KR20100138951A - Acrylic resin-containing film, process for producing acrylic resin-containing film, and polarizing plate and liquid crystal display device using the acrylic resin-containing film - Google Patents

Abstract

An object of the present invention is to provide an acrylic resin-containing film that is excellent in transparency, has high heat resistance, and has significantly improved brittleness. Moreover, by using the said acrylic resin containing film, the liquid crystal which improved the yield in the punching operation | work of a polarizing plate, operation | work of panel bonding, etc., reduced the color shift which arises depending on the viewing angle, and further improved contrast significantly. Provided is a display device. The acrylic resin containing film of this invention is an acrylic resin containing film containing 10-50 mass parts of cellulose ester resins (B) with respect to 50-90 mass parts of acrylic resins (A), The one side of the said acrylic resin containing film And a static friction coefficient at the time of superimposing the other surface with 0.3-0.8, a tension softening point of 105-145 degreeC, haze value less than 1%, and it does not produce ductile fracture.

Description

ACRYLIC RESIN-CONTAINING FILM, PROCESS FOR PRODUCING ACRYLIC RESIN-CONTAINING FILM, AND POLARIZING PLATE AND LIQUID CRYSTAL DISPLAY DEVICE USING THE ACRYLIC RESIN-CONTAINING FILM }

The present invention relates to an acrylic resin-containing film mainly composed of an acrylic resin, a polarizing plate and a display device using the same, and more particularly, by using an acrylic resin-containing film blended with an acrylic resin and a cellulose ester resin, The present invention relates to a liquid crystal display device in which a yield in work such as panel bonding is improved, color shifts generated depending on the viewing angle are reduced, and contrast is significantly improved.

Polymethyl methacrylate (hereinafter abbreviated as PMMA), which is a representative of conventional acrylic resins, has been suitably used as an optical film in view of its excellent transparency, dimensional stability, low hygroscopicity, and the like.

However, the PMMA film has a problem that the shape is changed in use under high temperature, long-term use, and the like because of insufficient heat resistance.

In order to solve this problem, the method of using the film which blended acrylic resin and cellulose ester resin is disclosed (for example, refer patent document 1 below). However, in the example of this document, since the low molecular weight cellulose resin was used from the compatibility viewpoint of an acrylic resin and a cellulose resin, there existed a problem that a film was soft and brittle.

On the other hand, the invention which adds silicone microparticles | fine-particles to a cellulose ester film and improves light transmittance and light resistance is disclosed (for example, refer patent document 2 below). However, it was difficult to use because the added fine particles agglomerated to cause haze or to have compatibility problems with UV agents.

Moreover, although the invention which improves heat resistance by forming the heat transfer protective layer so that exfoliation is possible at least one surface in one side of a cellulose ester film is disclosed (for example, refer patent document 3 below), trouble, process water, cost are Too much Moreover, the invention which adds a mat agent is disclosed in order to suppress generation | occurrence | production of the scratch failure in winding up a cellulose ester film, without reducing the transmittance | permeability of a cellulose ester film (for example, refer following patent document 4). In this case, when a mat agent is added too much, haze will generate | occur | produce, and there exists a limit in addition amount, and the said objective cannot fully be achieved.

Moreover, in order to improve the surface physical characteristics accompanying thinning of a cellulose ester film, convex rolling defect, etc. when winding up in roll shape, the surface roughness of a cellulose ester film, the amount of a mat agent, the amount of plasticizers, moisture content, etc. are specified ranges. The invention prescribed | regulated as is disclosed (for example, refer the following patent document 5). However, according to this method, there have been problems such as curl, dimensional change, and refractive index between the surface and the inside are different, and the front contrast (hereinafter also referred to as CR) is lowered.

Japanese Patent Laid-Open No. 5-119217 Japanese Patent Laid-Open No. 7-11056 Japanese Patent Laid-Open No. 2001-105749 Japanese Patent Laid-Open No. 2002-317059 Japanese Patent Laid-Open No. 2004-168981

Therefore, this invention is made | formed in view of the said subject, The objective is to provide the acrylic resin containing film which was very excellent in transparency, high heat resistance, and remarkably improved brittleness. Moreover, by using the said acrylic resin containing film, the liquid crystal which improved the yield in the punching operation | work of a polarizing plate, operation | work of panel bonding, etc., reduced the color shift which arises depending on the viewing angle, and further improved contrast significantly. It is providing a display apparatus.

The said objective of this invention can be achieved by the following structures.

1. It is the acrylic resin containing film which contained 10-50 mass parts of cellulose ester resins (B) with respect to 50-90 mass parts of acrylic resin (A), and superposed one surface and the other surface of the said acrylic resin containing film The static friction coefficient at the time is 0.3-0.8, the tension softening point is 105-145 degreeC, haze value is less than 1%, and it does not produce ductile fracture, The acrylic resin containing film characterized by the above-mentioned.

2. The weight average molecular weight (Mw) of the acrylic resin (A) of the said acrylic resin containing film is 80000-1 million, the total substitution degree (T) of the acyl group of a cellulose ester resin (B) is 2.00-3.00, and an acetyl group Substitution degree (ac) is 0.10-1.90, the part other than an acetyl group is substituted by the acyl group which consists of 3-7 carbon number, its substitution degree (r) is 1.10-2.90, and a weight average molecular weight (Mw) is 75000-280000, The said film contains 0.05-45 mass% of acrylic microparticles | fine-particles (C) with respect to the film total mass, and the said acrylic microparticles | fine-particles are in the area within 25% of the thickness of the whole film from both surfaces of a film. 40 to 60% of the total amount thereof is present. The acrylic resin-containing film according to 1 above.

3. The acrylic resin containing film as described in said 1 or 2 is extended | stretched 5 to 40% in one or more directions, and is manufactured, The acrylic resin containing film manufacturing method characterized by the above-mentioned.

4. The polarizing plate using the acrylic resin containing film of said 1 or 2 characterized by the above-mentioned.

5. The polarizing plate of said 4 is used, The liquid crystal display device characterized by the above-mentioned.

6. The film manufactured by the acrylic resin containing film manufacturing method of 3 is used, The polarizing plate characterized by the above-mentioned.

7. The polarizing plate of said 6 is used, The liquid crystal display device characterized by the above-mentioned.

According to the present invention, it is possible to provide an acrylic resin-containing film that is transparent, has high heat resistance, and has significantly improved brittleness, has reduced color shift, and further improved contrast.

BRIEF DESCRIPTION OF THE DRAWINGS The figure which shows typically the dope manufacturing process, casting process, and drying process of the solution casting film forming method used for this invention.

EMBODIMENT OF THE INVENTION Although the best form for implementing this invention below is demonstrated in detail, this invention is not limited to these.

SUMMARY OF THE INVENTION The present invention improves the property of poor heat resistance, which is a drawback of conventional acrylic resin-containing films, to change shape in low temperature use, long-term use, and the like, and to be brittle, and to improve acrylic resin (A) and cellulose ester resin ( By blending B), it was found that an acrylic resin-containing film having a transparent, high heat resistance and remarkably improved brittleness was obtained, thereby achieving the present invention.

Further, it has been found that the tension softening point is 105 to 145 ° C. and that no ductile fracture is satisfied to satisfy the heat resistance required as an optical film used for a liquid crystal display device or the like.

<Acrylic resin containing film>

The acrylic resin-containing film of the present invention has a haze value of less than 1%, a tensile softening point of 105 to 145 ° C, and a static friction coefficient at the time of overlapping one surface with the other surface is 0.3 to 0.8. .

The static friction coefficient at the time of overlapping one surface and the other surface of the acrylic resin containing film in this invention is 0.3-0.8. If it is this range, when the film formed into a film is wound up in the core center and stored for a long term, it will not stick to films and damage smoothness or an external appearance, and can be sent out smoothly when unwinding from winding. Moreover, if it is this range, films will be very slippery, and when it is wound up, it will not protrude in what is called a bamboo shoot shape, and there is no possibility of damaging quality. Moreover, it is also possible to obtain a long film of 4000-6000 m by controlling a static friction coefficient to 0.3-0.8.

The acrylic resin-containing film according to the present invention has a low haze, and considering its use in a high temperature environment such as a projector or a vehicle-mounted display device, its tension softening point is 105 ° C to 145 ° C. do. It is more preferable to control to 110 to 130 degreeC. By controlling the tension softening point within the above range, a clear image can be continuously displayed when the liquid crystal display device using the film is used for a long time. If it is this range, although also depending on a use environment, in the long term use, there is no possibility that the image quality, color taste, etc. of a display apparatus may be impaired, and it is not necessary to use very high heat resistant acrylic resin.

As a specific measuring method of the tension softening point temperature of an acrylic resin containing film, an acrylic resin containing film is cut out to 120 mm (length) x 10 mm (width) using the tensilon tester (RTC-1225A by Orientec Co., Ltd.), The temperature is continued at a temperature increase rate of 30 ° C./min while pulling at a tension of 10 N, the temperature at the time of 9 N can be measured three times, and the average value can be obtained.

Moreover, the acrylic resin containing film of this invention is characterized by being an acrylic resin film which does not produce ductile fracture.

The ductile fracture in the present invention is caused by the action of a stress greater than the strength of any material, and is defined as failure accompanied by significant elongation or shrinkage of the material until the final fracture. The wavefront has a feature in which a depression called a dimple is formed innumerably. Therefore, the "acrylic resin film in which ductile fracture does not occur" is characterized in that fracture such as fracture cannot be seen even if a large stress of bending the film into two is applied.

