WO2015037723A1

WO2015037723A1 - Polymer film, polymer film production method, polarization plate and liquid crystal display device

Info

Publication number: WO2015037723A1
Application number: PCT/JP2014/074301
Authority: WO
Inventors: 伸卓岩橋; 洋平 ▲濱▼地; 福重　裕一; 大作阿比留; 米山　博之
Original assignee: 富士フイルム株式会社
Priority date: 2013-09-13
Filing date: 2014-09-12
Publication date: 2015-03-19
Also published as: JP2015077794A; KR101789456B1; KR20160042050A; JP6054923B2

Abstract

Provided is a polymer film production method that can produce polymer films with a high surface hardness, and involves: a step for forming a laminate on a support body by co-casting, sequential casting, or casting and coating a polymerizable compound-containing composition that contains a polymerizable compound and a polymer and does not contain an initiator, and an initiator-containing composition that contains an initiator and does not contain a polymerizable compound; a step for separating the laminate from the support body; and a step for curing the laminate by light or heat. Also provided are a polymer film, a polarization plate and a liquid crystal display device.

Description

Polymer film, method for producing polymer film, polarizing plate and liquid crystal display device

The present invention relates to a polymer film, a method for producing the polymer film, a polarizing plate, and a liquid crystal display device. More specifically, the present invention relates to a polymer film having a high surface hardness, a method for producing a polymer film capable of producing a polymer film having a high surface hardness, and a polarizing plate and a liquid crystal display device using the polymer film.

Many sheet members used in optical devices such as liquid crystal displays are manufactured from polymer films. Many polymer films are scratched by contact with other objects and friction, so the sheet member is hard on the polymer film so that it will not be scratched during the manufacturing or use of optical equipment. There are many films (hard coat film) provided with a coat.

It has also been proposed to use a component that cures by irradiating the polymer film itself with light used for a hard coat layer, as a component of the solution-forming solution. For example, Patent Document 1 discloses an ethylenically unsaturated monomer and / or a functional group-containing ethylenically unsaturated monomer and light in a cellulose ester dope composition used for forming a cellulose ester film by a solution casting film forming method. The cellulose ester dope composition containing a polymerization initiator is cast on the endless metal support of the solution casting film forming apparatus until the drying of the web is completed in the drying apparatus. A method of irradiating with ultraviolet rays is described.

JP 2002-020410 A

However, for the purpose of improving the surface hardness of the polymer film, the inventors investigated the surface hardness of the cellulose ester film described in Patent Document 1 in which a monomer was added to the cellulose ester dope and exposed and cured after film formation. Due to insufficient curing, high surface hardness could not be obtained.

The problem to be solved by the present invention is to provide a method for producing a polymer film capable of producing a polymer film having a high surface hardness.

As a result of intensive studies by the present inventors for the above purpose, a polymerizable compound-containing composition containing a polymerizable compound and a polymer and not containing an initiator, and an initiator containing an initiator and not containing a polymerizable compound By forming the composition containing the solution on a support, the initiator is reacted more efficiently than when the composition containing the polymerizable compound, the polymer and the initiator is cast as a single layer, and the polymerizable compound is reacted. It was found that a method for producing a polymer film capable of producing a polymer film having a high surface hardness and a high surface hardness can be provided.
The present invention, which is a specific means for solving the above problems, is as follows.

[1] A polymerizable compound-containing composition that contains a polymerizable compound and a polymer and does not contain an initiator, and an initiator-containing composition that contains an initiator and does not contain a polymerizable compound are co-cast on a support, and sequentially flowed. Forming a laminate by rolling or casting and applying; and
Peeling the aforementioned laminate from the aforementioned support,
And a step of curing the laminate with light or heat.
[2] The method for producing a polymer film according to [1] preferably includes a step of stretching the laminate.
[3] In the method for producing a laminate film according to [1] or [2], the curing step is preferably a step of irradiating the laminate with ultraviolet rays once or more.
[4] The method for producing a polymer film according to any one of [1] to [3] preferably includes a step of drying the laminate after the curing step.
[5] The method for producing a polymer film according to any one of [1] to [4] includes 1% by mass or more of an ultraviolet absorber with respect to the polymer contained in the polymerizable compound-containing composition. Is preferred.
[6] In the method for producing a polymer film according to any one of [1] to [5], the thickness of the polymer film is preferably 20 to 100 μm.
[7] In the method for producing a polymer film according to any one of [1] to [6], the polymer is preferably a cellulose ester.
[8] The method for producing a polymer film according to any one of [1] to [7], wherein a hard coat layer, a low moisture permeable layer, an antiglare layer, an antistatic layer are further formed on the laminate after the curing step. It is preferable to include a step of laminating at least one of the layer, the antifouling layer and the antireflection layer.
[9] A polymer film produced by the method for producing a polymer film according to any one of [1] to [8].
[10] A polymerizable compound-containing composition containing a polymerizable compound and a polymer and not containing an initiator and an initiator-containing composition containing an initiator and not containing a polymerizable compound are laminated and further cured by light or heat. A polymer film having a laminate.
[11] The polymer film according to [9] or [10] includes a hard coat layer, a low moisture permeable layer, an antiglare layer, an antistatic layer, an antifouling layer, and an antireflection layer in addition to the laminate described above. It preferably has at least one layer.
[12] A polarizing plate having a polarizer and the polymer film according to any one of [9] to [11].
[13] A liquid crystal display device having a liquid crystal cell and the polymer film according to any one of [9] to [11] or the polarizing plate according to [12].

According to the present invention, it is possible to provide a method for producing a polymer film that can produce a polymer film having a high surface hardness.

It is the schematic of a casting apparatus. It is an enlarged view of a casting die. It is the schematic of a film manufacturing equipment.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

[Production method of polymer film]
The method for producing a polymer film of the present invention (hereinafter also referred to as the production method of the present invention) includes a polymerizable compound-containing composition containing a polymerizable compound and a polymer and not containing an initiator, and a polymerizable compound containing an initiator. A step of forming a laminate by co-casting, sequential casting, or casting and coating a non-initiator-containing composition on a support, a step of peeling the laminate from the support, and a laminate Curing with light or heat.
With such a configuration, according to the method for producing a polymer film of the present invention, a polymer film having a high surface hardness can be produced.

FIG. 1 shows an example of a casting apparatus 10 that can be used in the method for producing a polymer film of the present invention. The casting apparatus 10 includes a support 12 (hereinafter also referred to as a casting support, preferably a metal support) and a casting die 14. The support 12 may be a rotating drum or a band, but for example, a rotating drum as shown in FIG. 1 is preferable. The casting die 14 joins the flow of the first solution 16 (first solution flow) and the flow of the second solution 18 (second solution flow), and then discharge port 20 (FIG. 2) formed at the tip. The casting film 22 is formed by allowing it to flow out on the support 12 traveling from the reference). That is, the casting apparatus 10 forms the laminated body (casting film) 22 by a known co-casting method.

The first solution 16 forms a cast film 22a derived from the polymerizable compound-containing composition of the cast film 22, and is, for example, a composition containing a polymerizable compound and a polymer such as cellulose acylate. The polymer solution preferably has a viscosity of 100 Pa · s or less. On the other hand, the 2nd solution 18 forms the casting film 22b derived from the initiator containing composition of the laminated body (casting film) 22, The composition in which polymerizable compounds, such as a monomer and an oligomer, were melt | dissolved in the solvent. Preferably, it is a solution having a viscosity of 10 Pa · s or less. The viscosity ratio of the first and

second solutions

16 and 18 is preferably 10: 1 or more (where X / Y ≧ 10, where X is the viscosity of the first solution and Y is the viscosity of the second solution). Preferably satisfy). Examples of polymerizable compounds such as monomers and oligomers include a curing agent that is cured by ultraviolet rays and a curable polymerization agent.
However, the above embodiment is an example of the present invention, and any of the casting film 22a derived from the polymerizable compound-containing composition and the casting film 22b derived from the initiator-containing composition may be on the support side, that is, Any of them may be the first solution 16 or the second solution 18.

As shown in FIG. 2, the casting die 14 is formed with a first supply port 24, a second supply port 26, a first flow path 28, and a second flow path 30 in addition to the discharge port 20 described above. . The first solution 16 is supplied from the first supply port 24, and the second solution 18 is supplied from the second supply port 26. The first and second flow paths 28 and 30 are slit-shaped flow paths whose cross-sectional shape perpendicular to the direction in which the solution flows is long in the width direction of the casting film 22 (the depth direction in FIGS. 1 and 2). The first flow path 28 is formed so as to connect the first supply port 24 and the discharge port 20, and the second flow path 30 is formed so as to connect the second supply port 26 and the discharge port 20. Yes.

Thus, in the casting die 14, the most downstream ends of the first and second flow paths 28 and 30 are connected to the discharge port 20, and the first and

second solutions

16 and 18 are connected to the discharge port. After being merged in an area (merging portion) near 20, it is discharged from the discharge port 20 to the support 12.

Moreover, in the said embodiment, although the example which applies this invention to the casting apparatus which co-casts the 1st, 2nd solution was demonstrated, in addition to the 1st, 2nd solution, the 3rd solution is co-cast. The present invention may be applied to a casting apparatus.

Furthermore, the casting apparatus may be provided with a temperature control mechanism for adjusting the peripheral surface temperature of the support by heating or cooling the support. Further, a decompression chamber may be provided in the vicinity of the casting die on the upstream side in the rotational direction of the support, and the upstream side in the rotational direction of the support may be decompressed relative to the casting die. Furthermore, you may provide the air blower which blows in the circumferential direction of a support body, the duct for flowing the wind from an air blower along the outer periphery of a support body, etc. In addition, when blowing along the outer periphery of a support body, it is preferable to blow in the direction opposite to the moving direction of a support body.

Hereinafter, a film manufacturing facility 60 for manufacturing the polymer film 50 using the casting apparatus 10 (see FIG. 1) will be described with reference to FIG. In the film manufacturing facility 60, a drying unit 62 is provided on the downstream side of the casting apparatus 10. The laminate (casting film) 22 formed on the support 12 by the casting apparatus 10 is turned into a wet film 64 by cooling the support 12, for example. Then, the wet film 64 is peeled off from the support 12, conveyed by the roller 68, and sent to the drying unit 62.

The drying unit 62 is provided with a tenter 70. The tenter 70 is provided with a plurality of clips 72 as holding means for holding the side ends of the wet film 64 on both sides of the transport path of the wet film 64. When the wet film 64 cannot withstand gripping by the clip 72, for example, when the content of the solvent is too high and tears by gripping, the side end of the wet film 64 is replaced with a pin instead of the clip 72. A pin may be pierced into the portion, thereby holding the wet film 64.

The plurality of clips 72 are provided in an endless chain (not shown) that continuously travels, and the travel path of the clips 72 can be changed by displacing the travel path of the chain. The width of the wet film 64 may be regulated by appropriately adjusting the distance between the clip 72 and the clip 72 disposed on both sides of the wet film 64.

The tenter 70 is provided with a blower duct 74 that blows dry air whose temperature is adjusted to the wet film 64, and by this blow, the wet film 64 is dried while being held by the clip 72 and conveyed.

In addition, the tenter 70 may not be arranged when the roller can be supported by the peripheral surface of the roller and conveyed by the rotation of the roller.

The wet film 64 released from being held by the clip 72 is guided to a cutting device 76 provided downstream of the tenter 70. A grip mark remains at the grip position gripped by the clip 72 of the wet film 64. The cutting device 76 continuously cuts the side end portion of the wet film 64 so that the grip mark is separated from the central portion that is the product of the polymer film 50.

Downstream of the cutting device 76, there is a drying chamber 80 that is provided with a plurality of rollers 78 that support the wet film 64 with both ends cut off on the peripheral surface, and is supplied with dry air. The roller 78 includes a driving roller that conveys the wet film 64 by being rotationally driven in the circumferential direction. The supplied dry air is adjusted to a predetermined temperature and humidity. With this dry air, the wet film 64 is further dried and completely dried. The degree of “complete” is a degree of drying that does not cause a problem as a product, and the residual solvent amount does not necessarily have to be 0 (zero). The completely dried film is referred to as a dry film 82 in the following description.

The dried film 82 that has passed through the drying unit 62 is sent to the curing device 84. The curing device 84 has a light source that emits ultraviolet rays, and irradiates the guided dry film 82 with ultraviolet rays from the light source. By this irradiation, the curable compound is cured. When the curable compound is polymerized by irradiation, the progress of this polymerization corresponds to the progress of curing.

The curing device 84 may be provided in the casting device 10, the tenter 70, and the drying chamber 80 instead of downstream of the drying unit 62 as in the present embodiment. That is, you may irradiate an ultraviolet-ray with respect to any of the laminated body 22 which is a casting film, the wet film 64, and the dry film 82. FIG. In this manner, at least one of the laminate 22, the wet film 64, and the dry film 82 that is in the state of a cast film may be irradiated with ultraviolet rays.

The portion corresponding to the casting film 22b derived from the polymerizable compound-containing composition and the portion corresponding to the casting film 22a derived from the initiator-containing composition are both cured by the irradiation of the curing device 84 with ultraviolet rays. In this way, the polymer film 50 is obtained. And the obtained polymer film 50 is wound up by the winding core 88 set in the winding-up part 86 in roll shape.

