (i) oriented optically anisotropic fine particles, (ii) resins that interact with crystalline polyolefin resins, (iii) fats and oils (glycerin esters of fatty acids) Compounds) and waxes (ester compounds of higher fatty acids and higher monohydric alcohols) and the like used as plasticizers.

Examples of the oriented optically anisotropic fine particles include uniaxial or biaxial inorganic fine particles described in, for example, Japanese Patent No. 3060744, Japanese Patent Application Laid-Open No. 2007-154136, and the like. Knight, dickite, nacrite, halloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, hectorite, sodium tetrasilicon mica, sodium teniolite, muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, green mud Clay minerals such as stone, uniaxial crystals such as calcite (CaCO ₃ ), LiNbO ₃ , BaTiO ₃ ; carbonate particles such as calcium carbonate, strontium carbonate, barium carbonate (hereinafter referred to as “carbonate crystals” or “carbonate crystal particles”) Or the like). Among them, those having negative birefringence are more preferable, for example, uniaxial crystals such as calcite (CaCO ₃ ), LiNbO ₃ , BaTiO ₃ , carbonate particles such as calcium carbonate, strontium carbonate, and barium carbonate. Is mentioned.

  The oriented optically anisotropic fine particles are preferably carbonate particles from the viewpoint of having different refractive index values (anisotropy) in the axial direction of the crystal, and have a meteorite structure among the carbonate particles. Since it is a negative biaxial crystal, the above-mentioned calcium carbonate, strontium carbonate, and barium carbonate are more preferable. The inorganic fine particles may be used alone or in combination of two or more.

  Examples of the resin that interacts with the crystalline polyolefin-based resin include petroleum-based and natural product-based resins.

  The above petroleum-based and natural product-based resins are hydrocarbon resins obtained by polymerizing monomers (compositions) containing, as a main component, petroleum-derived monomers or monomers derived from natural products, or petroleum-derived or natural product-derived resins. It means a resin, and specifically includes an amorphous polyolefin resin, a thermoplastic elastomer, a terpene resin, a rosin resin, and the like.

The non-crystalline polyolefin resin means a polyolefin resin other than the crystalline polyolefin resin described later, and examples thereof include a norbornene resin and a cycloolefin resin. The said thermoplastic elastomer means the thermoplastic resin which shows rubber elasticity at room temperature, for example, a hydrogenated styrene-butadiene copolymer etc. are mentioned.

  The petroleum-based and natural product-based resins are low molecular weight thermoplastic polymers, and more preferably thermoplastic polymers having a number average molecular weight in the range of 500 to 2,000. The number average molecular weight is a value obtained by GPC, and can be obtained, for example, by dissolving a thermoplastic polymer to be measured in a THF solvent and converting the peak area of an elution chart obtained by GPC into polystyrene.

  The petroleum-based and natural product-based resins are more preferably aromatic hydrocarbon resins or alicyclic hydrocarbon resins.

  The aromatic hydrocarbon resin is a hydrocarbon resin obtained by polymerizing a monomer (composition) containing an aromatic hydrocarbon monomer as a main component. As the aromatic hydrocarbon monomer used, styrene, α- Examples include methylstyrene, vinyltoluene, indene, and methylindene.

  The alicyclic hydrocarbon resin is preferably a resin obtained by polymerizing a monomer (composition) containing an alicyclic hydrocarbon monomer having 5 to 25 carbon atoms as a main component. The alicyclic hydrocarbon monomer is a carbocyclic unsaturated compound having no aromatic ring, and examples thereof include cyclopentadiene, dicyclopentadiene, α-pinene, β-pinene, and dipentene.

  Furthermore, examples of the alicyclic hydrocarbon monomer having 5 to 25 carbon atoms include cyclopentene, cyclohexene, cycloheptene, methylcyclohexene, and ethylcyclohexene.

  As the alicyclic hydrocarbon resin, hydrogenation is performed on a resin obtained by addition polymerization of the alicyclic hydrocarbon monomer having 5 to 25 carbon atoms or a resin obtained by polymerizing an aromatic hydrocarbon monomer. And those obtained by modifying an aromatic ring structure to an alicyclic structure. The aromatic hydrocarbon resin and the alicyclic hydrocarbon resin may be obtained by polymerizing two or more types of monomers.

  In the present embodiment, the petroleum-based and natural product-based resins are derived from an aromatic hydrocarbon resin having a structural unit derived from an aromatic hydrocarbon monomer as a main component, and an alicyclic hydrocarbon monomer having 5 to 25 carbon atoms. One or more hydrocarbon resins selected from the group consisting of alicyclic hydrocarbon resins having the structural unit as a main component are preferable, more preferably a configuration derived from an alicyclic hydrocarbon monomer having 5 to 25 carbon atoms It is an alicyclic hydrocarbon resin having a unit as a main component. Further, these alicyclic hydrocarbon resins are more preferably alicyclic petroleum resins or alicyclic terpene resins, and particularly preferably hydrogenated alicyclic petroleum resins or hydrogenated alicyclic terpene resins.

  Here, the said alicyclic petroleum resin is resin (polymer) which has as a main component the structural unit derived from a C5-C25 alicyclic hydrocarbon monomer induced | guided | derived from a cracked petroleum fraction. The alicyclic terpene resin is a carbon atom synthesized by combining a plurality of isoprene units such as α-pinene, β-pinene, and limonene obtained by purifying plant-derived components such as pine tree and orange. It is resin (polymer) which has as a main component the structural unit derived from alicyclic hydrocarbon monomer of several 5-25.

  By hydrogenating the above petroleum-based and natural product-based resins under high temperature and high pressure to reduce unsaturated bonds in the hydrocarbon resin, the affinity with the crystalline polyolefin-based resin is increased, and the degree of retardation control is increased. improves.

  The content of the structural unit derived from the aromatic hydrocarbon monomer in the aromatic hydrocarbon resin is preferably in the range of 50 to 100% by mass, more preferably in the range of 80 to 100% by mass, Preferably it is 100 mass%. Similarly, the content of the structural unit derived from the alicyclic hydrocarbon monomer in the alicyclic hydrocarbon resin is preferably in the range of 50 to 100% by mass, more preferably in the range of 80 to 100% by mass. And most preferably 100% by weight.

  The content of the retardation control additive described above in the retardation film is usually 0.5 to 20 parts by mass when the mass of the layer containing the crystalline polyolefin resin and the retardation control additive is 100 parts by mass. It is within the range, and preferably within the range of 3 to 10 parts by mass. In addition, the content of the phase difference control additive may be a total amount within the above range when two or more types of phase difference control additives are used. If the content of the phase difference control additive is too small, the effect of phase difference control becomes weak, and if it is too large, bleeding out tends to occur.

  The method for adding the retardation controlling additive is not particularly limited as long as it can be uniformly dispersed in the film, and can be added by a usual method. For example, in a polymerization process for producing a crystalline polyolefin-based resin, an additive for phase difference control may be added to the polymerization reaction mixture during the polymerization reaction or immediately after the completion of the polymerization reaction. Here, the phase difference control additive may be added as a solution dissolved in a solvent, or may be added as a dispersant pulverized into a powder form so that it can be easily dispersed, or heated and melted. You may add in a state.

  Further, after the crystalline polyolefin resin is melt-kneaded and the phase difference controlling additive is added, it may be further melt-kneaded. These melt-kneading is performed using, for example, a kneader such as a ribbon blender, a mixing roll, a Banbury mixer, a roll, various kneaders, a single screw extruder, a twin screw extruder or the like. After the melt-kneading, the obtained composition may be subjected to a molding process in a molten state without being cooled, or may be cooled to pellets and then heated again to be subjected to a molding process. Moreover, after cooling, you may use for shaping | molding processes by methods, such as press molding, with a cooling state. When a plurality of phase difference control additives are used, the addition method is not limited, and each phase difference control additive may be added simultaneously, or may be added before and after each timing of addition.

Further, as described in JP-A-2005-161696, when producing a resin composition by melting and kneading a crystalline polyolefin resin and a plurality of phase difference control additives, the following first step to 4th process,
1st process: The process which mixes at least 2 or more types of phase difference control additives which are powders at normal temperature with the crystalline polyolefin resin of powder as needed, and manufactures the phase difference control additive masterbatch beforehand ;
2nd process: The process of storing the said additive difference batch for phase difference control in the additive storage hopper for phase difference control;
Third step: a step of transferring the phase difference control additive master batch of the phase difference control additive storage hopper to the phase difference control additive supply hopper;
4th process: The process which measures the said additive masterbatch for phase difference control, supplies it to a melt kneader, melts and kneads it with a crystalline polyolefin resin, and manufactures a crystalline polyolefin resin composition (pellet);
A manufacturing method or the like characterized by containing can also be used.

  These processes are more preferably performed in an inert gas atmosphere such as nitrogen gas. It is also more preferable to carry out a series of steps from polymerization powder to pelletization in a clean room environment. Furthermore, it is more preferable to incorporate a foreign matter removing system such as a polymer filter described later upstream of the die of the melt kneader (granulator) in this step.

  As a matter of course, the film forming process described later is performed in a clean room environment in the same manner as described above, performed in an inert gas atmosphere such as nitrogen gas, and the melt extruder used in the process. Incorporating a foreign matter removal system such as a polymer filter upstream of the die is a preferred method. In addition, it is more preferable to completely remove cellulose fibers, chemically synthesized fibers, and the like that are likely to be mixed as foreign substances from the work environment of a series of processes by means of not handling them in all processes.

  In the above description of the present embodiment, the case where the retardation control additive is used together with the crystalline polyolefin resin is described, but the present invention is not limited to this. For example, only other resins such as an amorphous polyolefin resin may be used instead of the crystalline polyolefin resin. As long as the retardation controlling additive described above is contained, the same effects as those of the present embodiment can be obtained regardless of the type of the retardation film.

  However, when the crystalline polyolefin-based resin is included as in this embodiment, the amount of change in retardation with respect to stretching in the case of not containing the retardation control additive is large, and thus the effect is particularly great.

  That is, the present invention is an additive for controlling retardation that is contained in a film before stretching when the film is stretched to form a retardation film, and is an aromatic carbonization composed of a structural unit derived from an aromatic hydrocarbon monomer. Retardation characterized in that it is at least one resin selected from the group consisting of hydrogen resins and alicyclic hydrocarbon resins consisting of structural units derived from alicyclic hydrocarbon monomers having 5 to 25 carbon atoms In other words, “control additive”.

(B) Crystalline polyolefin-based resin The crystalline polyolefin-based resin is a resin obtained by polymerizing a monomer (monomer composition) containing an olefin such as ethylene or α-olefin as a main component. Have crystallinity. Here, “having crystallinity” in the present specification means that the crystallinity is 1% or more, preferably 10% or more. The monomer composition may contain cycloolefin, polar vinyl monomer, and the like.

  The above crystallinity is measured by "Introduction to Polymer Chemistry" (Seizo Okamura et al., Chemical Doujin (1970)), "New Edition Polymer Analysis Handbook" (Japan Analytical Chemistry Society / Polymer Analysis Research Party, As described in Kinokuniya (1995), etc., it can be carried out by known methods such as X-ray method, density method, infrared absorption method, NMR method, and calorimetric method. "Crystallinity" in the book is a value measured by X-ray method (measured by wide-angle X-ray crystal diffraction and determined by Natta's formula (reference: Natta GJ Polym. Sci., 1955, 16, 143) Value).

  The glass transition temperature of the crystalline polyolefin resin according to the present embodiment is not particularly limited, but is preferably equal to or lower than the adhesion temperature, specifically, preferably 40 ° C. or lower, more preferably 20 ° C. or lower, and further Preferably it is 0 degrees C or less. The glass transition temperature can be determined by a differential scanning calorimeter or a viscoelasticity measuring device. The “glass transition temperature” in this specification is measured by a differential scanning calorimeter according to the method described in JIS K7121. Mean value.

  Specifically, the crystalline polyolefin resin according to the present embodiment can be roughly classified into a propylene resin, an ethylene resin, and modified products of these resins. Such various crystalline polyolefin-type resin may be used independently, and may be used in combination of 2 or more type.

[Propylene resin]
The propylene resin is a monomer (monomer composition) containing propylene as a main component (more preferably a monomer (monomer composition) containing 60% by mass or more of propylene, more preferably propylene. Is a resin obtained by polymerizing a monomer containing 70% by mass or more (monomer composition). Such a resin generally has crystallinity, and may be a propylene homopolymer or a copolymer with a comonomer copolymerizable with propylene.

  Examples of the comonomer copolymerizable with propylene include ethylene, an α-olefin having 4 to 20 carbon atoms, a cycloolefin, and a polar vinyl monomer.

Specific examples of the α-olefin include 1-butene, 2-methyl-1-propene (above C ₄ ); 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene (above C _5). ); 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3, 3-dimethyl-1-butene (above C ₆ ); 1-heptene, 2-methyl-1-hexene, 2,3-dimethyl-1-pentene, 2-ethyl-1-pentene, 2-methyl-3-ethyl -1-butene (above C ₇ ); 1-octene, 5-methyl-1-heptene, 2-ethyl-1-hexene, 3,3-dimethyl-1-hexene, 2-methyl-3-ethyl-1- Pentene, 2,3,4-trimethyl-1-pentene 2-propyl-1-pentene, 2,3-diethyl-1-butene (or C _8); 1-nonene (C _9); 1-decene (C _10); 1-undecene (C _11); 1-dodecene (C ₁₂ ); 1-tridecene (C ₁₃ ); 1-tetradecene (C ₁₄ ); 1-pentadecene (C ₁₅ ); 1-hexadecene (C ₁₆ ); 1-heptadecene (C ₁₇ ); 1-octadecene (C _18); nonadecene (C _19), and the like.

  Among the α-olefins, α-olefins having 4 to 12 carbon atoms are more preferable. Specifically, 1-butene, 2-methyl-1-propene; 1-pentene, 2-methyl-1-butene. 3-methyl-1-butene; 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl -1-pentene, 3,3-dimethyl-1-butene; 1-heptene, 2-methyl-1-hexene, 2,3-dimethyl-1-pentene, 2-ethyl-1-pentene, 2-methyl-3 1-octene, 5-methyl-1-heptene, 2-ethyl-1-hexene, 3,3-dimethyl-1-hexene, 2-methyl-3-ethyl-1-pentene, 2 , 3,4-Trimethyl-1-pen Ten, 2-propyl-1-pentene, 2,3-diethyl-1-butene; 1-nonene; 1-decene; 1-undecene; 1-dodecene and the like are more preferable.

  From the viewpoint of copolymerization, ethylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable, and 1-butene and 1-hexene are particularly preferable.

  Examples of the polar vinyl monomer include saturated carboxylic acid vinyl esters, unsaturated carboxylic acid vinyl esters, α, β-unsaturated carboxylic acid esters, unsaturated carboxylic acids and / or derivatives thereof.

The saturated carboxylic acid vinyl ester is preferably a vinyl ester of an aliphatic carboxylic acid having about 2 to 4 carbon atoms, and examples thereof include vinyl acetate, vinyl propionate, and vinyl butyrate.

  The unsaturated carboxylic acid vinyl ester is preferably a vinyl ester of an aliphatic carboxylic acid having about 2 to 5 carbon atoms, and examples thereof include vinyl acrylate and vinyl methacrylate.

  The α, β-unsaturated carboxylic acid ester is preferably an ester of an unsaturated carboxylic acid having about 3 to 8 carbon atoms, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-acrylate. -Alkyl esters of acrylic acid such as butyl, isobutyl acrylate, t-butyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid and alkyl esters of methacrylic acid such as t-butyl.

  Examples of unsaturated carboxylic acids and / or derivatives thereof include unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, acrylic acid and methacrylic acid; acids of unsaturated carboxylic acids such as maleic anhydride and itaconic anhydride Examples of anhydrides include ester compounds, amide compounds, imide compounds, and derivatives of unsaturated carboxylic acids such as metal salts. Such polar vinyl monomers may be used alone or in combination of two or more.