In recent years, the demand for brittleness of an optical film is increasing from the viewpoint of rework property and productivity with the widening of cotton and thin film of an optical film accompanying the enlargement of a liquid crystal display device, and the said ductile destruction is calculated | required not to occur.

In order to form the acrylic resin film which does not produce ductile fracture, it is achieved by selecting suitably material structures, such as an acrylic resin, a cellulose ester, acrylic microparticles | fine-particles, and other additives to be used.

It is preferable that the glass transition temperature (Tg) of the acrylic resin containing film of this invention is 110 degreeC or more. More preferably, it is 120 degreeC or more. Especially preferably, it is 150 degreeC or more.

In addition, the glass transition temperature here is the intermediate point glass transition measured by the temperature increase rate of 20 degree-C / min using a differential scanning calorimeter (DSC-7 type | mold by Perkin Elmer), and calculated | required according to JISK7121 (1987). Temperature (Tmg).

The acrylic resin containing film of this invention is one or less per square with a 10 cm diameter side fault of 5 micrometers or more in film inside. More preferably, it is 0.5 or less per square with 10 cm of one side, and more preferably 0.1 or less per square with 10 cm of one side.

Here, the diameter of a flaw shows the diameter when a flaw is circular, and when it is not circular, it determines the range of a flaw by observing with a microscope by the following method, and sets it as the largest diameter (diameter of an circumscribed circle).

The range of a fault is the magnitude | size of the shadow when a fault is observed with the transmitted light of a differential interference microscope, when a fault is a bubble or a foreign substance. In the case where the defect is a change in the surface shape such as transfer or scratching of the roll damage, the defect is observed by the reflected light of the differential interference microscope to confirm the size.

In addition, when observing with reflected light, if the magnitude | size of a fault is unclear, it will observe by depositing aluminum or platinum on a surface.

In order to obtain a product with excellent quality represented by such a defect frequency with high productivity, high-precision filtration of a polymer solution immediately before casting | flow_spread, raising the cleanliness around a casting machine, and setting the drying conditions after casting | flow_spread gradually, It is effective to suppress foaming and to dry efficiently.

If the number of defects is more than one per square of 10 cm on one side, for example, when the film is tensioned during processing in a post-process, the film may break at the defects and the productivity may be significantly reduced. Moreover, when the diameter of a fault becomes 5 micrometers or more, it can visually confirm by polarizing plate observation etc., and a bright spot may generate | occur | produce when used as an optical member.

Moreover, even when it cannot visually confirm, when a hard-coat layer etc. are formed on the said film, a coating agent cannot be formed uniformly and may become a fault (application omission). Here, a defect means the foreign substance in a film (foreign substance which arises from the cavity (foaming defect) in the film which arises from the rapid evaporation of a solvent in the drying process of a solution film forming, the foreign material in a film forming undiluted | stock solution, or the foreign material mixed in film forming. Defects).

In addition, in the measurement based on JIS-K7127-1999, it is preferable that the elongation at break of at least one direction is 10% or more, and, as for the acrylic resin containing film of this invention, More preferably, it is 20% or more.

Although the upper limit of breaking elongation is not specifically limited, In reality, it is about 250%. In order to enlarge breaking elongation, it is effective to suppress the fault in the film resulting from a foreign material and foaming.

It is preferable that the thickness of the acrylic resin containing film of this invention is 20 micrometers or more. More preferably, it is 30 micrometers or more.

Although the upper limit of thickness is not specifically limited, When film-forming by the solution film forming method, an upper limit is about 250 micrometers from a viewpoint of applicability | paintability, foaming, and solvent drying. In addition, the thickness of a film can be suitably selected according to a use.

It is preferable that the total light transmittance of the acrylic resin containing film of this invention is 90% or more, More preferably, it is 93% or more. Moreover, as a realistic upper limit, it is about 99%. In order to achieve the excellent transparency expressed by such a total light transmittance, it is necessary not to introduce an additive or a copolymerizing component that absorbs visible light, or to remove foreign substances in the polymer by high precision filtration to reduce the diffusion and absorption of light inside the film. Is valid.

Moreover, the surface roughness of the film contact part (cooling roll, calender roll, drum, belt, coating base material, conveyance roll in solution film forming, etc.) at the time of film forming is made small, and the surface roughness of a film surface is reduced, and the refractive index of an acrylic resin It is effective to reduce the diffusion and reflection of light on the surface of the film by making it smaller.

The acrylic resin-containing film of the present invention is characterized by having a haze value (turbidity) of 1.0% or less, which is one of the indicators showing transparency, but is preferably 0.5% or less in terms of brightness and contrast when assembled into a liquid crystal display device. .

In order to achieve such a haze value, it is effective to remove the foreign material in a polymer by high precision filtration and to reduce the spread of the light inside a film.

When using acrylic microparticles | fine-particles, it is also effective to make small the refractive index difference of acrylic resin (A) and acrylic microparticles | fine-particles (C).

Moreover, since surface roughness also affects haze value as surface haze, it is also effective to suppress the particle diameter and addition amount of acrylic microparticles | fine-particles (C) in the said range, or to make small the surface roughness of the film contact part at the time of film forming.

In addition, the total light transmittance and haze value of the said acrylic resin containing film are the values measured according to JIS-K7361-1-1997 and JIS-K7136-2000.

Although the acrylic resin containing film of this invention can be used suitably as an acrylic resin containing film for optics as long as it satisfies the above physical properties, the film excellent in workability and heat resistance can be obtained by setting it as the following compositions.

That is, in view of making processability and heat resistance compatible, the acrylic resin-containing film contains an acrylic resin (A) and a cellulose ester resin (B) in a mass ratio of 90:10 to 50:50, and the cellulose ester resin (B ), The total substitution degree (T) of the acyl group of 2.00 to 3.00, the acetyl group substitution degree (ac) of 0.10 to 1.90, the number of carbon atoms of the acyl groups other than the acetyl group is 3 to 7, and its substitution degree (r) is 1.10 It is-2.90, and the weight average molecular weight (Mw) is 75000-280000, The excellent effect of this invention can be acquired by the acrylic resin containing film.

In the acrylic resin-containing film of the present invention, the acrylic resin (A) and the cellulose ester resin (B) are contained in a mass ratio of 90:10 to 50:50, but preferably the acrylic resin (A) is 70% by mass or more. .

When the acrylic resin component increases, the dimensional change under high temperature and high humidity is suppressed, for example, and the curl of the polarizing plate and the curvature of the panel when used as a polarizing plate can be significantly reduced. Moreover, in the composition whose acrylic resin component is 70 mass% or more, it becomes possible to hold the said physical property for a longer time.

The acrylic resin containing film of this invention may be comprised containing resin other than an acrylic resin (A) and a cellulose ester resin (B).

The total mass of acrylic resin (A) and cellulose ester resin (B) is 55-100 mass% of an acrylic resin containing film, Preferably it is 60-99 mass%.

<Acrylic resin (A)>

The acrylic resin used for this invention also contains methacryl resin. Although it does not restrict | limit especially as resin, What consists of 50-99 mass% of methyl methacrylate units and 1-50 mass% of other monomeric units copolymerizable with this is preferable.

Examples of the other monomer copolymerizable include alkyl methacrylate having 2 to 18 carbon atoms in the alkyl group, alkyl acrylate having 1 to 18 carbon atoms in the alkyl group, α, β-unsaturated acids such as acrylic acid and methacrylic acid, maleic acid, fumaric acid, Aromatic vinyl compounds such as unsaturated group-containing divalent carboxylic acids such as itaconic acid, styrene, α-methylstyrene, and nuclear substituted styrene, α, β-unsaturated nitriles such as acrylonitrile and methacrylonitrile, maleic anhydride, Maleimide, N-substituted maleimide, glutaric anhydride, etc. are mentioned, These can be used individually or in combination of 2 or more types.

Among these, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, etc. are preferable from the viewpoint of the thermal decomposition resistance and fluidity of a copolymer, And methyl acrylate or n-butyl acrylate are particularly preferably used.

It is preferable that the weight average molecular weight (Mw) of the acrylic resin (A) used for the acrylic resin containing film of this invention is 80000-1 million from the mechanical strength as a film, and fluidity at the time of producing a film.

The weight average molecular weight of the acrylic resin of this invention can be measured by a gel permeation chromatography. Measurement conditions are as follows.

Solvent: Methylene Chloride

Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)

Column temperature: 25 ° C

Sample concentration: 0.1% by mass

Detector: RI Model 504 (made by GL Science)

Pump: L6000 (made by Hitachi Seisakusho Co., Ltd.)

Flow rate: 1.0ml / min

Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 2,800,000 to 500 The calibration curve by 13 samples was used. It is preferable to use 13 samples at substantially equal intervals.

There is no restriction | limiting in particular as a manufacturing method of an acrylic resin (A) in this invention, You may use any of well-known methods, such as suspension polymerization, emulsion polymerization, block polymerization, or solution polymerization. Here, as a polymerization initiator, a normal peroxide type and an azo type can be used, and it can also be set as a redox system. About superposition | polymerization temperature, it can implement at 30-100 degreeC by suspension or emulsion polymerization, and 80-160 degreeC by block or solution polymerization. In addition, in order to control the reduced viscosity of the resulting copolymer, polymerization may be carried out using alkylmercaptan or the like as a chain transfer agent.