<Step of forming a laminate>
The method for producing a polymer film of the present invention comprises a polymerizable compound-containing composition containing a polymerizable compound and a polymer and no initiator, and an initiator-containing composition containing an initiator and no polymerizable compound. The step of forming a laminate by co-casting, sequential casting, or casting and coating.

A polymerizable compound-containing composition containing a polymerizable compound and a polymer and not containing an initiator does not contain an initiator. When the polymerizable compound-containing composition contains no initiator, it means that the initiator is not substantially contained in the polymerizable compound-containing composition. Specifically, the polymerizable compound-containing composition is based on the polymerizable compound. The content is less than 1% by mass. In the polymerizable compound-containing composition, the content of the initiator with respect to the polymerizable compound is preferably less than 0.1% by mass, and more preferably less than 0.01% by mass.

An initiator-containing composition that contains an initiator and does not contain a polymerizable compound does not contain a polymerizable compound. “Initiator-containing composition does not contain a polymerizable compound” means that the initiator-containing composition is substantially free of a polymerizable compound, specifically, for the initiator of the polymerizable compound. The content is less than 1% by mass. In the initiator-containing composition, the content of the polymerizable compound with respect to the initiator is preferably less than 0.1% by mass, and more preferably less than 0.01% by mass.
The initiator-containing composition may further contain a polymer.

Hereinafter, the polymer, polymerizable compound, initiator and other additives used in the method for producing a polymer film of the present invention will be described.

(polymer)
The method for producing a polymer film of the present invention preferably uses the following polymer.

-Cellulose acylate-
In the method for producing a polymer film of the present invention, the polymer is preferably a cellulose ester, and more preferably cellulose acylate.
In cellulose acylate, the proportion of cellulose hydroxyl groups esterified with carboxylic acid, that is, the degree of acyl group substitution (hereinafter referred to as acyl group substitution degree) satisfies all the conditions of the following formulas (1) to (3). Particularly preferred are: In (1) to (3), A and B are both acyl group substitution degrees, the acyl group in A is an acetyl group, and the acyl group in B has 3 to 22 carbon atoms.
2.5 ≦ A + B ≦ 3.0 (1)
0 ≦ A ≦ 3.0 (2)
0 ≦ B ≦ 2.9 (3)

The glucose unit constituting cellulose and having β-1,4 bonds has free hydroxyl groups at the 2nd, 3rd and 6th positions. Cellulose acylate is a polymer in which some or all of the hydroxyl groups of cellulose are esterified, and the hydrogen of the hydroxyl group is substituted with an acyl group having 2 or more carbon atoms. Since the degree of substitution is 1 when esterification of one hydroxyl group in the glucose unit is 100%, in the case of cellulose acylate, the hydroxyl groups at the 2nd, 3rd and 6th positions are each 100% ester. The degree of substitution is 3.

Here, the total acyl group substitution degree obtained by “DS2 + DS3 + DS6”, where the acyl group substitution degree at the 2-position in the glucose unit is DS2, the acyl substitution degree at the 3-position is DS3, and the acyl substitution degree at the 6-position is DS6 is 2. It is preferably from 00 to 3.00, more preferably from 2.22 to 2.90, further preferably from 2.40 to 2.88, and from 2.60 to 2.88. Even more preferred. Further, “DS6 / (DS2 + DS3 + DS6)” is preferably 0.32 or more, more preferably 0.322 or more, and further preferably 0.324 to 0.340.

There may be only one kind of acyl group, or two or more kinds. When there are two or more acyl groups, it is preferable that one of them is an acetyl group. The sum of the substitution degrees of the hydrogen at the 2-, 3- and 6-position hydroxyl groups with acetyl groups is DSA, and the sum of the substitution degrees with acyl groups other than the acetyl groups at the 2-, 3- and 6-positions is DSB. In this case, the value of “DSA + DSB” is preferably 2.2 to 2.86, more preferably 2.40 to 2.88, and particularly preferably 2.60 to 2.88. DSB is preferably 1.50 or less, more preferably 0.5 or less, and particularly preferably 0. In DSB, 28% or more is preferably 6-position hydroxyl group substitution, more preferably 30% or more, further preferably 31% or more, particularly preferably 32% or more substitution of 6-position hydroxyl group. It is preferable. In addition, the value of “DSA + DSB” at the 6-position of cellulose acylate is preferably 0.75 or more, more preferably 0.80 or more, and particularly preferably 0.85 or more. By using the cellulose acylate as described above, preferable solubility for obtaining a polymer solution used for solution casting can be obtained, and a polymer solution having a low filterability and a preferable viscosity can be produced. In particular, when a non-chlorine organic solvent is used, the above cellulose acylate is preferable.

The acyl group having 2 or more carbon atoms may be an aliphatic group or an aryl group, and is not particularly limited. For example, there are cellulose alkylcarbonyl ester, alkenylcarbonyl ester, aromatic carbonyl ester, aromatic alkylcarbonyl ester, etc., and these may each further have a substituted group. Propionyl group, butanoyl group, pentanoyl group, hexanoyl group, octanoyl group, decanoyl group, dodecanoyl group, tridecanoyl group, tetradecanoyl group, hexadecanoyl group, octadecanoyl group, iso-butanoyl group, t-butanoyl group, cyclohexane Examples thereof include a carbonyl group, an oleoyl group, a benzoyl group, a naphthylcarbonyl group, and a cinnamoyl group. Among these, a propionyl group, a butanoyl group, a dodecanoyl group, an octadecanoyl group, a t-butanoyl group, an oleoyl group, a benzoyl group, a naphthylcarbonyl group, a cinnamoyl group, and the like are more preferable, and a propionyl group and a butanoyl group are particularly preferable.

-Acrylic resin-
The polymer film of the present invention preferably contains an acrylic resin.
In the present invention, the “acrylic resin” includes a methacrylic resin. Therefore, hereinafter, “acrylic resin” is also referred to as “(meth) acrylic resin”.
The polymer film of the present invention preferably contains a (meth) acrylic resin as a main component. Here, a main component refers to a component with the largest containing mass ratio among the components contained in a polymer film. The polymer film of the present invention preferably contains 10% by mass to 100% by mass of (meth) acrylic resin, more preferably 20% by mass to 100% by mass, and more preferably 30% by mass to 100% by mass. More preferably, it is contained below.

The (meth) acrylic resin is obtained by polymerizing a (meth) acrylic monomer, but may contain a structural unit obtained from a monomer other than the (meth) acrylic monomer.

Any appropriate (meth) acrylic monomer may be employed as the (meth) acrylic monomer within a range not impairing the effects of the present invention. For example, (meth) acrylic acid and (meth) acrylic acid ester are mentioned. Preferred examples include alkyl esters of 1 to 6 carbon atoms of (meth) acrylic acid, and more preferred is methyl methacrylate.
Only one type of (meth) acrylic monomer may be used, or two or more types may be used in combination.

The (meth) acrylic resin is preferably a (meth) acrylic resin having a lactone ring structure from the viewpoint of high heat resistance, high transparency, and high mechanical strength.

Examples of the (meth) acrylic resin having a lactone ring structure include JP 2000-230016, JP 2001-151814, JP 2002-120326, JP 2002-254544, and JP 2005. The above UV-absorbing monomer is further contained in the monomer composition for producing a (meth) acrylic resin having a lactone ring structure, as described in Japanese Patent No. 146084 and Japanese Patent Application Laid-Open No. 2006-171464. A (meth) acrylic resin produced from the monomer composition is preferred.

The weight average molecular weight (Mw) of the (meth) acrylic resin in the present invention is preferably from 1,000 to 2,000,000, more preferably from 5,000 to 1,000,000, and even more preferably from 10,000 to 1,000,000.

The (meth) acrylic resin may have a glutarimide unit represented by the following general formula (1).

Here, R ¹¹ and R ¹² each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, R ¹³ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, Or an aryl group having 6 to 10 carbon atoms.

(Polymerizable compound)
The polymerizable compound may be either a monomer or an oligomer. Although there is no restriction | limiting in particular in a polymeric compound, The monomer or oligomer same as the monomer or oligomer for matrix formation binders used for the below-mentioned hard-coat layer, and the below-mentioned multibranched compound can be mentioned, Among these, polyfunctional acrylate is mentioned. It is preferable to include at least. The polymerizable compound used in the polymerizable compound-containing composition may be used alone or in combination of two or more.

As the polymerizable compound, an ionizing radiation curable polyfunctional monomer or polyfunctional oligomer can be used, and as the functional group of such a polyfunctional monomer or polyfunctional oligomer, those having photopolymerization properties such as light, electron beam, and radiation polymerization can be used. Of these, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

-monomer-
The polymerizable compound used in the polymerizable compound-containing composition is more preferably a dipentaerythritol hexaacrylate (DPHA) represented by the following formula (I) as a monomer.

-Oligomer-
More preferably, the polymerizable compound used in the polymerizable compound-containing composition is an urethane acrylate as an oligomer.
As a polymerizable compound used in the polymerizable compound-containing composition, DPHA and urethane acrylate may be used in combination.

-Multi-branched compounds-
The polymerizable compound-containing composition or initiator-containing composition used in the production method of the present invention preferably contains a multi-branched compound in addition to the polyfunctional acrylate, and contains a polymerizable multi-branched compound described later. It is more preferable. Thereby, the cured film which has still higher hardness is obtained.

The hyperbranched compound is a compound having a molecular weight of 1300 or more having a high-order branched structure having a partial structure such as a so-called comb shape or star shape repeatedly in two or more stages. Multibranched compounds include those whose terminal group is a group selected from a carboxyl group, an amino group, an epoxy group, an acryloyl group, and a methacryloyl group. Among these, a particularly preferred terminal group is an acryloyl group or a methacryloyl group. Hereinafter, a compound having a molecular weight of 1300 or more having at least one group selected from an acryloyl group and a methacryloyl group (hereinafter, these groups are also collectively referred to as “(meth) acryloyl group”) as a terminal group is referred to as “polymerizable”. Also referred to as “multi-branched compound”. )
The hyperbranched compound is preferably a polymerizable hyperbranched compound. The polymerizable multi-branched compound preferably has at least 10 terminal (meth) acryloyl groups, more preferably 12 or more and 32 or less.
The hyperbranched compound is a compound having a molecular weight of 1300 or more, but the molecular weight is 1300 or more and 100,000 or less, more preferably 1300 or more and 20000 or less, and particularly preferably 1300 or more and 15000 or less. When it has a molecular weight of 1300 or more, it means a weight average molecular weight.

In the present invention, it is preferable that the multi-branched compound is selected from the group consisting of dendrimers and hyperbranched polymers because a cured film having high hardness can be easily obtained.
A dendrimer has a chemical structure in which a chemical structure constituting a core (hereinafter also referred to as “core part”) is regularly branched to the outside thereof, and has a spherical, highly controlled chemical structure and Has a molecular weight. Hyperbranched polymers have a chemical structure similar to dendrimers, but are not as highly regular branching structures or high molecular weight controls as in dendrimers, and the branches are formed according to a probability distribution and have a broad molecular weight distribution. It is what you have.
Dendrimers and hyperbranched polymers have excellent solubility, low viscosity when made into a solution, and have a large number of functional groups (for example, carboxyl group, amino group, epoxy group, acryloyl group, and methacryloyl group). Such a characteristic on the chemical structure seems to be a factor for obtaining a cured film having a high hardness at a low heating temperature by combination with a polymerizable compound.

Dendrimers and hyperbranched polymers are described in, for example, JP 2012-173549 A, WO 2008/047620 A, JP 2012-83594 A, and the like. These compounds have a core part, the branched chain part couple | bonded with this core part, and also the terminal group couple | bonded with this branched chain part. The branched chain portion includes a highly branched structure in which a two-dimensional or three-dimensional branched partial structure is repeated two or more steps, and the terminal group has a large number of functional groups (for example, a hydroxy group, a carboxyl group, an amino group). , Epoxy group, acryloyl group, and methacryloyl group). Such dendrimers and hyperbranched polymers are dendritic compounds having a molecular weight of 1300 or more.
The compound constituting the core is preferably synthesized using a branched polyhydric alcohol having three or more chain groups having a methylol group at the end, and further having a chain shape having a methylol group at the end. Those synthesized using a branched polyhydric alcohol having 4 or more groups are particularly preferred.
Preferable specific examples of the polyhydric alcohol include, for example, pentaerythritol, dipentaerythritol, trimethylolpropane and the like. A structure in which branching is repeated by connecting a linking group having a branched structure (hereinafter also referred to as a branched chain portion) to the hydroxy group of the polyhydric alcohol in two or more stages. That is, a branched chain part is bonded to each branched chain end of the branched structure closest to the hydroxy group of the polyhydric alcohol to form a highly branched compound, and at least a part of the functional group described above is formed at the terminal. Are combined. When a group other than a functional group is included at the terminal, these groups include an alkyl group such as a methyl group.
Examples of the core part include structural units represented by the following structures (1) to (4).