  The copolymer may be a random copolymer or a block copolymer. Preferable copolymers include propylene / ethylene copolymers and propylene / 1-butene copolymers. In the propylene / ethylene copolymer and the propylene / 1-butene copolymer, the content of the ethylene unit and the content of the 1-butene unit are, for example, those of “Polymer Analysis Handbook” (1995, published by Kinokuniya Shoten) Infrared (IR) spectrum measurement can be performed by the method described on page 616.

  From the viewpoint of increasing the transparency and workability of the retardation film, it is preferable to use a random copolymer of propylene as a main component and an arbitrary unsaturated hydrocarbon, and particularly preferable is a copolymer of ethylene.

  Specific examples of the random copolymer include propylene / ethylene random copolymer, propylene / 1-butene random copolymer, propylene / 1-hexene random copolymer, propylene / ethylene / 1-octene random copolymer. And propylene / ethylene / 1-butene random copolymer.

  When the copolymer is used, the unsaturated hydrocarbons other than propylene are preferably set to have a copolymerization ratio in the range of about 1 to 40% by mass, more preferably in the range of 2 to 30% by mass. Preferably, it is more preferable to set it within the range of 3 to 7% by mass. Moreover, it is preferable to make the copolymerization ratio of polar vinyl monomers, such as unsaturated carboxylic acid and / or its derivative (s), in the range of 3-10 mass%.

  By setting the unit of unsaturated hydrocarbons other than propylene to 1% by mass or more, processability and transparency tend to be improved. However, when the ratio exceeds 10% by mass, the melting point of the resin is lowered and the heat resistance tends to deteriorate. In addition, when setting it as the copolymer of two or more types of comonomers and propylene, it is preferable that the total content of the unit derived from all the comonomers contained in the copolymer is the said range.

The propylene-based resin according to the present embodiment has a melt flow rate (MFR) of 0.1 to 200 g measured at a temperature of 230 ° C. and a load of 21.18 N in accordance with JIS K 7210.
It is preferable that it is in the range of / 10 minutes, particularly in the range of 0.5 to 50 g / 10 minutes. By using a propylene resin having an MFR in this range, a uniform film can be obtained without imposing a large load on the extruder.

  The structure of the propylene-based resin is an isotactic structure, a syndiotactic structure or an atactic structure described in “Polypropylene Handbook” (edited by Edward P. Moore, Jr., Industrial Research Committee (1998)). Any structure may be sufficient, and these structures may be mixed. In the present embodiment, from the viewpoint of heat resistance, a propylene resin having a syndiotactic or isotactic structure is preferably used, and a propylene resin having a syndiotactic structure is particularly preferably used.

In the present embodiment, the propylene resin having the syndiotactic structure is 20.2 ppm based on tetramethylsilane in a ¹³ C-NMR spectrum measured with a 1,2,4-trichlorobenzene solution at 135 ° C. A value (syndiotactic pentad fraction [rrrr]) obtained by dividing the observed peak intensity by the total peak intensity attributed to the methyl group of the propylene unit is preferably in the range of 0.3 to 0.9. Means a polypropylene resin within the range of 0.5 to 0.9, more preferably within the range of 0.7 to 0.9. In addition, attribution of a necessary peak is A. It can be carried out according to the assignment of Zambelli et al. (Macromolecules, 6,925 (1973)).

  A method for producing a polypropylene resin having a syndiotactic structure is described in JP-A-5-17589, JP-A-5-131558, etc., and a slurry method is used as a process for producing a propylene-based resin having a syndiotactic structure. A gas phase fluidized bed method and a bulk method are preferable.

  The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the propylene-based resin having a syndiotactic structure is preferably in the range of 1.5 to 3.5. Preferably it exists in the range of 1.8-3.3, More preferably, it exists in the range of 2.0-3.0. If Mw / Mn exceeds the above range, the transparency tends to decrease, and if it is less than the above range, the processing suitability tends to deteriorate, for example, the extrusion load increases or draw resonance tends to occur. Examples of a method for adjusting Mw / Mn to a predetermined range include a method of selecting an appropriate metallocene catalyst described later as a polymerization catalyst.

  Examples of the α-olefin that can be preferably used as a comonomer in the production of the propylene-based resin having the syndiotactic structure include ethylene and 1-olefin having 4 to 18 carbon atoms. Specifically, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene-1, 4-methyl-hexene-1, 4,4-dimethylpentene-1, etc. These may be used alone or in combination of two or more.

Specific examples of the propylene-based copolymer having a syndiotactic structure include propylene units in the range of 88 to 99.5% by mass, preferably in the range of 91 to 99% by mass, and more preferably 92 to 98.5% by mass. %, Within a range of 0.5 to 12% by mass, preferably within a range of 1 to 10% by mass, more preferably within a range of 1.5 to 8% by mass. And a copolymer. When there are few propylene units, the heat resistance of the film tends to decrease, and when there are many propylene units, flexibility tends to be impaired. Here, the propylene unit and the α-olefin unit are values measured by ¹³ C-NMR method.

The propylene-based resin having the syndiotactic structure has a melting point of about 130 to 150 ° C., a density of about 0.880 g / cm ³ and a crystallinity of about 30 to 40%, so that it has transparency and gloss. A retardation film excellent in adhesiveness and the like can be obtained.

  As the propylene-based resin according to the present embodiment, a metallocene catalyst-based propylene-based resin that is polymerized using a metallocene catalyst described later is preferably used. The metallocene catalyst-based propylene-based resin may contain a high-pressure radical polymerization low-density polyethylene, a linear low-density polyethylene, an olefin-based rubber component, and the like.

  The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the metallocene catalyst-based propylene-based resin is preferably in the range of 1.5 to 3.5, more preferably 1 Within the range of .8 to 3.3, more preferably within the range of 2.0 to 3.0. When Mw / Mn exceeds the above range, the transparency tends to decrease. When the Mw / Mn exceeds the above range, the processing suitability tends to deteriorate, for example, the extrusion load increases or draw resonance is likely to occur. Mw / Mn can be adjusted to a predetermined range by selecting an appropriate metallocene catalyst as a polymerization catalyst.

  Examples of the α-olefin that can be preferably used as a comonomer of propylene in the production of the metallocene catalyst-based propylene-based resin include ethylene or 1-olefin having 4 to 18 carbon atoms. Specifically, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene-1, 4-methyl-hexene-1, 4,4-dimethylpentene-1, etc. Is mentioned. The said alpha olefin may be used independently and may use 2 or more types together.

Specific examples of the metallocene catalyst-based propylene-based copolymer include propylene units in the range of 88 to 99.5% by mass, preferably in the range of 91 to 99% by mass, and more preferably in the range of 92 to 98.5% by mass. Among them, co-polymer containing α-olefin units in the range of 0.5 to 12% by mass, preferably in the range of 1 to 10% by mass, more preferably in the range of 1.5 to 8% by mass. Coalescence is mentioned. When there are few propylene units, the heat resistance of the film tends to decrease, and when there are too many propylene units, the flexibility tends to decrease. Propylene units and α-olefin units are values measured by ¹³ C-NMR method.

  The metallocene catalyst-based propylene-based resin is preferably a resin whose melting peak is observed in a range of 120 to 170 ° C., more preferably a melting peak in a range of 150 to 170 ° C., by a differential scanning calorimeter (DSC). Is observed. If no melting beak is observed in this range, the heat resistance and bleed resistance may be inferior.

The isotactic pentad fraction of the metallocene catalyst-based propylene-based resin is preferably in the range of 0.95 to 1, more preferably in the range of 0.96 to 1, from the viewpoint of improving bleed resistance. . Incidentally, isotactic pentad ^fraction, the 13 C-NMR spectrum, A. This is a value calculated from the equation [mmmm peak intensity / total peak intensity in the methyl region] according to the assignment of Zambelli et al. (Macromolecules, 8, 687 (1975)).

  Further, the 20 ° C. xylene-soluble part amount (CXS) of the metallocene catalyst-based propylene-based resin is preferably 0.9% by mass or less, more preferably 0.9% by mass or less, more preferably 100% by mass of the resin from the viewpoint of improving bleeding resistance. 0.5% by mass or less.

<Propylene-based resin production method>
The propylene-based resin according to the present embodiment is obtained by a method of homopolymerizing propylene using a known polymerization catalyst, or a method of copolymerizing propylene and another copolymerizable comonomer.
Can be manufactured. As a known polymerization catalyst, for example,
(1) Ti—Mg-based catalyst comprising a solid catalyst component containing magnesium, titanium and halogen as essential components,
(2) a catalyst system in which an organic aluminum compound and, if necessary, a third component such as an electron donating compound are combined with a solid catalyst component containing magnesium, titanium and halogen as essential components, (3) a metallocene catalyst,
Etc.

  Among these catalyst systems, in the production of the propylene-based resin used as the retardation film according to the present embodiment, an organoaluminum compound and an electron donating compound are added to a solid catalyst component containing magnesium, titanium, and halogen as essential components. Combined catalysts can be most commonly used.

  More specifically, the organoaluminum compound is preferably triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, tetraethyldialumoxane, etc., and the electron donating compound is preferably cyclohexylethyldimethoxy. Examples include silane, tert-butylpropyldimethoxysilane, tert-butylethyldimethoxysilane, and dicyclopentyldimethoxysilane.

  On the other hand, examples of the solid catalyst component containing magnesium, titanium and halogen as essential components include the catalysts described in JP-A-61-218606, JP-A-61-287904, JP-A-7-216017, and the like. System.

  The metallocene catalyst is a co-catalyst that can be activated to a stable ionic state by reacting with a metallocene compound and a transition metal compound of Group 4 of the periodic table (so-called metallocene compound) containing a ligand having a cyclopentadienyl skeleton. And a catalyst comprising an organoaluminum compound if necessary. Examples of the metallocene catalyst include catalyst systems described in Japanese Patent No. 2587251, Japanese Patent No. 2627669, Japanese Patent No. 2668732, and the like.

As said metallocene compound, for example, the following general formula MLaXn-a
(In the formula, M is a group 4 or lanthanide series transition metal atom of the periodic table of elements. L is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, at least one of which is cyclo A group having a pentadiene-type anion skeleton, wherein a plurality of L's may be cross-linked to each other, X is a halogen atom, hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, n is a valence of a transition metal atom A is an integer satisfying 0 <a ≦ n.)
And may be used alone or in combination of at least two kinds. Specifically, JP-A-58-19309, JP-A-59-95292, JP-A-59-23011, JP-A-60-35006, JP-A-60-35007, JP 60-35008 A, JP 60-35209 A, JP 61-130314 A, JP 3-163088 A, European Patent Application No. 420,436, US Pat. No. 5,055,438, WO 92/07123 pamphlet and the like.

More specific examples of the metallocene compound include bis (cyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, bis (azurenyl) zirconium dichloride, bis (4,5,6,7 -Tetrahydroindenyl) zirconium dichloride, (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, methylenebis (cyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (3,4 Dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadiene) ) (3,5-dimethylpentadienyl) zirconium dichloride, methylenebis (indenyl) zirconium dichloride, ethylenebis (2-methylindenyl) zirconium dichloride, ethylene 1,2-bis (4-phenylindenyl) zirconium dichloride, Ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (4,5,6 , 7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (cyclope Tadienyl) (octahydrofluorenyl) zirconium dichloride, methylphenylsilylenebis [1- (2-methyl-4,5-benzo (indenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4,5) -Benzoindenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4H-azurenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4- (4-chlorophenyl) -4H-azurenyl] ] Zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azulenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4-naphthyl-4H-azurenyl) ] Zirconium dichloride, diph Phenylsilylenebis [1- (2-methyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4- (phenylindenyl))] zirconium dichloride, Dimethylsilylenebis [1- (2-ethyl-4- (phenylindenyl))] zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4-naphthyl-4H-azurenyl)] zirconium dichloride, dimethylgermylenebis Zirconium compounds such as (indenyl) zirconium dichloride and dimethylgermylene (cyclopentadienyl) (fluorenyl) zirconium dichloride are exemplified.

  In the metallocene compound, a compound in which zirconium is replaced with hafnium may be used in the same manner. In some cases, a mixture of a zirconium compound and a hafnium compound can also be used.

The metallocene compound may be used by being supported on an inorganic or organic compound carrier. As the carrier, a porous oxide of an inorganic or organic compound is preferable, and specifically, an ion-exchange layered silicate, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO. , ZnO, BaO, ThO _{2 and the} like, and mixtures thereof.

  Examples of the co-catalyst for the metallocene catalyst include organoaluminum oxy compounds (aluminoxane compounds), ion-exchange layered silicates, Lewis acids, boron compounds, lanthanoid salts such as lanthanum oxide, tin oxide, and the like.

  Examples of the organoaluminum compounds that can be included in the metallocene catalyst include trialkylaluminums such as triethylaluminum, triisopropylaluminum, and triisobutylaluminum; dialkylaluminum halides; alkylaluminum sesquihalides; alkylaluminum dihalides; Examples include alkoxide.

The propylene-based resin according to the present embodiment is, for example, a solution polymerization method using an inert solvent typified by a hydrocarbon compound such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and the like. Can be produced by a bulk polymerization method using the above monomer as a solvent, a gas phase polymerization method in which a gaseous monomer is polymerized as it is, or the like. Polymerization by these methods may be carried out batchwise or continuously.

  In addition, as a process for producing a metallocene catalyst-based propylene resin using a metallocene catalyst, a slurry method, a gas phase fluidized bed method, and a bulk method are preferable.

  The metallocene catalyst as described above includes (1) a Ti—Mg catalyst comprising a solid catalyst component having magnesium, titanium and halogen as essential components, and (2) a solid catalyst component having magnesium, titanium and halogen as essential components. In addition, unlike a so-called Ziegler-Natta catalyst, which is a catalyst system in which an organoaluminum compound and, if necessary, a third component such as an electron donating compound are combined, it is called a homogeneous catalyst.

  A Ziegler-Natta catalyst has a plurality of polymerization active sites, whereas a homogeneous catalyst in principle has a single polymerization active site.

  Examples of such homogeneous catalysts include those using a specific transition metal complex in addition to a metallocene catalyst, particularly those using a late transition metal complex. US Pat. No. 5,866,663, US Pat. No. 5,955,555 The catalysts disclosed in JP-T-2007-517108, JP-A-9-302018, JP-A-9-302019, JP-A-10-195128, and the like. Examples of the polymerization method include the same methods as in the case of the metallocene catalyst.

[Ethylene resin]
The ethylene-based resin is a monomer (monomer composition) containing ethylene as a main component (more preferably a monomer (monomer composition) containing 60% by mass or more of ethylene, more preferably ethylene. Is a resin obtained by polymerizing a monomer containing 70% by mass or more (monomer composition). Such a resin is generally crystalline and may be an ethylene homopolymer or a copolymer of ethylene and a comonomer copolymerizable with ethylene. Specific examples of the ethylene-based resin include (i) ethylene / α-olefin copolymer, (ii) high-density polyethylene, (iii) high-pressure low-density polyethylene, and (iv) ethylene / ethylenically unsaturated carboxylic acids. And polymers.

(I) Ethylene / α-olefin copolymer The ethylene / α-olefin copolymer is a homogeneous product obtained by copolymerizing ethylene and an α-olefin having 4 to 20 carbon atoms using a metallocene catalyst or the like. And ethylene / α-olefin copolymers obtained by copolymerizing ethylene and α-olefins having 4 to 20 carbon atoms using a catalyst-based ethylene / α-olefin copolymer or a Ziegler-Natta catalyst. It is done. These may be obtained by copolymerizing the same α-olefin, or may be obtained by copolymerizing different α-olefins.

Specific examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 2-methyl-1-propene (above C ₄ ); 1-pentene, 2-methyl-1-butene, 3-methyl- 1-butene (above C ₅ ); 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl -1-pentene, 3,3-dimethyl-1-butene (above C ₆ ); 1-heptene, 2-methyl-1-hexene, 2,3-dimethyl-1-pentene, 2-ethyl-1-pentene, 2-methyl-3-ethyl-1-butene (above C ₇ ); 1-octene, 5-methyl-1-heptene, 2-ethyl-1-hexene, 3,3-dimethyl-1-hexene, 2-methyl -3-ethyl-1
-Pentene, 2,3,4-trimethyl-1-pentene, 2-propyl-1-pentene, 2,3-diethyl-1-butene (above C ₈ ); 1-nonene (C ₉ ); 1-decene ( C _10); 1-undecene (C _11); 1- dodecene (C _12); 1- tridecene (C _13); 1- tetradecene (C _14); 1- pentadecene (C _15); 1- hexadecene (C ₁₆ 1-heptadecene (C ₁₇ ); 1-octadecene (C ₁₈ ); 1-nonadecene (C ₁₉ ) and the like. Moreover, said C4-C20 alpha olefin may be used independently and may use 2 or more types together.