By setting it as this molecular weight, both heat resistance and brittleness can be aimed at.

As the acrylic resin of the present invention, a commercially available one can be used. For example, Delpet 60N, 80N (made by Asahi Kasei Chemicals Co., Ltd.), diamond BR52, BR80, BR83, BR85, BR88 (made by Mitsubishi Rayon Co., Ltd.), KT75 (made by Denki Kagaku Kogyo Co., Ltd.) Etc. can be mentioned.

<Cellulose cellulose resin (B)>

The cellulose ester resin (B) of the present invention may be substituted with any of an aliphatic acyl group and an aromatic acyl group, but is preferably substituted with an acetyl group.

When the cellulose ester resin (B) of the present invention is an ester with an aliphatic acyl group, the aliphatic acyl group has 2 to 20 carbon atoms, specifically acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl, Hexanoyl, octanoyl, lauroyl, stearoyl and the like.

In the present invention, the above-mentioned aliphatic acyl group is meant to include those having a substituent. Examples of the substituent include those exemplified as substituents for the benzene ring when the aromatic ring is a benzene ring.

When the said cellulose ester resin (B) is ester with an aromatic acyl group, the number of substituents X substituted by an aromatic ring is 0 or 1-5, Preferably it is 1-3, Especially preferable is 1 or 2.

In addition, when the number of substituents substituted in the aromatic ring is two or more, they may be the same as or different from each other, and may also be linked to each other to form a condensed polycyclic compound (for example, naphthalene, indene, indane, phenanthrene, quinoline, isoquinoline, and chromen). , Chromman, phthalazine, acridine, indole, indolin, etc.) may be formed.

In the cellulose ester resin (B), those having a structure selected from at least one of a substituted or unsubstituted aliphatic acyl group and a substituted or unsubstituted aromatic acyl group are used as the structure used in the cellulose resin of the present invention. It may be a single or mixed acid ester of cellulose.

Substitution degree of the cellulose ester resin (B) of this invention is 2.00-3.00 total substitution degree (T) of an acyl group, an acetyl group is not necessarily required, and it is preferable that acetyl group substitution degree (ac) is 0.10-1.90. Do. More preferably, the acyl group substitution degree (r) other than an acetyl group is 1.10-2.90.

It is preferable that acyl groups other than an acetyl group have 3 to 7 carbon atoms.

In the cellulose ester resin (B) of this invention, what has a C3-C7 acyl group as a substituent, ie cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate benzoate And at least one selected from cellulose benzoate.

Among these, especially preferable cellulose ester resin (B) is cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate.

As the mixed fatty acid, more preferably, it is a lower fatty acid ester of cellulose acetate propionate or cellulose acetate butyrate and preferably has an acyl group having 3 to 4 carbon atoms as a substituent.

The part which is not substituted by the acyl group exists normally as a hydroxyl group. These can be synthesized by a known method.

In addition, substitution degree of an acetyl group and substitution degree of another acyl group are calculated | required by the method of the prescription | regulation to ASTM-D 817-96.

If the weight average molecular weight (Mw) of the cellulose ester resin (B) of this invention is 75000 or more, even if it is about 1 million, the objective of this invention can be achieved, but considering productivity, it is preferable that it is 75000-280000, and it is 100000 It is more preferable that it is to 240000.

<Acrylic fine particles (C)>

In this invention, you may contain acrylic microparticles | fine-particles in an acrylic resin containing film.

The acrylic fine particles (C) according to the present invention are characterized by being present in the state of particles in the acrylic resin (A), the cellulose ester resin (B) and the acrylic resin-containing film (also referred to as an emergency state).

The said acrylic fine particle (C) collects the acrylic resin containing film manufactured, for example, predetermined amount, melt | dissolves in a solvent, and stirs, melt | dissolves and disperse | distributes sufficiently, and makes the pore diameter less than the average particle diameter of acrylic fine particle (C). It is preferable to filter using the membrane filter made from PTFE which has, and the weight of the insoluble material collected by filtration is 90 mass% or more of the acrylic fine particle (C) added to the acrylic resin containing film.

Although the acrylic fine particle (C) used for this invention is not specifically limited, It is preferable that it is acrylic fine particle (C) which has a layer structure of two or more layers, and it is especially preferable that it is the following multilayer structure acrylic granular composite_body | complex.

The multi-layered acrylic granular composite refers to a particulate acrylic polymer having a structure in which an innermost hard layer polymer, a crosslinked soft layer polymer exhibiting rubber elasticity, and an outermost hard layer polymer are laminated in a layer form from the center portion to the outer circumferential portion. .

The following are mentioned as a preferable aspect of the multilayered structure acrylic granular composite_body | complex used for the acrylic resin composition of this invention. (a) 80 to 98.9 mass% of methyl methacrylate, 1 to 20 mass% of alkylacrylates having 1 to 8 carbon atoms of an alkyl group, and the innermost hard product obtained by superposing | polymerizing the monomer mixture which consists of 0.01 to 0.3 mass% of polyfunctional grafting agents. In the presence of the layer polymer and (b) the innermost hard layer polymer, 75 to 98.5% by mass of alkyl acrylate having 4 to 8 carbon atoms of alkyl group, 0.01 to 5% by mass of polyfunctional crosslinking agent and 0.5 to 5% by mass of polyfunctional grafting agent Crosslinked soft layer polymer obtained by superposing | polymerizing the monomer mixture which consists of (c) 80-99 mass% of methylmethacrylate and alkyl of 1-8 carbon atoms in presence of the polymer which consists of said innermost hard layer and crosslinked soft layer. 3-layer sphere composed of the outermost hard layer polymer obtained by polymerizing a monomer mixture composed of 1 to 20% by mass of acrylate In addition, the obtained three-layer structure polymer consists of 5-40 mass% of innermost hard layer polymers (a), 30-60 mass% of soft layer polymers (b), and 20-50 mass% of outermost hard layer polymers (c). When it classifies as acetone, there exists an insoluble part, The acrylic granular composite whose methyl ethyl ketone swelling degree of the insoluble part is 1.5-4.0 is mentioned.

In addition, as disclosed in Japanese Patent Publication No. 60-17406 or Japanese Patent Publication No. Hei 3-39095, not only the composition and particle diameter of each layer of the multilayered acrylic granular composite are defined, but also the multilayered acrylic system By setting the tensile modulus of elasticity of the granular composite and the methyl ethyl ketone swelling degree of the acetone insoluble portion within a specific range, it is possible to realize a sufficient balance of impact resistance and stress whitening resistance.

Here, the innermost hard layer polymer (a) constituting the multilayered acrylic granular composite includes 80 to 98.9 mass% of methyl methacrylate, 1 to 20 mass% of alkyl acrylate having 1 to 8 carbon atoms of the alkyl group, and a polyfunctional grafting agent. It is preferable that it is obtained by superposing | polymerizing the monomer mixture which consists of 0.01-0.3 mass%.

As the alkyl acrylate having 1 to 8 carbon atoms in the alkyl group, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like can be given. Methyl acrylate or n-butyl acrylate can be used preferably.

The proportion of the alkyl acrylate units in the innermost hard layer polymer (a) is 1 to 20% by mass, and if the unit is less than 1% by mass, the thermal decomposition of the polymer is increased, while the unit is more than 20% by mass. Since the glass transition temperature of an innermost hard layer polymer (c) falls and the impact resistance imparting effect of a three-layered acryl-type granular composite lowers, it is unpreferable.

As a polyfunctional graft agent, the polyfunctional monomer which has a different polymerizable functional group, for example, the allyl ester of acrylic acid, methacrylic acid, maleic acid, and fumaric acid, etc. are mentioned, Allyl methacrylate is used preferably. A polyfunctional graft agent is used for chemically bonding an innermost hard layer polymer and a soft layer polymer, and the ratio used at the time of innermost hard layer polymerization is 0.01-0.3 mass%.

The crosslinked soft layer polymer (b) constituting the acrylic granular composite is 75-98.5 mass% of alkyl acrylate having 1 to 8 carbon atoms of an alkyl group and 0.01 to 5 polyfunctional crosslinking agent in the presence of the innermost hard layer polymer (a). It is preferable to obtain by superposing | polymerizing the monomer mixture which consists of mass% and 0.5-5 mass% of polyfunctional grafting agents.

Here, as the alkyl acrylate having 4 to 8 carbon atoms in the alkyl group, n-butyl acrylate and 2-ethylhexyl acrylate are preferably used.

Moreover, it is also possible to copolymerize another 25 mass% or less copolymerizable other monofunctional monomer with these polymerizable monomers.

Other monofunctional monomers copolymerizable include styrene and substituted styrene derivatives. The proportion of alkyl acrylate having 4 to 8 carbon atoms and styrene in the alkyl group is such that the higher the number of electrons, the lower the glass transition temperature of the produced polymer (b), that is, the softer it can be.

On the other hand, from the viewpoint of transparency of the resin composition, it is more advantageous to bring the refractive index at room temperature of the soft layer polymer (b) closer to the innermost hard layer polymer (a), the outermost hard layer polymer (c), and the rigid thermoplastic acrylic resin. In consideration of these, the ratio of both is selected.

