JP6734877B2 - Laminated body, polarizing plate and image display device - Google Patents

Description

The present invention relates to a laminated body, a polarizing plate using the laminated body, and an image display device.

Image display devices typified by electroluminescence displays (ELDs) or liquid crystal display devices (LCDs) are increasingly required to be thin. In addition, the environment in which the image display device is used is diversifying, including outdoor applications, and the image display device has the ability to stably maintain good image quality even under harsh environments (high durability). Is being demanded.
The deterioration of the image quality in the image display device is due to the fact that water enters the polarizing plate and deteriorates the polarizer. The polarizer is protected by laminating a protective film (optical film) on the surface thereof, and the protective film is also required to be thin. If the protective film is made thin, moisture is more likely to come into contact with the polarizer, and the image quality is likely to deteriorate. Further, such deterioration in image quality becomes more apparent when used in a harsh environment such as an outdoor application.

As the protective film, a cellulose resin or an acrylic resin is widely used from the viewpoint of versatility or processability. Due to the need to further enhance durability, modification of optical films is being promoted (for example, Patent Documents 1 to 5).

International Publication No. 2009/047924 JP 2012-172062A JP, 2006-83225, A JP, 2013-101281, A JP, 9-197128, A

The present inventors, as a result of repeated studies from the viewpoint of suppressing deterioration of the polarizer, in the conventional protective film including the film described in each of the above patent documents, when highly thinned to the required level described above, It has become clear that it is difficult to sufficiently prevent the penetration of water and it is difficult to sufficiently suppress the deterioration of the polarizer.
By the way, it is considered that the deterioration of the polarizer can be suppressed by providing a hydrophobic resin layer on the protective film for protecting the polarizer. However, it was found by the present inventors that when a hydrophobic resin layer was laminated on a layer containing cellulose ester, the adhesiveness at the laminated interface was poor and the layers were separated from each other.

INDUSTRIAL APPLICABILITY The present invention uses a laminate having high adhesion between layers, excellent hydrophobicity on the surface, and capable of effectively suppressing deterioration of the polarizer when used as a protective film for the polarizer. An object is to provide a polarizing plate and an image display device using this polarizing plate.

The present inventors have conducted extensive studies in view of the above problems, and as a result, a polymer having a specific primary structure consisting of at least one repeating unit having a solubility parameter within a specific range has a contact angle when formed into a layer. And a high adhesion to a layer containing cellulose ester, and a laminate of the layer containing the polymer and the layer containing the cellulose ester is used as a protective film for a polarizer. Therefore, it was found that the deterioration of the polarizer can be effectively suppressed. The present invention has been completed through further studies based on these findings.

一般式２中、Ｒ ^５ は水素原子又はアルキル基を表す。
Ｒ ^６ 及びＲ ^７ は、各々独立に、水素原子、アルキル基、アリール基又はアルコキシカルボニル基を表す。
Ｒ ^８ は炭素数１〜２０のアルキル基又は炭素数３〜２０のシクロアルキル基を表す。

一般式３中、Ｒ ^９ 、Ｒ ^１０ 及びＲ ^１１ は、各々独立に、水素原子、ハロゲン原子、アルキル基又はアリール基を表す。
Ｒ ^１２ 、Ｒ ^１３ 、Ｒ ^１４ 、Ｒ ^１５ 及びＲ ^１６ は、各々独立に、水素原子、ハロゲン原子、水酸基、アルキル基、アルケニル基、アリール基、アルコキシ基、アシル基、アシルオキシ基又はアルコキシカルボニル基を表す。
The above problems of the present invention have been solved by the following means.
<1> A laminate having a layer containing a cellulose ester and a layer containing an adhesive polymer,
The layer containing the adhesive polymer is adjacent to at least one surface of the layer containing the cellulose ester,
The adhesive polymer has a graft structure, a branch structure or a star structure composed of one kind of repeating unit, or a block structure, a graft structure, a branch structure or a star structure composed of two or more kinds of repeating units, and the repeating structure units see contains recurring units [a] solubility parameter δt is calculated is less than 13.5 or 20.0 by Hoy method,
A laminate, wherein the repeating unit [a] is a repeating unit represented by the following general formula 2 or 3 .

In General Formula 2, R ⁵ represents a hydrogen atom or an alkyl group.
R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
R ⁸ represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.

In formula 3, R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group.
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an acyl group, an acyloxy group or an alkoxycarbonyl group. Represent

<2> The laminate according to <1>, wherein the adhesive polymer has a block structure, a graft structure, a branch structure or a star structure, which is composed of two or more kinds of repeating units.
<3> The laminated body according to <1> or <2>, in which the adhesive polymer has 2 to 250 end portions per molecule.
<4> The laminated body according to any one of <1> to <3>, in which the adhesive polymer has a block structure or a graft structure.
<5> Any of <1> to <4>, wherein the two or more repeating units include a repeating unit [b] having a solubility parameter δt calculated by the Hoy method of 20.0 or more and 26.0 or less. The laminated body according to one.