  Among the α-olefins, α-olefins having 4 to 12 carbon atoms are more preferable. Specifically, 1-butene, 2-methyl-1-propene; 1-pentene, 2-methyl-1-butene. 3-methyl-1-butene; 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl -1-pentene, 3,3-dimethyl-1-butene; 1-heptene, 2-methyl-1-hexene, 2,3-dimethyl-1-pentene, 2-ethyl-1-pentene, 2-methyl-3 1-octene, 5-methyl-1-heptene, 2-ethyl-1-hexene, 3,3-dimethyl-1-hexene, 2-methyl-3-ethyl-1-pentene, 2 , 3,4-Trimethyl-1-pen Ten, 2-propyl-1-pentene, 2,3-diethyl-1-butene; 1-nonene; 1-decene; 1-undecene; 1-dodecene and the like are more preferable.

  From the viewpoint of copolymerizability, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable, and 1-butene and 1-hexene are particularly preferable.

  Specific examples of the ethylene / α-olefin copolymer include, for example, an ethylene / butene-1 copolymer, an ethylene / 4-methyl-pentene-1 copolymer, and an ethylene / hexene-1 copolymer, regardless of the catalyst system. Polymer, ethylene / octene-1 copolymer, and the like, preferably ethylene / hexene-1 copolymer, ethylene / 4-methyl-pentene-1, ethylene / octene-1 copolymer, and more preferably. Is an ethylene / hexene-1 copolymer.

  The melt flow rate (based on MFR JIS K 7210: 1999) of the ethylene / α-olefin copolymer is preferably in the range of 0.01 to 100 g / 10 min, more preferably 0.1 to 40 g / 10 min. Within the range, more preferably within the range of 0.4 to 5 g / 10 min. When the melt flow rate (MFR) of the ethylene / α-olefin copolymer is less than 0.01 g / 10 minutes, the melt viscosity becomes too high and the extrudability may deteriorate, exceeding 100 g / 10 minutes. In such a case, the mechanical strength and heat resistance may decrease.

The density of the ethylene / alpha-olefin copolymer is preferably in the range of 880~945kg / ^{m 3,} more preferably in the range of 890~930kg / ^{m 3,} more preferably 900~925kg / ^{m 3} Is within the range. The density of the ethylene / alpha-olefin copolymer, in the case of less than 880 kg / ^{m 3,} crystallinity is too low heat resistance is lowered, it may heat sealing of the film takes place, a 945 kg / ^{m 3} When it exceeds, impact strength and transparency may be lowered.

  As a method for producing a homogeneous catalyst-based ethylene / α-olefin copolymer according to the present embodiment, a known polymerization method using a metallocene catalyst may be mentioned. Examples of such known polymerization methods include solution polymerization methods, slurry polymerization methods, high pressure ion polymerization methods, and gas phase polymerization methods, and gas phase polymerization methods, solution polymerization methods, and high pressure ion polymerization methods are more preferable. Further, a gas phase polymerization method is more preferable.

  Examples of the metallocene catalyst include the same catalysts as the metallocene catalyst described above in [Propylene-based resin production method].

  Furthermore, the metallocene catalyst may be used in combination with an alumoxane compound such as methylalumoxane and / or an ionic compound such as trityltetrakispentafluorophenylborate and N, N-dimethylanilinium tetrakispentafluorophenylborate.

The metallocene catalyst comprises the metallocene compound, an organoaluminum compound, an alumoxane compound and / or an ionic compound, a particulate inorganic carrier such as SiO ₂ and Al ₂ O ₃ , and a particulate organic polymer such as polyethylene and polystyrene. It may be a catalyst supported or impregnated on a support.

  Examples of the ethylene / α-olefin copolymer obtained by polymerization using the metallocene catalyst include ethylene / α-olefin copolymers described in JP-A-9-183816. Further, a late transition metal complex catalyst or the like may be used as the homogeneous catalyst.

  Examples of the late transition metal complexes include US Pat. No. 5,866,663, US Pat. No. 5,955,555, JP-T 2007-517108, JP-A-9-302018, JP-A-9-302019, JP-A-10-195128, and the like. And the disclosed catalyst. Examples of the polymerization method include the same methods as in the case of the metallocene catalyst.

  As another method for producing an ethylene / α-olefin copolymer, a known polymerization method using a known polymerization catalyst may be mentioned. Examples of known polymerization catalysts include Ziegler-Natta catalysts. As a well-known polymerization method, the polymerization method similar to the polymerization method used by the manufacturing method of the ethylene / alpha-olefin copolymer mentioned above is mentioned.

(Ii) High-density polyethylene The high-density polyethylene means an ethylene homopolymer whose density is in the range of 945 to 970 kg / m ³ , preferably in the range of 945 to 965 kg / m ³ . When the density of the high density polyethylene is within the above range, a high density polyethylene excellent in heat-resistant fusion resistance and impact strength can be obtained.

  The melt flow rate (based on MFR JIS K 7210: 1999) of the high-density polyethylene is preferably in the range of 0.01 to 100 g / 10 minutes, more preferably in the range of 0.1 to 40 g / 10 minutes. More preferably, it exists in the range of 0.3-10 g / 10min. When the melt flow rate (MFR) of the high-density polyethylene is less than 0.01 g / 10 minutes, the melt viscosity may become too high and the extrudability may deteriorate, and when it exceeds 100 g / 10 minutes, Strength may decrease.

  As a manufacturing method of the high-density polyethylene which concerns on this Embodiment, the well-known polymerization method using a well-known polymerization catalyst is mentioned. Examples of the catalyst used for the production of high-density polyethylene include Ziegler-Natta catalysts, metallocene catalysts, specific transition metal complexes (particularly, late transition metal complexes), and the like. Examples of known polymerization methods include polymerization methods similar to those used in the above-described ethylene / α-olefin copolymer production method. Specifically, solution polymerization methods, slurry polymerization methods, high-pressure ion weight polymerization methods, and the like. Examples thereof include a combination method and a gas phase polymerization method.

(Iii) High-pressure method low-density polyethylene The high-pressure method low-density polyethylene means that the density is within a range of 915 to 935 kg / m ³ ,
From the viewpoint of preventing a decrease in heat-resistant fusibility and a decrease in impact strength, ethylene is preferably in the range of 915 to 930 kg / m ³ , more preferably in the range of 918 to 930 kg / m ^3. It means a polymer.

  The melt flow rate (based on MFR JIS K 7210: 1999) of the high-pressure low-density polyethylene described above prevents the melt viscosity from becoming too high and extruding process from being deteriorated, and the mechanical strength from being extremely lowered. From the viewpoint, it is preferably within a range of 0.01 to 100 g / 10 minutes, more preferably within a range of 0.1 to 40 g / 10 minutes, and further preferably within a range of 0.3 to 10 g / 10 minutes. It is.

  As a method for producing a high-pressure low-density polyethylene according to the present embodiment, using a tank reactor or a tube reactor, in the presence of a radical generator, a polymerization pressure of 140 to 300 MPa, a polymerization temperature of 200 to A general method for polymerizing ethylene under conditions within the range of 300 ° C. is mentioned. In order to adjust the melt flow rate, hydrogen, hydrocarbons such as methane and ethane are used as molecular weight regulators.

(Iv) Ethylene / ethylenically unsaturated carboxylic acid copolymer The ethylene / ethylenically unsaturated carboxylic acid copolymer is a copolymer of ethylene and an ethylenically unsaturated carboxylic acid. Acids are carboxylic acids and are compounds having an ethylenically unsaturated bond which is a polymerizable carbon-carbon unsaturated bond such as a carbon-carbon double bond.

  Examples of the ethylenically unsaturated carboxylic acids include saturated carboxylic acid vinyl esters, unsaturated carboxylic acid vinyl esters, α, β-unsaturated carboxylic acid esters, unsaturated carboxylic acids and / or derivatives thereof.

  The saturated carboxylic acid vinyl ester is preferably a vinyl ester of an aliphatic carboxylic acid having about 2 to 4 carbon atoms, and examples thereof include vinyl acetate, vinyl propionate, and vinyl butyrate.

  The unsaturated carboxylic acid vinyl ester is preferably a vinyl ester of an aliphatic carboxylic acid having about 2 to 5 carbon atoms, and examples thereof include vinyl acrylate and vinyl methacrylate.

  The α, β-unsaturated carboxylic acid ester is preferably an ester of an unsaturated carboxylic acid having about 3 to 8 carbon atoms, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-acrylate. -Alkyl esters of acrylic acid such as butyl, isobutyl acrylate, t-butyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid and alkyl esters of methacrylic acid such as t-butyl.

  Examples of unsaturated carboxylic acids and / or derivatives thereof include unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, acrylic acid and methacrylic acid; acids of unsaturated carboxylic acids such as maleic anhydride and itaconic anhydride Examples of anhydrides include ester compounds, amide compounds, imide compounds, and derivatives of unsaturated carboxylic acids such as metal salts.

The ethylenically unsaturated carboxylic acids may be used alone or in combination of two or more. In addition, these hydrolysates, for example, saponified ethylene-vinyl acetate copolymers obtained by hydrolysis of ethylene-vinyl acetate copolymers are also preferably used.

  Among the ethylenically unsaturated carboxylic acids, vinyl acetate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate are preferable, and vinyl acetate is more preferable.

  Further, as the ethylene / ethylenically unsaturated carboxylic acid copolymer, a polymer obtained by copolymerizing ethylene with glycidyl methacrylate or maleic anhydride is also preferable. The ethylene / ethylenically unsaturated carboxylic acid copolymer may further have other monomer units such as the above-mentioned α-olefin.

  The ethylene unit content in the ethylene / ethylenically unsaturated carboxylic acid copolymer is usually in the range of 1 to 99% by mass, preferably in the range of 1 to 50% by mass, and the content of the ethylenically unsaturated carboxylic acid unit. The amount is usually in the range of 1 to 99% by mass, preferably in the range of 50 to 99% by mass.

  Moreover, when the said ethylenically unsaturated carboxylic acid is unsaturated carboxylic acid and / or its derivative (s), it is preferable that the copolymerization ratio of ethylenically unsaturated carboxylic acid shall be in the range of 3-10 mass%.

  Melt flow rate of ethylene / ethylenically unsaturated carboxylic acid copolymer (conforms to MFR JIS K 7210: 1999), melt viscosity becomes too high, extrudability deteriorates, and mechanical strength is extremely reduced From the viewpoint of preventing it, it is preferably within a range of 0.01 to 100 g / 10 minutes, more preferably within a range of 0.1 to 40 g / 10 minutes, and further preferably 0.3 to 10 g. Within the range of / 10 minutes.

  As a method for producing an ethylene / ethylenically unsaturated carboxylic acid copolymer, generally, a tank reactor or a tubular reactor is used, in the presence of a radical generator, within a polymerization pressure range of 140 to 300 MPa, a polymerization temperature. Examples include a method of copolymerizing ethylene and an ethylenically unsaturated carboxylic acid under conditions in the range of 200 to 300 ° C. In order to adjust the melt flow rate, carbon such as hydrogen, methane, and ethane is used as a molecular weight regulator. Hydrogen is used. Further, a late transition metal complex catalyst or the like may be used as the homogeneous catalyst. Examples of the late transition metal complexes include US Pat. No. 5,866,663, US Pat. No. 5,955,555, JP-T 2007-517108, JP-A-9-302018, JP-A-9-302019, JP-A-10-195128, and the like. And the disclosed catalyst.

[Modified polyolefin resin]
As the crystalline polyolefin resin according to the present embodiment, a resin (modified polyolefin resin) modified by polymerizing a polar vinyl monomer or the like with respect to the polyolefin resin such as propylene resin or ethylene resin described above. Can be used.

Specifically, as a modified polyolefin resin,
(1) a modified polyolefin resin obtained by graft polymerization of a polar vinyl monomer to an olefin homopolymer;
(2) a modified polyolefin resin obtained by graft polymerization of a polar vinyl monomer to a copolymer of at least two olefins, and
(3) A modified polyolefin resin obtained by graft polymerizing a polar vinyl monomer to a block copolymer obtained by copolymerizing at least two olefins after homopolymerizing the olefin,
Etc. These modified polyolefin resins may be used alone or in combination of two or more.

  As a method for producing the modified polyolefin resin, for example, “Practical Polymer Alloy Design” (Fumio Ide, Industrial Research Committee (issued in 1996)), Prog. Polym. Sci. 24, 81-142 (1999), Japanese Patent Application Laid-Open No. 2002-308947, and the like, and any of a solution method, a bulk method, and a melt-kneading method may be used. Moreover, the manufacturing method which combined these methods may be sufficient.

  The polar vinyl monomer used in the modified polyolefin resin includes, in addition to the polar vinyl monomer described above in [Propylene-based resin], dehydrated unsaturated carboxylic acid in the step of grafting to polypropylene, such as citric acid and malic acid. And the like.

  Specifically, a modified polyolefin resin obtained by graft-polymerizing maleic anhydride to a polyolefin resin having a unit derived from ethylene and / or propylene as a main constituent unit of a polymer is more preferable as the modified polyolefin resin. preferable.

  The content of the unit derived from the polar vinyl monomer, which is a constituent unit of the modified polyolefin resin, is preferably in the range of 0.1 to 10% by mass from the viewpoint of mechanical strength such as impact strength. .

  Examples of other modified polyolefin resins include those obtained by reacting monomers (coupling agents) containing elements such as silicon, titanium, and fluorine, and polymers containing them with polyolefin resins.

[Additives contained in crystalline polyolefin resin]
The crystalline polyolefin resin according to the present embodiment may be blended with known additives as long as the effects of the present invention are not impaired. However, the amount of the additive in the crystalline polyolefin resin is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, based on 100 parts by mass of the crystalline polyolefin resin. It is preferably 3 parts by mass or less, more preferably 0.1 parts by mass or less, and particularly preferably 0.05 parts by mass or less from the viewpoint of suppressing a decrease in adhesive force. Moreover, it is preferable that the additive amount in crystalline polyolefin resin is 0.005 mass part or more with respect to 100 mass parts of crystalline polyolefin resin.

  When the amount of the additive exceeds 1 part by mass with respect to 100 parts by mass of the crystalline polyolefin-based resin, a decrease in adhesive force is likely to occur due to a bleed-out phenomenon over time. The smaller the amount of the additive, the better. These additives may be used alone or in combination of two or more.

  Examples of the additives include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, ultraviolet absorbers, light stabilizers, peroxide scavengers, hydroxylamines, lubricants, plasticizers, flame retardants, Nucleating agent, metal deactivator, antistatic agent, surfactant (including antifogging agent), pigment, filler, anti-blocking agent, processing aid, foaming agent, foaming aid, emulsifier, brightener, medium Coloring agents such as a summing agent, 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, and benzofuranones (US Pat. Nos. 4,325,853, 4,338,244, 5,175,312) No. 5216053, No. 5252643, No. 4316611, German Patent Publication No. 4316622, No. 4316876, European Patent Application Hirakidai 589839 JP, the 591102 JP etc.) may be added co-stabilizer such as indoline, a crosslinking agent or the like.