For example, in applications where the coating layer thickness is small, the styrene may not necessarily be copolymerized.

As a polyfunctional graft agent, what was illustrated by the term of said innermost hard layer polymer (a) can be used. The polyfunctional graft agent used here is used for chemically bonding a soft layer polymer (b) and an outermost hard layer polymer (c), and the ratio used at the time of innermost hard layer polymerization is 0.5 from a viewpoint of impact resistance provision effect. 5 mass% is preferable.

As a polyfunctional crosslinking agent, although generally known crosslinking agents, such as a divinyl compound, a diallyl compound, a diacryl compound, a dimethacryl compound, can be used, polyethyleneglycol diacrylate (molecular weight 200-600) is used preferably.

The polyfunctional crosslinking agent used here is used in order to produce a crosslinked structure at the time of superposition | polymerization of a soft layer (b), and to express the effect of imparting impact resistance. However, when the above-mentioned multifunctional graft agent is used in the polymerization of the soft layer, to some extent, a crosslinked structure of the soft layer (b) is produced. Therefore, the multifunctional crosslinking agent is not an essential component, but the polyfunctional crosslinking agent is used during the soft layer polymerization. As for the ratio used for, 0.01-5 mass% is preferable from a viewpoint of an impact resistance provision effect.

The outermost hard layer polymer (c) constituting the multilayered acrylic granular composite has 80 to 99 mass% of methyl methacrylate and carbon number of the alkyl group in the presence of the innermost hard layer polymer (a) and the soft layer polymer (b). It is preferable to obtain by superposing | polymerizing the monomer mixture which consists of 1-20 mass% of alkylacrylates which are 1-8.

Here, although the above-mentioned thing is used as alkyl acrylate, methyl acrylate and ethyl acrylate are used preferably. As for the ratio of the alkylacrylate unit in an outermost hard layer (c), 1-20 mass% is preferable.

In addition, in order to improve compatibility with an acrylic resin (A) at the time of superposition | polymerization of an outermost hard layer (c), in order to adjust molecular weight, it is also possible to use alkyl mercaptan etc. as a chain transfer agent, and to carry out.

In particular, it is preferable to provide a gradient in which the molecular weight gradually decreases from the inner side to the outer side in the outermost hard layer in order to improve the balance between elongation and impact resistance. As a specific method, it is possible to divide the monomer mixture for forming an outermost hard layer into 2 or more, and to make molecular weight small from inside to outside by the method of sequentially increasing the amount of the chain transfer agent added for each time.

The molecular weight formed at this time can also be investigated by polymerizing the monomer mixture used for each time on the same conditions independently, and measuring the molecular weight of the obtained polymer.

Although it does not specifically limit about the particle diameter of the acryl-type granular composite which is a multilayered structure polymer used preferably for this invention, It is preferable that it is 10 nm or more and 1000 nm or less, It is more preferable that it is 20 nm or more and 500 nm or less, Especially 50 nm or more, Most preferably, it is 400 nm or less.

In the acrylic granular composite, which is a multilayered structure polymer that is preferably used in the present invention, the mass ratio of the core and the shell is not particularly limited, but when the entire multilayered structure polymer is 100 parts by mass, the core layer is 50 parts by mass or more, 90 It is preferable that it is mass parts or less, and it is more preferable that it is 60 mass parts or more and 80 mass parts or less.

Examples of commercially available products of such multilayered acrylic granular composites include, for example, "Metablene" manufactured by Mitsubishi Rayon, "Kane Ace" manufactured by Kanegachichi Kagaku Kogyo Co., Ltd. "Parloid" manufactured by Kureha Kagaku Kogyo Co., Ltd. And "acryloid", "Staphyloid" manufactured by Gantz Kasei Kogyo Co., Ltd., "Paparapet SA" manufactured by Kureray Corporation, and the like, and these may be used alone or two or more kinds.

Moreover, as a specific example of the acryl microparticles | fine-particles (c-1) which are a graft copolymer suitably used as an acryl microparticles | fine-particles (C) used suitably for this invention, an unsaturated carboxylic ester type monomer and unsaturated carboxyl in presence of a rubbery polymer The graft copolymer which copolymerized the monomer mixture which consists of an acidic monomer, an aromatic vinylic monomer, and the other vinylic monomer copolymerizable with these as needed is mentioned.

There is no restriction | limiting in particular in the rubbery polymer used for the acrylic fine particle (c-1) which is a graft copolymer, A diene rubber, an acrylic rubber, ethylene rubber, etc. can be used. Specific examples include polybutadiene, styrene-butadiene copolymers, block copolymers of styrene-butadiene, acrylonitrile-butadiene copolymers, butyl-butadiene acrylates, polyisoprene, butadiene-methyl methacrylate copolymers, and butyl acrylates. Methyl methacrylate copolymer, butadiene-ethyl acrylate copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-isoprene copolymer, ethylene-methyl acrylate copolymer and the like. These rubbery polymers can be used by 1 type, or 2 or more types of mixtures.

Moreover, when each refractive index of an acrylic resin (A) and an acrylic fine particle (C) is approximating, since transparency of the acrylic resin containing film of this invention can be obtained, it is preferable. Specifically, the refractive index difference between the acrylic fine particles (C) and the acrylic resin (A) is preferably 0.05 or less, more preferably 0.02 or less, particularly preferably 0.01 or less.

In order to satisfy such refractive index conditions, the refractive index difference is adjusted by a method of adjusting the monomer unit composition ratio of the acrylic resin (A), and / or by preparing a composition ratio of the rubbery polymer or monomer used for the acrylic fine particles (C). It can be made small and the acrylic resin containing film excellent in transparency can be obtained.

In addition, the refractive index difference referred to here means that the acrylic resin-containing film of the present invention is sufficiently dissolved in a solvent in which the acrylic resin (A) is available under appropriate conditions to give a cloudy solution, and this is a solvent-soluble part by an operation such as centrifugal separation. It separates into an insoluble part, and refine | purifies this soluble part (acrylic resin (A)) and an insoluble part (acrylic microparticles | fine-particles (C)), respectively, and shows the difference of the measured refractive index (23 degreeC, measurement wavelength: 550 nm).

There is no restriction | limiting in particular in the method of mix | blending an acrylic fine particle (C) with an acrylic resin (A) in this invention, After blending an acrylic resin (A) and other arbitrary components previously, Usually in 200-350 degreeC, A method of uniformly melt kneading by a single screw or twin screw extruder while adding the acrylic fine particles (C) is preferably used.

Moreover, the method which adds the solution which disperse | distributed acrylic microparticles | fine-particles (C) in advance to the solution (dope liquid) which melt | dissolved acrylic resin (A) and cellulose ester resin (B), and mixes, acrylic microparticles | fine-particles (C) and other arbitrary The method of dissolving and adding the mixed solution of in-line may be used.

As the acrylic fine particles (C) of the present invention, a commercially available one can be used. For example, metablen W-341 (C2) (made by Mitsubishi Rayon Co., Ltd.), Chemi Snow MR-2G (C3), MS-300X (C4) (made by Sogaku Kagaku Co., Ltd.), etc. are mentioned. .

In the acrylic resin containing film of this invention, it is preferable to contain 0.5-45 mass% acrylic fine particles (C) with respect to the gross mass of resin which comprises the said film.

Moreover, it is preferable that the said acrylic microparticles | fine-particles (C) exist in the area within 25% of the thickness of the whole film from both surfaces of an acrylic resin containing film, respectively, 40-60% of the total amount of its existence. Distribution of such acrylic microparticles | fine-particles (C) is made by the preferable film forming method of the acrylic resin containing film mentioned later as an example.

When this amount is less than 40%, there is not enough slipperiness in a film, and when a winding is made, films will stick together and handling becomes difficult. Moreover, when more than 60%, a tension softening point may fall or a haze value may rise.

The presence ratio of acrylic microparticles | fine-particles photographs the cross section of an acrylic resin containing film about 10000-50000 times in magnification using a high-resolution scanning electron microscope (SEM), analyzes the SEM photograph obtained, and analyzes the obtained SEM photograph with respect to the film thickness direction of acrylic microparticles | fine-particles. It calculates as an abundance ratio.

〈Other additives〉

In the acrylic resin containing film of this invention, in order to improve the fluidity | liquidity and flexibility of a composition, it is also possible to use a plasticizer together. Phthalic acid ester type, fatty acid ester type, trimellitic acid ester type, phosphate ester type, polyester type, or epoxy type etc. are mentioned as a plasticizer.

In this, the plasticizer of polyester type and phthalic acid ester type is used preferably. The polyester plasticizer is superior in non-migration and extraction resistance to phthalic acid ester plasticizers such as dioctyl phthalate, but the plasticizing effect and compatibility are slightly inferior.

Therefore, it can apply to a wide range of uses by selecting or using these plasticizers according to a use.

Although the polyester plasticizer is a reactant of monovalent to tetravalent carboxylic acid and monovalent to hexavalent alcohol, what is obtained by mainly reacting divalent carboxylic acid and glycol is used. Representative divalent carboxylic acids include glutaric acid, itaconic acid, adipic acid, phthalic acid, azelaic acid, sebacic acid, and the like.

In particular, when adipic acid, phthalic acid, or the like is used, an excellent plasticizing property is obtained. Examples of the glycol include glycols such as ethylene, propylene, 1,3-butylene, 1,4-butylene, 1,6-hexamethylene, neopentylene, diethylene, triethylene and dipropylene. These divalent carboxylic acids and glycols may be used alone or in combination.

