KR20060099742A - Composition of polyvinyl alcohol resin and film of polyvinyl alcohol using them - Google Patents

Abstract

The present invention relates to a polyvinyl alcohol composite resin composition and a polyvinyl alcohol film using the same, and more particularly, to a polyvinyl alcohol resin in the saponification process, by impregnating certain anionic and nonionic hydrophilicity enhancers and plasticizers in a certain component ratio The polyvinyl alcohol composite resin composition in which hydrogen bonds are suppressed by widening the spacing between the chains and the polyvinyl alcohol composite resin composition are processed by the extrusion method, so that the surface tension, the contact angle, the polarization rate and the transmittance are improved to be equal or more, and in particular, It relates to a polyvinyl alcohol film suitable for the polarization of the liquid crystal display is improved significantly the number of seafood, color deviation and the like.

Anionic and nonionic hydrophilicity enhancers, plasticizers, polarizers, polyvinyl alcohol films

Description

Polyvinyl Alcohol Composite Resin Composition and Polyvinyl Alcohol Film Using the Same {Composition of Polyvinyl Alcohol Resin and Film of Polyvinyl Alcohol using them}

The present invention relates to a polyvinyl alcohol composite resin composition and a polyvinyl alcohol film using the same, and more particularly, to a polyvinyl alcohol resin in the saponification process, by impregnating certain anionic and nonionic hydrophilicity enhancers and plasticizers in a certain component ratio The polyvinyl alcohol composite resin composition in which hydrogen bonds are suppressed by widening the spacing between the chains and the composite resin composition are processed by an extrusion method, and the surface tension, contact angle, polarization rate and transmittance are improved to be equal or more, and in particular, It is related with the polyvinyl alcohol film which the color deviation etc. improve significantly and are suitable for the polarization of a liquid crystal display.

The polarizing plate has a structure in which a protective plate such as a 3-cellulose acetate (TAC) film is attached to both surfaces of a polarizing film prepared by stretching and dyeing a polyvinyl alcohol film (hereinafter referred to as 'PVA') in one axis. Used for liquid crystal display. In general, there are several precautions for uniformity of polarization performance, such as using a PVA film having a uniform thickness, uniform dyeing of a dichroic dye, and adhesion without staining, but are greatly constrained depending on the performance of the PVA film. PVA film has no residual undissolved matter and it is important to use a color deviation does not occur, which depends on the polyvinyl alcohol resin as a main component.

Unlike general thermoplastic resins, polyvinyl alcohol resins have a very close melting point and pyrolysis temperature, and thus, film forming by a simple hot melting method is impossible. Therefore, in order to manufacture a film using a polyvinyl alcohol resin, a method of lowering the processing temperature and molding using a large amount of a plasticizer such as water and a polyhydric alcohol is generally performed.

As a method of manufacturing a polyvinyl alcohol film, the solution casting method, the extrusion method, etc. are known.

In the solution casting method, a polyvinyl alcohol resin is stirred with a solvent such as water for a long time to prepare a low concentration solution of about 5 to 20% by weight, and then a film forming process is performed. It was contained in large amounts, which entailed a process for drying it and was not economically efficient.

Due to the disadvantage that the solution casting method is not economical, the extrusion method, which is commonly used in manufacturing a polyvinyl alcohol film for polarization, is performed by using an extruder to perform a film forming process. Inevitably, cosmetics have occurred. Thus, in order to minimize the generation of cosmetics through sufficient kneading, two or more uniaxial or multiaxial extruders are connected in series, or methods of removing the generated cosmetics by a plurality of filters are currently used. However, this method does not prevent the residue of many undissolved products in the final product because a large amount of undissolved products can easily pass through the filter through the shape conversion and the technology for filtering the high-viscosity solution is also limited. As known from Japanese Patent Laid-Open No. 2000-120600 using this method, conventional polarizing films have more than 100 undissolved debris having a particle size of 300 μm ² or more per square meter.

In addition, the polyvinyl alcohol film is produced as a polarizing film through a continuous process such as swelling, stretching, dyeing, fixing, washing and drying process. The swelling process is divided into dry and wet depending on the type. In this process, the film is difficult to swell uniformly within a short time, and the uneven swelling degree also causes wrinkles during the subsequent stretching process or uneven salt during the dyeing process. It may cause color deviation, causing color deviation. In addition, in the washing process of removing the dyeing solution or the fixing solution on the film surface, the surface water of the film surface is present in the water droplets rather than uniformly distributed in nature, which causes a difference in the dye concentration between the water droplets and the surroundings during drying. Color deviation is generated.