[In structure (1), * part represents a binding site with a branched chain part. ]

[In the structure (2), n represents an integer of 0 to 2, and the * part has the same meaning as described above. ]

[In structure (3), the * part has the same meaning as described above. ]

[In structure (4), the * part has the same meaning as described above. ]

The branched chain portion is preferably a structural unit having three or more branched structures, and examples thereof include polyamide, polyester, polyether, polyurethane, and polyurea. Of these, polyester units and polyurethane units are preferred. As the branched chain part, a polyhydroxycarboxylic acid unit is preferable, and a unit represented by the following structure (5) or structure (6) is more preferable. Further, the branched chain portion may include a structure in which two or more units represented by the following structure (5) or structure (6) are independently connected.

[In structure (5), * part represents a binding site with a core part or a branched chain unit. ]

[In structure (6), * part represents a binding site with a core part or a branched chain unit. ]

The core part and the branched chain part may be bonded by a single bond, or may be bonded via a bonding site derived from an alkylene oxide such as ethylene oxide or propylene oxide. In the case of bonding via a bonding site derived from alkylene oxide, it is preferable that the oxygen terminal side of alkylene oxide is bonded to the branched chain part * part.

The group bonded to the terminal of the multi-branched compound is preferably a group having an ethylenically unsaturated bond, and examples of such a group include a (meth) acryloyl group and a vinyloxy group. Of these, a (meth) acryloyl group is preferable.

In addition, the alkali-developable multi-branched polymer described in International Publication No. 2008/047620 is more advantageous for pattern formation by alkali development because of increased solubility before curing by radiation.

These compounds can be produced, for example, by a method described in International Publication No. 2008/047620 pamphlet or Japanese Patent Application Laid-Open No. 2008-174518.
The molecular weight or the weight average molecular weight of these compounds is 1300 or more and 100,000 or less, more preferably 1300 or more and 20000 or less, further preferably 1300 or more and 15000 or less. The viscosity at 25 ° C. is preferably 100 Pa · s to 500,000 Pa · s, more preferably 300 to 300,000 Pa · s.

Specifically, for example, compounds represented by the following structural formulas (B-1) to (B-5) can be given.

Also, under the trade names, Esdrimer HU-22 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Biscote # 1000 (manufactured by Osaka Organic Chemical Co., Ltd.), STAR-501 (manufactured by Osaka Organic Chemical Co., Ltd.), A-HBR-5 Names of “Hypertech” (manufactured by Shin-Nakamura Chemical Co., Ltd.), New Frontier R-1150 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), SN-2301 (manufactured by Sartomer), and Nissan Chemical Industries, Ltd. Products sold in Japan, such as UR-101, can be used. The compounds selected from the group consisting of these dendrimers and hyperbranched polymers may be used alone or in combination of two or more.

The polymerizable compound used in the polymerizable compound-containing composition is a polymer (however, when the initiator-containing composition contains a polymer, the total of the polymer contained in the polymerizable compound-containing composition and the initiator-containing composition). It is preferably used in the range of 50 to 200 parts by mass, more preferably in the range of 70 to 180 parts by mass, and particularly preferably in the range of 100 to 150 parts by mass with respect to 100 parts by mass.

(Initiator)
As the initiator, a known photopolymerization initiator or a known thermal polymerization initiator can be used. The concentration of the initiator is preferably in the range of 1% by mass to 8% by mass with respect to the mass of the polymerizable compound. The concentration of the initiator is a value obtained by {V11 / Z11} × 100, where Z11 is the mass of the polymerizable compound and V11 is the mass of the initiator.

Photo radical polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfides Examples include compounds, fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Various examples are described in the latest UV curing technology (P.159, issuer; Kazuhiro Takashiro, publisher; Technical Information Association, Inc., published in 1991), which is useful for the present invention.
Preferable examples of commercially available photocleavable photoradical polymerization initiators include Irgacure series (IrgOXE01, Irg127, Irg651, Irg184, Irg907) manufactured by BASF Corporation.
Further, as described in JP-A-6-41468, it is also preferable to use two kinds of photopolymerization initiators in combination.
The initiator contained in the initiator-containing composition is preferably used in a range of 0.1 to 15 parts by mass with respect to 100 parts by mass with respect to the polymerizable compound contained in the polymerizable compound-containing composition. More preferably, it is in the range of 1 to 10 parts by mass. Further, the initiator contained in the initiator-containing composition is a polymer contained in the polymerizable compound-containing composition (however, when the initiator-containing composition contains a polymer, the polymerizable compound-containing composition and the initiator are contained). It is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the total of the polymers contained in the composition.

In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.
Further, instead of or in addition to the photopolymerization initiator, a thermal polymerization initiator such as a thermal radical initiator may be used to cause the polymerization reaction by heating.

Examples of the thermal radical polymerization initiator include azo compounds and peroxides, with azo compounds being preferred. Examples of the azo compound include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), and dimethyl-2,2′-. Azobis (2-methylpropionate), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis [N- ( 2-propenyl) 2-methylpropionamide], 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2 ′ -Azobis (N-cyclohexyl-2-methylpropionamide) and the like. Commercially available azo compounds exemplified above include V-70, V-65, V-60, V-59, V-40, V-30, V-501, V-601, VE-073, and VA-080. , VA-086, VF-096, VAm-110, VAm-111, VA-044, VA-046B, VA-060, VA-061, V-50, VA-057, VA-067, VR-110 (or more And Wako Pure Chemical Industries, Ltd.).
Examples of the peroxide include t-butyl peroxybenzoate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and the like. Examples of commercially available peroxides include Perbutyl Z, Perhexa 25B (manufactured by NOF Corporation), and the like.
Of these thermal radical polymerization initiators, those having a 10-hour half-life temperature of 20 to 150 ° C. are preferred, those having 40 to 130 ° C. are more preferred, those having 60 to 110 ° C. are more preferred, and 70 ° C. A temperature of ˜100 ° C. is particularly preferred.

(Other additives)
The polymerizable compound-containing composition or initiator-containing composition used in the production method of the present invention may contain an ultraviolet absorber (hereinafter also referred to as UV absorber or UV agent), other oligomers or polymers. .
Hereinafter, the other additive used for the process of forming the laminated body of the manufacturing method of this invention is demonstrated.

-UV absorber-
The method for producing a polymer film of the present invention preferably contains 1% by mass or more of the ultraviolet absorber relative to the polymer contained in the polymerizable compound-containing composition, and contains 1.5 to 20% by mass of the ultraviolet absorber. More preferably, it contains 2 to 10% by mass of an ultraviolet absorber. The ultraviolet absorber contributes to improvement of the durability of the polarizer. In particular, in an embodiment in which the polymer film of the present invention is used as a surface protective film for a liquid crystal display device, the addition of an ultraviolet absorber is effective.
Furthermore, when the initiator-containing composition contains a polymer, it is preferable to contain 1% by mass or more of an ultraviolet absorber with respect to the total of the polymer contained in the polymerizable compound-containing composition and the initiator-containing composition, More preferably, it contains 1.5 to 20% by mass of an ultraviolet absorber, and particularly preferably 2 to 10% by mass of an ultraviolet absorber.
According to the method for producing a polymer film of the present invention, even when a relatively large amount of an ultraviolet absorber is added in this way, the reaction rate of the polymerizable compound is increased when the polymerizable compound is crosslinked by UV exposure. And the surface hardness of the resulting polymer film can be increased. Although not bound by any theory, the influence of the UV absorber dispersed in the film is suppressed by providing a concentration gradient so that the initiator increases on the side of the UV exposed surface and performing UV exposure. In particular, it is not necessary to add a large amount of an initiator, and it is not necessary to make a particularly high UV irradiation amount, and the exposure and curing can proceed efficiently.
In the method for producing a polymer film of the present invention, either one of the polymerizable compound-containing composition and the initiator-containing composition may contain an ultraviolet absorber, or both may contain an ultraviolet absorber. The polymerizable compound-containing composition preferably contains an ultraviolet absorber, and only the polymerizable compound-containing composition contains an ultraviolet absorber from the viewpoint of increasing the reaction rate of the polymerizable compound.

There is no particular limitation on the ultraviolet absorber that can be used in the present invention. Any ultraviolet absorber conventionally used in cellulose acylate films can be used. Examples of the ultraviolet absorber include compounds described in JP-A-2006-184874. Polymer ultraviolet absorbers can also be preferably used. In particular, polymer type ultraviolet absorbers described in JP-A-6-148430 are preferably used.

As an example, an ultraviolet absorber having the following structure is given, but the ultraviolet absorber to be added is not limited to the ultraviolet absorber having the following structure.

-Other oligomers and polymers-
In order to impart brittleness to the polymer film of the present invention, other oligomers and / or polymers having a weight average molecular weight of 500 or more may be added.
Examples of other oligomers and polymers include cellulose-based and styrene-based polymers and polyester acrylates.
It is preferable that other oligomers and / or polymers in the polymer film of the present invention are not included in the polymer film of the present invention. When included in the polymer film of the present invention, for example, it is preferably 5 to 80% by mass, more preferably 25 to 70% by mass, particularly preferably 35 to 65% by mass based on the total mass of the polymer film of the present invention. %.

(solvent)
There is no restriction | limiting in particular as a solvent used for a polymeric compound containing composition and an initiator containing composition, A well-known solvent can be used. For example, it is preferable to use a known solvent used for solution casting of a cellulose ester film.
It is preferable that the polymerizable compound-containing composition and the initiator-containing composition used in the present invention form a dope, which is cast on a support to form a film. At this time, since it is necessary to evaporate the solvent after casting, it is preferable to use a volatile solvent.
Furthermore, it does not react with a reactive metal compound or a catalyst, and does not dissolve the casting support. Two or more solvents may be mixed and used.
Here, an organic solvent having good solubility in a polymer is called a good solvent, and shows a main effect on dissolution, and an organic solvent used in a large amount among them is a main (organic) solvent or a main (organic) solvent. That's it.

Examples of good solvents include ketones such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethers such as tetrahydrofuran (THF), 1,4-dioxane, 1,3-dioxolane, 1,2-dimethoxyethane, formic acid Esters such as methyl, ethyl formate, methyl acetate, ethyl acetate, amyl acetate, γ-butyrolactone, methyl cellosolve, dimethylimidazolinone, dimethylformamide, dimethylacetamide, acetonitrile, dimethylsulfoxide, sulfolane, nitroethane, chloride Examples include methylene and methyl acetoacetate, and 1,3-dioxolane, THF, methyl ethyl ketone, acetone, methyl acetate and methylene chloride are preferred.

The dope preferably contains 1 to 40% by mass of an alcohol having 1 to 4 carbon atoms in addition to the organic solvent.
After casting the dope onto the support for casting, the solvent starts to evaporate and the ratio of alcohol increases, so that the dope of the polymerizable compound-containing composition or the initiator-containing composition is formed on the support. (The name of the dope film after casting is referred to as web or casting film) is used as a gelling solvent that makes it easy to peel off from the support for casting, or the ratio of these is small Sometimes, it also has a role of promoting the dissolution of the polymer of the non-chlorine organic solvent, and also has a role of suppressing the gelation, precipitation, and viscosity increase of the reactive metal compound.

Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol, and propylene glycol monomethyl ether.
Of these, methanol, ethanol, and n-butanol are preferred because they are excellent in dope stability, have a relatively low boiling point, have good drying properties, and are not toxic. Two or more alcohols having 1 to 4 carbon atoms may be used in combination. In the production method of the present invention, a combination of methanol and n-butanol is most preferable from the viewpoints of solubility and gelation. When a cellulose ester is used as a polymer, these organic solvents alone are not soluble in the cellulose ester and are referred to as poor solvents.

When cellulose ester is used as the polymer in the present invention, the cellulose ester that is a raw material of the cellulose ester contains hydrogen bonding functional groups such as hydroxyl groups, esters, and ketones, and is therefore preferably 5 to 30% by mass in the total solvent. From the viewpoint of reducing the peeling load from the casting support, it is preferable to contain 7 to 25% by mass, more preferably 10 to 20% by mass of alcohol.
Further, in the present invention, it is effective to contain a small amount of water to increase the solution viscosity and the film strength in the wet film state at the time of drying, or to increase the dope strength at the time of casting the drum method. The content may be 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, and particularly 0.2 to 2% by mass.

Examples of combinations of organic solvents preferably used as the solvent for the polymer solution in the present invention are listed in JP-A-2009-262551.

If necessary, a non-halogen organic solvent can be used as the main solvent, and detailed description can be found in the Japan Society for Invention and Technology (Publication No. 2001-1745, published on March 15, 2001, Invention Association). There is a description.

In the production method of the present invention, the solvent of the polymerizable compound-containing composition and the solvent of the initiator-containing composition may have the same composition ratio or different composition ratios, but preferably have the same composition ratio. .
Among them, in the present invention, the combination of the solvent of the polymerizable compound-containing composition and the initiator-containing composition is preferably in the following range from the viewpoint of adjusting the viscosity during co-casting.
Solvent of polymerizable compound-containing composition: Mixed solvent of methylene chloride, methanol, butanol Initiator-containing composition Solid content concentration: Mixed solvent of methylene chloride, methanol, butanol of polymerizable compound-containing composition used in the production method of the present invention As an example of the composition ratio of the solvent and the solvent of the initiator-containing composition, for example, methylene chloride: methanol: butanol = 79: 20: 1 (mass ratio) is preferable.

The polymer concentration in the polymer solution in the present invention is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and most preferably 15 to 30% by mass.
The polymer concentration can be adjusted to a predetermined concentration when the polymer is dissolved in a solvent. Alternatively, a solution having a low concentration (for example, 4 to 14% by mass) may be prepared in advance and then concentrated by evaporating the solvent or the like. Furthermore, after preparing a high concentration solution in advance, it may be diluted. Moreover, the concentration of the polymer can be lowered by adding an additive.