The ester plasticizer may be any of ester, oligoester, and polyester types, and the molecular weight is preferably in the range of 100 to 10000, but preferably in the range of 600 to 3000. The plasticizing effect is large.

Moreover, although the viscosity of a plasticizer has a correlation with molecular structure and molecular weight, in the case of an adipic acid type plasticizer, the range of 200-5000 mPa * s (25 degreeC) is good from a relationship of compatibility and plasticization efficiency. Moreover, you may use several polyester plasticizers together.

It is preferable that a plasticizer adds 0.5-30 mass parts with respect to 100 mass parts of compositions containing an acrylic resin (A). When the addition amount of a plasticizer exceeds 30 mass parts, since the surface is sticky, it is not preferable practically.

It is preferable that the composition containing the acrylic resin (A) of this invention contains a ultraviolet absorber, and the thing of a benzotriazole type, 2-hydroxy benzophenone type, or a salicylic acid phenyl ester type etc. is mentioned as a ultraviolet absorber used. have. For example, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole Triazoles such as 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzo Benzophenone, such as phenone and 2,2'- dihydroxy-4- methoxy benzophenone, can be illustrated.

Here, among the ultraviolet absorbers, the ultraviolet absorber having a molecular weight of 400 or more is difficult to volatilize at a high boiling point and hardly to scatter even at high temperature molding, so that weather resistance can be effectively improved by the addition of a relatively small amount.

Moreover, since the transfer property from a thin coating layer to a board | substrate layer is also small, and it is hard to be deposited also on the surface of a laminated board, it is preferable at the point of the amount of the ultraviolet absorber contained for a long time being maintained, and excellent in the durability of a weather resistance improvement effect.

Examples of the ultraviolet absorbent having a molecular weight of 400 or more include 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2-benzotriazole and 2,2-methylenebis [4- (1, 1,3,3-tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol] such as benzotriazole-based, bis (2,2,6,6-tetramethyl-4-piperidyl) Hindered amines, such as sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, further 2- (3,5-di-t-butyl-4-hydride Oxybenzyl) -2-n-butylmalonic acid bis (1,2,2,6,6-pentamethyl-4-piperidyl), 1- [2- [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6- The hybrid type which has the structure of a hindered phenol and a hindered amine together in molecule | numerators, such as tetramethyl piperidine, These can be used individually or in combination of 2 or more types. Among them, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2-benzotriazole or 2,2-methylenebis [4- (1,1,3,3 -Tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol] is particularly preferred.

In addition, various antioxidants may be added to the acrylic resin (A) used in the acrylic resin-containing film of the present invention in order to improve the thermal decomposability and thermochromic properties during molding. Moreover, it is also possible to add an antistatic agent and to provide antistatic performance to an acrylic resin containing film.

As an acrylic resin composition of this invention, you may use the flame-retardant acrylic resin composition which mix | blended the phosphorus flame retardant.

Examples of the phosphorus flame retardant used herein include red phosphorus, triaryl phosphate ester, diaryl phosphate ester, monoaryl phosphate ester, aryl phosphonic acid compound, aryl phosphine oxide compound, condensed aryl phosphate ester, halogenated alkyl phosphate ester, halogen-containing condensed phosphate ester 1 type, or 2 or more types of mixtures chosen from halogen-containing condensation phosphonic acid ester, halogen-containing phosphite ester, etc. are mentioned.

Specific examples include triphenyl phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenylphosphonic acid, tris (β-chloroethyl) phosphate, tris (dichloropropyl) phosphate, Tris (tribromoneopentyl) phosphate etc. are mentioned.

<Film forming of acrylic resin containing film>

Although the example of the film forming method of an acrylic resin containing film is demonstrated, this invention is not limited to this.

As a film forming method of the acrylic resin containing film of this invention, manufacturing methods, such as an inflation method, the T-die method, a calendering method, the cutting method, the casting method, the emulsion method, and the hot press method, can be used, but it suppresses coloring and suppresses a foreign material fault. Solution film forming by the casting method is preferable from the viewpoint of suppressing optical defects such as die lines and the like.

(Organic solvent)

The organic solvent useful for forming the dope in the case of producing the acrylic resin-containing film of the present invention by the solution casting method can be used without limitation as long as it dissolves the acrylic resin (A), the cellulose ester resin (B) and other additives at the same time. have.

For example, as the chlorine organic solvent, methylene chloride, as the non-chlorine organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone Ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3 , 3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro 1-propanol, nitroethane, etc. are mentioned, Methylene chloride, methyl acetate, ethyl acetate, acetone can be used preferably.

It is preferable to make dope contain 1-40 mass% linear or branched aliphatic alcohol of 1-40 mass% of carbon atoms other than the said organic solvent. When the proportion of alcohol in the dope increases, the web gels, and peeling from the metal support becomes easy, and when the proportion of alcohol is low, dissolution of the acrylic resin (A) and cellulose ester resin (B) in a non-chlorine organic solvent system. There is also a role to promote.

In particular, three kinds of an acrylic resin (A), a cellulose ester resin (B), and an acrylic fine particle (C) are added to a solvent containing methylene chloride and a linear or branched aliphatic alcohol having 1 to 4 carbon atoms. It is preferable that it is the dope composition which melt | dissolved-45 mass%.

Examples of the linear or branched aliphatic alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol. Ethanol is preferable from the viewpoint that the stability and boiling point of these dope resistances are relatively low, and dryness is also good.

Hereinafter, the preferable film forming method of the acrylic resin containing film of this invention is demonstrated.

1) melting process

In the organic solvent which mainly uses a good solvent for an acrylic resin (A) and a cellulose ester resin (B), the said acrylic resin (A), a cellulose ester resin (B), an acryl fine particle (C), and the said The process of forming a dissolution dope, stirring an external additive, or the said acrylic resin (A) and a cellulose ester resin (B) solution, if necessary, mixing an acrylic fine particle (C) solution and another additive solution as a main solution liquid It is a process of forming dope.

To dissolve the acrylic resin (A) and the cellulose ester resin (B), a method performed at ordinary pressure, a method performed below the boiling point of the main solvent, a method performed by pressurizing above the boiling point of the main solvent, and Japanese Patent Application Laid-Open No. 9-95544 , A method of performing by a cooling dissolution method as described in Japanese Patent Application Laid-Open No. 9-95557, or Japanese Patent Application Laid-open No. Hei 9-95538, a method performed at a high pressure as described in Japanese Patent Application Laid-open No. Hei 11-21379, and the like. Although a dissolution method can be used, the method of performing pressurization especially above the boiling point of a main solvent is preferable.

It is preferable that the acrylic resin (A) and cellulose ester resin (B) in dope are 15-45 mass% of systems. Additives are added to the dope during or after dissolution to dissolve and disperse, and then, filtered through a filter medium, degassed and sent to the next step by a liquid feeding pump.

Filtration is 0.5-5 micrometers of trapping particle diameters, and it is preferable to use the filter medium of 10-25 sec / 100 ml of filtered water time.

In this method, only aggregates can be removed by using a filter medium having a collecting particle diameter of 0.5 to 5 µm and a filtration time of 10 to 25 sec / 100 ml, for the aggregates remaining at the time of particle dispersion and the aggregates generated at the time of main dope addition. In main dope, since the particle | grain concentration is also low enough compared with an addition liquid, aggregates adhere to each other at the time of filtration, and a sudden filtration pressure does not rise.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows typically the dope manufacturing process, casting process, and drying process of the solution casting film forming method preferable for this invention.

If necessary, a large aggregate is removed from the acrylic fine particle input kiln 41 by the filter 44, and the liquid is sent to the storage tank 42. Then, the acrylic fine particle addition liquid is added from the storage tank 42 to the main dope dissolution kiln 1.

Then, the main dope liquid is filtered by the main filter 3, and the ultraviolet absorber addition liquid is added inline from code | symbol 16 to this.

In most cases, about 10-50 mass% of half-cuts may be contained in main dope. Acrylic fine particles may be contained in the half board, and in that case, it is preferable to control the addition amount of the acrylic fine particle addition liquid according to the addition amount of the half board.

It is preferable to contain 0.5-10 mass% of acrylic microparticles | fine-particles in the addition liquid containing acrylic microparticles, It is more preferable to contain 1-10 mass%, It is most preferable to contain 1-5 mass%.

The smaller the content of the acrylic fine particles is easier to handle at a lower viscosity, and the higher the content of the acrylic fine particle is, the smaller the addition amount is and the easier the addition to the main dope is preferable.

Semi-finished material is a finely pulverized acrylic resin-containing film, and is used to cut out both side portions of the film generated when forming an acrylic resin-containing film, or an acrylic resin-containing film raw material specified out from scratches or the like. do.

Moreover, what knead | mixed and pelletized acrylic resin, cellulose ester resin, and acryl fine particles in some cases can be used preferably.

2) flexible process

The dope is fed to the pressure die 30 through a liquid feeding pump (for example, a pressure metering gear pump), and an endless metal support 31 for transferring indefinitely, for example, a stainless steel belt or a rotating metal drum. It is a process of casting dope from a press die slit to a casting position on a metal support body.