As described above, the cosmetics and color deviations are a major disadvantage when applied to the polarizer film of polyvinyl alcohol, and in particular, as the liquid crystal display products are gradually widened and high quality, the importance is further emphasized. There is a situation.

Accordingly, the present inventors have tried to solve the polarization performance problems due to residual undissolved matter and color deviation of the polyvinyl alcohol film produced by the extrusion method.

As a result, (A) polyvinyl alcohol resin in the saponification process is impregnated with specific anionic and nonionic hydrophilicity enhancers and plasticizers in a certain component ratio, swelling the resin to widen the interval between molecular chains, and inhibiting hydrogen bonding. The composite resin composition and the film produced using the resin realize that physical properties such as surface tension, contact angle, polarization ratio, transmittance, number of undissolved debris, and color deviation are improved to be equal or more than in the prior art, thereby completing the present invention. It became.

Accordingly, the present invention improves the surface tension, the contact angle, the polarization rate and the transmittance by an equivalent or more by using the polyvinyl alcohol composite resin composition containing a specific component in the polyvinyl alcohol resin in the saponification process, and in particular, The purpose of the present invention is to provide a polyvinyl alcohol film with an improved number of unsealed seafood and color deviation.

The present invention relates to (A) 100 parts by weight of a polyvinyl alcohol resin having a saponification degree of 75.0 to 99.8 mol%, (B) 0.001 to 0.3 parts by weight of an anionic hydrophilic enhancer represented by the following general formula (1); (C) 0.001 to 0.3 parts by weight of a nonionic hydrophilic enhancer represented by the following formula (2); And (D) 0.0001 to 385 parts by weight of two or more plasticizers selected from water, polyhydric alcohols, and phthalate compounds, and have a saponified saponification degree of 99.9 mol% or more.

[Formula 1]

[Formula 2]

In Formula 1 or Formula 2, R ¹ is H or an alkyl group having 1 to 20 carbon atoms, R ² is H, or COOR ¹ , M is an alkali metal or alkaline earth metal atom, m is an integer of 1 to 20, n is an integer of 0-20, x is an integer of 0-7, and x + y represents the integer of 9-11.

In addition, the present invention has another feature of the polyvinyl alcohol film produced by extrusion molding the polyvinyl alcohol composite resin composition.

Hereinafter, the present invention will be described in detail.

In order to improve the polarization performance of the polyvinyl alcohol film, the polyvinyl alcohol resin in the saponification reaction is impregnated with a specific anionic and nonionic hydrophilicity enhancer and a plasticizer in a certain component ratio to swell the resin before the saponification is completed. The polyvinyl alcohol composite resin composition, which effectively widens the spacing between chains and suppresses hydrogen bonding, and the polyvinyl alcohol composite resin are extruded to improve surface tension, contact angle, polarization rate, and transmittance equal to or more. And a polyvinyl alcohol film and a method for producing the same, which are greatly improved when applied to a polarizing plate, such as color deviation.

The polyvinyl alcohol composite resin composition according to the present invention and a polyvinyl alcohol film using the composition and a manufacturing method thereof will be described in more detail.

The present invention has a technical construction feature in a polyvinyl alcohol composite resin composition in which a saponification reaction is completed by containing a specific anionic and nonionic hydrophilicity enhancer and a plasticizer in a certain component ratio during the saponification reaction performed during the preparation of the polyvinyl alcohol resin. .

The degree of saponification refers to the extent to which the acetate groups in the molecular chain of the polyvinyl alcohol resin are substituted with hydroxy groups. Even when the molecular weight is the same, the degree of saponification is divided into water solubility, poor solubility, and insolubility according to the difference in saponification degree. In other words, as the acetate group having a relatively large functional group is substituted with the hydroxy group, the interval between the molecular chains is narrowed, and strong hydrogen bonds are formed by the hydroxy groups between the molecular chains.