一般式１中、Ｒ^１は水素原子又はアルキル基を表す。
Ｒ^２及びＲ^３は、各々独立に、水素原子、アルキル基、アリール基又はアルコキシカルボニル基を表す。
Ｌは、単結合、又は、アルキレン基、アリーレン基、−Ｃ（＝Ｏ）−、−Ｏ−及び−Ｎ（Ｒ^４）−から選ばれる２価の連結基若しくはこれらの連結基の２種以上を組み合わせてなる２価の連結基を示す。Ｒ^４は水素原子又はアルキル基を表す。<6> The laminate according to <5>, wherein the repeating unit [b] is a repeating unit represented by the following general formula 1.

In General Formula 1, R ¹ represents a hydrogen atom or an alkyl group.
R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
L is a single bond or a divalent linking group selected from an alkylene group, an arylene group, —C(═O)—, —O— and —N(R ⁴ )— or two or more of these linking groups. A divalent linking group formed by combining R ⁴ represents a hydrogen atom or an alkyl group.

< 7 > The laminate according to any one of < 1 > to <6>, in which the repeating unit [a] is a repeating unit represented by the general formula 2.
< 8 > The laminate according to any one of <1> to < 7 >, in which the cellulose ester is cellulose acylate.
< 9 > A polarizing plate having a laminate according to any one of the above <1> to < 8 > and a polarizer.
< 10 > An image display device having the polarizing plate according to < 9 >.

The laminate of the present invention has high adhesion to the layer containing cellulose ester and has excellent hydrophobicity on the surface. The laminated body of the present invention can effectively prevent the deterioration of the polarizer even under high temperature and high humidity conditions by being laminated on the polarizer.
In addition, the polarizing plate and the image display device of the present invention can effectively suppress the deterioration of the polarizer by using the laminate having the above-mentioned excellent effects and exhibit high durability.
In the present specification, the degree of suppressing deterioration of the polarizer is also referred to as “polarizer durability” or “polarizing plate durability”.
The above and other features and advantages of the present invention will become more apparent from the following description with reference to the accompanying drawings as appropriate.

FIG. 1 is a sectional view showing an embodiment of the laminated body of the present invention. FIG. 2 is a schematic view showing an outline of an embodiment of a liquid crystal display device provided with a polarizing plate incorporating the polarizing plate protective film of the present invention. FIG. 3A is a diagram showing an example of a block structure of the adhesive polymer of the present invention. FIG. 3B is a diagram showing an example of a block structure of the adhesive polymer of the present invention. FIG. 3C is a diagram showing an example of a block structure of the adhesive polymer of the present invention. FIG. 3D is a diagram showing an example of a block structure of the adhesive polymer of the present invention. FIG. 3E is a diagram showing an example of a block structure of the adhesive polymer of the present invention. FIG. 4A is a diagram showing an example of a graft structure of the adhesive polymer of the present invention. FIG. 4B is a diagram showing an example of a graft structure of the adhesive polymer of the present invention. FIG. 4C is a diagram showing an example of a graft structure of the adhesive polymer of the present invention. FIG. 4D is a diagram showing an example of a graft structure of the adhesive polymer of the present invention. FIG. 4E is a diagram showing an example of a graft structure of the adhesive polymer of the present invention. FIG. 4F is a diagram showing an example of a graft structure of the adhesive polymer of the present invention. FIG. 4G is a diagram showing an example of a graft structure of the adhesive polymer of the present invention. FIG. 5 is a diagram illustrating a method of synthesizing an adhesive polymer having a graft structure. FIG. 6A is a diagram showing an example of a star structure included in the adhesive polymer of the present invention. FIG. 6B is a diagram showing an example of a star structure included in the adhesive polymer of the present invention. FIG. 6C is a diagram showing an example of a star structure included in the adhesive polymer of the present invention. FIG. 6D is a diagram showing an example of a star structure included in the adhesive polymer of the present invention. FIG. 7A is a diagram showing an example of a branch structure of the adhesive polymer of the present invention. FIG. 7B is a diagram showing an example of a branch structure of the adhesive polymer of the present invention. FIG. 7C is a diagram showing an example of a branch structure of the adhesive polymer of the present invention. FIG. 7D is a diagram showing an example of a branch structure of the adhesive polymer of the present invention. FIG. 7E is a diagram showing an example of a branch structure of the adhesive polymer of the present invention. FIG. 7F is a diagram showing an example of a branch structure of the adhesive polymer of the present invention.