The pressurization die which can adjust the slit shape of the die | dye part of die | dye and is easy to make film thickness uniform is preferable. There exist a coat hanger die, a T die, etc. in pressurization die | dye, and all are used preferably. The surface of the metal support is mirror surface. In order to raise a film forming speed | rate, two or more press dies may be provided on a metal support body, and you may divide | stack and dope amount. Or it is also preferable to obtain the film of a laminated structure by the co-combustion method which casts a plurality of dope simultaneously.

3) solvent evaporation process

It is a process of evaporating a solvent by heating a web (the dope film formed by casting dope on a flexible support body is called a web) on a casting support.

In order to evaporate the solvent, there is a method of blowing air from the web side and / or a method of heat transfer from the back surface of the support by liquid, a method of heat transfer from the front and back by radiant heat, and the like. . Moreover, the method of combining them is also used preferably.

It is preferable to dry the web on the support body after casting | flow_spread on a support body in 40-100 degreeC atmosphere. In order to maintain in 40-100 degreeC atmosphere, it is preferable to make the warm air of this temperature contact a web upper surface, or to heat by infrared rays or other means.

In view of surface quality, moisture permeability, and peelability, it is preferable to peel the web from the support within 30 to 120 seconds.

4) peeling process

It is a process of peeling the web in which the solvent evaporated on the metal support body at a peeling position. The peeled web is sent to the next process.

Preferably the temperature in the peeling position on a metal support body is 10-40 degreeC, More preferably, it is 11-30 degreeC.

In addition, although the amount of residual solvent at the time of peeling of a web on a metal support at the time of peeling off is preferable to peel in 50-120 mass% by the strength of dry conditions, the length of a metal support, etc., When peeling at many points of time, if the web is too soft, the planarity at the time of peeling is likely to be impaired, or drag and vertical streaks are likely to occur due to peeling tension, so the amount of residual solvent at the time of peeling is determined by the balance between economic speed and quality.

The residual solvent amount of the web is defined by the following formula.

Residual solvent amount (%) = (mass before heat treatment of web-mass after heat treatment of web) / (mass after heat treatment of web) × 100

In addition, the heat processing at the time of measuring the residual solvent quantity shows performing heat processing for 1 hour at 115 degreeC.

Although the peeling tension at the time of peeling a metal support body and a film is 196-245 N / m normally, when wrinkles are easy to enter at the time of peeling, it is preferable to peel with a tension of 190 N / m or less, and also the minimum tension which can peel Although it is preferable to peel at 166.6 N / m and then the minimum tension-137.2 N / m, Especially preferably, it peels at the minimum tension-100 N / m.

In this invention, it is preferable to make temperature in the peeling position on the said metal support body into -50-40 degreeC, 10-40 degreeC is more preferable, and it is most preferable to set it as 15-30 degreeC.

5) drying and stretching process

After peeling, a web is dried using the tenter extending | stretching apparatus 34 which clips and conveys both ends of a web with the drying apparatus 35 and / or a clip which alternately passes a web through the roll arrange | positioned in multiple drying apparatuses, and / or a clip. .

Drying means generally blow hot air on both sides of the web, but there are also means for heating by applying microwaves instead of wind. Too rapid drying tends to impair the planarity of the finished film. It is preferable to perform drying by high temperature from about 8 mass% or less of residual solvent. Throughout the whole, drying is performed at about 40-250 degreeC. It is especially preferable to dry at 40-160 degreeC.

When using a tenter stretching apparatus, it is preferable to use the apparatus which can independently control the holding | gripping length (distance from holding start to holding end) of a film by right and left holding means of a tenter. It is also desirable to make compartments with intentionally different temperatures in the tenter process to improve planarity.

It is also desirable to provide a neutral band so that each compartment does not interfere between different temperature compartments.

Moreover, extending | stretching operation may be divided | segmented into multistep, and it is also preferable to carry out biaxial stretching in the casting | flow_spread direction and the width direction. In addition, when biaxial stretching is performed, simultaneous biaxial stretching may be performed and you may carry out in steps.

In this case, the step can be carried out, for example, stretching in which the stretching directions are different from each other, the stretching in the same direction can be divided into multiple stages, and the stretching in different directions can be added at any stage. That is, the following extending steps are also possible, for example.

ㆍ stretch in the flexible direction -stretch in the width direction-stretch in the flexible direction-stretch in the flexible direction

ㆍ stretch in the width direction -stretch in the width direction -stretch in the flexible direction-stretch in the flexible direction

In addition, simultaneous biaxial stretching also includes the case where the stretching is performed in one direction and the other is relaxed by shrinking the tension. The draw ratio with which simultaneous biaxial stretching is preferable can be taken in the range of x1.01 times-x 1.5 times in the width direction and the longitudinal direction.

It is preferable that the amount of residual solvent of a web at the time of tenter extending | stretching is 20-100 mass% at the time of tenter start, and it is preferable to dry, adding a tenter until the amount of residual solvent of a web becomes 10 mass% or less. More preferably, it is 5 mass% or less.

30-150 degreeC is preferable, as for the drying temperature in the case of tenter extending | stretching, 50-120 degreeC is more preferable, and 70-100 degreeC is the most preferable.

In the tenter stretching step, a smaller temperature distribution in the width direction of the atmosphere is preferable from the viewpoint of increasing the uniformity of the film, and the temperature distribution in the width direction in the tenter stretching step is preferably within ± 5 ° C, and within ± 2 ° C. Is more preferable, and most is within +/- 1 degreeC.

6) winding process

After the amount of residual solvent in a web becomes 2 mass% or less, it is a process of winding up by the winding machine 37 as an acrylic resin containing film, and the film with favorable dimensional stability can be obtained by making the amount of residual solvent into 0.4 mass% or less.

As a winding method, what is generally used may be used, and there exist a positive torque method, the positive tension method, the taper tension method, the program tension control method with constant internal stress, etc., and may use them separately.

It is preferable that the acrylic resin containing film of this invention is a long film, Specifically, it shows the thing of about 100m-5000m, and is a thing of the form provided in roll shape normally. Moreover, it is preferable that it is 1.3-4 m, and, as for the width | variety of a film, it is more preferable that it is 1.4-3 m.

Although there is no restriction | limiting in particular in the film thickness of the acrylic resin containing film of this invention, When used for the polarizing plate protective film mentioned later, it is preferable that it is 20-200 micrometers, It is more preferable that it is 25-100 micrometers, It is 30-80 micrometers Is particularly preferred.

<Polarizing plate>

The polarizing plate used for this invention can be manufactured by a general method. It is preferable to form an adhesion layer on the back surface side of the acrylic resin containing film of this invention, and to bond to at least one surface of the polarizer manufactured by immersion extending | stretching in the iodine solution.

You may use the said film for the other surface, or you may use another polarizing plate protective film. For example, commercially available cellulose ester films (e.g., Konica Minolta Tag KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KV8UY-HA, KV8UX-RHA, or higher) Konica Minolta Opto Co., Ltd. etc. are used preferably.

The polarizer, which is a main component of the polarizing plate, is a device that passes only light of a polarization plane in a certain direction, and a representative polarizing film known at present is a polyvinyl alcohol polarizing film, which is similar to the dyeing of iodine on a polyvinyl alcohol film. Some have been dyed with dichroic dyes.

The polarizer forms a polyvinyl alcohol aqueous solution, uniaxially stretches and dyes it, or after uniaxially stretches after dyeing, the thing which carried out durability treatment with the boron compound is used preferably.

As an adhesive used for the said adhesion layer, it is preferable that the adhesive whose storage elastic modulus in 25 degreeC is 1.0 * 10 <^4> Pa-1.0 * 10 <^9> Pa in at least one part of an adhesion layer is used, apply | coating an adhesive, After bonding, a curable pressure sensitive adhesive which forms a high molecular weight or crosslinked structure by various chemical reactions is suitably used.

As a specific example, curable adhesives, such as a urethane type adhesive, an epoxy type adhesive, an aqueous polymer-isocyanate type adhesive, and a thermosetting acrylic adhesive, a moisture-curable urethane adhesive, a polyether methacrylate type, an ester type methacrylate type, an oxidation type, for example Anaerobic adhesives, such as a polyether methacrylate, cyanoacrylate type | system | group instant adhesive, an acrylate and a peroxide type | system | group two-component type | mold adhesive etc. are mentioned.

As said adhesive, 1-component type may be sufficient, and the type | mold which mixes and uses 2 or more liquids before use may be sufficient.

The pressure-sensitive adhesive may be a solvent type containing an organic solvent as a medium, or may be an aqueous type such as an emulsion type, a colloidal dispersion type, an aqueous solution type, or a solvent type, which is a medium containing water as a main component. What is necessary is just to determine the density | concentration of the said adhesive liquid suitably by the film thickness after adhesion, application | coating method, application | coating conditions, etc., and it is 0.1-50 mass% normally.

<Liquid crystal display device>

By assembling the polarizing plate which bonded the acrylic resin containing film of this invention to a liquid crystal display device, the liquid crystal display device excellent in various visibility can be manufactured. The polarizing plate which concerns on this invention is bonded to a liquid crystal cell through the said adhesion layer etc.

The polarizing plate according to the present invention is preferably used as a reflective, transmissive, semi-transmissive LCD or LCD of various driving methods such as TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), and IPS type. do. In particular, in the display device of a large screen of 30 or more types, especially 30 to 54 types, there is no pinhole or the like at the periphery of the screen, and the effect is maintained for a long time.