Examples of the phenol-based antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,6-di-t-butylphenol, 2- t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t- Butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-diocudadecyl-4-methylphenol, 2,4, 6-tricyclohexylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6 (1′-methylundecyl-1′-yl) phenol, 2,4-dimethyl-6- (1′-methylheptadecyl-1′-yl) phenol, 2,4-dimethyl-6- (1′- Alkyltriphenols such as methyltridecyl-1′-yl) phenol and mixtures thereof; 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2, Alkylthiomethylphenols such as 4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol and mixtures thereof; 2,6-di-t-butyl-4-methoxyphenol, 2, 5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2,6-diphenyl-4-octadecyloxypheno 2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyphenyl stearate, bis (3,5 Hydroquinones and alkylated hydroquinones such as -di-t-butyl-4-hydroxyphenyl) adipate and mixtures thereof; tocopherols such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof; 2'-thiobis (6-t-butylphenol), 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (3 -Methyl-6-t-butylphenol), 4,4'-thiobis (2-methyl-6-t-butylphenol), 4,4'- Hydroxylated thiodiphenyl ethers such as bis (3,6-di-t-amylphenol), 4,4 '-(2,6-dimethyl-4-hydroxyphenyl) disulfide; 2,2'-methylenebis (4-methyl- 6-t-butylphenol), 2,2′-methylenebis (4-ethyl-6-t-butylphenol), 2,2′-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol)], 2, 2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (4-methyl-6-nonylphenol), 2,2'-methylenebis (4,6-di-t-butylphenol), 2 , 2'-ethylidenebis (4,6-di-t-butylphenol), 2,2'-ethylidenebis (4-isobutyl-6-t-butylphenol) ), 2,2′-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2′-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4 ′. -Methylenebis (6-tert-butyl-2-methylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5) -Methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl) Til-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis-3′-tert-butyl-4′-hydroxyphenyl) butyrate], bis (3- t-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3′-t-butyl-2′-hydroxy-5′-methylbenzyl) -6-t-butyl-4-methyl Phenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-t-butyl-4-hydroxyphenyl) propane, 2,2- Bis (5-t-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5-t-butyl-4-hydroxy-) - methylphenyl) pentane, 2
-T-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,4-di-t-pentyl-6- [1- (2 -Hydroxy-3,5-di-t-pentylphenyl) ethyl] phenyl acrylate and mixtures thereof and the like, and alkylidene bisphenols and derivatives thereof; 3,5,3 ', 5'-tetra-t-butyl-4,4' -Dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tris (3,5-di-t-butyl-4-hydroxybenzyl) amine, bis (4-t-butyl-3- Hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide, isooctane O-, N- and S-benzyl derivatives such as di-3,5-di-t-butyl-4-hydroxybenzyl mercaptoacetate and mixtures thereof; dioctadecyl-2,2-bis (3,5-di- t-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-t-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecylmercaptoethyl-2,2-bis (3,5-di -T-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-t-butyl-4- Hydroxybenzylated malonate derivatives such as hydroxybenzyl) malonate and mixtures thereof; 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl- -Hydroxybenzyl) benzene, 1,4-bis (3,5-di-t-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3 Aromatic hydroxybenzyl derivatives such as 5-t-butyl-4-hydroxybenzyl) phenol and mixtures thereof; 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t- Butylanilino) -1,3,5-triazine, 2-n-octylthio-4,6-bis (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2-n- Octylthio-4,6-bis (4-hydroxy-3,5-di-t-butylphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-t-butyl- 4-phenoxy) -1,3 , 5-triazine, tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4 , 6-Tris (3,5-di-t-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 2,4,6-tris (3,5-di-t-butyl-4- Hydroxyphenylpropyl) -1,3,5-triazine, tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate, tris [2- (3 ′, 5′-di-t-butyl-4′-hydroxy) Cinnamoyloxy) ethyl] isocyanurate and mixtures thereof such as triazine derivatives; dimethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, die 3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-t-butyl-4-hydroxy- Benzylphosphonate derivatives such as 3-methylbenzylphosphonate, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoester and mixtures thereof; 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide Acylaminophenol derivatives such as octyl-N- (3,5-di-t-butyl-4-hydroxyphenyl) carbanate and mixtures thereof; β- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionic acid and methanol, ethanol, octanol, octadeca Diol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, Pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl- Esters with mono- or polyhydric alcohols such as 1-phospha-2,6,7-trioxabicyclo [2,2,2] octane and mixtures thereof; β- (5-t-butyl-4-hydroxy- 3-methylphenyl) propion And methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene Glycol, spiroglycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, Esters with mono- or polyhydric alcohols such as trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane and mixtures thereof; β- (3 , 5-Di Chlohexyl-4-hydroxyphenyl) propionic acid and methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol , Neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3- One such as thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane and mixtures thereof Or esters with polyhydric alcohols; 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis ( Hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2, 2] Esters with mono- or polyhydric alcohols such as kutan and mixtures thereof; N, N′-bis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionyl] hydrazine, N , N′-bis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionyl] hexamethylenediamine, N, N′-bis [3- (3 ′, 5′-di Β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid amides such as -t-butyl-4'-hydroxyphenyl) propionyl] trimethylenediamine and mixtures thereof.

  Further, for example, a composite type phenolic antioxidant having a unit having both a phenolic antioxidant mechanism and a phosphorus antioxidant mechanism in one molecule may be used.

Particularly preferable examples of the phenolic antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, and 2,4-dioctylthiomethyl-6- Methylphenol, 2,2'-thiobis (6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-) Butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol)], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (4,6-di-t-butylphenol), 2,2′-ethylidenebis (4,6-di) -T-butylphenol), 4,4'-methylenebis (6-t-butyl-2-methylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-butylidenebis ( 3-methyl-6-tert-butylphenol), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1 , 3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, ethylene glycol bis [3,3-bis-3′-t-butyl-4′-hydroxyphenyl) butyrate], 2 -T-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,4-di-t-pentyl-6- [1- (2 Hydroxy-3,5-di-tert-pentylphenyl) ethyl] phenyl acrylate, 2,4,6-tris (3,5-di-tert-butyl-4-phenoxy) -1,3,5-triazine, tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, bis (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, tris [2- (3 ′, 5 '-Di-t-butyl-4'-hydroxycinnamoyloxy) ethyl] isocyanurate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, di-n-octadecyl-3,5-di Tert-butyl-4-hydroxybenzylphosphonate, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoester, n-octade Sil-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, neopentanetetrayltetrakis (3,5-di-t-butyl-4-hydroxycinnamate), thiodiethylenebis (3,5-di-tert-butyl-4-hydroxycinnamate), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene 3,6-dioxaoctamethylene bis (3,5-di-t-butyl-4-hydroxycinnamate), hexamethylene bis (3,5-di-t-butyl-4-hydroxycinnamate), tri Ethylene glycol = bis (5-t-tyl-4-hydroxy-3-methylcinnamate), 3,9-bis [2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) Propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5 · 5] undecane, N, N′-bis [3- (3 ′, 5′-di-t-) Butyl-4′-hydroxyphenyl) propionyl] hydrazine, N, N′-bis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionyl] hexamethylenediamine and the like, These may be used alone or in combination of two or more.

  Examples of the sulfur antioxidant include dilauryl-3,3′-thiodipropionate, tridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, and distearyl-3. , 3′-thiodipropionate, lauryl stearyl-3,3′-thiodipropionate, neopentanetetrayltetrakis (3-laurylthiopropionate), and the like.

  Examples of the phosphorus antioxidant include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, Distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) ) Pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite , Tristearyl sorbitol trifo Phyto, tetrakis (2,4-di-t-butylphenyl) -4,4'-diphenylenediphosphonite, 2,2'-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite 2,2′-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, bis (2,4 -Di-t-butyl-6-methylphenyl) methyl phosphite, 2- (2,4,6-tri-t-butylphenyl) -5-ethyl-5-butyl-1,3,2-oxaphosphorinane 2,2 ′, 2 ″ -nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra-t-butyl-1,1′-biphenyl-2,2′-diyl) phosphite and their Mixture etc. And the like. Moreover, the phosphorus antioxidant described in JP-A-2002-69260 is also preferable.

  Particularly preferable examples of the phosphorus antioxidant include tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, bis (2 , 4-Di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl) -4-methylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-diphenylenediphosphonite, 2,2'-methylenebis (4,6-di-) t-butylphenyl) 2-ethylhexyl phosphite, 2,2′-ethylidenebis (4,6-di-t-butylphenol) ) Fluorophosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, 2- (2,4,6-tri-t-butylphenyl) -5-ethyl-5 Butyl-1,3,2-oxaphosphorinane, 2,2 ′, 2 ″ -nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra-t-butyl-1,1′-biphenyl- 2,2′-diyl) phosphite and the like, and these may be used alone or in admixture of two or more.

Examples of the ultraviolet absorber include phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, 4 -T-octylphenyl salicylate, bis (4-t-butylbenzoyl) resorcinol, benzoylresorcinol, hesisadecyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate, octadecyl-3', 5'-di Salicylates such as t-butyl-4'-hydroxybenzoate, 2-methyl-4,6-di-t-butylphenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate and mixtures thereof Derivatives; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-o Toxibenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2 ′, 4,4′-tetrahydroxybenzophenone and mixtures thereof, etc. 2- (2-hydroxybenzophenone derivative); 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3 ′, 5′-di-t-butyl-2′-hydroxyphenyl) benzotriazole, 2- (5 '-T-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (3-t-butyl-2-hydroxy-5-methyl) Phenyl) -5-chlorobenzotriazole, 2- (3′-s-butyl-2′-hydroxy-5′-t-butyl) Enyl) benzotriazole, 2- (2′-hydroxy-4′-octyloxyphenyl) benzotriazole, 2- (3 ′, 5′-di-t-amyl-2′-hydroxyphenyl) benzotriazole, 2- [ 2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-[(3′-t-butyl-2′-hydroxyphenyl) -5 ′-( 2-octyloxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2- [3′-t-butyl-5 ′-[2- (2-ethylhexyloxy) carbonylethyl] -2′-hydroxyphenyl] -5 -Chlorobenzotriazole, 2- [3'-t-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl] -5-chlorobenzotriazol 2- [3′-t-butyl-2′-hydroxy-5 ′-(2-methoxycarbonylethyl) phenyl] benzotriazole, 2- [3′-t-butyl-2′-hydroxy-5- (2 -Octyloxycarbonylethyl) phenyl] benzotriazole, 2- [3'-t-butyl-2'-hydroxy-5 '-[2- (2-ethylhexyloxy) carbonylethyl] phenyl] benzotriazole, 2- [2 -Hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzo Triazole, 2- (3′-dodecyl-2′-hydroxy-5′-methylphenyl) benzotriazole and 2- [3′-t-
A mixture of butyl-2′-hydroxy-5 ′-(2-isooctyloxycarbonylethyl) phenyl] benzotriazole, 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1 , 1,3,3-tetramethylbutyl) phenol, 2,2′-methylenebis [4-tert-butyl-6- (2H-benzotriazol-2-yl) phenol], poly (3-11) (ethylene glycol) ) And 2- [3′-t-butyl-2′-hydroxy-5 ′-(2-methoxycarbonylethyl) phenyl] benzotriazole, poly (3-11) (ethylene glycol) and methyl-3 -Condensate with [3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl] propionate, 2-ethylhexyl-3 -[3-t-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, octyl-3- [3-t-butyl-5- (5-chloro- 2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, methyl-3- [3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] 2- (2′-hydroxyphenyl) such as propionate, 3- [3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionic acid and mixtures thereof Examples include benzotriazole.

  Particularly preferable examples of the ultraviolet absorber include phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-. Hydroxybenzoate, 4-t-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3 ′ , 5'-Di-t-butyl-2'-hydroxyphenyl) benzoto Azole, 2- (5'-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (3-t-butyl-2 -Hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (3'-s-butyl-2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-4) '-Octyloxyphenyl) benzotriazole, 2- (3', 5'-di-t-amyl-2'-hydroxyphenyl) benzotriazole, 2- [2'-hydroxy-3 ', 5'-bis (α , Α-dimethylbenzyl) phenyl] -2H-benzotriazole and the like, and these may be used alone or in admixture of two or more.

Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ((2,2,6,6-tetramethyl-4-piperidyl) succinate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6) -Pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,6-tetramethyl) Ru-4-piperidyl) -2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1,2,2,6,6-pentamethyl-4) -Piperidyl decandioate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -1- [ 2- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2, 6,6-tetramethyl-4-piperidyl) amino-
N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxyl Rate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2 1,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol mixed esterified product; 1,2,3,4-butanetetrabonic acid and 2,2,6,6-tetramethyl-4-piperidinol and Mixed esterified product with 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy) Loxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5 · 5] undecane, 1,2,3,4-butanetetracarboxylic acid and 2,2, Mixed ester with 6,6-tetramethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane Compound, polycondensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, poly [(6-morpholino-1,3,5-triazine -2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)], poly [( -(1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl ((2,2,6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)], N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2 -Polycondensate with dibromoethane, N, N ', 4,7-tetrakis [4,6-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, N, N ′, 4-tris [4,6-bis (N-butyl-N- (2, 2,6,6-tetramethyl-4-piperidyl) amino) -1,3,5-triazine -2-yl] -4,7-diazadecane-1,10-diamine, N, N ′, 4,7-tetrakis [4,6-bis (N-butyl-N- (1,2,2,6, 6-pentamethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, N, N ′, 4-tris [4,6-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10- Hindered amine light stabilizers such as diamines and mixtures thereof, ethyl-α-cyano-β, β-diphenyl acrylate, isooctyl-α-cyano-β, β-diphenyl acrylate, methyl-α-carbomethoxycinnamate, methyl α -Cyano-β-methyl p-methoxycinnamate, butyl-α-cyano-β-methyl-p-methoxycinnamate, methyl-α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2- Acrylate light stabilizers such as methylindoline and mixtures thereof, nickel complexes of 2,2′-thiobis- [4- (1,1,3,3-tetramethylbutyl) phenol], nickel dibutyldithiocarbamate, monoalkyl Nickel-based light stabilizers such as nickel salts of esters, nickel complexes of ketoximes and mixtures thereof, 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy -5,5'-di-t-butylanilide, 2,2'-didodecyloxy-5,5'-di-t-butylanilide, -Ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-t-butyl-2'-ethoxyanilide, 2-ethoxy-5,4 ' -Oxamide light stabilizers such as di-t-butyl-2'-ethyloxanilide and mixtures thereof, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5 -Triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2,4-dihydroxyphenyl-4 , 6-Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-
Dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2 -Hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxy) Propoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl]- Examples include 2- (2-hydroxyphenyl) -1,3,5-triazine-based light stabilizers such as 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and mixtures thereof. It is.

  Further, particularly preferable examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl). Sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di -T-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) -2,2-bis (3,5-di − -Butyl-4-hydroxybenzyl) -2-butylmalonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -1- [2- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl Oxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6, 6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1 2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl Mixed esterified product of -4-piperidinol and 1-tridecanol, mixed esterified product of 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2, Mixed esterified product of 4,8,10-tetraoxaspiro [5.5] undecane, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-pipe Mixed esterified product of lysinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, dimethyl succinate and 1- ( 2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [(6-morpholino-1,3,5-triazine-2,4-diyl) (( 2,2,6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)], poly [(6- (1,1,1, 3,3-tetramethylbutyl) -1,3,5-triazine-2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2,2, 6,6-tetramethyl-4 Piperidyl) imino)], and the like, which may be used alone or in combination, respectively.

Examples of the metal deactivator include N, N′-diphenyloxamide, N-salicyl-N′-salicyloylhydrazine, N, N′-bis (salicyloyl) hydrazine, N, N′-bis ( 3,5-di-t-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bis Examples thereof include phenyl hydrazide, N, N′-bis (salicyloyl) oxalyl dihydrazide, N, N′-bis (salicyloyl) thiopropionyl dihydrazide, and mixtures thereof.

  Examples of the hydroxylamine include N, N-dibenzylhydroxyamine, N, N-diethylhydroxyamine, N, N-dioctylhydroxyamine, N, N-dilaurylhydroxyamine, and N, N-ditetradecylhydroxy. Examples thereof include amines, N, N-dihexadecylhydroxyamine, N, N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl-N-octadecylhydroxyamine, and mixtures thereof.

  Examples of the neutralizing agent include calcium stearate, zinc stearate, magnesium stearate, hydrotalcite (basic magnesium, aluminum, hydroxy, carbonate, hydrate), melamine, amine, polyamide, polyurethane, and mixtures thereof. Can be mentioned.