In the present specification, the numerical range represented by “to” means that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

In the present specification, when there are a plurality of substituents or linking groups and the like (hereinafter referred to as substituents) represented by a specific code, or when a plurality of substituents or the like are defined simultaneously or alternatively, It means that the substituents and the like may be the same or different from each other. This also applies to the definition of the number of substituents and the like. Further, when a plurality of substituents and the like are close to each other (particularly adjacent to each other), they may be linked to each other or condensed to form a ring.

In the present specification, the term "compound" is used to mean not only the compound itself, but also its salts and its ions. In addition, it is meant to include those in which a part of the structure is changed as long as the intended effect is not impaired. The salt of the compound is, for example, an acid addition salt of the compound formed with the compound and an inorganic acid or an organic acid, or a base addition salt of the compound formed with the compound and an inorganic base or an organic base. Is mentioned. Examples of the compound ions include ions generated by dissolving the salt of the above compound in water or a solvent.
In the present specification, with respect to a substituent group (unlike the linking group) which is not specified as substituted or unsubstituted, it means that the group may have any substituent group as long as the desired effect is not impaired. is there. This is also synonymous with compounds or repeating units for which substitution or non-substitution is not specified.
In the present specification, the term “substituent” simply means a group selected from the following substituent group T unless otherwise specified. Further, when only a substituent having a specific range is described (for example, only when it is described as an “alkyl group”), the corresponding group of the following substituent group T (an alkyl group in the above case) The preferred ranges and specific examples in are applicable.
In this specification, when defining the carbon number of a group, this carbon number means the carbon number of the entire group. That is, when this group is in the form of further having a substituent, it means the total number of carbon atoms including this substituent.
In the present specification, when a group can form an acyclic skeleton and a cyclic skeleton, the group includes a non-cyclic skeleton group and a cyclic skeleton group, unless otherwise specified. For example, alkyl groups include straight chain alkyl groups, branched chain alkyl groups, and cyclic (cyclo)alkyl groups, unless otherwise specified. When a group forms a cyclic skeleton, the lower limit of the number of carbon atoms in the group of the cyclic skeleton is preferably 3 or more, and more preferably 5 or more, regardless of the lower limit of the number of carbon atoms specifically described in the group.

In this specification, the term “(meth)acrylic acid” is used to include both methacrylic acid and acrylic acid. This also applies to “(meth)acrylamide”. Further, in the present specification, the term “acrylic acid” is used in a broader sense than usual. That is, "acrylic ^acid" refers to _{^{R A -C (= CR B 2}} ) used in the sense to include all compounds having the structure of COOH ^{(R A} and ^{R B} are each independently a hydrogen atom or a substituent. However , R ^A is methyl, meaning methacrylic acid)). The same applies to "acrylamide".

Substituent group T:
Alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12, particularly preferably 1 to 8 carbon atoms, for example, methyl group, ethyl group, isopropyl group, tert-butyl group, n-octyl group, Examples thereof include an n-decyl group, an n-hexadecyl group, etc. In the case of a cycloalkyl group, the number of carbon atoms is preferably 3 to 20, more preferably 3 to 12, and particularly preferably 3 to 8. , A cyclopropyl group, a cyclopentyl group, a cyclohexyl group, etc.) and an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 and particularly preferably 2 to 8), such as vinyl group and allyl. Group, 2-butenyl group, 3-pentenyl group and the like.), alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 and particularly preferably 2 to 8), for example, propargyl group, 3-pentynyl group and the like.), aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 and particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenyl group, a biphenyl group and a naphthyl group. ), an amino group (preferably having a carbon number of 0 to 20, more preferably 0 to 10, and particularly preferably 0 to 6), and examples thereof include an amino group, a methylamino group, a dimethylamino group, a diethylamino group, and a dibenzyl. Amino groups and the like), alkoxy groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 and particularly preferably 1 to 8), and examples thereof include a methoxy group, an ethoxy group and a butoxy group. ), an aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenyloxy group and a 2-naphthyloxy group). A group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 and particularly preferably 1 to 12 and examples thereof include an acetyl group, a benzoyl group, a formyl group and a pivaloyl group), an alkoxycarbonyl group ( It preferably has 2 to 20 carbon atoms, more preferably 2 to 16 and particularly preferably 2 to 12, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group.), an aryloxycarbonyl group (preferably having a carbon atom number). 7 to 20, more preferably 7 to 16, and particularly preferably 7 to 10, and examples thereof include a phenyloxycarbonyl group, etc., and an acyloxy group (preferably having 2 to 12 carbon atoms). 20, more preferably 2 to 16, and particularly preferably 2 to 10, and examples thereof include an acetoxy group and a benzoyloxy group. ), an acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetylamino group and a benzoylamino group) and an alkoxycarbonylamino group ( It preferably has 2 to 20 carbon atoms, more preferably 2 to 16 and particularly preferably 2 to 12 and includes, for example, a methoxycarbonylamino group and the like), an aryloxycarbonylamino group (preferably 7 to 12 carbon atoms). 20, more preferably 7 to 16, particularly preferably 7 to 12, and examples thereof include a phenyloxycarbonylamino group and the like.), a sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms). , Particularly preferably 1 to 12, and examples thereof include a methanesulfonylamino group and a benzenesulfonylamino group, and a sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 and particularly preferably 0). To 12 and examples thereof include a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, and a phenylsulfamoyl group.), a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 1). 16, particularly preferably 1 to 12, and examples thereof include a carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group, and a phenylcarbamoyl group. An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms). 16, particularly preferably 1 to 12, and examples thereof include a methylthio group and an ethylthio group.), an arylthio group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 and particularly preferably 6 to 12). A phenylthio group, etc.), a sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms), and examples thereof include a mesyl group and a tosyl group. ), a sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 and particularly preferably 1 to 12 and examples thereof include a methanesulfinyl group and a benzenesulfinyl group), a urethane group, a ureido. A group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 and particularly preferably 1 to 12 and examples thereof include an ureido group, a methylureido group, a phenylureido group, etc.), a phosphoric acid amide group ( It preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms. It is preferably 1 to 12, and examples thereof include diethylphosphoric acid amide and phenylphosphoric acid amide. ), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxy group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, Heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the heteroatom include a nitrogen atom, an oxygen atom, and a sulfur atom. A condensed ring is preferable, and specific examples thereof include an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a piperidyl group, a morpholino group, a benzoxazolyl group, a benzimidazolyl group, and a benzthiazolyl group. A silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group).
These substituents may further have a substituent. When there are two or more substituents, they may be the same or different. Further, adjacent substituents may be linked to each other to form a ring.