Moreover, there was little color unevenness, glitter, and wavy unevenness, and there was an effect that eyes do not get tired even if it is long-term appreciation.

Example

Although an Example is given to the following and this invention is concretely demonstrated to it, this invention is not limited to these.

Example 1

<Production of acrylic resin containing film>

(Manufacture of acrylic resin containing film 1)

(Manufacture of dope liquid)

70 parts by mass of BR85 (acrylic resin made by Mitsubishi Rayon)

Cellulose ester (cellulose acetate propionate, acyl group total substitution degree 2.75, acetyl group substitution degree 0.19, propionyl group substitution degree 2.56, Mw = 200000)

30 parts by mass

2 parts by mass of acrylic fine particles (C1)

300 parts by mass of methylene chloride

40 parts by mass of ethanol

<Production of Acrylic Fine Particles (C1)>

38.2 liters of ion-exchanged water and 111.6 g of sodium dioctylsulfosuccinate were added to a reactor having a volumetric 60 liter reflux cooler, and the temperature was raised to 75 ° C. under a nitrogen atmosphere while stirring at 250 rpm, and the influence of oxygen was reduced. It was virtually absent. 0.36 g of APS was added, and after stirring for 5 minutes, a monomer mixture consisting of 1657 g of MMA, 21.6 g of BA, and 1.68 g of ALMA was added in a batch, and after the detection of the exothermic peak, the mixture was held for 20 minutes to further polymerize the innermost hard layer. Completed

Then, 3.48 g of APS was added, and after stirring for 5 minutes, a monomer mixture consisting of BA 8105 g, 31.9 g of PEGDA (200), and 264.0 g of ALMA was continuously added over 120 minutes, and further maintained for 120 minutes after the addition was completed. The polymerization of the soft layer was completed.

Next, 1.32 g of APS was added, and after stirring for 5 minutes, the monomer mixture consisting of MMA 2106 g and BA 201.6 g was continuously added over 20 minutes, and after the addition was completed, the mixture was held for 20 minutes to complete the polymerization of the outer hard layer 1. did.

Subsequently, 1.32 g of APS was added, and after 5 minutes, a monomer mixture consisting of 3148 g of MMA, 201.6 g of BA, and 10.1 g of n-OM was continuously added over 20 minutes, and further maintained for 20 minutes after the addition was completed. Then, it heated up at 95 degreeC and hold | maintained for 60 minutes, and completed superposition | polymerization of outermost hard layer 2.

Thus obtained small amount of the polymer latex was obtained, and the average particle diameter was determined by the absorbance method, and found to be 0.10 µm. The remaining latex was poured into a 3 mass% sodium sulfate hot water solution, salted and coagulated, and after repeated dehydration and washing, it dried and obtained the acrylic fine particle (C1) of a three-layered structure.

Said symbol is respectively the following material.

MMA: Methyl methacrylate

MA: methyl acrylate

BA: n-butylacrylate

ALMA: allyl methacrylate

PEGDA: polyethylene glycol diacrylate (molecular weight 200)

n-OM: n-octyl mercaptan

APS: Ammonium Persulfate

(Film forming of acrylic resin containing film)

The dope liquid prepared above was cast | flow_spreaded uniformly to the stainless steel band support body at the temperature of 22 degreeC, and 2 m width using the belt casting apparatus. In the stainless steel band support body, the solvent was evaporated until the amount of residual solvent became 100%, and it peeled from the stainless steel band support body on peeling tension 162 N / m. The solvent was evaporated and the web of the peeled acrylic resin was slitted at a width of 1.6 m, and then dried at a drying temperature of 135 ° C while being stretched 1.1 times in the width direction by a tenter. At this time, the amount of residual solvent when extending | stretching was started by a tenter was 10%. After extending | stretching with a tenter and relaxing for 5 minutes at 130 degreeC, drying is terminated, conveying the drying zone of 120 degreeC and 130 degreeC with many rolls, it slitted to 1.5 m width, and width 10mm height 5 at both ends of a film. The knurling process of micrometers was performed, it wound up to 6-inch inner diameter core at the initial tension of 220 N / m, and final tension of 110 N / m, and obtained the acrylic resin containing film 1. The draw ratio in the MD direction calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.10 times, and the TD direction was 1.01 times. The residual solvent amount of the acrylic resin containing film 1 of Table 2 and Table 3 was 0.1%, the film thickness was 60 micrometers and the winding number was 5000 m.

Hereinafter, the quantity, type, and composition ratio of acrylic resin (A), cellulose ester resin (B), and acrylic fine particles (C) are changed as shown in Table 2, Table 3, and it contains acrylic resin similarly to acrylic resin containing film 1. Films 2 to 34 were prepared.

The acrylic resins used for the acrylic resin-containing films 1 to 28 and 33 and 34 are Delpet 80N (manufactured by Asahi Kasei Chemicals Co., Ltd.), diamond BR52, BR80, BR83, BR85, and BR88 (manufactured by Mitsubishi Rayon). Shown in

Acrylic resin A1-A4 used for the acrylic resin containing films 29-32 were manufactured by the well-known method.

A1: poly (MMA-MA) mass ratio 98: 2 Mw70000

A2: poly (MMA-MA) mass ratio 97: 3 Mw800000

A3: poly (MMA-MA) mass ratio 97: 3 Mw930000

A4: poly (MMA-MA) mass ratio 94: 6 Mw1100000

MMA: Methyl methacrylate

MA: methyl acrylate

In addition, the symbol of the column of the substitution degree of a cellulose ester resin (B) shown in Table 2, Table 3 is as follows.

ac: acetyl group

p: propionyl group

b: butyryl

bz: benzoyl group

oc: Octanoyl group

ph: phthalyl group

In addition, acrylic resin containing films 6 and 11 added the following ultraviolet absorber, and produced dope.

Acrylic resin-containing film 6

Tinubin 109 (product of Shiba Japan Co., Ltd.) 1.5 parts by mass

Tinuvin 171 (product of Shiba Japan Corporation) 0.7 mass part

Acrylic resin-containing film 11

LA-31 (made by ADEKA Corporation) 1.5 parts by mass

In addition, the cellulose triacetate films 1-3 of comparative were manufactured with the following method.

(Production of Comparative Cellulose Triacetate Film 1)

100 parts by mass of cellulose triacetate (acetization degree: 61%), 12 parts by mass of TPP (triphenylphosphate), 320 parts by mass of methylene chloride, 50 parts by mass of methanol and 10 parts by mass of 1-butanol were added to a dope mixing tank and heated. By stirring, cellulose triacetate was dissolved to prepare dope. Separately, 15 mass parts of the following ultraviolet absorbers of UV-1, 80 mass parts of methylene chloride, and 20 mass parts of methanol were put into another mixing tank, and the mixture was heated and stirred to dissolve the ultraviolet absorber to prepare a solution containing a ultraviolet absorber. Furthermore, 0.5 mass parts of silicon dioxide microparticles | fine-particles (brand name: aerosil R972D, the average particle diameter of a primary particle: 0.016 micrometers; Nippon Aerosil Co., Ltd. product) are thrown in and mixed, it transfers to a disperser, and the said microparticles | fine-particles in the dispersion liquid It disperse | distributed so that it might be set to 0.3 micrometer in average particle diameter, and the dispersion liquid was produced and it was set as the ultraviolet absorber containing solution. With respect to 100 mass parts of dope prepared above, the ultraviolet absorber containing solution was added at the ratio of 2 mass parts, it fully mixed in the mixing tank, and it was then cast on a flexible band as 50 degreeC dope. Casting was performed so that the thickness of the film after drying might be 80 micrometers. After drying from a flexible band, it peeled and dried at 145 degreeC for 15 minutes in the drying zone, and the comparative cellulose triacetate film 1 (shown as comparison 1 in Table 5) of thickness 80micrometer was produced.

(Production of Comparative Cellulose Triacetate Film 2)

As a mat solution, 0.7 mass% of silicon dioxide (2 micrometers of average particle diameters, 16 nm of primary particle diameters), 3.3 mass% of cellulose triacetates (average acetonitrile 61%), 88 mass% of methylene chlorides, and 8 masses of methanol It manufactured so that it might become%. Next, the dope of the mixed composition of 17 mass of cellulose triacetate (average acetate degree 61%), 2 mass% of plasticizers, 71 mass% of methylene chloride, 6 mass% of methanol, and 4 mass% of said mat agent solutions was prepared previously. After dope was swollen, it cooled to -70 degreeC. Moreover, dope was introduce | transduced into the autoclave substituted by nitrogen atmosphere, and it melt | dissolved at 160 degreeC and 0.98 Mpa for 10 minutes. The solution was filtered and then cast on a flexible band as a dope at 50 ° C. Casting was performed so that the thickness of the film after drying might be 80 micrometers. It peeled after drying from a casting band, and after drying at 145 degreeC for 15 minutes in the drying zone, the 80-micrometer-thick comparative cellulose triacetate film 2 (shown as comparison 2 in Table 5) was obtained. In addition, the mat agent content rate of the obtained film was 0.15 mass%.

(Production of Comparative Cellulose Triacetate Film 3)

The dope liquid of a cellulose triacetate was manufactured as follows.