  Examples of the lubricant include aliphatic hydrocarbons such as paraffin and wax, higher aliphatic acids having 8 to 22 carbon atoms such as stearic acid, and higher aliphatic acid metals having 8 to 22 carbon atoms (Al, Ca, Mg, Zn) salt, aliphatic alcohol having 8 to 22 carbon atoms, polyglycol, ester of higher fatty acid having 4 to 22 carbon atoms and aliphatic monohydric alcohol having 4 to 18 carbon atoms, higher aliphatic having 8 to 22 carbon atoms Examples include amides, silicone oils, rosin derivatives, and the like. For example, erucic acid amide, oleic acid amide, ethylene bisstearylamide, erucylamide, dimethylpolysiloxane and the like can be mentioned.

  The antistatic agent may be any of a polymer type, an oligomer type, and a monomer type. Examples thereof include polyhydric alcohol fatty acid esters such as glycerin fatty acid esters, polyoxyethylene alkylamine mixed compositions, nonionic surfactants, and the like. Also, for example, alkyl diethanolamides, alkyl diethanol monoesters, lauryl diethanolamide, myristyl diethanolamide, palmityl diethanolamide, stearyl diethanolamide, alkyl diethanolamide monolaurate, alkyl diethanolamide monomyristic ester, Examples thereof include monopalmitic acid esters of alkyldiethanolamide, monostearic acid esters of alkyldiethanolamide, and the like.

Examples of the surfactant include cationic surfactants, anionic surfactants, amphoteric surfactants, and nonionic surfactants, and are not particularly limited, but are compatible with resins and heat stable. From the viewpoint of safety, a nonionic surfactant is preferably used. Specifically, sorbitan-based interfaces such as sorbitan monopalmitate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monomontanate, sorbitan monooleate, sorbitan fatty acid esters such as sorbitan dioleate and alkylene oxide adducts thereof Activator: glycerin monopalmitate, glycerin monostearate, diglycerin distearate, triglycerin monostearate, tetraglycerin dimontanate, glycerin monooleate, diglycerin monooleate, diglycerin sesquioleate, tetraglycerin Monooleate, hexaglycerin monooleate, hexaglycerin trioleate, tetraglycerin trioleate, tetraglycerin monolaurate, hexaglyceride Glycerin surfactants such as glycerin fatty acid esters and alkylene oxide adducts thereof such as polyethylene monolaurate; polyethylene glycol surfactants such as polyethylene glycol monopalmitate and polyethylene glycol monostearate; alkylene oxide adducts of alkylphenols; Esters of sorbitan / glycerin condensate and organic acid, polyoxyethylene (2 mol) stearylamine, polyoxyethylene (4 mol) stearylamine, polyoxyethylene (2 mol) stearylamine monostearate, polyoxyethylene (4 Mol) Polyoxyethylene alkylamines such as laurylamine monostearate and fatty acid esters thereof.

  Examples of the surfactant include fluorine compounds having a perfluoroalkyl group, ω-hydrofluoroalkyl group, etc. (especially fluorine surfactants), and silicone compounds having an alkylsiloxane group (especially silicone surfactants). Etc. Specific examples of the fluorosurfactant include “Unidyne DS-403”, “DS-406”, “DS-401” (trade name) manufactured by Daikin Industries, Ltd., and “Surflon” manufactured by Seimi Chemical Co., Ltd. KC-40 "(trade name) and the like, and examples of the silicone surfactant include" SH-3746 "(trade name) manufactured by Toray Dow Corning Silicon Co., Ltd.

  As the anti-blocking agent, fine particles having a spherical shape or a shape close thereto can be used regardless of inorganic type or organic type. Specific examples include calcium carbonate, silicon dioxide, polymethylsilsesquioxane, aluminum silicate salt, and a crosslinked polymethyl methacrylate.

  Examples of the nucleating agent include sorbitol nucleating agents, organophosphate nucleating agents, and polymer nucleating agents such as polyvinylcycloalkane. Specifically, sodium = 2, 2 '-Methylenebis (4,6-di-t-butylphenyl) phosphate, [phosphoric acid-2,2'-methylenebis (4,6-di-t-butylphenyl)] = dihydroxyaluminum, bis [phosphoric acid- 2,2′-methylenebis (4,6-di-t-butylphenyl)] hydroxyaluminum, tris [phosphate-2,2′-methylenebis (4,6-di-t-butylphenyl)] aluminum, sodium = Bis (4-tert-butylphenyl) phosphate, benzoic acid metal salts such as sodium benzoate, aluminum pt-butylbenzoate, 1,3: 2,4-bis (o-benzylidene) sol Tol, 1,3: 2,4-bis (o-methylbenzylidene) sorbitol, 1,3: 2,4-bis (o-ethylbenzylidene) sorbitol, 1,3-o-3,4-dimethylbenzylidene-2 , 4-o-benzylidene sorbitol, 1,3-o-benzylidene-2,4-o-3,4-dimethylbenzylidene sorbitol, 1,3: 2,4-bis (o-3,4-dimethylbenzylidene) sorbitol 1,3-op-chlorobenzylidene-2,4-o-3,4-dimethylbenzylidene sorbitol, 1,3-o-3,4-dimethylbenzylidene-2,4-op-chlorobenzylidene sorbitol 1,3: 2,4-bis (op-chlorobenzylidene) sorbitol and mixtures thereof, rosin alkali metal salts, alkaline earth metal salts, The lithium salt of rosin, sodium salts, potassium salts, calcium salts, magnesium salts, compounds such as aluminum salts. Moreover, polymer nucleating agents such as polyvinylcycloalkane are also used. These may be used alone or in combination of two or more.

  Examples of the filler include calcium carbonate, silicate, glass fiber, asbestos, talc, kaolin, mica, barium sulfate, carbon black, carbon fiber, zeolite, and mixtures thereof, and these are used alone. Alternatively, two or more kinds may be used in combination.

  Examples of the foaming agent and foaming aid include azocarboxylic acid derivatives such as azodicarboxylic acid amide, N.I. Examples thereof include nitroso compounds such as N'-dinitrosopentamethylenetetramine, and sulfonyl hydrazide compounds such as p, p'-oxybisbenzenesulfonyl hydrazide.

Examples of the crosslinking agent include dicumyl peroxide, t-butylcumyl peroxide, 3,5-dimethyl-2,5- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di -(T-butyl-peroxy) hexane-3,4,4'-bis (t-butylperoxy) diisopropylbenzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, etc. Is mentioned. Among these additives, phenol antioxidants, phosphorus antioxidants, ultraviolet absorbers, hindered amine light stabilizers, peroxide scavengers and neutralizers are preferably used.

  The addition method of the said additive will not be specifically limited if it is a method which can disperse | distribute uniformly, It can add by a normal method. Specifically, the addition method described in the above-mentioned “(A) Additive for phase difference control” can be employed.

[Catalyst residue in crystalline polyolefin resin]
In the crystalline polyolefin resin according to the present embodiment, a catalyst residue at the time of polymerization usually remains. It is preferable that the catalyst residue is small because appearance defects such as fish eyes when formed into a film are reduced. Moreover, the thermal deterioration suppression effect at the time of protective film manufacture is also produced.

  The amount of catalyst residue is preferably 0.02 parts by mass or less, more preferably 0.01 parts by mass or less, and particularly preferably 0.005 parts by mass or less with respect to 100 parts by mass of the crystalline polyolefin resin. In addition, the amount of silicon in the catalyst residue is preferably 0.01 parts by mass or less and more preferably 0.005 parts by mass or less with respect to 100 parts by mass of the crystalline polyolefin resin. The amount of the catalyst residue and the amount of silicon in the catalyst residue can be quantified by the method described below.

<Measurement of catalyst residue>
100 g of crystalline polyolefin resin sample is precisely weighed and incinerated in an electric furnace at 800 ° C. The ashed sample is precisely weighed and the amount of catalyst residue can be determined by the following formula.
Catalyst residue (mass ppm) = (crystalline polyolefin resin after ashing (g) / crystalline polyolefin resin before ashing (g)) × 10 ⁶
<Measurement of silicon content>
Take 1 g of crystalline polyolefin resin sample in a platinum dish, add 1 ml of sulfuric acid, carbonize with a hot plate, and then incinerate at 550 ° C. in an electric furnace. To the residue after ashing, 0.5 g of sodium carbonate was added, melted with a burner, adjusted to 50 ml with ultrapure water, and then IICP-AES (inductively coupled plasma emission spectrometer model: Optima 3000) manufactured by PerkinElmer. The amount of silicon can be quantified.

  Further, as the retardation film, the residue when incinerated by the method according to the above <Measurement of catalyst residue> is 0.05 parts by mass or less, further 0.02 parts by mass with respect to 100 parts by mass of the retardation film. Hereinafter, it is particularly preferably 0.001 part by mass or less.

(C) Retardation film The retardation film which concerns on this Embodiment has at least one layer containing crystalline polyolefin resin mentioned above and the additive for phase difference control. That is, in the present embodiment, a resin composition containing the above-described crystalline polyolefin resin and a retardation control additive is formed into a film to obtain a raw film, and the raw film is stretched to obtain a retardation. Used as a film. The retardation film may be, for example, a single layer film made of the resin composition, or a multilayer film having at least one layer made of the resin composition. The multilayer film can be, for example, a multilayer film having a layer made of the resin composition in at least one outermost layer.

The content of the crystalline polyolefin resin in the retardation film according to the present embodiment is not particularly limited, but from the viewpoint of effectively exhibiting the effects of the present invention, the total mass of the layer is 100 parts by mass. Usually, it is 50 parts by mass or more, more preferably 70 parts by mass or more, and more preferably 90 parts by mass or more.

  The components other than the crystalline polyolefin resin and the retardation control additive in the retardation film are not particularly limited, and are used as known retardation films such as an amorphous polyolefin resin, for example. Resin or the like can be used.

  The retardation film may be provided with functions such as an antireflection function, an antiglare function, an anti-scratch function, an antifouling function, an ultraviolet protection function, an antistatic function, and the like by a known technique, and has an adhesive layer. It may be.

  The antireflection function refers to a function of suppressing reflection by external light in a polarizing plate, a laminated optical member, and a liquid crystal display device. Specifically, it means a function of setting the reflectance in the wavelength region of visible light to preferably 2% or less, more preferably 1% or less, and still more preferably 0.2% or less. Such reflection of external light reduces the contrast of the screen display and makes it difficult to see the screen. Such an antireflection function can be imparted, for example, by forming an antireflection layer on the film surface.

  The antiglare function refers to a function of suppressing an image from being reflected by reflection of external light in a polarizing plate, a laminated optical member, and a liquid crystal display device. Specifically, as an index of the antiglare function, for example, a value of glossiness (gloss) is used, which means a function of setting the gloss at an incident angle of 60 ° to 100 or less, preferably 60 or less. Such image reflection due to reflection of external light makes it difficult to see the image display. Since the reflection is based on an image formed by regular reflection, the reflection can be suppressed by scattering the reflected light. For example, such an antiglare function can be imparted by forming an antiglare layer on the film surface.

  The scratch preventing function refers to a function of suppressing scratches on the screen in polarizing plates, laminated optical members, and liquid crystal display devices. Specifically, the pencil hardness symbol in the pencil scratch test (JIS K5400) means a function of 2H or more, preferably 4H or more, more preferably 5H or more. This function can be imparted by forming a hard coat layer on the outermost surface or reducing the friction coefficient.

  The antifouling function refers to a function of suppressing smudges such as fingerprints on the screen in polarizing plates, laminated optical members, and liquid crystal display devices. Specifically, it means a function of making the contact angle with water 80 ° or more, more preferably 100 ° or more. This function can be imparted by forming a water repellent layer using a silicon compound or a fluorine compound on the outermost surface.

  The ultraviolet ray preventing function refers to a function of making it difficult for ultraviolet rays to enter the polarizer and the liquid crystal and suppressing the optical deterioration of the polarizer and the liquid crystal in the polarizing plate, the laminated optical member, and the liquid crystal display device. Specifically, as an index of the ultraviolet ray prevention function, it means a function of setting the light transmittance at a wavelength of 380 nm or less to 10% or less and the light transmittance at a wavelength of 400 nm to 80% or less (preferably 70% or less). This function can be imparted by using an ultraviolet absorber or an ultraviolet reflector.

The antistatic function refers to a function of preventing dust or the like from being attached to the polarizing plate, the laminated optical member, or the liquid crystal display device, or preventing the circuit from being damaged by discharging. Specifically, it means a function of making the surface resistance value 10 ¹² Ω / □ or less, preferably 10 ¹¹ Ω / □ or less, more preferably 10 ¹⁰ Ω / □ or less. This function can be imparted by forming an antistatic layer on the surface or inside.

  The method for producing the raw film is not particularly limited, such as an extrusion molding method from a molten resin, a solvent casting method in which a resin dissolved in an organic solvent is cast on a flat plate, and the solvent is removed to form a film. It can be produced by a conventionally known method.

  In terms of cost, an extrusion molding method from a molten resin is excellent, and a T-die molding method, an inflation molding method and the like are preferably used. When the retardation film is a multilayer film, a multilayer T-die molding method, a multilayer inflation molding method, an extrusion laminate molding method, a sand laminate molding method, a dry laminate molding method, a wet laminate molding method, a hot melt laminate molding method, etc. are preferable. Used.

  In the T-die molding method and the multilayer T-die molding method, a film having a small in-plane retardation can be obtained by reducing the stress applied to the film as much as possible by a method such as an air chamber, an air knife, or electrostatic pinning. . Further, in the case of a cooling method using a soft nip method such as a flex roll or a steel belt method, the transparency can be improved.

[Saturated water content and amount of transpiration when the molten resin is extruded]
In the production of the retardation film, particularly when a molten resin extrusion molding method is performed, the transpiration product during processing adversely affects film formation. When performing extrusion molding from a molten resin, the saturated water absorption at 23 ° C. of the crystalline polyolefin resin or the like is preferably 1% or less, more preferably 0.5% or less, and particularly preferably 0.1% or less. Also, the amount of transpiration at 180 ° C. is preferably 1% or less, more preferably 0.5% or less, and particularly preferably 0.1% or less. The amount of the transpiration product of the crystalline polyolefin resin can be reduced by heating and drying such as hot aeration with air or inert gas.

(Extrusion molding method)
The method for producing the raw film will be described in detail below, taking as an example a case where a propylene-based resin is used as the crystalline polyolefin-based resin and the extrusion molding is performed by a T-die molding method (multilayer T-die molding method). .

  In the T-die molding method, a resin composition containing a propylene-based resin is melt-kneaded by rotation of a screw in an extruder and extruded from a T-die into a sheet shape. The temperature of the extruded molten sheet is in the range of about 180 to 300 ° C. If the temperature of the molten sheet at this time is lower than 180 ° C., the spreadability is not sufficient, the thickness of the obtained film becomes non-uniform, and there is a possibility that the film has a phase difference unevenness. Further, when the temperature exceeds 300 ° C., the resin is likely to be deteriorated or decomposed, and bubbles may be generated or carbides may be contained in the sheet.

  The extruder may be a single screw extruder or a twin screw extruder. For example, in the case of a single screw extruder, L / D, which is the ratio of the screw length L to the diameter D, is about 24 to 36, the space volume of the screw groove in the resin supply unit, and the space of the screw groove in the resin metering unit A compression ratio that is a ratio to the volume (the former / the latter) is about 1.5 to 4, and a screw of a full flight type, a barrier type, or a type having a Maddock type kneading portion can be used.

  A barrier having an L / D in the range of 28 to 36 and a compression ratio in the range of 2.5 to 3.5 from the viewpoint of suppressing deterioration and decomposition of the propylene-based resin and the like and uniformly melting and kneading. It is preferred to use a type of screw.

Moreover, in order to suppress deterioration and decomposition | disassembly of propylene-type resin etc. as much as possible, it is preferable to make the inside of an extruder into nitrogen atmosphere or a vacuum. Furthermore, in order to remove the volatile gas generated when the propylene-based resin or the like deteriorates or decomposes, it is also preferable to provide an orifice of 1 mmφ to 5 mmφ at the tip of the extruder to increase the resin pressure at the tip of the extruder. Increasing the resin pressure at the leading end of the extruder by means of the orifice means increasing the back pressure at the leading end, thereby improving the stability of extrusion. The diameter of the orifice to be used is more preferably 2 mmφ or more and 4 mmφ or less.