Moreover, the solid content concentration of the polymerizable compound-containing composition and the solid content concentration of the initiator-containing composition may be the same or different. Among these, in the present invention, the solid content concentration of the polymerizable compound-containing composition and the initiator-containing composition is preferably in the following range from the viewpoint of adjusting the viscosity during co-casting.
Polymeric compound-containing composition solid content concentration: preferably 15 to 45% by mass, more preferably 25 to 35% by mass.
Initiator-containing composition solid content concentration: preferably 10 to 40% by mass, more preferably 20 to 30% by mass.
As solid content concentrations of the polymerizable compound-containing composition and the initiator-containing composition used in the production method of the present invention, the following examples can be given when cellulose acylate is used as the polymer.
Polymeric compound-containing cellulose acylate solution concentration: 24%
Initiator-containing cellulose acylate solution concentration: 8% (cellulose acylate concentration: 4%)
Cellulose acylate solution concentration when the polymerizable compound-containing composition and the initiator-containing composition are completely mixed: 20%

The timing of adding the additive can be appropriately determined according to the type of the additive. For example, the UV absorber is added to the dope after dissolving the UV absorber in an alcohol such as methanol, ethanol, butanol, an organic solvent such as methylene chloride, methyl acetate, acetone, dioxolane, or a mixed solvent thereof, or You may add directly in dope composition. For an inorganic powder that does not dissolve in an organic solvent, it is preferable to use a dissolver or a sand mill in the organic solvent and the cellulose ester to disperse them before adding them to the dope.

(1) Dissolution Step In a dissolution vessel, the polymer and additives are dissolved in an organic solvent mainly composed of a good solvent for the polymer while stirring to form a polymerizable compound-containing composition dope, or the additive solution is added to the polymer solution. It is preferable to include a step of mixing polymerizable compounds to form a polymerizable compound-containing composition dope.
When the initiator-containing composition contains a polymer, it is preferable that the initiator-containing composition also forms an initiator-containing composition dope.
For the dissolution of the polymer, a method carried out at normal pressure, a method carried out below the boiling point of the main solvent, a method carried out under pressure above the boiling point of the main solvent, JP-A-9-95544, JP-A-9-95557, or Various dissolution methods such as a method using a cooling dissolution method as described in JP-A-9-95538 and a method using a high pressure as described in JP-A-11-21379 can be used. A method in which pressure is applied as described above is preferable.
The concentration of the polymer in the polymerizable compound-containing composition dope is preferably 10 to 35% by mass. It is preferred that an additive is added to the polymerizable compound-containing composition dope during or after dissolution to dissolve and disperse, and then filtered through a filter medium, defoamed, and sent to the next step with a liquid feed pump.

(2) Casting step In the present invention, a polymerizable compound-containing composition containing a polymerizable compound and a polymer and not containing an initiator, and an initiator-containing composition containing an initiator and not containing a polymerizable compound are formed on a support. The laminate is formed by co-casting, sequential casting, or casting and coating. In the casting process, the dope is fed to a pressure die through a liquid feed pump (for example, a pressurized metering gear pump), and an endless metal belt such as a stainless steel belt or a rotating metal drum or the like is supported infinitely. It is preferable that the dope is cast from the pressure die slit at the casting position on the (preferably metal support).
A pressure die that can adjust the slit shape of the die base and facilitates uniform film thickness is preferred. The pressure die includes a coat hanger die and a T die, and any of them is preferably used. The surface of the support is preferably a mirror surface. In order to increase the film forming speed, two or more pressure dies may be provided on a support (preferably a metal support), and the dope amount may be divided and stacked. Or it is also preferable to obtain the film of a laminated structure by the co-casting method which casts several dope simultaneously. As the co-casting, sequential casting, or the method of casting and coating, the contents described in JP2011-132396 can be used, and the contents described in this gazette are incorporated in the present invention. Among these, the co-casting method is preferable from the viewpoint of suppressing air entrained between the polymerizable compound-containing layer and the initiator-containing layer during casting.

In the simultaneous co-casting method (multi-layer simultaneous casting), the casting dope of each layer (which may be two layers or more) is simultaneously applied from another slit or the like on the casting support (band or drum). This is a casting method in which a dope is extruded from a casting caster to be extruded, and each layer is cast simultaneously, peeled off from a support at an appropriate time, and dried to form a film. In the present invention, an embodiment in which a co-casting giusa and a dope for a surface layer and a dope for a core layer are simultaneously extruded on a casting support and shown in FIG. Can be used.

In the sequential casting method, a dope for an outermost layer is first extruded from a casting giusa on a casting support, cast, and dried or dried without being dried or dried. The dope for casting is extruded from a casting beam caster, and if necessary, the dope is cast and laminated sequentially up to the third layer or more, peeled off from the support at an appropriate time, and dried to form a film. The casting method.

On the other hand, the coating method generally includes a polymer and forms the thickest core layer film into a film by a solution casting method, prepares a coating solution to be applied to the surface layer, and uses an appropriate coating machine. In this method, a film having a laminated structure is formed by applying and drying a coating solution onto a film one side at a time or both sides simultaneously.

In the method for producing a polymer film of the present invention, the laminate may be formed to have two layers or may be formed to have three or more layers, but the polymerizable compound contains so that the laminate has two layers. It is preferable to form a layer derived from the composition and a layer derived from the initiator-containing composition.
In the method for producing a polymer film of the present invention, the stacking order of the polymerizable compound-containing composition and the initiator-containing composition is not particularly limited. For example, when forming so that a laminated body may become two layers, you may laminate | stack in order of a polymeric compound containing composition and an initiator containing composition from a support side, and an initiator containing composition and a polymeric compound containing are included from the support side. You may laminate | stack in order of a composition. Among them, it is preferable to laminate the polymerizable compound-containing composition and the initiator-containing composition in this order from the support side.
When either one of the polymerizable compound-containing composition and the initiator-containing composition is formed by casting and the other is formed by coating, a known method can be used as the coating method.

(3) Solvent evaporation process The web (before the polymer film is finished, which still contains a lot of solvent) is heated on the support until the web becomes peelable from the support. This is a step of evaporating the solvent.
In order to evaporate the solvent, there are a method of blowing air from the web side and / or a method of transferring heat from the back side of the support by a liquid, a method of transferring heat from the front and back by radiant heat, and the like. The drying efficiency is preferable. A method of combining them is also preferable. In the case of backside liquid heat transfer, it is preferable to heat at or below the boiling point of the main solvent of the organic solvent used in the dope or the organic solvent having the lowest boiling point.

(4) Peeling process It is the process of peeling the web which the solvent evaporated on the support body in a peeling position. The peeled web is sent to the next process. It should be noted that if the residual solvent amount of the web at the time of peeling (the following formula) is too large, peeling is difficult, or conversely, if the film is peeled off after being dried sufficiently on the support, a part of the web is peeled off in the middle. Or
Here, there is a gel casting method (gel casting) as a method for increasing the film forming speed (the film forming speed can be increased by peeling while the residual solvent amount is as large as possible). For example, there are a method in which a poor solvent for the polymer is added to the dope and the gel is formed after casting the dope, a method in which the temperature of the support is lowered and the gel is formed. By making it gel on the support and increasing the strength of the film at the time of peeling, it is possible to speed up the peeling and increase the film forming speed.
The amount of residual solvent at the time of peeling of the web on the support is preferably 5 to 150% by weight depending on the strength of drying conditions, the length of the support, etc., but when the amount of residual solvent is larger In the case of peeling, the amount of residual solvent at the time of peeling is determined in consideration of the economic speed and quality. In the present invention, the temperature at the peeling position on the support is preferably −50 to 40 ° C., more preferably 10 to 40 ° C., and most preferably 15 to 30 ° C.

Further, the residual solvent amount of the web at the peeling position is preferably 10 to 150% by mass, and more preferably 10 to 120% by mass.
The amount of residual solvent can be represented by the following formula.
Residual solvent amount (% by mass) = [(MN) / N] × 100
Here, M is the mass of the web at an arbitrary point in time, and N is the mass when the mass M is dried at 110 ° C. for 3 hours.

(5) Drying or heat treatment process, stretching process After the peeling process, a drying apparatus that alternately conveys the web through a plurality of rolls arranged in the drying apparatus, and / or a tenter apparatus that clips and conveys both ends of the web with clips. The web is preferably dried using

When heat treatment is performed in the present invention, the heat treatment temperature is less than Tg-5 ° C, preferably Tg-20 ° C or more and less than Tg-5 ° C, and preferably Tg-15 ° C or more and less than Tg-5 ° C. More preferred.
The heat treatment temperature is preferably 30 minutes or less, more preferably 20 minutes or less, and particularly preferably about 10 minutes.

As a means of drying and heat treatment, hot air is generally blown on both sides of the web, but there is also a means of heating by applying a microwave instead of the wind. The temperature, air volume, and time vary depending on the solvent used, and the conditions may be appropriately selected according to the type and combination of the solvents used.

(6) Winding The length of the polymer film obtained as described above is preferably wound at 100 to 10000 m per roll, more preferably 500 to 7000 m, still more preferably 1000 to 6000 m. is there. The width of the film is preferably 0.5 to 5.0 m, more preferably 1.0 to 3.0 m, and still more preferably 1.0 to 2.5 m. When winding, knurling is preferably applied to at least one end, the knurling width is preferably 3 mm to 50 mm, more preferably 5 mm to 30 mm, and the height is preferably 0.5 to 500 μm, more preferably 1 to 200 μm. is there. This may be a single push or a double push.

The web thus obtained can be wound to obtain a polymer film.

<Extension>
The method for producing a polymer film of the present invention preferably includes a step of stretching the laminate from the viewpoint of increasing the surface hardness.
Although an extending process may be performed before hardening a laminated body or after hardening, it is preferable from a viewpoint of raising the surface hardness of the polymer film obtained by performing before hardening.
The stretching step may be performed on the support before peeling the laminate from the support or after the laminate is peeled from the support, but preferably after the laminate is peeled from the support. .
The stretching step is preferably performed before the laminate is completely dried.

The stretching treatment may be performed in one direction of MD and TD, or may be biaxially stretched in both directions. Stretching in the TD direction is preferred. Stretching may be performed in one stage or in multiple stages.

The stretching ratio in stretching in the film conveying direction MD is preferably 0 to 20%, more preferably 0 to 15%, and particularly preferably 0 to 10%. The stretch ratio (elongation) of the web during stretching can be achieved by the difference in peripheral speed between the support speed and the stripping speed (stripping roll draw). For example, when an apparatus having two nip rolls is used, the film can be preferably stretched in the conveying direction (longitudinal direction) by increasing the rotational speed of the nip roll on the outlet side rather than the rotational speed of the nip roll on the inlet side. it can. By performing such stretching, the tensile modulus of MD can be adjusted.
Here, the “stretch ratio (%)” means that obtained by the following formula.
Stretch ratio (%) = 100 × {(Length after stretching) − (Length before stretching)} / Length before stretching

The stretching ratio in stretching in the direction TD perpendicular to the film conveying direction is preferably 0 to 30%, more preferably 1 to 20%, and particularly preferably 2 to 15%.
In addition, in this invention, it is preferable to extend | stretch using a tenter apparatus as a method of extending | stretching to the direction TD orthogonal to a film conveyance direction.

In the biaxial stretching, a desired retardation value can be obtained by relaxing in the longitudinal direction, for example, 0.8 to 1.0 times. The draw ratio is set according to various purposes. When producing a polymer film, it can also be uniaxially stretched in the longitudinal direction.

It is preferable that the temperature during stretching is Tg or less because the tensile elastic modulus in the stretching direction is increased. The Tg of cellulose triacetate is about 130 to 140 ° C. The stretching temperature is preferably Tg-90 ° C. to Tg, more preferably Tg-80 ° C. to Tg-5 ° C.

<Curing>
The method for producing a polymer film of the present invention includes a step of curing the laminate by light or heat.
The step of curing the laminate with light or heat is preferably a step of curing the laminate with light. In the method for producing a polymer film of the present invention, the curing step irradiates the laminate with ultraviolet rays once or more. More preferably, it is a process to perform.
The curing step such as ultraviolet irradiation may be performed at any place after casting the dope until the complete drying of the film is completed, and is particularly preferably performed after the film is peeled off from the support, More preferably, after stretching.

Examples of the ultraviolet irradiation source include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, and sunlight. Photopolymerization by irradiation with ultraviolet rays can be performed in air or an inert gas, but in the case of using an ethylenically unsaturated monomer, it may be in air, but oxygen may be used as much as possible to shorten the induction period of polymerization. A gas with a low concentration is preferred. The irradiation intensity of ultraviolet rays to be irradiated is preferably about 0.1 to 100 mW / cm ² , and the irradiation amount is preferably about 100 to 20000 mJ / cm ² .

In the method for producing a polymer film of the present invention, the reaction rate of the polymerizable compound after the curing step is preferably 70% or more, more preferably 75% or more, and particularly preferably 80% or more. More preferably, it is 85% or more.