From this, the main cause of undissolved residues remaining in the polyvinyl alcohol film produced by the extrusion method is due to the strong hydrogen bonds between the molecular chains in the polyvinyl alcohol resin previously formed before the extrusion process of the film. In particular, unlike water-soluble or mold release applications, the polarized polyvinyl alcohol resin having a degree of saponification of 99.9 mol% or more has a stronger molecular chain bonding structure, and thus it is difficult to prepare a perfect melt without undissolved products by a short extrusion process.

Therefore, it should be suppressed as much as possible to have a hydrogen bond structure between molecular chains of the polyvinyl alcohol resin before processing by the extrusion method. The present invention is an anionic hydrophilic enhancer represented by the formula (1) and a nonionic hydrophilic enhancer and plasticizer represented by the formula (2) before the saponification degree of the resin in the saponification process of the polyvinyl alcohol resin manufacturing process is 99.9 mol% After the impregnation is added to complete the saponification process.

In order to improve the surface tension and contact angle of the polyvinyl alcohol resin, the added hydrophilic enhancer uses the anionic hydrophilic enhancer of Formula 1 and the nonionic hydrophilic enhancer of Formula 2. In Formula 2, more preferably, m is an integer of 3 to 18. The hydrophilicity enhancer is used in 0.001 to 0.3 parts by weight, preferably 0.002 to 0.1 parts by weight based on 100 parts by weight of polyvinyl alcohol. When the amount of each hydrophilic enhancer is less than 0.001 parts by weight, the effect of improving the surface tension and contact angle is insignificant. When the amount of the hydrophilic agent is increased by more than 0.3 parts by weight, it is easily transferred to the film surface, and wrinkles due to adhesion between films are easily generated during long-term storage. Therefore, it is preferable to maintain the above range, and in this case, uniform swelling, dyeing and drying are possible, thereby enabling the production of a polarizing plate without color deviation.

In addition, the plasticizers commonly used in the art in order to lower the temperature during processing in addition to the hydrophilicity enhancer, in addition to the above role in the present invention, these are essential roles for inhibiting hydrogen bonds between resin chains and maintaining molecular chain spacing. Do this. The plasticizer may be used two or more selected from polyhydric alcohols, water and phthalate compounds, and specifically, for example, polyhydric alcohols may be glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and the like. As the phthalate compound, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, diisooctyl phthalate, dinonyl phthalate, di isononyl phthalate and diisodecyl phthalate can be used.

Such plasticizers are used in an amount of 1 to 35 parts by weight, preferably 5 to 25 parts by weight, water of 30 to 350 parts by weight, preferably 80 to 250 parts by weight, based on 100 parts by weight of the polyvinyl alcohol resin. The phthalate compound is used in an amount of 1 to 100 ppm, preferably 3 to 50 ppm. If the amount of the polyhydric alcohol used in the plasticizer is less than 1 part by weight, the effect is insignificant, and if the amount exceeds 35 parts by weight, the polarizing plate is not completely removed and remains in the optical properties and is too flexible due to the problem of difficult handling. It is desirable to maintain. If the amount of water used in the plasticizer is less than 30 parts by weight, the thermal decomposition of the polyvinyl alcohol occurs easily, and if it exceeds 350 parts by weight, it is difficult to handle the transfer, etc. in the extruder, and because the amount of water to be removed is too large, the process is inefficient. It is preferable to maintain the above range. If the amount of the phthalate-based compound in the plasticizer is less than 1 ppm, the effect is insignificant, and if it exceeds 100 ppm, the problem of lowering the transmittance of the film occurs, so it is preferable to maintain the above range.

In particular, polyhydric alcohols such as glycerin and phthalate-based plasticizers are less volatile than water alone, which is more effective in preventing hydrogen bonds in raw materials and increases stability and long-term integrity. To improve the flowability of the particles. This role enables a uniform feed of feed in the feeder during the extrusion process and consequently a film of uniform thickness.

Meanwhile, the polyvinyl alcohol composite resin composition prepared by impregnating a hydrophilicity enhancer and a plasticizer during the saponification process is extruded using a conventional method used in the art. At this time, the extrusion temperature is 50 ~ 150 ℃, preferably mixed into a multi-screw extruder adjusted to the range 80 ~ 120 ℃ melt to be uniformly melted with little generation of undissolved matter. If the temperature is less than 50 ℃ is not melted because extrusion is impossible, and if it exceeds 150 ℃ polyvinyl alcohol resin is partially pyrolyzed due to the problem of discoloration is good to maintain the above range.