The T-die used for extrusion preferably has no fine steps or scratches on the resin flow path surface, and its lip portion is plated or coated with a material having a low coefficient of friction with the molten resin composition. Further, it is preferable to have a sharp edge shape in which the lip tip is polished to 0.3 mmφ or less. Examples of the material having a small friction coefficient include tungsten carbide type and fluorine type special plating. By using such a T-die, it is possible to suppress the generation of eyes and simultaneously suppress the die line, so that a resin film having excellent appearance uniformity can be obtained. In the T-die, the manifold has a coat hanger shape and preferably satisfies the following condition (1) or (2), and more preferably satisfies the condition (3) or (4).
When the lip width of the T die is less than 1500 mm: T die thickness direction length> 180 mm (1) When the T die lip width is 1500 mm or more: T die thickness direction length> 220 mm (2) T die When the lip width is less than 1500 mm: T-die height length> 250 mm (3) When the T-die lip width is 1500 mm or more: T-die height direction length> 280 mm (4)
By using a T die that satisfies such conditions, the flow of the molten resin composition inside the T die can be adjusted, and the lip portion can be extruded while suppressing thickness unevenness. A retardation film having excellent thickness accuracy and a more uniform retardation can be obtained.

  From the viewpoint of suppressing extrusion fluctuation of the resin composition, it is preferable to attach a gear pump via an adapter between the extruder and the T die. In addition, it is preferable to attach a leaf disk filter to remove foreign substances in the resin composition.

  The molten sheet extruded from the T-die is between a metal cooling roll (also referred to as a chill roll or a casting roll) and a touch roll including an elastic body that presses and rotates in the circumferential direction of the metal cooling roll. A desired film can be obtained by clamping and solidifying by cooling. In this case, the touch roll may be one in which an elastic body such as rubber is directly on the surface, or may be one in which the surface of the elastic body roll is covered with an outer cylinder made of a metal sleeve. When a touch roll whose surface is covered with an outer cylinder made of a metal sleeve is used, cooling is usually performed by directly sandwiching a molten sheet of the resin composition between the metal cooling roll and the touch roll. On the other hand, in the case of using a touch roll whose surface is an elastic body, a biaxially stretched film of a thermoplastic resin may be interposed between the molten sheet of the resin composition and the touch roll to sandwich the pressure.

  When the molten sheet of the resin composition is cooled and solidified by being sandwiched between the cooling roll and the touch roll as described above, both the cooling roll and the touch roll have their surface temperatures lowered, and the molten sheet is It needs to be cooled quickly. Specifically, the surface temperature of both rolls is adjusted within the range of 0 ° C. or higher and 30 ° C. or lower. When these surface temperatures exceed 30 ° C., it takes time to cool and solidify the molten sheet, so that the crystal component in the propylene-based resin grows, and the resulting film is inferior in transparency. On the other hand, when the surface temperature of the roll is lower than 0 ° C., the surface of the metal cooling roll is dewed and water droplets adhere to the surface, which tends to deteriorate the appearance of the film.

Since the surface state of the metal cooling roll to be used is transferred to the surface of the resin film, there is a possibility that the thickness accuracy of the resulting raw film is lowered when the surface is uneven. Therefore, it is preferable that the surface of the metal cooling roll is in a mirror surface state as much as possible. Specifically, the roughness of the surface of the metal cooling roll is preferably 0.3 S or less, expressed in the standard sequence of the maximum height, and further within the range of 0.1 S to 0.2 S. Is more preferable.

  As for the touch roll forming the nip portion with the metal cooling roll, the surface hardness of the elastic body is in the range of 65 to 80 as a value measured by a spring type hardness test (A type) defined in JIS K 6301. It is preferably within the range, and more preferably within the range of 70-80. By using a rubber roll having such a surface hardness, it becomes easy to maintain a uniform linear pressure applied to the molten sheet, and a bank of the molten sheet (resin pool) is provided between the metal cooling roll and the touch roll. ) Can be easily formed into a film.

  The pressure (linear pressure) when sandwiching the molten sheet is determined by the pressure for pressing the touch roll against the metal cooling roll. The linear pressure is preferably in the range of 50 N / cm to 300 N / cm, and more preferably in the range of 100 N / cm to 250 N / cm. By setting the linear pressure within the above range, it becomes easy to produce a raw film while maintaining a constant linear pressure without forming a bank.

  When sandwiching a biaxially stretched film of a thermoplastic resin together with a molten sheet of a resin composition between a metal cooling roll and a touch roll, the thermoplastic resin constituting the biaxially stretched film is composed of a propylene resin and Any resin that does not strongly heat-seal can be used. Specific examples include polyester, polyamide, polyvinyl chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and polyacrylonitrile. Among these, polyesters that have little dimensional change due to humidity, heat, and the like are most preferable. In this case, the thickness of the biaxially stretched film is usually in the range of about 5 to 50 μm, and preferably in the range of 10 to 30 μm.

  In the above method, the distance (air gap) from the lip of the T die to the pressure between the metal cooling roll and the touch roll is preferably 200 mm or less, and more preferably 160 mm or less. The molten sheet extruded from the T-die is stretched between the lip and the roll, and orientation is likely to occur. By shortening the air gap as described above, a film having a smaller orientation can be obtained. The lower limit value of the air gap is determined by the diameter of the metal cooling roll to be used, the diameter of the touch roll, and the tip shape of the lip to be used, and is usually 50 mm or more.

  The processing speed when producing the raw film by the above method is determined by the time required for cooling and solidifying the molten sheet. When the diameter of the metal cooling roll to be used is increased, the distance at which the molten sheet is in contact with the cooling roll becomes longer, so that production at a higher speed is possible.

  The molten sheet sandwiched between the metal cooling roll and the touch roll is cooled and solidified by contact with the roll. And after slitting an edge part as needed, it is wound up by a winder and becomes a film. Under the present circumstances, in order to protect the surface until it uses a film, you may wind up in the state which bonded the surface protection film which consists of another thermoplastic resin to the single side | surface or both surfaces. When a molten sheet of propylene resin is sandwiched between a metal cooling roll and a touch roll together with a biaxially stretched film made of a thermoplastic resin, the biaxially stretched film is used as one surface protective film. You can also.

  The raw film for retardation film according to the present embodiment can be produced by the method as described above.

In the above description, the case where a propylene resin is used as the crystalline polyolefin resin has been described, but the scope of the present invention is not limited thereto. Even other crystalline polyolefin resins such as ethylene resins can be molded in the same manner as propylene resins by appropriately changing molding conditions and the like.

  In the above description, the case of molding by the T-die molding method (multilayer T-die molding method) has been described, but the scope of the present invention is not limited to this. Even other extrusion molding methods such as the inflation molding method and solvent casting methods can be molded in substantially the same manner as the T-die molding method by appropriately changing the molding conditions and the like.

  In the above description, the method for adding the retardation control additive is not mentioned, but the addition method is not particularly limited as long as the retardation control additive can be uniformly dispersed in the raw film. . For example, in the polymerization step for producing the crystalline polyolefin-based resin, a phase difference controlling additive is added to the polymerization reaction mixture in the middle of the polymerization reaction or immediately after the completion of the polymerization reaction, so that the resin composition before melting is added to the resin composition. The phase difference controlling additive may be dispersed uniformly, or after the phase difference controlling additive is added while melt kneading the resin composition not containing the phase difference controlling additive, and further melt kneaded. You may disperse | distribute the additive for phase difference control uniformly.

[Stretching]
A retardation film can be obtained by stretching the original film for retardation film obtained as described above.

  In the present embodiment, since the raw film contains a crystalline polyolefin resin and a retardation control additive, when the raw film is stretched, the retardation control additive acts and stretches. The amount of change in the phase difference with respect to the stress applied sometimes becomes small, and the deviation of the phase difference of the film can be suppressed.

  As the stretching method, conventionally known stretching methods can be employed, and specific examples include longitudinal stretching, lateral stretching, sequential biaxial stretching, and simultaneous biaxial stretching. In the case of sequential biaxial stretching, the stretching may be performed by any of the method of performing longitudinal stretching and then performing transverse stretching, or the method of performing longitudinal stretching after performing lateral stretching first. Hereinafter, sequential biaxial stretching will be described as an example.

<Sequential biaxial stretching (longitudinal)>
Examples of the longitudinal stretching method include a method of stretching a raw film by a difference in rotational speed between two or more rolls, and a long span stretching method. The long span stretching method is a method of stretching by using a longitudinal stretching machine having two pairs of nip rolls and an oven between them and heating the raw film in the oven by a difference in rotational speed between the two pairs of nip rolls. Since a retardation film having high optical uniformity can be obtained, the long span longitudinal stretching method is more preferable. In particular, it is preferable to use an air floating oven.

  The air floating type oven has a structure in which hot air can be blown from both the upper nozzle and the lower nozzle onto both sides of the original film when the original film is introduced into the oven. In the oven, a plurality of upper nozzles and lower nozzles are alternately arranged in the film flow direction. Stretching is performed in the oven so that the raw film does not come into contact with either the upper nozzle or the lower nozzle.

  In this case, the stretching temperature (that is, the temperature of the atmosphere in the oven) is preferably in the range of 90 ° C. or more and the melting point or less of the propylene resin. When the oven is divided into two or more zones, the temperature setting of each zone may be the same or different.

Although the longitudinal draw ratio is not limited, it is usually in the range of 1.01 to 2 times, and since a retardation film that is superior in optical uniformity is obtained, it is in the range of 1.05 to 1.8 times. More preferably.

<Sequential biaxial stretching (horizontal)>
Examples of the transverse stretching method include a tenter method in which the original film having both ends fixed with a chuck or the like is stretched in an oven with a wide chuck interval. The transverse draw ratio is usually in the range of 2 to 10 times, and more preferably in the range of 4 to 7 times from the viewpoint that the obtained retardation film has high optical uniformity. In particular, the following steps (i) to (iii),
(I) A step of preheating the raw film or the longitudinally stretched film at a preheating temperature equal to or higher than the melting point of the propylene-based resin constituting the film;
(Ii) stretching the preheated film in the transverse direction at a stretching temperature lower than the preheating temperature;
(Iii) a step of heat-setting the film stretched in the transverse direction;
It is preferable to perform transverse stretching through the steps.

  When transverse stretching is performed by the tenter method, it is preferable to use an apparatus in which the oven temperatures of the zone for performing the preheating step, the zone for performing the stretching step, and the zone for performing the heat setting step can be independently adjusted. By performing transverse stretching under the above conditions, a retardation film having excellent axial accuracy and a uniform retardation can be obtained.

  The pre-heating step for transverse stretching is a step installed before the step of stretching the film in the width direction, and is a step of heating the film to a temperature high enough to stretch the film. Here, the preheating temperature in the preheating step means the temperature of the atmosphere in the zone where the oven preheating step is performed, and is a temperature equal to or higher than the melting point of the polypropylene resin of the film to be stretched. The preheating temperature greatly affects the axial accuracy of the obtained retardation film, and a uniform retardation cannot be achieved in the obtained retardation film at a preheating temperature lower than the melting point.

  The preheat process residence time of the stretched film is preferably in the range of 30 to 120 seconds. If the residence time in this preheating process is less than 30 seconds, stress is dispersed when the film is stretched in the stretching process, which may adversely affect the uniformity of the retardation film axis and retardation. If the residence time exceeds 120 seconds, the film may receive heat more than necessary, and the film may partially melt and draw down (drop down). The preheating step residence time is more preferably in the range of 30 to 60 seconds.

  The stretching process of lateral stretching is a process of stretching the film in the width direction. The stretching temperature in this stretching process (which means the temperature of the atmosphere in the zone where the oven stretching process is performed) is lower than the preheating temperature. By stretching the preheated film at a temperature lower than that in the preheating step, the film can be stretched uniformly. As a result, a retardation film excellent in uniformity of the optical axis and retardation is obtained. The stretching temperature is preferably 5 to 20 ° C lower than the preheating temperature in the preheating step, and more preferably 7 to 15 ° C.

  The heat setting step of transverse stretching is a step of passing the film through an atmosphere at a predetermined temperature in an oven while maintaining the film width at the end of the stretching step. In order to effectively improve the stability of optical properties such as phase difference and optical axis of the film, the heat setting temperature is from 5 ° C. lower than the stretching temperature in the stretching step to 30 ° C. higher than the stretching temperature. It is preferable to be within the range.

The step of transverse stretching may further include a heat relaxation step. In the tenter method, this step is usually performed in a thermal relaxation zone that is provided between the stretching zone and the heat setting zone and the temperature can be set independently from the other zones. Specifically, in the thermal relaxation, after the film is stretched to a predetermined width in the stretching process, the chuck interval is narrowed by several% (usually within a range of 0.5 to 7%), and unnecessary strain is reduced. It is done by removing.

  In the above description, the case where the film is stretched by sequential biaxial stretching has been described, but the scope of the present invention is not limited to this. Even in the case of uniaxial stretching or simultaneous biaxial stretching, a retardation film can be similarly produced by applying conventionally known molding conditions.

  In the above description, the case where a propylene resin is used as the crystalline polyolefin resin has been described. However, the scope of the present invention is not limited to this. Even other crystalline polyolefin resins such as ethylene resins can be stretched in the same manner as propylene resins by applying conventionally known stretching conditions.

  In the description of the present embodiment described above, the case where the raw film includes a crystalline polyolefin-based resin has been described. However, the present invention is not limited to this. For example, instead of the crystalline polyolefin-based resin, a raw film containing only another resin such as an amorphous polyolefin-based resin and a retardation control additive may be used. If the raw film contains the above-described retardation control additive, substantially the same effects as those of the present embodiment can be obtained.

  However, when the crystalline polyolefin-based resin is included as in this embodiment, the amount of change in retardation with respect to stretching in the case of not containing the retardation control additive is large, and thus the effect is particularly great.

[Physical properties of retardation film]
Although the retardation required for the retardation film according to the present embodiment varies depending on the type of liquid crystal display device in which the retardation film is incorporated, the required in-plane retardation R ₀ is usually in the range of 30 to 300 nm. . When used in a vertical alignment mode liquid crystal display described later, from the viewpoint of excellent viewing angle characteristics, the in-plane retardation R ₀ is in the range of 40 to 70 nm, and the thickness direction retardation R _th is 90 to 230 nm. It is preferable to be within the range.

  The thickness of the retardation film is usually in the range of 10 to 100 μm, and preferably in the range of 10 to 60 μm. A retardation film having a desired retardation can be obtained by controlling the stretching ratio when producing the retardation film and the thickness of the retardation film to be produced.

  Since the retardation film according to the present embodiment has at least one layer containing a crystalline polyolefin-based resin and a retardation control additive, the retardation in the film plane (in the plane of 500 mm width × 500 mm length) The difference between the maximum value and the minimum value is 10 nm or less, and the optical axis is in the range of −1 ° to + 1 ° when the optical axis in the width direction of the film is 500 mm, and the optical uniformity is high. It is easy to make a retardation film.

  In addition, the retardation film according to the present embodiment is not limited in thickness, but is set, for example, within a range of about 5 to 1000 μm, preferably within a range of 10 μm to 500 μm, more preferably 15 μm to 150 μm. It can be set within the following range. As a matter of course, these thicknesses can be appropriately changed depending on the application.

Furthermore, in the retardation film according to the present embodiment, the number of foreign matters having a diameter of 0.1 mm or more in the film is preferably 0.1 pieces / m ² or less. The number of foreign substances having a diameter of 0.1 mm or more in the film is more preferably 0.01 pieces / m ² or less.

In order to make the number of foreign substances in the above range, it is preferable to filter small foreign substances with a polymer filter disposed between the extruder and the die and to extrude the molten film from the die. Place breaker plate or screen changer and gear pump in this order, filter large foreign matter with screen arranged on breaker plate or screen changer, filter small foreign matter with polymer filter through gear pump Is preferred.