Cellulose Triacetate (TAC): 100kg

Tinuvin 326 (made by Shiba Japan): 0.3 kg

Tinuvin 171 (made by Shiba Japan): 0.5 kg

Tinuvin 109 (made by Shiba Japan): 0.5 kg

Ethylphthalyl ethyl glycolate: 2 kg

Triphenylphosphate (TPP): 9.7 kg

Aerosil 200V (made by Nippon Aerosil): 0.09 kg

Methylene chloride: 320 kg

Ethanol: 20 kg

These were put into a sealed container and completely dissolved while being kept warm and stirred at 80 ° C under pressure.

After filtering the said dope liquid, it was cast on a flexible band as dope of 33 degreeC. Casting was performed so that the thickness of the film after drying might be 80 micrometers. After drying from a casting band, it peeled and dried at 145 degreeC for 15 minutes in the drying zone, and obtained the comparative cellulose triacetate film 3 (shown as comparison 3 in Table 5) of 80 micrometers in film thickness.

"Assessment Methods"

The following evaluation is performed about the obtained acrylic resin containing films 1-34 and the comparative cellulose triacetate films 1-3, and a result is shown in Table 4 and Table 5.

(Calculation of Amount of Particles)

The cross-sectional SEM image of the produced acrylic resin containing films 1-3, the comparative cellulose triacetate films 1-3, and the comparative acrylic resin containing film 34 were analyzed, and the existence ratio with respect to the film thickness direction of acrylic microparticles | fine-particles and silicon dioxide was computed.

(Haze)

For each film sample prepared above, after humidifying for 24 hours in an air-conditioned room at 23 ° C. and 55% RH, one film sample was subjected to haze meter (NDH2000 type, Nippon Denshoku Kogyo Co., Ltd.) under JIS K-7136 under the above conditions. It was measured using the note)).

(Tension softening point)

The following evaluation was performed using the tensilon tester (RTC-1225A by the Orientec company).

The acrylic resin-containing film moistened for 24 hours in an air-conditioned room at 23 ° C. and 55% RH was cut at 120 mm (length) x 10 mm (width) under the above conditions, and pulled out at a tension of 10 N at a temperature increase rate of 30 ° C./min. The temperature was continued, the temperature at the time of 9N was measured 3 times, and the average was taken.

(Ductile destruction)

The acrylic resin containing film humidified for 24 hours in the air-conditioning room of 23 degreeC and 55% RH is cut out to 100 mm (length) x 10 mm (width) under the said conditions, and it is curvature radius 0mm and bending angle 180 degrees in the center part of a longitudinal direction. The film was bent once in two with a crevice and a corrugator so that the film overlapped, and this evaluation was measured 3 times and evaluated as follows. In addition, the crack which is evaluation here shows that it was broken and separated into two or more pieces.

○… All three times do not diverge.

×… At least one of the three splits.

(Static Friction Coefficient)

About each film sample produced above, it humidified for 24 hours in 23 degreeC and 55% RH air conditioning chamber, and measured using friction measuring device TR-2 (made by Toyo Seiki Co., Ltd.).

(Film deformation)

Each film sample prepared above was left to stand for 1000 hours in an atmosphere of 90 ° C. and DRY (relative humidity of 5% RH or less), and then the degree of film deformation was visually observed under the conditions of 23 ° C. and 55% RH.

○: no deformation of the film.

(Triangle | delta): The deformation | transformation of a film is confirmed.

X: The deformation | transformation of a remarkable film is confirmed.

(Cutting property)

The film which was humidified for 24 hours in the air-conditioning room of 23 degreeC and 55% RH was tear | felled the film using the light load tear (Elmendorf) tester (made by Toyo Seiki Co., Ltd.) on the said conditions, and evaluated as follows.

(Circle): A tear surface is very smooth and it is torn straight.

(Triangle | delta): Although it has a little burr on a tearing surface, it is torn straight.

X: Burr exists in a tearing surface considerably, and it is not ripped straight.

(Film appearance)

About the produced film, the external appearance of the film humidified for 24 hours in 23 degreeC and 55% RH air conditioning room was visually evaluated, and it evaluated as follows.

(Circle): It is very smooth flatness.

(Triangle | delta): A little drag, a wrinkle, and a step | step can be confirmed.

×: The attraction, wrinkles, and step can be confirmed with certainty.

(Manufacture of Polarizing Plate)

The long roll polyvinyl alcohol film with a thickness of 120 µm was immersed in 100 parts by mass of an aqueous solution containing 1 part by mass of iodine and 4 parts by mass of boric acid, and stretched in the conveyance direction at 5 times at 50 ° C to form a polarizing film. Next, it bonded together after performing the corona treatment to the acrylic resin containing film 1 manufactured in Example 1 using the acrylic adhesive agent on one side of this polarizing film. Furthermore, KC4UY by Konica Minolta Opto Co., which is a retardation film subjected to alkali saponification treatment, was bonded to the other side of the polarizing film, and dried to prepare a polarizing plate P1. In the same manner, polarizing plates P2 to P37 (corresponding film Nos are shown in Tables 4 and 5, respectively) were prepared using acrylic resin-containing films 2 to 34 and comparative cellulose triacetate films 1 to 3. The polarizing plate using the acrylic resin containing film of this invention was excellent in film cutting property, and was easy to process.

(Characteristic evaluation as a liquid crystal display device)

<Production of liquid crystal display device>

Using the liquid crystal television Wooo32 H-90 made by Hitachi which is an IPS mode type | mold liquid crystal display device, the polarizing plate of the visual recognition side which was bonded previously was peeled off, and the acrylic resin containing film of this invention produced the said polarizing plates P1-P37 of a liquid crystal cell. It bonded together so that it might become a glass surface. In that case, it bonded together so that an absorption axis might face in the same direction as the polarizing plate previously bonded. As described above, the liquid crystal display devices 1 to 37 were manufactured.

(Viewing angle change)

The following evaluation was performed using the liquid crystal display devices 1-37 which were manufactured as mentioned above.

The viewing angle measurement of the liquid crystal display device was performed using EZ-Contrast160D by ELDIM company in the environment of 23 degreeC and 55% RH. Subsequently, the thing which processed the said polarizing plate for 1000 hours at 60 degreeC and 90% RH was measured similarly, and the following reference | standard evaluated four steps.

○: no change in viewing angle.

(Triangle | delta): The viewing angle fluctuation is confirmed.

X: The viewing angle fluctuation is very large.

(Color shift)

The polarizing plate was affixed similarly to the viewing angle evaluation of the said base material, and liquid crystal display devices 1-37 were manufactured. Next, the display was made into black display, and the color change at the time of observing from the angle of 45 degrees of front and inclination was evaluated based on the following reference | standard.

(Circle): There is no color change.

(Triangle | delta): A color change is confirmed.

X: The color change is very large.

Table 4 and Table 5 show the results of the above evaluation.

From Table 4 and Table 5, the acrylic resin containing film of this invention is excellent in transparency, high heat resistance, and brittleness is remarkably improved, and punching work of a polarizing plate, panel bonding, etc. are used by using the said acrylic resin containing film. Improve the yield in the work of the film, and further increase the length of the film winding, can increase the work efficiency, further reduce the color shift generated depending on the viewing angle when used in the liquid crystal display device, the contrast is remarkable It can be seen that the improved liquid crystal display device is obtained.

1: melting kiln
3, 6, 12, 15: filter
4, 13: storage tank
5, 14: liquid pump
8, 16: conduit
10: UV absorber input kiln
20: confluence
21: Mixer
30: die
31: metal support
32: Web
33: peeling position
34: tenter stretching device
35: roll drying device
41: Particulate input kiln
42: storage tank
43: pump
44: filter

Claims (7)

It is an acrylic resin containing film containing 10-50 mass parts of cellulose ester resins (B) with respect to 50-90 mass parts of acrylic resins (A), and when one side and the other side of the said acrylic resin containing film are overlapped The static friction coefficient is 0.3-0.8, the tension softening point is 105-145 degreeC, haze value is less than 1%, and it does not produce ductile fracture, The acrylic resin containing film characterized by the above-mentioned. The weight average molecular weight (Mw) of the acrylic resin (A) of the said acrylic resin containing film is 80000-1000000, and the total substitution degree (T) of the acyl group of a cellulose ester resin (B) is 2.00-3.00. Acetyl group substitution degree (ac) is 0.10-1.90, the part other than an acetyl group is substituted by the acyl group which consists of C3-C7, its substitution degree (r) is 1.10-2.90, and a weight average molecular weight (Mw) is 75000 to 280000, and the said film contains 0.05-45 mass% of acrylic microparticles | fine-particles (C) with respect to a film total mass, and the said acrylic microparticles are 25% of the thickness of the whole film from both surfaces of a film, respectively. 40 to 60% of its total amount is present in the within-area region, characterized in that the acrylic resin-containing film. The acrylic resin containing film of Claim 1 or 2 is extended | stretched 5 to 40% in one or more directions, and is manufactured, The acrylic resin containing film manufacturing method characterized by the above-mentioned. The acrylic resin containing film of Claim 1 or 2 is used, The polarizing plate characterized by the above-mentioned. The polarizing plate of Claim 4 is used, The liquid crystal display device characterized by the above-mentioned. The film manufactured by the acrylic resin containing film manufacturing method of Claim 3 is used, The polarizing plate characterized by the above-mentioned. The polarizing plate of Claim 6 is used, The liquid crystal display device characterized by the above-mentioned.

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