The molten melt is transformed into a film form while passing through a gear pump and a die, followed by a filter installed for the purpose of removing foreign substances, and then cast on a continuously rotating casting roll. Thereafter, the cast film is first dried on a casting roll, and the moisture contained therein is lowered to 5 to 70 parts by weight based on 100 parts by weight of polyvinyl alcohol resin. At this time, if a large amount of water is rapidly removed for a short time, it is the main cause of the film warping due to the moisture content gradient between the casting surface and the atmospheric surface of the film due to the casting characteristics, and on the contrary, when a sufficient amount of moisture is not removed, Forces acting on the film cause film deformation. The peeled film has a non-uniform moisture content inside and outside due to the characteristics of the process, which may cause distortion of the electrical during the next drying process. Therefore, it is possible to stabilize the non-uniform moisture by arranging several drying rolls of small diameter after the casting roll. Moisture stabilization by passing through a roll dryer ultimately results in a film having a desired moisture content by passing through a floating dryer consisting of a plurality of air nozzles and maintained at 30 to 180 ° C. The film, dried to a certain moisture content, cuts off edges of non-uniform thickness and is wound on rolls in the winder. At this time, the film is wound in a tensionless state in order to minimize deformation of the film and adhesion between the films.

The polyvinyl alcohol film prepared according to the present invention as described above is to produce a polarizing film through a swelling, stretching, dyeing, fixing, washing and drying process, looking at each process as follows. The swelling process can be both dry and wet, but it is important that the polyvinyl alcohol film has a uniform swelling property in a short time. If the time is longer, wrinkles are generated on the surface of the film in the stretching process, which is a major cause of color non-uniformity. Such swelling can be improved by lowering the surface tension of the film.

In addition, the stretching process is carried out uniaxial stretching, it is possible to stretch in the swelling tank and dye bath, and the dyeing process is carried out using iodine or dichroic dye to uniform dyeing so that the color deviation of the final polarizer does not occur It is important to follow.

The fixing process for stabilizing the adsorbed dye is carried out in the presence of boron or boron compounds, washing with water to remove dyes and fixatives remaining on the surface, and the water remaining on the surface after washing is removed by drying. At this time, the contact angle of the film should be low enough so that the moisture does not exist in the form of water during drying and thus does not cause color deviation.

This invention will be described in more detail based on Examples. The present invention is not limited by the following examples.

Example 1

In the production of polyvinyl alcohol (hereinafter referred to as 'PVA') having a degree of saponification of 99.98 mol% and a polymerization degree of 2,400, 11 parts by weight of glycerin, 150 parts by weight of water, and dioctylphthalate 30 to 100 parts by weight of PVA during the saponification process 0.05 ppm by weight of dibutylsodiumsulfuradiate and 0.050 parts by weight of polyoxyethylene were impregnated with ppm and a hydrophilic enhancer.

The impregnated raw material was added to a multi-screw extruder hopper having a temperature set at 100 ° C. to prepare a composite resin composition. The composite resin composition homogeneously mixed and melted in the extruder was deformed into a film while passing through a T die, and then discharged onto a casting roll at 85 ° C. to perform a first drying process. The dried film was again dried in a floating dryer equipped with a plurality of air nozzles up and down, and then cut a non-uniform portion of the edge was produced a polyvinyl alcohol film wound on a roll in a winder.

Extrusion direction thickness deviation, surface tension, contact angle, polarization ratio, transmittance of the number of undissolved lysates and color deviation of the polyvinyl alcohol film prepared above were measured by the following method, and the results are shown in Table 2 below.

[Measurement of physical properties]

(1) Surface tension: Surface tension of the solution of 1% by weight of polyvinyl alcohol film at 20 ° C. (Crusus Model K10T).

(2) Contact angle: Measurement of the contact angle of the polyvinyl alcohol film (Face Corp. Model CA-DT).

(3) Number of unsealed seafoods, color deviation: Using a Polarisscope with a polarizer of 1 square square meter, color deviations and unsealed seafoods of 300 µm ² or more based on particle area were measured (Phigi Instruments Model 243).