In order to reduce the number of foreign matters having a diameter of 0.1 mm or more in the film to 0.1 pieces / m ² or less, filtration accuracy can be achieved by using a polymer filter having a range of 3 to 80 μm.

  Here, one embodiment of the polymer filter is shown in FIG. As shown in FIG. 1, the polymer filter is a leaf disc filter 2 made by laminating and sintering a nonwoven fabric of metal fine fibers so that the filtration accuracy sequentially increases from the upstream side to the downstream side. The filtration area is adjusted by attaching a plurality of pieces to the center post 3 disposed in the housing 1 so that the foreign matter is most efficiently filtered. The highest filtration accuracy is, for example, 3 to 80 μm. Is. If the filtration accuracy is lower than the above range, the effect of reducing foreign matter will be low, and if the filtration accuracy is higher than the above range, the back pressure will be too high and a very large filtration area will be required, so the number of leaf discs will be extremely There is a tendency that the residence time in the polymer filter becomes long, such as an increase in the diameter or the diameter of the leaf disk, and the thermal degradation easily occurs, and the clogging with foreign substances tends to become severe.

  Moreover, it is preferable that the retardation film which concerns on this embodiment is excellent in transparency. Transparency can be evaluated by HAZE measurement as described in JIS K7136.

  The total HAZE of the retardation film according to this embodiment is preferably 10% or less, more preferably 5% or less, still more preferably 2% or less, and particularly preferably 1% or less. Of the total HAZE, the part derived from the inside of the film is called internal HAZE. The internal HAZE of the retardation film according to this embodiment is preferably 3% or less, more preferably 1% or less, still more preferably 0.5% or less, and particularly preferably 0.2% or less. Of course, this is not the case when the retardation film has an antiglare function or the like.

(D) Polarizing plate In the polarizing plate according to the present embodiment, the above-described retardation film is laminated on at least one surface of a polarizer.

[Polarizer]
The above-mentioned polarizer is obtained by adsorbing and orienting a dichroic dye on a polyvinyl alcohol-based resin film so as to obtain predetermined polarization characteristics. As the dichroic dye, iodine or a dichroic organic dye is used. Specific examples of the polarizer include an iodine polarizing film in which iodine is adsorbed and oriented on a polyvinyl alcohol resin film, and a dye polarizing film in which a dichroic organic dye is adsorbed and oriented on a polyvinyl alcohol resin film.

  The polyvinyl alcohol resin can be obtained by saponifying a polyvinyl acetate resin. Examples of the polyvinyl acetate resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and a copolymer with vinyl acetate and other monomers copolymerizable therewith.

  Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, and unsaturated sulfonic acids.

  The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal modified with aldehydes, polyvinyl acetal, polyvinyl butyral, and the like can be used.

  The polarizing plate is usually a humidity adjusting step for adjusting the moisture of the polyvinyl alcohol-based resin film, a step for uniaxially stretching the polyvinyl alcohol-based resin film, and the dichroic pigment by dyeing the polyvinyl alcohol-based resin film with a dichroic pigment. The process of adsorbing, the process of treating the polyvinyl alcohol resin film with the dichroic dye adsorbed and oriented with the boric acid aqueous solution, the washing process of washing off the boric acid aqueous solution, and the dichroic dye being adsorbed and oriented by these steps It is manufactured through a step of bonding a retardation film to a uniaxially stretched polyvinyl alcohol resin film.

  Uniaxial stretching may be performed before dyeing, may be performed during dyeing, or may be performed during boric acid treatment after dyeing. Moreover, you may uniaxially stretch in these several steps. For uniaxial stretching, rolls having different peripheral speeds may be uniaxially stretched or uniaxially stretched using a hot roll. Moreover, the dry-type extending | stretching which extends | stretches in air | atmosphere may be sufficient, and the wet extending | stretching which extends | stretches in the state swollen with the solvent may be sufficient. The draw ratio is usually about 4 to 8 times. Moreover, the thickness of a polyvinyl alcohol-type polarizer can be about 5-50 micrometers, for example.

〔Polarizer〕
For adhesion between the polarizer and the retardation film, for example, an adhesive containing an epoxy resin, a urethane resin, a cyanoacrylate resin, an acrylamide resin, or the like can be used. A preferable adhesive from the viewpoint of thinning the adhesive layer includes a water-based adhesive, that is, an adhesive in which an adhesive component is dissolved in water or an adhesive in which water is dispersed. Another preferred adhesive is a solventless adhesive, specifically, an adhesive that forms a layer of adhesive by reacting and curing a monomer or oligomer by heating or irradiation with active energy rays.

  Hereinafter, the water-based adhesive will be described. Examples of the adhesive component that can be a water-based adhesive include water-soluble crosslinkable epoxy resins and urethane resins.

  Examples of water-soluble crosslinkable epoxy resins include polyamides obtained by reacting epichlorohydrin with polyamide polyamines obtained by reacting polyalkylene polyamines such as diethylenetriamine and triethylenetetramine with dicarboxylic acids such as adipic acid. An epoxy resin is mentioned. Examples of such commercially available polyamide epoxy resins include “Smiles Resin 650” and “Smiles Resin 675” (both trade names) sold by Sumika Chemtex Co., Ltd.

  When a water-soluble epoxy resin is used as the adhesive component, it is preferable to mix other water-soluble resins such as a polyvinyl alcohol-based resin in order to further improve coatability and adhesiveness. Polyvinyl alcohol resins include partially saponified polyvinyl alcohol and fully saponified polyvinyl alcohol, as well as modified polyvinyl alcohol such as carboxyl group-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, methylol group-modified polyvinyl alcohol, and amino group-modified polyvinyl alcohol. Alcohol-based resins may be used. Among these, a saponified product of a copolymer of vinyl acetate and unsaturated carboxylic acid or a salt thereof, that is, carboxyl group-modified polyvinyl alcohol is preferably used. Here, the “carboxyl group” includes not only a carboxyl group (—COOH) but also a salt thereof.

Examples of suitable commercially available carboxyl group-modified polyvinyl alcohol include “Kuraraypoval KL-506”, “Kuraraypoval KL-318” and “Kuraraypoval KL-118” (available from Kuraray Co., Ltd.) All are trade names), “GOHSENAL T-330” and “GOHSENAL T-350” (trade name) sold by Nippon Synthetic Chemical Industry Co., Ltd., and “DR” sold by Denki Kagaku Kogyo Co., Ltd. -0415 "(trade name)," AF-17 "," AT-17 ", and" AP-17 "(all trade names) sold by Nippon Vinegar Poval Co., Ltd.

  When an adhesive containing a water-soluble epoxy resin is used as the adhesive, the epoxy resin and other water-soluble resin such as a polyvinyl alcohol-based resin added as necessary are dissolved in water to obtain an adhesive solution. Make it. In this case, the water-soluble epoxy resin preferably has a concentration in the range of about 0.2 to 2 parts by mass per 100 parts by mass of water. Moreover, when mix | blending polyvinyl alcohol-type resin, it is preferable to make the quantity into the range of about 1-10 mass parts per 100 mass parts of water, and it is still more preferable to set it as the range of about 1-5 mass parts. .

  On the other hand, when a water-based adhesive containing a urethane resin is used, examples of suitable urethane resins include ionomer-type urethane resins, particularly polyester-based ionomer-type urethane resins.

  Here, the ionomer type is obtained by introducing a small amount of an ionic component (hydrophilic component) into the urethane resin constituting the skeleton. The polyester ionomer type urethane resin is a urethane resin having a polyester skeleton, into which a small amount of an ionic component (hydrophilic component) is introduced. Such an ionomer type urethane resin is suitable as a water-based adhesive because it is emulsified directly into water without using an emulsifier and becomes an emulsion. Examples of commercially available polyester ionomer-type urethane resins include “Hydran AP-20” and “Hydran APX-101H” (both trade names) sold by Dainippon Ink and Chemicals, Inc. Both are available in the form of emulsions.

  When an ionomer type urethane resin is used as an adhesive component, it is usually preferable to further add a crosslinking agent such as an isocyanate-based crosslinking agent. The isocyanate-based crosslinking agent is a compound having at least two isocyanate groups (—NCO) in the molecule. Examples thereof include 2,4-tolylene diisocyanate, phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1, In addition to polyisocyanate monomers such as 6-hexamethylene diisocyanate and isophorone diisocyanate, adducts in which a plurality of these molecules are added to a polyhydric alcohol such as trimethylolpropane, and 3 molecules of diisocyanate are each at one terminal isocyanate group. There are a trifunctional isocyanurate body in which an isocyanurate ring is formed, a polyisocyanate modified body such as a burette body formed by hydration and decarboxylation of three diisocyanate molecules at each one-end isocyanate group. Examples of commercially available isocyanate-based crosslinking agents that can be suitably used include “Hydran Assist C-1” (trade name) sold by Dainippon Ink and Chemicals, Inc.

  In the case of using an aqueous adhesive containing an ionomer type urethane resin, from the viewpoint of viscosity and adhesiveness, the concentration of the urethane resin is within a range of about 10 to 70% by mass, further 20% by mass or more, and 50% by mass. What was dispersed in water so that it may become% or less is preferable. When the isocyanate crosslinking agent is blended, the blending amount may be appropriately selected so that the isocyanate crosslinking agent is within the range of about 5 to 100 parts by mass with respect to 100 parts by mass of the urethane resin.

  A water-based adhesive as described above is applied to the adhesive surface of the retardation film and / or the polarizer, and both are bonded together to form a polarizing plate.

The method for laminating the polarizer and the retardation film is not particularly limited. For example, an adhesive is uniformly applied to the surface of the polyvinyl alcohol polarizer or the retardation film, and the other side is applied to the coated surface. The method etc. of laminating | stacking and laminating | stacking and bonding with a roll etc. are mentioned.

  Drying is performed at a temperature in the range of about 60 to 100 ° C., for example. After drying, it is preferable to carry out curing for about 1 to 10 days at a temperature slightly higher than room temperature, for example, a temperature in the range of about 30 to 50 ° C., from the viewpoint of further increasing the adhesive strength.

  Next, the solventless adhesive will be described. The solventless type adhesive does not contain a significant amount of solvent, and is generally an adhesive composed of a curable compound that is polymerized by heating or irradiation with active energy rays, and a polymerization initiator. . From the viewpoint of reactivity, those that are cured by cationic polymerization are preferred, and epoxy adhesives are particularly preferred.

  In the polarizing plate according to the present embodiment, in one preferred embodiment, the polarizer and the retardation film are laminated via a solventless epoxy adhesive. The adhesive is more preferably cured by cationic polymerization by heating or irradiation with active energy rays. In particular, from the viewpoint of weather resistance, refractive index, and the like, an epoxy compound that does not contain an aromatic ring in the molecule is suitably used as the curable compound.

  An adhesive using an epoxy compound that does not contain an aromatic ring in the molecule is described in, for example, Japanese Patent Application Laid-Open No. 2004-245925. Examples of such an epoxy compound that does not contain an aromatic ring include a hydride of an aromatic epoxy compound, an alicyclic epoxy compound, an aliphatic epoxy compound, and the like. The curable epoxy compound used for the adhesive usually has two or more epoxy groups in the molecule.

  The hydride of the aromatic epoxy compound can be obtained by selectively hydrogenating the aromatic epoxy compound to the aromatic ring under pressure in the presence of a catalyst.

  Examples of the aromatic epoxy compound include bisphenol type epoxy compounds such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of bisphenol S; phenol novolac epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde Examples thereof include novolak-type epoxy resins such as phenol novolak epoxy resins; polyfunctional epoxy compounds such as glycidyl ether of tetrahydroxydiphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and epoxidized polyvinylphenol. Among these hydrides of aromatic epoxy compounds, hydrogenated bisphenol A diglycidyl ether is preferred.

  Next, an alicyclic epoxy compound is demonstrated. The alicyclic epoxy compound is a compound having at least one epoxy group bonded to the alicyclic ring in the molecule, as shown in the following formula.

(In the formula, m represents an integer of 2 to 5)
A compound in which a group in which one or more hydrogen atoms in (CH ₂ ) _m in the above formula are removed is bonded to another chemical structure can be an alicyclic epoxy compound. Further, the hydrogen forming the alicyclic ring may be appropriately substituted with a linear alkyl group such as a methyl group or an ethyl group. Among these, it is more preferable to use a compound having an epoxycyclopentane ring (m = 3 in the above formula) or an epoxycyclohexane ring (m = 4 in the above formula). Specific examples of the alicyclic epoxy compound include the following compounds.

  3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, ethylenebis (3,4-epoxy Cyclohexanecarboxylate), bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, diethylene glycol bis (3,4-epoxycyclohexylmethyl ether), ethylene glycol bis ( 3,4-epoxycyclohexyl methyl ether), 2,3,4,15-diepoxy-7,11,18,21-tetraoxatrispiro- [5.2.2.5.2.2] henicosane (or 3,4-epoch Cycyclohexanespiro-2 ′, 6′-dioxanespiro-3 ″, 5 ″ -dioxanespiro-3 ″ ′, 4 ′ ″-epoxycyclohexane compound), 4- (3,4-epoxy (Cyclohexyl) -2,6-dioxa-8,9-epoxyspiro [5.5] undecane, 4-vinylcyclohexene dioxide, bis-2,3-epoxycyclopentyl ether, dicyclopentadiene dioxide, and the like.

  Examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. Specifically, for example, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, Polyethers of polyether polyols obtained by adding one or more alkylene oxides (ethylene oxide or propylene oxide) to aliphatic polyhydric alcohols such as diglycidyl ether of propylene glycol, ethylene glycol, propylene glycol and glycerin A glycidyl ether etc. are mentioned.

  The epoxy compounds illustrated here may be used alone or in combination with a plurality of epoxy compounds.

  The epoxy equivalent of the epoxy compound used for the solventless adhesive is usually in the range of 30 to 3,000 g / equivalent, and preferably in the range of 50 to 1,500 g / equivalent. If the epoxy equivalent is less than 30 g / equivalent, the flexibility of the retardation film after curing may be reduced, or the adhesive strength may be reduced. On the other hand, if it exceeds 3,000 g / equivalent, the compatibility with other components may decrease.

  In order to cure the epoxy compound by cationic polymerization, a cationic polymerization initiator is blended. The cationic polymerization initiator generates a cationic species or a Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, or by heating, and initiates an epoxy group polymerization reaction. Regardless of the type of cationic polymerization initiator, it is preferable from the viewpoint of workability that potential is imparted.

  Hereinafter, the cationic photopolymerization initiator will be described. Use of a cationic photopolymerization initiator enables curing at room temperature, reduces the need to consider the heat resistance of the polarizer or distortion due to expansion, and allows the retardation film to adhere well. Moreover, since the photocationic polymerization initiator acts catalytically by light, it is excellent in storage stability and workability even when mixed with an epoxy compound.

  Examples of the compound that generates a cation species or a Lewis acid by irradiation with active energy rays include aromatic diazonium salts, onium salts such as aromatic iodonium salts and aromatic sulfonium salts, and iron-allene complexes. Among these, aromatic sulfonium salts are particularly preferably used because they have ultraviolet absorption characteristics even in a wavelength region of 300 nm or more, and can provide a cured product having excellent curability and good mechanical strength and adhesive strength. It is done.

  These photocationic polymerization initiators can be easily obtained as commercial products, for example, “Kayarad PCI-220” and “Kayarad PCI-620” (manufactured by Nippon Kayaku Co., Ltd.) under the trade names, respectively. "UVI-6990" (manufactured by Union Carbide), "Adekaoptomer SP-150", "Adekaoptomer SP-170" (manufactured by ADEKA Corporation), "CI-5102", "CIT-1370" ", CIT-1682", "CIP-1866S", "CIP-2048S", "CIP-2064S" (manufactured by Nippon Soda Co., Ltd.), "DPI-101", "DPI-102", "DPI" -103 "," DPI-105 "," MPI-103 "," MPI-105 "," BBI-101 "," BBI-102 "," BBI-103 " , “BBI-105”, “TPS-101”, “TPS-102”, “TPS-103”, “TPS-105”, “MDS-103”, “MDS-105”, “DTS-102”, “ DTS-103 "(manufactured by Midori Chemical Co., Ltd.)," PI-2074 "(manufactured by Rhodia) and the like. In particular, “CI-5102” manufactured by Nippon Soda Co., Ltd. is one of preferred initiators.