<Drying>
It is preferable that the manufacturing method of the polymer film of this invention includes the process of drying until a laminated body runs out of a solvent after a hardening process.
When drying after the stretching step, the drying temperature, the amount of drying air and the drying time differ depending on the solvent used, and the drying conditions may be appropriately selected according to the type and combination of the solvents used. In the present invention, the drying temperature after the stretching step is preferably lower than the stretching temperature in the stretching step from the viewpoint of increasing the front contrast when the polymer film is incorporated into a liquid crystal display device.

<Lamination of hard coat layers, etc.>
In the method for producing a polymer film of the present invention, at least one of a hard coat layer, a low moisture permeable layer, an antiglare layer, an antistatic layer, an antifouling layer and an antireflection layer is further formed on the laminate after the curing step. It is preferable to include a step of laminating, more preferably including a step of laminating at least one of a hard coat layer, a low moisture-permeable layer, an antiglare layer and an antireflection layer, and in particular, laminating a hard coat layer. preferable.

(Hard coat layer)
The hard coat layer is preferably formed by curing the curable composition. The curable composition is preferably prepared as a liquid coating composition. An example of the coating composition contains a matrix-forming binder monomer or oligomer, polymers, and an organic solvent. A hard coat layer can be formed by curing the coating composition after coating. For curing, a crosslinking reaction or a polymerization reaction can be used.

-Monomers or oligomers for matrix forming binders-
Examples of matrix forming binder monomers or oligomers that can be used include ionizing radiation curable polyfunctional monomers and polyfunctional oligomers. The polyfunctional monomer or polyfunctional oligomer is preferably a monomer capable of crosslinking reaction or polymerization reaction. The functional group of the ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.

Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as (meth) acryloyl group, vinyl group, styryl group, and allyl group, and ring-opening polymerizable functional groups such as epoxy compounds. Of these, a (meth) acryloyl group is preferred.

As a specific example of a photopolymerizable polyfunctional monomer having a photopolymerizable functional group,
(Meth) acrylic acid diesters of alkylene glycol such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate;
(Meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2,2-bis {4- (acryloxy-diethoxy) phenyl} propane and 2,2-bis {4- (acryloxy-polypropoxy) phenyl} propane ;
Etc.

Furthermore, urethane (meth) acrylates, polyester (meth) acrylates, isocyanuric acid acrylates and epoxy (meth) acrylates are also preferably used as the photopolymerizable polyfunctional monomer.

Among the above, esters of polyhydric alcohol and (meth) acrylic acid are preferable, and polyfunctional monomers having three or more (meth) acryloyl groups in one molecule are more preferable.
Specifically, (di) pentaerythritol tri (meth) acrylate, (di) pentaerythritol tetra (meth) acrylate, (di) pentaerythritol penta (meth) acrylate, (di) pentaerythritol hexa (meth) acrylate, tri Pentaerythritol triacrylate, tripentaerythritol hexatriacrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO-modified phosphate tri (meth) acrylate, 1,2,4-cyclohexanetetra (meth) acrylate, Printer glycerol triacrylate, 1,2,3-cyclohexane tetramethacrylate, polyester polyacrylate and caprolactone-modified tris (acryloyloxyethyl) isocyanurate, and the like.
In the present specification, “(meth) acrylate”, “(meth) acrylic acid”, and “(meth) acryloyl” represent “acrylate or methacrylate”, “acrylic acid or methacrylic acid”, and “acryloyl or methacryloyl”, respectively. .

Furthermore, resins having three or more (meth) acryloyl groups, such as relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins And oligomers or prepolymers such as polyfunctional compounds such as polyhydric alcohols.
As specific compounds of polyfunctional acrylate compounds having three or more (meth) acryloyl groups, JP-A-2007-256844 [0096] and the like can be referred to.

As urethane acrylates, for example, alcohols, polyols, and / or hydroxyl group-containing compounds such as hydroxyl group-containing acrylates are reacted with isocyanates, and if necessary, polyurethane compounds obtained by these reactions (meth) Mention may be made of urethane acrylate compounds obtained by esterification with acrylic acid.
As specific examples of specific compounds, reference can be made to the description of [0017] in JP-A-2007-256844.

Examples of the isocyanuric acid acrylates include isocyanuric acid diacrylates and isocyanuric acid triacrylates, and examples of specific compounds refer to [0018] to [0021] of JP-A-2007-256844. be able to.

In the hard coat layer, an epoxy compound can be further used for reducing shrinkage due to curing. As the monomers having an epoxy group for constituting this, monomers having two or more epoxy groups in one molecule are used, and examples thereof include JP-A Nos. 2004-264563 and 2004-264564. Examples thereof include epoxy monomers described in 2005-37737, 2005-37738, 2005-140862, 2005-140862, 2005-140863, 2002-322430 and the like. It is also preferable to use a compound having both epoxy and acrylic functional groups such as glycidyl (meth) acrylate.

-Polymer compounds-
The hard coat layer may contain a non-curable polymer compound. Description and preferred specific examples of the polymer compound are the same as those described in JP 2012-215812 A, and the contents described in this gazette are incorporated in the present specification.

-Curable composition-
Description and preferred specific examples of the curable composition that can be used for forming the hard coat layer are the same as those described in JP 2012-215812 A, and the contents described in this gazette are described in this specification. Incorporated.

(Low moisture permeability layer)
There is no restriction | limiting in particular in the low moisture-permeable layer in the polymer film of this invention.
The low moisture permeable layer contains 50 to 99 of at least one of (A) a compound having a cyclic aliphatic hydrocarbon group and an ethylenically unsaturated double bond and a compound having a fluorene ring and an ethylenically unsaturated double bond. It is preferably formed from a composition for forming a low moisture-permeable layer containing 1% by mass and (B) a rosin compound. If necessary, a curable composition containing a polymerization initiator, translucent particles, a fluorine-containing or silicone compound, and a solvent is added to a base film (polymerizable compound-containing composition and initiator after the curing step). It can be formed by coating, drying and curing directly on the laminate of the containing composition) or via another layer. Each component will be described below.

-Compounds having cycloaliphatic hydrocarbon groups and ethylenically unsaturated double bonds-
A compound having a cyclic aliphatic hydrocarbon group and an ethylenically unsaturated double bond can function as a binder.
By using a compound having a cyclic aliphatic hydrocarbon group and an ethylenically unsaturated double bond, low moisture permeability can be realized, and excellent adhesion between the base film and other layers, and the low moisture permeability layer, Furthermore, light leakage from the polarizing plate can be prevented. Although the details are not clear, by using a compound having a cycloaliphatic hydrocarbon group in the molecule, a hydrophobic cycloaliphatic hydrocarbon group is introduced into the low moisture-permeable layer, and is hydrophobized. It can prevent the uptake of molecules and reduce the water vapor transmission rate. Moreover, by having an ethylenically unsaturated double bond in a molecule | numerator, a crosslinking point density is raised and the diffusion path | route of the water molecule in a low moisture-permeable layer is restrict | limited. Increasing the crosslink point density also has the effect of relatively increasing the density of the cyclic aliphatic hydrocarbon group, making the inside of the low moisture permeable layer more hydrophobic, preventing the adsorption of water molecules, and reducing the moisture permeability. it is conceivable that.
In order to increase the crosslinking point density, the number of ethylenically unsaturated double bonds in the molecule is more preferably 2 or more.

The cyclic aliphatic hydrocarbon group is preferably a group derived from an alicyclic compound having 7 or more carbon atoms, more preferably a group derived from an alicyclic compound having 10 or more carbon atoms, and further preferably Is a group derived from an alicyclic compound having 12 or more carbon atoms.
The cycloaliphatic hydrocarbon group is particularly preferably a group derived from a polycyclic compound such as bicyclic or tricyclic.
More preferably, the central skeleton of the compound described in the claims of Japanese Patent Application Laid-Open No. 2006-215096, the central skeleton of the compound described in Japanese Patent Application Laid-Open No. 2001-10999, or the skeleton of an adamantane derivative may be used.

Specific examples of the cycloaliphatic hydrocarbon group include a norbornane group, a tricyclodecane group, a tetracyclododecane group, a pentacyclopentadecane group, an adamantane group, and a diamantane group.

As the cyclic aliphatic hydrocarbon group (including a linking group), a group represented by any one of the following general formulas (I) to (V) is preferable, and the following general formula (I), (II), or (IV) Is more preferable, and a group represented by the following general formula (I) is more preferable.

In general formula (I), L and L ′ each independently represent a single bond or a divalent or higher valent linking group. n represents an integer of 1 to 3.

In general formula (II), L and L ′ each independently represent a single bond or a divalent or higher valent linking group. n represents an integer of 1 to 2.

In general formula (III), L and L ′ each independently represent a single bond or a divalent or higher valent linking group. n represents an integer of 1 to 2.

In general formula (IV), L and L ′ each independently represent a single bond or a divalent or higher valent linking group, and L ″ represents a hydrogen atom, a single bond or a divalent or higher valent linking group.

In general formula (V), L and L ′ each independently represent a single bond or a divalent or higher linking group.
The divalent or higher valent linking group for L, L ′ and L ″ includes an optionally substituted alkylene group having 1 to 6 carbon atoms, an amide bond which may be substituted at the N position, and a substitution at the N position. Examples thereof include a urethane bond, an ester bond, an oxycarbonyl group, an ether bond and the like obtained by combining two or more thereof.

Examples of the ethylenically unsaturated double bond include polymerizable functional groups such as (meth) acryloyl group, vinyl group, styryl group, and allyl group. Among them, (meth) acryloyl group and —C (O) OCH═CH ₂ is preferred. More preferably, a compound containing two or more (meth) acryloyl groups in one molecule described below can be used. Particularly preferably, a compound containing three or more (meth) acryloyl groups in one molecule described below can be used.

The compound having a cycloaliphatic hydrocarbon group and having two or more ethylenically unsaturated double bonds in the molecule has the above-described cycloaliphatic hydrocarbon group and group having an ethylenically unsaturated double bond. It is configured by bonding through a linking group.

These compounds include, for example, polyols such as diols and triols having the above cyclic aliphatic hydrocarbon groups, and carboxylic acids and carboxylic acid derivatives of compounds having (meth) acryloyl groups, vinyl groups, styryl groups, allyl groups, etc. It can be easily synthesized by a one-step or two-step reaction with an epoxy derivative, an isocyanate derivative or the like.
Preferably, compounds such as (meth) acrylic acid, (meth) acryloyl chloride, (meth) acrylic anhydride, glycidyl (meth) acrylate, and compounds described in WO2012 / 00316A (eg, 1,1-bis ( (Acryloxymethyl) ethyl isocyanate) can be synthesized by reacting with a polyol having the above cyclic aliphatic hydrocarbon group.

Hereinafter, preferred specific examples of the compound having a cycloaliphatic hydrocarbon group and having an ethylenically unsaturated double bond are shown, but the present invention is not limited thereto.

-Compounds having a fluorene ring and an ethylenically unsaturated double bond-
A compound having a fluorene ring and an ethylenically unsaturated double bond that can be contained in the low moisture-permeable layer can function as a binder. In addition, a compound having a fluorene ring and an ethylenically unsaturated double bond can function as a curing agent, and can improve the strength and scratch resistance of the coating film and at the same time impart low moisture permeability. be able to.
In order to increase the crosslinking point density, the number of ethylenically unsaturated double bonds in the molecule is more preferably 2 or more.

The compound having a fluorene ring and an ethylenically unsaturated double bond is preferably represented by the following general formula (VI).

(In formula (VI), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a monovalent substituent, and m, n, p and q are each independently 0 Represents an integer of ˜4, and at least one of R ¹ and R ² represents a monovalent organic group having an ethylenically unsaturated double bond.)

As a compound having a fluorene skeleton and an ethylenically unsaturated double bond in the molecule, a preferred embodiment of the general formula (VI) is represented by the following general formula (VII).

(Wherein R ₇ and R ₈ represent hydrogen or a methyl group, and r and s each represent an integer of 0 to 5)
(A) The content of at least one of the compound having a cycloaliphatic hydrocarbon group and an ethylenically unsaturated double bond and the compound having a fluorene ring and an ethylenically unsaturated double bond is the low moisture permeable layer. When the total solid content of the forming composition is 100% by mass, it is preferably 50 to 99% by mass with respect to the total solid content, and the moisture permeability can be reduced by the synergistic effect of the above (A) and (B). From the viewpoint of saliency, it is more preferably more than 50% by mass and 99% by mass or less, particularly preferably 55 to 95% by mass, and further preferably 60 to 90% by mass.

-Compounds having an ethylenically unsaturated double bond not having a cycloaliphatic hydrocarbon group and a fluorene ring-
The composition for forming a low moisture-permeable layer preferably contains a compound having an ethylenically unsaturated double bond that does not have a cyclic aliphatic hydrocarbon group and a fluorene ring in the molecule.

The compound having an ethylenically unsaturated double bond not having a cycloaliphatic hydrocarbon group and a fluorene ring is preferably a (meth) acrylate compound not having a cycloaliphatic hydrocarbon group and a fluorene ring, (Meth) acrylic acid diesters of alkylene glycol, (meth) acrylic acid diesters of polyoxyalkylene glycol, (meth) acrylic acid diesters of polyhydric alcohols, (meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts , Epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, and the like.