Example 2

In the same manner as in the above 1, 100 parts by weight of PVA with a degree of saponification of 99.95 mol% and a polymerization degree of 1,700, 9 parts by weight of glycerin as a plasticizer, 100 parts by weight of water, 30 ppm of dioctylphthalate, and dibutylsodium sulfadione as a hydrophilic enhancer. The polyvinyl alcohol film was manufactured by setting the temperature of the multiaxial extruder to 0.05 degreeC using the pate 0.050 weight part and the polyoxyethylene also 0.050 weight part of decyl ether.

Extrusion direction thickness deviation, surface tension, contact angle, polarization rate, transmittance of the number of undissolved debris and color deviation of the polyvinyl alcohol film prepared above were measured, and the results are shown in Table 2 below.

Example 3

In the same manner as in Example 1, but with a degree of saponification of 99.98 mol%, 100 parts by weight of PVA having a degree of polymerization of 2,400, 11 parts by weight of glycerin as a plasticizer, 150 parts by weight of water, 30 ppm of dioctylphthalate and 0.050 of potassium lauryl acid as a hydrophilic enhancer. A polyvinyl alcohol film was prepared using 0.05 parts by weight of polyoxyethylene dodecyl ether.

Extrusion direction thickness deviation, surface tension, contact angle, polarization rate, transmittance of the number of undissolved debris and color deviation of the polyvinyl alcohol film prepared above were measured, and the results are shown in Table 2 below.

Example 4

In the same manner as in Example 1, but 100. parts by weight of PVA with a degree of saponification of 99.98 mol%, a polymerization degree of 2,400, 11 parts by weight of glycerin as a plasticizer, 150 parts by weight of water, 30 ppm of dioctylphthalate and a hydrophilicity enhancing agent with dibutylsodiumsulfuradi A polyvinyl alcohol film was prepared using 0.050 part by weight of pate and 0.050 part by weight of diethanolamide oleate.

Extrusion direction thickness deviation, surface tension, contact angle, polarization rate, transmittance of the number of undissolved debris and color deviation of the polyvinyl alcohol film prepared above were measured, and the results are shown in Table 2 below.

Comparative Example 1

In the same manner as in Example 1, but without impregnating a plasticizer and a hydrophilicity enhancer during the PVA resin saponification process, it was put directly into the extruder to prepare a polyvinyl alcohol film.

Extrusion direction thickness deviation, surface tension, contact angle, polarization rate, transmittance of the number of undissolved debris and color deviation of the polyvinyl alcohol film prepared above were measured, and the results are shown in Table 2 below. At this time, 200 undissolved seafoods were found, which resulted in a long striped color deviation of 5 to 10 mm in width and 50 to 100 mm in length due to dyeing unevenness.

Comparative Example 2

In the same manner as in Example 1, a polyvinyl alcohol film was prepared by impregnating the saponified dry resin without impregnating the plasticizer and the hydrophilicity enhancer during the PVA resin saponification process.

Extrusion direction thickness deviation, surface tension, contact angle, polarization rate, transmittance of the number of undissolved debris and color deviation of the polyvinyl alcohol film prepared above were measured, and the results are shown in Table 2 below. At this time, 110 undissolved seafoods were found, which resulted in a long striped color deviation having a width of 3 to 6 mm and a length of 30 to 60 mm due to dyeing unevenness.

Comparative Example 3

A polyvinyl alcohol film was prepared in the same manner as in Example 1, except that dibutylsodiumsulfurate, a hydrophilic enhancer, and polyoxyethylene dodecyl ether were used.

Extrusion direction thickness deviation, surface tension, contact angle, polarization rate, transmittance of the number of undissolved debris and color deviation of the polyvinyl alcohol film prepared above were measured, and the results are shown in Table 2 below. At this time, 40 undissolved lysates were found, and color deviations on long ellipses having a width of 5 to 20 mm and a length of 30 to 300 mm due to dyeing unevenness occurred.

Table 1 summarizes the components used, such as PVA resin, plasticizer and hydrophilicity enhancer used in Examples 1 to 4 and Comparative Examples 1 to 3, amount of use, injection of components during saponification, and the like.