  The compounding quantity of a photocationic polymerization initiator is in the range of 0.5-20 mass parts normally with respect to 100 mass parts of epoxy compounds, Preferably it is 1 mass part or more, Preferably it is 15 mass parts or less.

  Furthermore, a photosensitizer can be used in combination as necessary. By using a photosensitizer, the reactivity is improved, and the mechanical strength and adhesive strength of the cured product can be improved. Examples of the photosensitizer include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreductive dyes. When mix | blending a photosensitizer, the quantity exists in the range of about 0.1-20 mass parts, for example by making photocationic polymerizable epoxy resin composition into 100 mass parts.

  Next, the thermal cationic polymerization initiator will be described. Examples of the compound that generates a cationic species or a Lewis acid by heating include benzylsulfonium salt, thiophenium salt, thiolanium salt, benzylammonium, pyridinium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, and amine imide. These thermal cationic polymerization initiators can also be easily obtained as commercial products. For example, “ADEKA OPTON CP77” and “ADEKA OPTON CP66” (manufactured by ADEKA Corporation), “CI-” 2639 "and" CI-2624 "(manufactured by Nippon Soda Co., Ltd.)," Sun-Aid SI-60L "," Sun-Aid SI-80L "and" Sun-Aid SI-100L "(manufactured by Sanshin Chemical Industry Co., Ltd.) ) And the like.

  In addition, it is also a useful technique to use the above-described photocationic polymerization and thermal cationic polymerization in combination.

  The epoxy adhesive may further contain a compound that promotes cationic polymerization, such as oxetanes and polyols.

Moreover, also when using a solvent-free-type adhesive agent, the adhesive agent can be apply | coated to the adhesive surface of a phase difference film and / or a polarizer, and both can be bonded together and it can be set as a polarizing plate. There is no particular limitation on the method of applying the solvent-free adhesive to the polarizer or the retardation film. For example, various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater are used. be able to. Moreover, since each coating method has an optimum viscosity range, the viscosity may be adjusted using a small amount of solvent. The solvent used for this purpose only needs to dissolve the epoxy adhesive well without degrading the optical performance of the polarizer. For example, hydrocarbons typified by toluene, esters typified by ethyl acetate, and the like. Organic solvents, such as a kind, can be used. When an epoxy adhesive is used, the thickness of the adhesive layer is usually 50 μm or less, preferably 20 μm or less, more preferably 10 μm or less, and usually 1 μm or more.

  As described above, after the retardation film is bonded to the polarizer through the uncured adhesive layer, the epoxy adhesive layer is cured by irradiating active energy rays or heating, and The retardation film is fixed on the polarizer. In the case of curing by irradiation with active energy rays, ultraviolet rays are preferably used. Specific examples of the ultraviolet light source include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a black light lamp, and a metal halide lamp. The irradiation intensity and irradiation amount of active energy rays or ultraviolet rays may be appropriately selected so as to sufficiently activate the polymerization initiator and not adversely affect the cured adhesive layer, polarizer, and retardation film. .

  In addition, when curing by heating, it can be heated by a generally known method, and the temperature and time at that time sufficiently activate the polymerization initiator, and the cured adhesive layer or polarizer The selection may be made as appropriate so as not to adversely affect the retardation film.

  In the production of the polarizing plate according to the present embodiment, various surface treatments such as corona discharge treatment, ozone treatment, electron beam treatment, UV treatment, anchor coat treatment, etc. are performed on the adhesive surface of the polarizer and / or retardation film. It is preferable that Thereby, the adhesive force of the phase difference film after bonding a polarizer through the above adhesives and a polarizer can be improved. Of various surface treatments, corona discharge treatment is more preferable.

  The corona discharge treatment is a treatment in which a high voltage is applied between the electrodes to discharge and activate the film disposed between the electrodes. The effect of the corona discharge treatment varies depending on the type of electrode, electrode interval, voltage, humidity, type of film used, etc. The conditions of the corona discharge treatment are, for example, the electrode interval within the range of 1 to 5 mm, and the moving speed. It is preferable to set within a range of about 3 to 20 m / min. After the corona discharge treatment, a polarizer is bonded to the treated surface via an adhesive as described above. In the case where the retardation film is laminated on one surface of the polarizer and the resin film is laminated on the other surface, the same surface treatment as described above may be used.

  In the case where the retardation film is laminated on only one side of the polarizer, the polarizing plate has a resin film different from the retardation film on a surface different from the surface on which the retardation film is laminated. You may laminate.

  Examples of the resin constituting the resin film include cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose, amorphous polyolefin resins (cycloolefin resins) such as norbornene resins, polyester resins, acrylic resins, and polycarbonates. Based resins and the like. Moreover, these polarizing plates are good also as a polarizing plate with an adhesive, forming an adhesive layer in the outer side of one phase difference film.

Considering the ease of adhesion with the polarizer, the ease of forming the surface treatment layer, and the like, a cellulose acetate resin film, particularly a triacetyl cellulose film can be suitably used as the resin film. When a cellulose acetate resin film is used as the resin film, it is desirable to saponify the surface with an alkaline aqueous solution prior to bonding with a polarizer.

  The thickness of the resin film is usually in the range of about 30 to 200 μm, preferably in the range of 30 to 120 μm, and more preferably in the range of 30 to 85 μm. You may have various surface treatment layers, such as an antireflection layer and a glare-proof layer, in the polarizing plate surface on the side different from the surface bonded to a liquid crystal cell.

  When laminating the retardation film on one side of the polarizer and laminating the resin film on the other side, the same adhesive as described above may be used, or a different adhesive may be used. However, it is more preferable to use the same adhesive on both sides of the polarizer because the number of steps and materials can be reduced.

  As described above, a polarizing plate is provided in which a retardation film having at least one layer containing a crystalline polyolefin-based resin and a retardation controlling additive is laminated.

  The polarizing plate thus obtained can be formed into a polarizing plate with an adhesive by forming an adhesive layer on the outside of one retardation film. In this case, the surface of the pressure-sensitive adhesive layer is usually covered with a release film.

(E) Laminated optical member When the polarizing plate is used, a laminated optical member in which an optical layer showing an optical function other than the polarizing function is provided on at least one surface can be used. Examples of the optical layer that can be laminated on the polarizing plate for the purpose of forming a laminated optical member include, for example, a reflective layer, a transflective reflective layer, a light diffusing layer, a retardation film, a light condensing sheet, a brightness enhancement film, etc. Examples include various optical layers used for forming a display device. Among these, the reflective layer, the transflective reflective layer, and the light diffusion layer are used when forming a laminated optical member composed of a reflective, transflective, diffusive, or dual-use polarizing plate. .

  A laminated optical member as a reflective polarizing plate is used in a liquid crystal display device of a type that reflects and displays incident light from the viewing side. Since a light source such as a backlight can be omitted, the liquid crystal display device can be easily thinned. The laminated optical member as a transflective polarizing plate is used in a liquid crystal display device of a type that displays as a reflective type in a bright place and displays through a light source such as a backlight in a dark place.

  A laminated optical member as a reflective polarizing plate can be produced, for example, by attaching a foil or vapor deposition film made of a metal such as aluminum to a retardation film on a polarizer and forming a reflective layer. A laminated optical member as a transflective polarizing plate is formed, for example, by using the above reflective layer as a half mirror, or by adhering a reflective plate exhibiting light transmittance to the polarizing plate by containing a pearl pigment or the like. Can be made. On the other hand, the laminated optical member as a diffusion type polarizing plate has various methods such as a method of performing a mat treatment on a retardation film on a polarizing plate, a method of applying a resin containing fine particles, and a method of bonding a film containing fine particles. The method can be used to form a fine concavo-convex structure on the surface.

  Furthermore, formation of the laminated optical member as a polarizing plate for both reflection and diffusion can be performed by, for example, a method of providing a reflective layer reflecting the concavo-convex structure on the fine concavo-convex structure surface of the diffusion polarizing plate. The reflective layer having a fine concavo-convex structure has the advantage that incident light can be diffused by irregular reflection, directivity and glare can be prevented, and uneven brightness can be suppressed. In addition, the resin layer or film containing fine particles also has an advantage that incident light and its reflected light are diffused when passing through the fine particle-containing layer, and uneven brightness can be further suppressed.

The reflective layer reflecting the surface fine concavo-convex structure is, for example, vacuum deposition, ion plating,
It can be formed by attaching a metal directly to the surface of the fine concavo-convex structure by a method such as vapor deposition such as sputtering or plating. Examples of the fine particles to be blended to form the surface fine uneven structure include, for example, silica, aluminum oxide, titanium oxide, zirconia, tin oxide, indium oxide, cadmium oxide having an average particle diameter in the range of 0.1 to 30 μm, and Inorganic fine particles such as antimony oxide, organic fine particles composed of a crosslinked or uncrosslinked polymer, and the like can be used.

  On the other hand, the above-mentioned retardation film as an optical layer is used for the purpose of compensation of retardation by a liquid crystal cell. Examples thereof include a birefringent film composed of stretched films of various plastics, a film in which a discotic liquid crystal or a nematic liquid crystal is oriented and fixed, and a film in which the above liquid crystal layer is formed on a film substrate. In this case, a cellulose-based resin film such as triacetyl cellulose is preferably used as the film substrate that supports the oriented liquid crystal layer.

  Examples of the plastic forming the birefringent film include amorphous polyolefin resin (cycloolefin resin), cellulose acetate resin, polycarbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polypropylene and other polyolefins, polyacrylate, Examples thereof include polyamide.

  Examples of the stretched film include those processed by an appropriate stretching method such as uniaxial stretching or biaxial stretching. Moreover, the birefringent film which controlled the refractive index of the thickness direction of a film by applying shrinkage force and / or extending | stretching force on adhesion | attachment with a heat-shrinkable film may be sufficient. Note that two or more retardation films may be used in combination for the purpose of controlling optical characteristics such as broadening the bandwidth.

  The light condensing sheet is used for the purpose of optical path control and can be formed as a prism array sheet, a lens array sheet, a dot-attached sheet, or the like.

  The brightness enhancement film is used for the purpose of improving the brightness in a liquid crystal display device or the like. For example, a plurality of thin film films having different refractive index anisotropies are laminated to make the reflectance anisotropy. Examples thereof include a reflection-type polarization separation sheet designed so as to occur, a circularly polarized light separation sheet in which an alignment film of a cholesteric liquid crystal polymer and an alignment liquid crystal layer thereof are supported on a film substrate.

  The laminated optical member is a single layer or two selected from the polarizing plate, the reflective layer, the transflective reflective layer, the light diffusing layer, the retardation film, the condensing sheet, and the brightness enhancement film described above according to the purpose of use. Two or more optical layers can be combined to form a laminate of two layers or three or more layers. In that case, two or more optical layers such as a light diffusion layer, a retardation film, a condensing sheet, and a brightness enhancement film may be disposed. There is no particular limitation on the arrangement of each optical layer.

  The various optical layers forming the laminated optical member are integrated using an adhesive, but the adhesive used for this purpose is not particularly limited as long as the adhesive layer is well formed. For example, “( The adhesive agent mentioned above in "D) Polarizing plate" is mentioned. Moreover, it is also preferable to use the adhesive mentioned later from the viewpoints of easy bonding work and prevention of optical distortion.

Such a laminated optical member is also bonded to the liquid crystal cell via an adhesive on a desired surface, like the polarizing plate. As the pressure-sensitive adhesive, those using a base polymer such as an acrylic ester, methacrylic ester, butyl rubber, or silicone can be used. More specifically, polymers based on (meth) acrylate esters such as butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Polymers based on copolymers using two or more of these (meth) acrylic acid esters are preferably used.

  The pressure-sensitive adhesive usually has a polar monomer copolymerized in these base polymers. Examples of the polar monomer include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, and (meth) acrylic acid 2. And monomers having a carboxyl group, a hydroxyl group, an amino group, an epoxy group, and the like, such as -hydroxypropyl, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate.

  The base polymer may be mixed with a crosslinking agent. Examples of the crosslinking agent include divalent or polyvalent metal salts that form carboxylic acid metal salts with carboxyl groups, polyisocyanate compounds that form amide bonds with carboxyl groups, and the like. One type or two or more types are used by mixing with the base polymer.

  The thickness of a general pressure-sensitive adhesive layer is in the range of about 5 to 50 μm. When the pressure-sensitive adhesive layer is applied to the polarizing plate, depending on the situation, surface treatment such as corona treatment may be applied to the surface of the retardation film of the polarizing plate.

(F) Liquid crystal display device The polarizing plate or the laminated optical member according to the present embodiment is bonded to a liquid crystal cell via an adhesive in a state of being laminated with another optical layer as described above as necessary. It can be a display device. In making a liquid crystal display device, as described above, an adhesive layer is formed on the outside of one retardation film to form a polarizing plate with an adhesive, and the adhesive layer side is bonded so that the liquid crystal cell faces. . In the case of a laminated optical member, it may be bonded to the liquid crystal cell on the surface other than the retardation film of the polarizing plate. The liquid crystal cell constituting the liquid crystal display device is a liquid crystal of various modes known in this field such as TN (Twisted Nematic), STN (Super Twisted Nematic), VA (Vertical Alignment), IPS (In-Plane Switching), etc. A cell can be employed.

  As described above, by using the method of the present embodiment, a retardation film having high axial accuracy and uniform retardation can be obtained. In addition, the retardation film improves the viewing angle dependency without phase difference and optical axis unevenness due to optical non-uniformity even when used in a large-screen liquid crystal display device such as a large liquid crystal television. It is excellent in effect. Furthermore, the liquid crystal display device according to the present embodiment provided with the retardation film having high axial accuracy and uniform retardation has excellent viewing angle characteristics and durability.

  In the above description of the present embodiment, the case where the crystalline polyolefin-based resin is a propylene-based resin, an ethylene-based resin, and a modified product of these resins is mainly described, but the present invention is not limited to this. For example, a resin obtained by polymerizing a monomer composition containing 50% by mass or more of ethylene and propylene, a resin obtained by modifying the resin, and the like may be used. Also in this case, the same comonomer as the above-mentioned propylene-based resin and ethylene-based resin can be used, and it can be manufactured by the same manufacturing method.

  In the description of the present embodiment described above, only the case where the retardation film includes a crystalline polyolefin-based resin has been described. However, the present invention is not limited to this. For example, other resins such as an amorphous polyolefin resin may be used instead of the crystalline polyolefin resin. If the above-mentioned phase difference control additive is contained, substantially the same effect as in the present embodiment can be obtained.

However, when the crystalline polyolefin-based resin is included as in this embodiment, the amount of change in retardation with respect to stretching in the case of not containing the retardation control additive is large, and thus the effect is particularly great.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

  Since the retardation film of the present invention has at least one layer containing a crystalline polyolefin resin and a retardation control additive, it has high axial accuracy and uniform retardation. For this reason, it can be suitably used for a liquid crystal display device, particularly a phase difference film that requires high axial accuracy and a uniform phase difference, such as a phase difference film for a large screen liquid crystal display device such as a large liquid crystal television. .

It is a schematic diagram which shows schematic structure of the polymer filter used for the manufacturing method of the retardation film which concerns on this Embodiment.

Explanation of symbols

1 housing 2 leaf disk 3 center post 4 inlet 5 outlet

Claims (4)

  A retardation film comprising at least one layer containing a crystalline polyolefin resin and a retardation control additive.   The additive for phase difference control is an aromatic hydrocarbon resin comprising a structural unit derived from an aromatic hydrocarbon monomer, and an alicyclic carbonization comprising a structural unit derived from an alicyclic hydrocarbon monomer having 5 to 25 carbon atoms. The retardation film according to claim 1, wherein the retardation film is at least one resin selected from the group consisting of hydrogen resins. The retardation film according to claim 1, wherein the number of foreign matters having a diameter of 0.1 mm or more is 0.1 piece / m ² or less.   The retardation film of any one of Claims 1-3 is laminated | stacked on the at least single side | surface of a polarizer, The polarizing plate characterized by the above-mentioned.

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