Of these, esters of polyhydric alcohol and (meth) acrylic acid are preferred. For example, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate , Pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, EO modified Tri (meth) acrylate phosphate, trimethylolethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate Rate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyurethane polyacrylate, polyester polyacrylate and caprolactone-modified tris (acryloyloxyethyl) isocyanurate.

Commercially available polyfunctional acrylate compounds having a (meth) acryloyl group can be used, such as NK Ester A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd., KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd. Can be mentioned. The polyfunctional monomer is described in paragraphs [0114] to [0122] of JP-A-2009-098658, and the same can be used in the present invention.

The compound having an ethylenically unsaturated double bond that does not have a cycloaliphatic hydrocarbon group is a compound having a hydrogen-bonding substituent, adhesion to the above-mentioned laminate, low curl, which will be described later From the viewpoint of the fixing property of the fluorine-containing or silicone compound. The hydrogen-bonding substituent refers to a substituent in which an atom such as nitrogen, oxygen, sulfur, or halogen and a hydrogen bond are covalently bonded, specifically, —OH, —SH, —NH—, —CHO. , —CONH—, —OCONH— and the like, and urethane (meth) acrylates and (meth) acrylates having a hydroxyl group are preferred. Commercially available polyfunctional acrylates having a (meth) acryloyl group can also be used, such as NK Oligo U4HA manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-TMM-3, KAYARAD manufactured by Nippon Kayaku Co., Ltd. And PET-30.
The content in the case of containing a compound having an ethylenically unsaturated double bond not having a cyclic aliphatic hydrocarbon group and a fluorene ring is 100% by mass of the total solid content of the composition for forming a low moisture permeable layer. Is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and still more preferably 3 to 15% by mass with respect to the total solid content.

-Rosin compounds-
The rosin compound (B) in the composition for forming a low moisture permeable layer is at least one selected from rosin, hydrogenated rosin (also referred to as hydrogenated rosin), acid-modified rosin and esterified rosin (also referred to as rosin ester). Preferably there is.
Examples of the rosin include unmodified rosins such as tall oil rosin, gum rosin, and wood rosin mainly composed of a resin acid such as abietic acid, levopimaric acid, pastrinic acid, neoabietic acid, dehydroabietic acid, or dihydroabietic acid.
The hydrogenated rosin means a hydrogenated rosin. Examples include those containing a high content (for example, 50% by mass or more) of a tetrahydro compound such as tetrahydroabietic acid. Examples of acid-modified rosins include unsaturated acid-modified rosins in which unsaturated acids such as maleic acid, fumaric acid and acrylic acid have been added by Diels-Alder addition reaction, and more specifically, maleopimar in which maleic acid is added to rosin. Examples thereof include fumaropimaric acid added with acid and fumaric acid, acrylopimaric acid added with acrylic acid, and the like. Examples of esterified rosins include alkyl esters of rosin, glycerin esters obtained by esterifying rosin and glycerin, and pentaerythritol esters obtained by esterifying rosin and pentaerythritol.

Examples of the rosin ester include super ester E-720, super ester E-730-55, super ester E-650, super ester E-786-60, tamanor E-100, emulsion AM-1002, emulsion SE-50 (or more All trade names, special rosin ester emulsion, manufactured by Arakawa Chemical Industries, Ltd.), Super Ester L, Super Ester A-18, Super Ester A-75, Super Ester A-100, Super Ester A-115, Super Ester A- 125, Superester T-125 (all trade names, special rosin esters, manufactured by Arakawa Chemical Industries, Ltd.) and the like.
As rosin esters, ester gum AAG, ester gum AAL, ester gum A, ester gum AAV, ester gum 105, ester gum HS, ester gum AT, ester gum H, ester gum HP, ester gum HD, Pencel A, Pencel AD, Pencel AZ, Pencel C, Pencel D-125, Pencel D-135, Pencel D-160, Pencel KK (all trade names, rosin ester resins, manufactured by Arakawa Chemical Industries, Ltd.).

In addition, other rosins include Longis R, Longes K-25, Longes K-80, Longes K-18 (all trade names, rosin derivatives, manufactured by Arakawa Chemical Industries, Ltd.) Pine Crystal KR-85, Pine Crystal KR-120, Pine Crystal KR-612, Pine Crystal KR-614, Pine Crystal KE-100, Pine Crystal KE-311, Pine Crystal KE-359, Pine Crystal KE-604, Pine Crystal 30PX, Pine Crystal D-6011, Pine Crystal D-6154, Pine Crystal D-6240, Pine Crystal KM-1500, Pine Crystal KM-1550 (all brand names are ultra-light colored rosin derivatives, manufactured by Arakawa Chemical Industries, Ltd.), Aradym R-140, Aladim R- 5 (all trade names, polymerized rosin, manufactured by Arakawa Chemical Co., Ltd.), HYPER CH (all trade names, hydrogenated rosin, manufactured by Arakawa Chemical Co., Ltd.), beam set 101 (all trade names, rosin) Acrylate, Arakawa Chemical Industries, Ltd.) and the like.

The acid value of the rosin compound is preferably 150 to 400 mgKOH / g, more preferably 200 to 400 mgKOH / g, and particularly preferably 280 to 400 mgKOH / g. When the substrate film is a cellulose acylate film, by controlling the acid value of the rosin compound within this range, a very good adhesion effect can be obtained while maintaining the moisture permeability reduction effect of the cured layer.
Examples of the rosin compound having an acid value in the above range include the above-mentioned acid-modified rosin. In particular, a rosin compound obtained by adding maleic acid or fumaric acid by Diels-Alder reaction is preferably used in the present invention.
In the present invention, it is preferable to use a rosin compound that has been acid-modified and then hydrogenated. By performing the hydrogenation treatment, it is possible to prevent the residual double bond of the rosin compound from being oxidized in the low moisture permeable layer and coloring the film.
The softening point of the rosin compound is preferably 70 to 170 ° C. When the softening point of the rosin compound is 70 ° C. or higher, the cured layer is not soft and has excellent blocking properties. When the softening point is less than 170 ° C., the solubility in a solvent can be maintained, and there is an advantage that the haze of the cured layer is difficult to increase.
In the present invention, the softening point of the rosin compound can be measured by the ring and ball method of JIS K-2531.
(B) The content of the rosin compound is 1 to 50% by mass with respect to the total solid content when the total solid content of the low moisture-permeable layer forming composition is 100% by mass. From the standpoint of the remarkable reduction of moisture permeability due to the synergistic effect with (B), the content is preferably 10 to 40% by mass, and more preferably 20 to 30% by mass.

-Polymerization initiator-
The composition for forming a low moisture permeable layer preferably contains a polymerization initiator. As the polymerization initiator, a photopolymerization initiator is preferable.
As photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, Examples include fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, and coumarins. Specific examples, preferred embodiments, commercially available products, and the like of the photopolymerization initiator are described in paragraphs [0133] to [0151] of JP-A-2009-098658, and can be suitably used in the present invention as well. it can.

“Latest UV Curing Technology” {Technical Information Association, Inc.} (1991), p. 159, and “UV Curing System” written by Kiyomi Kato (published by the General Technology Center in 1989), p. Various examples are also described in 65 to 148 and are useful in the present invention.

Commercially available photocleavable photoradical polymerization initiators include “Irgacure 651”, “Irgacure 184”, “Irgacure 819”, “Irgacure 907” manufactured by BASF (formerly Ciba Specialty Chemicals), “Irgacure 1870” (CGI-403 / Irgacure 184 = 7/3 mixed initiator), “Irgacure 500”, “Irgacure 369”, “Irgacure 1173”, “Irgacure 2959”, “Irgacure 4265”, “Irgacure 4263”, “Irgacure 127”, “OXE01”, etc .; “Kaya Cure DETX-S”, “Kaya Cure BP-100”, “Kaya Cure BDK”, “Kaya Cure BTX”, “Kaya Cure BMS”, “Kaya Cure 2” manufactured by Nippon Kayaku Co., Ltd. -EAQ "," Kaya "Sure ABQ", "Kaya Cure CPTX", "Kaya Cure EPD", "Kaya Cure ITX", "Kaya Cure QTX", "Kaya Cure BTC", "Kaya Cure MCA", etc .; "Esacure (KIP100F, KB1, EB3, BP, X33, KTO46, KT37, KIP150, TZT) "and the like, and combinations thereof are preferable examples.

The content of the photopolymerization initiator in the composition for forming a low moisture permeable layer is set so that the polymerizable compound contained in the composition is polymerized and the starting point is set not to increase too much. The total solid content is preferably 0.5 to 8% by mass, and more preferably 1 to 5% by mass.

-UV absorber-
The polymer film including the low moisture permeable layer is preferably used for a polarizing plate or a liquid crystal display device member, but from the viewpoint of preventing deterioration of the polarizing plate or the liquid crystal, the low moisture permeable layer contains an ultraviolet absorber. Thus, ultraviolet absorption can be imparted to the polymer film.
A well-known thing can be used as a ultraviolet absorber. Examples thereof include ultraviolet absorbers described in JP-A No. 2001-72782 and JP-T-2002-543265.

-solvent-
The composition for forming a low moisture-permeable layer can contain a solvent. As the solvent, various solvents can be used in consideration of the solubility of the monomer, the drying property during coating, the dispersibility of the translucent particles, and the like. Examples of such organic solvents include dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole, phenetole, dimethyl carbonate, carbonate Methyl ethyl, diethyl carbonate, acetone, methyl ethyl ketone (MEK), diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, Methyl propionate, ethyl propionate, γ-ptyrolactone, methyl 2-methoxyacetate, methyl 2-ethoxyacetate, ethyl 2-ethoxyacetate, ethyl 2-ethoxypropionate, 2-metho Siethanol, 2-propoxyethanol, 2-butoxyethanol, 1,2-diacetoxyacetone, acetylacetone, diacetone alcohol, methyl alcohol such as methyl acetoacetate and ethyl acetoacetate, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, cyclohexyl Alcohol, isobutyl acetate, methyl isobutyl ketone (MIBK), 2-octanone, 2-pentanone, 2-hexanone, ethylene glycol ethyl ether, ethylene glycol isopropyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, ethyl carbitol, butyl carbitol , Hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, benzene, tolu Examples thereof include ene and xylene, and these can be used alone or in combination of two or more.

Among the above solvents, it is preferable to use at least one of dimethyl carbonate, methyl acetate, ethyl acetate, methyl ethyl ketone, acetylacetone, and acetone, more preferably dimethyl carbonate or methyl acetate, and methyl acetate is used. It is particularly preferred.

It is preferable to use a solvent so that the solid content of the composition for forming a low moisture-permeable layer is in the range of 20 to 80% by mass, more preferably 30 to 75% by mass, and still more preferably 40 to 70% by mass. %.

-Composition and manufacturing method of low moisture permeability layer-
The low moisture permeability layer may be a single layer or a plurality of layers. The method for laminating the low moisture permeable layer is not particularly limited, but the low moisture permeable layer is produced as a co-cast with the base film, or the low moisture permeable layer is applied on the base film. Preferably, the low moisture-permeable layer is provided on the base film by coating.

-Film thickness of low moisture permeability layer-
The thickness of the low moisture permeable layer is preferably 0.5 to 25 μm, more preferably 1 to 20 μm, still more preferably 2 to 18 μm, and particularly preferably 3 to 17 μm.

It is also preferable that the low moisture permeable layer has a moisture permeable hard coat layer function, an antireflection function, an antifouling function and the like.

[Polymer film]
The polymer film of the present invention comprises a polymerizable compound-containing composition containing a polymerizable compound and a polymer and not containing an initiator, and an initiator-containing composition containing an initiator and not containing a polymerizable compound, and further laminated with light or heat. It has the laminated body hardened | cured by.
The polymer film of the present invention is preferably excellent in surface hardness. Specifically, when a pencil hardness test as an index of surface hardness is carried out, it is preferable to achieve 2H or higher, more preferably 3H or higher, still more preferably 4H or higher, 5H It is particularly preferable to achieve the above.
Moreover, the polymer film of this invention can be manufactured with the manufacturing method of the polymer film of this invention.
The thickness of the polymer film of the present invention obtained by the method for producing a polymer film is preferably 20 to 100 μm, and more preferably 20 to 70 μm. Further, the thickness of the polymer film not including the hard coat layer is preferably 20 to 60 μm. From the viewpoint of further thinning, the thickness of the polymer film not including the hard coat layer is more preferably 20 to 40 μm.

The polymer film of the present invention preferably has at least one of a hard coat layer, a low moisture permeable layer, an antiglare layer, an antistatic layer, an antifouling layer and an antireflection layer in addition to the laminate described above. It is more preferable to include a step of laminating at least one of a coat layer, a low moisture permeability layer, an antiglare layer and an antireflection layer, and it is particularly preferable to have a hard coat layer.
The hard coat layer is preferably excellent in surface hardness. Specifically, the polymer film of the present invention having a hard coat layer preferably achieves 3H or higher, and more preferably achieves 4H or higher, when a pencil hardness test is performed as an index of surface hardness. More preferably, 5H or higher is achieved.
The hard coat layer preferably has a thickness of 0.1 to 10 μm, more preferably 3 to 7 μm. By having a thin hard coat layer in the above range, a polymer film including a hard coat layer that has improved physical properties such as brittleness and curl suppression, reduced weight, and reduced manufacturing costs is obtained.
The hard coat layer used in the present invention is a layer for imparting hardness and scratch resistance to the polymer film. The hard coat layer may be formed, for example, by applying and curing the coating composition on a base film (a laminate of the polymerizable compound-containing composition and the initiator-containing composition after the curing step)). it can. Moreover, you may laminate | stack another functional layer on a hard-coat layer for the purpose of adding another function. Also, by adding fillers and additives to the hard coat layer, chemical performance such as mechanical, electrical and optical physical performance and water / oil repellency can be imparted to the hard coat layer itself. .