division Resin polymerization degree Resin saponification degree (mol%) Injection during inspection process Hydrophilic Enhancer (parts by weight) Plasticizer (parts by weight) Anionic Nonionic Alcohol water Phthalates (ppm) Example 1 2400 99.98 O BS (0.05) OE (0.05) 11 150 30 Example 2 1700 99.95 O BS (0.05) OE (0.05) 9 100 30 Example 3 2400 99.98 O LK (0.05) OE (0.05) 11 150 30 Example 4 2400 99.98 O BS (0.05) OA (0.05) 11 150 30 Comparative Example 1 2400 99.98 × BS (0.05) OE (0.05) 11 150 30 Comparative Example 2 2400 99.98 × BS (0.05) OE (0.05) 11 150 30 Comparative Example 3 2400 99.98 O Do not use 11 150 30 BS: Dibutyl sodium sulfa adipate OE: Polyoxyethylene dodecyl ether LK: Potassium laurate OA: Diethanolamide oleate

division Extrusion direction film thickness deviation (㎛) Surface tension (dyne / cm) Contact angle (degree) Polarization rate (%) Transmittance (%) Beauty Seafood Count Color deviation Example 1 75 ± 0.5 35 11 99.3 44.1 5 none Example 2 75 ± 0.5 36 13 98.4 43.5 4 none Example 3 75 ± 1.0 36 12 97.3 43.3 9 none Example 4 75 ± 2.0 36 12 97.1 43.0 8 none Comparative Example 1 75 ± 5.0 40 18 95.6 40.5 200 has exist Comparative Example 2 75 ± 3.0 38 17 96.7 41.1 110 has exist Comparative Example 3 75 ± 3.0 69 38 94.6 42.3 40 has exist

As shown in Table 2, the polyvinyl alcohol films of Examples 1 to 4 prepared using the specific components according to the present invention and injected during the PVA saponification process, have a surface tension and a contact angle compared to Comparative Examples 1 to 3. , Polarization, transmittance, number of undissolved products, color deviation, and the like, it could be confirmed that the superiority was shown. In particular, the polarizing film using the conventional polyvinyl alcohol acts as a barrier to widening due to the residual undissolved matter and color deviation, but the polyvinyl alcohol film according to the present invention is significantly reduced in the number and color deviation of the undissolved seafood. It was confirmed that the better effect can be brought.

As described above, according to the present invention, a plasticizer and a specific anionic and nonionic hydrophilic neutralizing agent are mixed and mixed in a certain component ratio during the PVA resin saponification process, so that the surface tension, contact angle, polarization rate, transmittance, and number of undissolved salts are used. And it is expected that the effect is excellent when applied as a polarizer of various LCD applications because it shows an excellent or better than the equivalent in color deviation, especially the number of unsealed seafood and color deviation.

Claims (5)

(A) To 100 parts by weight of polyvinyl alcohol resin having saponification degree of 75.0 to 99.8 mol%, (B) 0.001 to 0.3 parts by weight of anionic hydrophilicity enhancer represented by the following formula (1); (C) 0.001 to 0.3 parts by weight of a nonionic hydrophilic enhancer represented by the following formula (2); And (D) 0.0001 to 385 parts by weight of two or more plasticizers selected from water, polyhydric alcohols and phthalate compounds Polyvinyl alcohol composite resin composition having a saponification degree of 99.9 mol% or more, characterized in that it is saponified. [Formula 1]

[Formula 2]

In Formula 1 or Formula 2, R ¹ is H or an alkyl group having 1 to 20 carbon atoms, R ² is H, or COOR ¹ , M is an alkali metal or alkaline earth metal atom, m is an integer of 1 to 20, n is an integer of 0-20, x is an integer of 0-7, and x + y represents the integer of 9-11. The method of claim 1, wherein the plasticizer is based on 100 parts by weight of polyvinyl alcohol resin A polyvinyl alcohol composite resin composition, comprising 30 to 350 parts by weight of water, 1 to 35 parts by weight of polyhydric alcohols, and 1 to 100 ppm of a phthalate compound. The polyvinyl alcohol composite resin composition according to claim 1, wherein the polyhydric alcohol is selected from glycerin, ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol. The method of claim 1, wherein the phthalate compound is polyvinyl, characterized in that selected from dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, diisooctyl phthalate, dinonyl phthalate, diisononyl phthalate and diisodecyl phthalate Alcohol composite resin composition. A polyvinyl alcohol film prepared by extrusion molding the polyvinyl alcohol composite resin composition of any one of claims 1 to 4. The polyvinyl alcohol film for polarization which is 95-100, and the transmittance | permeability is 42 or 45 and the number of undissolved matter which has a particle area of 300 micrometer <^2> or more per unit area (m <2>) is 10 or less.