[Polarizer]
Next, the aspect which uses the polymer film of this invention as a protective film of a polarizing plate is demonstrated.
The polarizing plate of the present invention has a polarizer and the polymer film of the present invention. An example of the polarizing plate of this invention consists of a polarizer and two polarizing plate protective films (transparent film) which protect both surfaces, and has the polymer film of this invention as at least one polarizing plate protective film.
Since the polymer film of the present invention has a high surface hardness, it is particularly preferably used as a polarizing plate protective film on the viewing side of the upper polarizing plate disposed on the viewing side with respect to the liquid crystal cell.

As the polarizing plate protective film on the side where the polymer film of the present invention is not used, a retardation film is preferably used. As such a retardation film, various additives may be blended or stretched in a cellulose acylate film. Examples thereof include a retardation film that exhibits a desired retardation, and a retardation film having an optically anisotropic layer made of a liquid crystal composition on the surface of a support film. Specifically, the description of JP-A-2008-262161 can be referred to, and the contents thereof are incorporated in the present specification.

As the polarizer, for example, a film obtained by immersing and stretching a polyvinyl alcohol film in an iodine solution can be used. When a polarizer obtained by immersing a polyvinyl alcohol film in an iodine solution and stretching is used, the surface-treated surface of the polymer film of the present invention can be directly bonded to at least one surface of the polarizer using an adhesive. As the adhesive, an aqueous solution of polyvinyl alcohol or polyvinyl acetal (for example, polyvinyl butyral) or a latex of a vinyl-based polymer (for example, polybutyl acrylate) can be used. A particularly preferred adhesive is an aqueous solution of fully saponified polyvinyl alcohol.

The method of laminating the polymer film of the present invention to the polarizer is preferably such that the transmission axis of the polarizer and the slow axis of the polymer film of the present invention used as a polarizing plate protective film are substantially parallel. . The slow axis can be measured by various known methods, for example, using a birefringence meter (KOBRA DH, manufactured by Oji Scientific Instruments).
Here, being substantially parallel means that the deviation between the direction of the main refractive index nx of the polymer film and the direction of the transmission axis of the polarizing plate is within 5 °, preferably within 1 °, preferably It is preferably within 0.5 °. If the deviation is within 1 °, the polarization degree performance under the polarizing plate crossed Nicol is unlikely to deteriorate, and light leakage is less likely to occur.

<Functionalization of polarizing plate>
The polarizing plate of the present invention includes an antireflection film for improving display visibility, a brightness enhancement film, a hard coat layer, a low moisture permeable layer, a forward scattering layer, an anti-glare (in the range not departing from the gist of the present invention). It is also preferably used as a functionalized polarizing plate combined with a polymer film having functional layers such as an antiglare layer, an antistatic layer, an antifouling layer and an antireflection layer. Details of these can be referred to the descriptions in paragraphs 0229 to 0242, paragraphs 0249 to 0250 and paragraphs 0086 to 0103 in JP 2012-215812 A, and the contents thereof are incorporated in the present specification. It is.

[Liquid Crystal Display]
The liquid crystal display device of the present invention includes a liquid crystal cell and the polymer film of the present invention or the polarizing plate of the present invention. Details of the liquid crystal display device can be referred to the descriptions in paragraphs 0251 to 0260 of JP2012-082235A, the contents of which are incorporated herein.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[Example 8]
<Film formation of cellulose ester film>
(Preparation of polymerizable compound-containing cellulose ester solution)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a polymerizable compound-containing cellulose ester solution.
――――――――――――――――――――――――――――――――――
90 parts by mass of cellulose acetate having a degree of acetyl substitution of 2.86 and a degree of polymerization of 350 KAYARAD DPHA
(Nippon Kayaku: dipentaerythritol hexaacrylate) 100 parts by weight UV absorber (UV agent below) 4 parts by weight Methylene chloride (first solvent) 639 parts by weight Methanol (second solvent) 162 parts by weight n-butanol (No. 1) 3 solvents) 8 parts by mass ――――――――――――――――――――――――――――――――――

(Preparation of initiator-containing cellulose ester solution)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare an initiator-containing cellulose ester solution.
――――――――――――――――――――――――――――――――――
Cellulose acetate having an acetyl substitution degree of 2.86 and a polymerization degree of 350 10 parts by weight IrgOXE01 (manufactured by BASF: polymerization initiator) 10 parts by weight Methylene chloride (first solvent) 198 parts by weight Methanol (second solvent) 50 parts by weight n-butanol (Third solvent) 3 parts by mass ――――――――――――――――――――――――――――――――――

(Co-casting)
From the leading edge die, co-cast so that the polymerizable compound-containing cellulose ester solution and the initiator-containing cellulose ester solution are laminated in this order from the support side to the polymerizable compound-containing cellulose ester solution and the initiator-containing cellulose ester solution. Then, a two-layer laminate was formed on a drum support at 5 ° C. Then, 40 degreeC dehumidification air was applied on the drum and the laminated body was peeled off from the drum support body.
Then, using a tenter type stretching apparatus with a clip, the laminate was transversely stretched 7% in a direction (TD direction) perpendicular to the film transport direction while applying dry air at 70 ° C.
Then, 600 mJ / cm < ² > of ultraviolet rays were irradiated with the ultraviolet irradiation apparatus of the metal halide lamp, the polymeric compound was polymerized, and it was set as the polymer.
Then, 120 degreeC drying wind was applied and the film after extending | stretching was completely dried, and the cellulose-ester film of Example 8 was obtained.
The cellulose ester film of Example 8 had a thickness of 60 μm.

[Examples 1, 3-7, 10, 11 and 15-17]
Example 1, 3-7, except that the composition of the polymerizable compound-containing cellulose ester solution, the composition of the initiator-containing cellulose ester solution and the film thickness were changed as described in Table 1 below. Cellulose ester films of 10, 11, and 15-17 were prepared.
However, in Example 15, 50 parts by mass of DPHA and Esdrimer HU-22 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) were used as the polymerizable compounds. In Examples 16 and 17, Irg127 (manufactured by BASF) and Irg184 (manufactured by BASF) were used as initiators in place of IrgOXE01, respectively. In Example 7, VF-096 (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the initiator instead of IrgOXE01.
In Examples 1, 3 to 7, 10, and 15 to 17, no stretching was performed.
In Example 7, ultraviolet rays were not irradiated. In Example 7, the polymerization of the polymerizable compound is started by the heat of drying air at 120 ° C.

[Example 9]
(Formation of hard coat layer)
An example with a hard coat layer in which the following hard coat layer solution was applied to the surface of the cellulose ester film produced in Example 8 and cured by irradiating with ultraviolet rays to form a hard coat (HC) layer having a thickness of 6 μm. 9 cellulose ester films were prepared.
――――――――――――――――――――――――――――――――――
Monomer Pentaerythritol triacrylate /
Pentaerythritol tetraacrylate (mixing mass ratio 3/2)
53.5 parts by weight UV initiator Irgacure TM907
(BASF) 1.5 parts by weight ethyl acetate 45 parts by weight ------------- -

[Examples 2 and 12]
The cellulose ester films of Examples 2 and 12 were produced in the same manner as in Example 9 except that the composition of the polymerizable compound-containing cellulose ester solution and the composition of the initiator-containing cellulose ester solution were changed as shown in Table 1 below. did.
However, in Example 2, no stretching was performed.

[Example 13]
As shown in Table 1 below, the composition of the polymerizable compound-containing cellulose ester solution and the composition of the initiator-containing cellulose ester solution were changed, and the polymerization from the first die was performed instead of co-casting at the leading confluence die. Example 8 except that the compound-containing cellulose ester solution was cast on a support, and the initiator-containing cellulose ester solution was sequentially cast on the polymerizable compound-containing cellulose ester solution from the second die downstream in the flow direction. Similarly, the cellulose ester film of Example 13 was produced.

[Example 14]
The composition of the polymerizable compound-containing cellulose ester solution and the composition of the initiator-containing cellulose ester solution were changed as shown in Table 1 below, and the polymerizable compound-containing cellulose was changed from the die in place of co-casting at the leading confluence die. The cellulose ester of Example 14 was cast in the same manner as in Example 8, except that the ester solution was cast on the support, the web was peeled off from the support, and then the initiator-containing cellulose ester solution was coated on the web. A film was produced.

[Comparative Examples 1 to 3]
The composition of the polymerizable compound-containing cellulose ester solution was changed as shown in Table 1 below, and only the polymerizable compound-containing cellulose ester solution was simply put on the support from the die instead of co-casting with the tip merging die. Cellulose ester films of Comparative Examples 1 to 3 were produced in the same manner as in Example 8 except that the layers were cast and not stretched.
In Comparative Examples 1 to 3, the initiator-containing cellulose ester solution was not used.

[Evaluation]
<Pencil hardness>
According to JIS K5400, the surface of the cellulose ester film of each Example and Comparative Example was scratched 10 times with a pencil having the hardness shown in Table 1 below, and the case where the number of scratches was 0 to 2 times, A, 3 to 6 times The case of B was evaluated as B and the case of 7-10 times was evaluated as C.
The obtained results are shown in Table 1 below.

<Reaction rate of polymerizable compound>
The transmission IR spectrum of the cellulose ester film of each Example and Comparative Example was measured with a Fourier transform infrared spectrometer Nicolet 6700 (manufactured by ThermoElectron Corporation), and a peak near 810 cm ⁻¹ derived from the polymerizable unsaturated double bond of DPHA was measured. The area was obtained, and the ratio with the area obtained by measurement of the unexposed film produced by the same method as each Example and Comparative Example except that the exposure was not performed in the production of the cellulose ester film of each Example and Comparative Example. And the reaction rate of the polymerizable compound was calculated.
The obtained results are shown in Table 1 below.

From the said Table 1, it turned out that the cellulose-ester film of each Example which is a polymer film of this invention is excellent in pencil hardness, and surface hardness is high.
On the other hand, from Comparative Example 1, it was found that the cellulose ester film obtained by casting a single layer without using a polymerizable compound or a polymerization initiator had poor pencil hardness and low surface hardness. From Comparative Examples 2 and 3, the cellulose ester film obtained by adding a polymerizable compound and a polymerization initiator to the same layer as the polymer and casting a single layer has poor pencil hardness and surface hardness. I found it low.

[Examples 101 to 117]
<Preparation of polarizing plate>
(Saponification treatment of polarizing plate protective film)
Each cellulose ester film obtained in Examples 1 to 17 was immersed in a 2.3 mol / L sodium hydroxide aqueous solution at 55 ° C. for 3 minutes. It wash | cleaned in the room temperature water-washing bath, and neutralized using 0.05 mol / L sulfuric acid at 30 degreeC. Again, it was washed in a water bath at room temperature and further dried with hot air at 100 ° C. Thus, the surface saponification process was performed about the cellulose-ester film.

(Preparation of polarizing plate)
A polarizer was prepared by adsorbing iodine to a stretched polyvinyl alcohol film.
The saponified cellulose ester film was attached to one side of the polarizer using a polyvinyl alcohol-based adhesive. A commercially available cellulose triacetate film (Fujitac TD80UF, manufactured by FUJIFILM Corporation) is subjected to the same saponification treatment, and is opposite to the side where each cellulose ester film prepared above is attached using a polyvinyl alcohol adhesive. A cellulose triacetate film after saponification treatment was attached to the surface of the polarizer on the side.
At this time, the transmission axis of the polarizer and the slow axis of the obtained cellulose ester film were arranged in parallel. Further, the transmission axis of the polarizer and the slow axis of the commercially available cellulose triacetate film were arranged so as to be orthogonal to each other.
In this way, polarizing plates of Examples 101 to 117 were produced.

<Production of liquid crystal display device>
The polarizing plate on the viewing side of a commercially available liquid crystal television (Sony Co., Ltd. BRAVIA J5000) is peeled off. A liquid crystal display device was obtained by sticking one sheet at a time to the viewer side via an adhesive so that the cell side would be the opposite side.
In this manner, liquid crystal display devices of Examples 101 to 117 were produced.
The display performance of the liquid crystal display devices of Examples 101 to 117 was good.

[Examples 201 to 217, 301 to 317: Polymer film having a low moisture permeability layer, polarizing plate, liquid crystal display device]
<Production Example 1>
(Production of purified rosin R)
A sealable reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube was charged with 3000 g of unpurified Chinese gum rosin (acid number: 171 mg KOH / g, softening point: 74 ° C., color tone: 6 G), and 400 Pa of nitrogen purge was performed. Distillation under reduced pressure gave an acid value of 176.3 mgKOH / g, a softening point of 80.5 ° C., and a main fraction of color tone Gardner 2 (yield: 86.3%) as purified gum rosin R. The resin acid value is a value measured according to the method described in JIS K-5601. The softening point is a value measured by the ring and ball method of JIS K-2531.

(Production of unsaturated acid-modified rosin A)
Into a reaction vessel equipped with a stirrer, a reflux condenser with a water separator and a thermometer, 1,000 parts by mass of the purified gum rosin R prepared above was charged, and the temperature was raised to 180 ° C. while stirring in a nitrogen atmosphere. Melted. Next, 267 parts by mass of fumaric acid was charged, and the temperature was raised to 230 ° C. with stirring and kept for 1 hour, followed by cooling to obtain a solid resin of unsaturated acid-modified rosin A. The resin acid value was 342.0 mgKOH / g, and the softening point was 125 ° C.

(Production of unsaturated acid-modified rosin B)
A maleic acid-modified rosin was synthesized using the above purified gum rosin R and maleic acid with reference to Preparation Example 3 of JP-A No. 2007-1111735. The resin acid value was 315 mgKOH / g, and the softening point was 155 ° C.

(Production of unsaturated acid-modified rosin C)
An acrylic acid-modified rosin was synthesized using the purified gum rosin R and acrylic acid described above with reference to Preparation Example 2 of JP-A No. 2007-1111735. The resin acid value was 241 mgKOH / g, and the softening point was 130 ° C.

(Production of hydrogenated rosin D)
A hydrogenated rosin was synthesized with reference to Example 1 of JP-A-2001-181400.
The acid value was 176 mgKOH / g, and the softening point was 80 ° C.

<Production Example 2>
[Preparation of composition for forming a low moisture-permeable layer]
Prepared as shown below.

(Composition of composition BL-1 for forming a low moisture permeable layer)
A-DCP 77.0 parts by weight Unsaturated acid-modified rosin A (acid value 342 mgKOH / g) 20.0 parts by weight Irgacure 907 3.0 parts by weight SP-13 0.04 parts by weight MEK (methyl ethyl ketone) 40.9 parts by weight Methyl acetate 40.9 parts by mass The solid content concentration of the low moisture-permeable layer forming composition BL-1 was 55% by mass.

(Composition of composition for low moisture permeable layer BL-2)
A-DCP 77.0 parts by weight Unsaturated acid-modified rosin B (acid value 315 mgKOH / g) 20.0 parts by weight Irgacure 907 3.0 parts by weight SP-13 0.04 parts by weight MEK 40.9 parts by weight Methyl acetate 40 .9 parts by mass The solid content concentration of the low moisture-permeable layer forming composition BL-2 was 55% by mass.

(Composition of the composition BL-3 for forming a low moisture permeable layer)
A-DCP 77.0 parts by weight Unsaturated acid-modified rosin C (acid value 241 mgKOH / g) 20.0 parts by weight Irgacure 907 3.0 parts by weight SP-13 0.04 parts by weight MEK 40.9 parts by weight Methyl acetate 40 .9 parts by mass The solid content concentration of the low moisture-permeable layer forming composition BL-3 was 55% by mass.

(Composition of composition BL-4 for forming a low moisture permeable layer)
A-DCP 77.0 parts by mass Pine Crystal KE604 (acid value 238 mgKOH / g)
20.0 parts by mass Irgacure 907 3.0 parts by mass SP-13 0.04 parts by mass MEK 40.9 parts by mass Methyl acetate 40.9 parts by mass The low moisture-permeable layer forming composition BL-4 has a solid content concentration of 55 It was mass%.

(Composition of composition BL-5 for forming a low moisture permeable layer)
A-DCP 77.0 parts by mass Pine Crystal KR614 (acid value 175 mgKOH / g)
20.0 parts by mass Irgacure 907 3.0 parts by mass SP-13 0.04 parts by mass MEK 40.9 parts by mass Methyl acetate 40.9 parts by mass The composition BL-5 for forming a low moisture permeable layer has a solid content concentration of 55 It was mass%.

<Preparation of Low Moisture Permeability Layer Compositions BL-6 to BL-17>
In the preparation of the low moisture permeable layer forming composition BL-1, except that the low moisture permeable layer forming composition is as described in the following table, the same as the low moisture permeable layer forming composition BL-1, Low moisture permeable layer forming compositions BL-6 to BL-17 were prepared.

The materials used are shown below.
A-DCP: Tricyclodecane dimethanol diacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.]
DCP: tricyclodecane dimethanol dimethacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.]
FA-513AS: dicyclopentanyl acrylate [manufactured by Hitachi Chemical Co., Ltd.]
FA-513M: dicyclopentanyl methacrylate [manufactured by Hitachi Chemical Co., Ltd.]
AA-BPEF: 9,9-bis [4- (2acryloyloxyethoxy) phenyl] fluorene [made by Shin-Nakamura Chemical Co., Ltd.]
PET30: A mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate [manufactured by Nippon Kayaku Co., Ltd.]
・ Pine Crystal KR614 (trade name, ultra-light rosin, manufactured by Arakawa Chemical Industries, Ltd.)
・ Pine Crystal KE604 (trade name, acid-modified ultra-light rosin, manufactured by Arakawa Chemical Industries, Ltd.)
・ Irgacure 907: Polymerization initiator [manufactured by BASF]
・ Leveling agent

SP-13 (in the following formula, the composition ratio 60:40 is a molar ratio):

The unit of numerical values in the table below represents parts by mass.

<Preparation of polymer film 201>
From the roll form, the cellulose ester film (width 1,340 mm, thickness 60 μm) obtained in Example 1 was used as a base film (a laminate of a polymerizable compound-containing composition and an initiator-containing composition after the curing step). Unwinding and using the above-mentioned composition BL-1 for forming a low moisture permeable layer, the die coating method using the slot die described in Example 1 of Japanese Patent Application Laid-Open No. 2006-122889, and carried out at a conveyance speed of 30 m / min. It apply | coated on the cellulose-ester film obtained in Example 1, and was dried at 60 degreeC for 150 second. Thereafter, using an air-cooled metal halide lamp (produced by Eye Graphics Co., Ltd.) with an oxygen concentration of about 0.1% under a nitrogen purge, ultraviolet light having an illuminance of 400 mW / cm ² and an irradiation amount of 120 mJ / cm ² is used. The coating layer was cured by irradiation and wound up. The coating amount was adjusted so that the thickness of the low moisture permeable layer was 10 μm.
The resulting polymer film was designated as polymer film 201.

<Preparation of polymer films 202 to 217>
In the production of the polymer film 201, the polymer films 202 to 217 were the same as the polymer film 201 except that the low moisture permeable layer forming composition BL-1 was changed to BL-2 to BL-17 in Table 2 above, respectively. Was made.

[Panel Evaluation]
<Preparation of polarizing plate>
1) Saponification of film Commercially available cellulose acylate film (Fujitack ZRD40, manufactured by Fuji Film Co., Ltd.), commercially available cellulose acylate film TD60 (manufactured by Fuji Film Co., Ltd.) and polymer films 201-217 were kept at 55 ° C. After immersing in a 1.5 mol / L NaOH aqueous solution (saponification solution) for 2 minutes, the film was washed with water, then immersed in a 0.05 mol / L sulfuric acid aqueous solution at 25 ° C. for 30 seconds, and then further washed with a water washing bath. The film was neutralized by passing under flowing water. Then, draining with an air knife was repeated three times, and after dropping water, the film was retained in a drying zone at 70 ° C. for 15 seconds and dried to produce a saponified film.

2) Production of Polarizer According to Example 1 of Japanese Patent Application Laid-Open No. 2001-141926, iodine was adsorbed to a stretched polyvinyl alcohol film to produce a polarizer having a thickness of 20 μm.

3) Bonding (preparing front side polarizing plates 201 to 217)
Polymer films 201 to 217 after saponification (arranged so that the surface of each polymer film on which the low moisture-permeable layer is not laminated is in contact with the polarizer), the polarizer prepared above, and the cellulose acylate film after saponification ZRD40 was bonded in this order with a PVA adhesive and heat-dried to prepare polarizing plates 201 to 217.
At this time, the longitudinal direction of the produced polarizer roll and the longitudinal direction of the polymer films 201 to 217 were arranged in parallel. Moreover, it arrange | positioned so that the longitudinal direction of the roll of a polarizer and the longitudinal direction of the roll of the said cellulose acylate film ZRD40 may become parallel.

(Preparation of front-side polarizing plates 301 to 317)
The surface on which the low moisture-permeable layers of the produced polymer films 201 to 217 were laminated using an acrylic adhesive on one side of the polarizer produced as described above was subjected to corona treatment and then bonded. Using the polyvinyl alcohol adhesive on the other side of the polarizer prepared above, the saponified commercially available cellulose acylate film ZRD40 is attached and dried at 70 ° C. for 10 minutes or longer to produce polarizing plates 301 to 317. did.
At this time, the longitudinal direction of the produced polarizer roll and the longitudinal direction of the polymer films 201 to 217 were arranged in parallel. Moreover, it arrange | positioned so that the longitudinal direction of the roll of a polarizer and the longitudinal direction of the roll of the said cellulose acylate film ZRD40 may become parallel.
The obtained polarizing plates were designated as polarizing plates 301 to 317, respectively.

(Preparation of rear-side polarizing plate)
The saponified cellulose acylate film TD60, the obtained stretched iodine-based PVA polarizer, and the saponified cellulose acylate film ZRD40 were bonded in this order with a PVA-based adhesive, and then heat-dried to rear-side polarized light. I got a plate.
Under the present circumstances, it arrange | positioned so that the longitudinal direction of the roll of the produced polarizer and the longitudinal direction of the cellulose acylate film TD60 may become parallel. Moreover, it arrange | positioned so that the longitudinal direction of the roll of a polarizer and the longitudinal direction of the roll of the said cellulose acylate film ZRD40 may become parallel.

<Implementation to IPS panel>
The upper and lower polarizing plates of the IPS mode liquid crystal cell (made by LGD 42LS5600) are peeled off, and the polarizing plates 201 to 217 and 301 to 317 described above as the front polarizing plates are provided on the front side (viewing side), and the rear polarizing plates are provided on the rear side. As described above, the polarizing plates described above were attached to the front side and the rear side one by one through an adhesive so that the cellulose acylate film ZRD40 was on the liquid crystal cell side. The crossed Nicols were arranged so that the absorption axis of the front-side polarizing plate was in the longitudinal direction (left-right direction) and the transmission axis of the rear-side polarizing plate was in the longitudinal direction (left-right direction). The thickness of the glass used for the liquid crystal cell was 0.5 mm.
When the obtained liquid crystal display devices were evaluated as the light leakage of the liquid crystal display devices of Examples 201 to 217 and 301 to 317 manufactured as the liquid crystal display devices of Examples 201 to 217 and 301 to 317, respectively, all were good. It was.

DESCRIPTION OF SYMBOLS 10 Casting apparatus 12 Support body 14 Casting die 16 1st solution 18 2nd solution 20 Discharge port 22 Laminated body (casting film)
22a Casting film derived from polymerizable compound-containing composition 22b Casting film derived from initiator-containing composition 24 First supply port 26 Second supply port 28 First flow channel 30 Second flow channel 50 Polymer film 60 Film production facility 62 Drying unit 64 Wet film 68 Roller 70 Tenter 72 Clip 74 Air duct 76 Cutting device 78 Roller 80 Drying chamber 82 Dry film 84 Curing device 86 Winding unit 88 Winding core

Claims

A polymerizable compound-containing composition containing a polymerizable compound and a polymer and not containing an initiator, and an initiator-containing composition containing an initiator and not containing a polymerizable compound are co-cast, sequentially cast on the support, or A step of forming a laminate by casting and coating;
Peeling the laminate from the support;
And a step of curing the laminate with light or heat.
The manufacturing method of the polymer film of Claim 1 including the process of extending | stretching the said laminated body.
The method for producing a polymer film according to claim 1 or 2, wherein the curing step is a step of irradiating the laminate with ultraviolet rays once or more.
The method for producing a polymer film according to any one of claims 1 to 3, comprising a step of drying the laminate after the curing step.
The method for producing a polymer film according to any one of claims 1 to 4, comprising 1% by mass or more of an ultraviolet absorber with respect to the polymer contained in the polymerizable compound-containing composition.
6. The method for producing a polymer film according to claim 1, wherein the polymer film has a thickness of 20 to 100 μm.
The method for producing a polymer film according to any one of claims 1 to 6, wherein the polymer is a cellulose ester.
The method further comprises a step of laminating at least one of a hard coat layer, a low moisture permeable layer, an antiglare layer, an antistatic layer, an antifouling layer and an antireflection layer on the laminate after the curing step. The method for producing a polymer film according to any one of 1 to 7.
A polymer film produced by the method for producing a polymer film according to any one of claims 1 to 8.
A laminate comprising a polymerizable compound-containing composition containing a polymerizable compound and a polymer and no initiator, and an initiator-containing composition containing an initiator and no polymerizable compound, and further cured by light or heat. Having a polymer film.
The polymer film according to claim 9 or 10, which has at least one of a hard coat layer, a low moisture-permeable layer, an antiglare layer, an antistatic layer, an antifouling layer and an antireflection layer in addition to the laminate.
A polarizing plate comprising a polarizer and the polymer film according to any one of claims 9 to 11.
A liquid crystal cell;
A liquid crystal display device comprising the polymer film according to any one of claims 9 to 11 or the polarizing plate according to claim 12.