A preferred embodiment of the present invention will be described below.

[Laminate]
As shown in FIG. 1, a laminated body 10 as a preferred example of the present invention has a layer (also referred to as a cellulose ester layer) 11 containing a cellulose ester and a layer adjacent to at least one surface of the cellulose ester layer 11. And a layer containing an adhesive polymer (also referred to as an adhesive polymer layer) 12.
In the present invention, the term “adjacently laminated” means that both layers are directly laminated without interposing an adhesive layer (adhesive layer) for closely adhering or adhering both layers between the cellulose ester layer and the adhesive polymer layer. It means that they are overlapped.

The laminated body of the present invention is not particularly limited in other constitutions as long as it has the above-mentioned laminated structure.
For example, it may have a three-layer laminated structure in which an adhesive polymer layer is laminated adjacent to both surfaces of the cellulose ester layer. Further, as the adhesive polymer layer, two or more adhesive polymer layers having different composition ratios may be provided on the cellulose ester layer. Further, the surface of the adhesive polymer layer may have various functional layers specialized for specific functions. Examples of such a functional layer include a hard coat layer, an antireflection layer, a light scattering layer, an antifouling layer, an antistatic layer, and the like.

<Layer containing adhesive polymer>
The adhesive polymer layer constituting the laminate of the present invention will be described.
In the present invention, the “adhesive polymer layer” means a layer containing an adhesive polymer described later in an amount of 50% by mass or more. The content of the adhesive polymer in the adhesive polymer layer is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 85% by mass or more. The higher the content of the adhesive polymer, the better the adhesiveness with the cellulose ester layer, which is preferable. Therefore, the content of the adhesive polymer in the adhesive polymer layer may be 100% by mass, usually 99% by mass or less. When the content of the adhesive polymer in the adhesive polymer layer is not 100% by mass, the balance may contain various additives described below.
Two or more kinds of adhesive polymers may be used in combination. That is, adhesive polymers having different composition ratios and/or molecular weights may be used together. In this case, the total amount of the adhesive polymer is within the above range.
In the present specification, the term "adhesive polymer" simply means a polymer that can adhere to the cellulose ester layer, and is used only to facilitate understanding of the present invention. Such "adhesive polymer" includes all the polymers defined in the present invention regardless of the degree of the adhesiveness. That is, when determining the gist or technical scope of the present invention, the term "adhesion" is not considered as a matter for specifying the invention that restrictively interprets the present invention.

-Adhesive polymer-
The adhesive polymer that constitutes the adhesive polymer layer has a primary structure described below.
The primary structure is a graft structure, a branch structure or a star structure when the repeating unit forming the adhesive polymer is one kind, and a block structure, a graft structure or a branch structure when the repeating unit is two or more kinds. It also has a star structure.
The adhesive polymer may have one type or two or more types of the above primary structure.

First, the primary structure of the adhesive polymer will be described with reference to the schematic diagram, but the present invention is not limited to these primary structures.
In the following description, for the sake of understanding, a polymer (copolymer) composed of 1 to 4 types of repeating units A to D is given as an example, but in the present invention, the repeating units are 1 to 4 as described later. Not limited to species. Further, the repeating units A, B, C and D in the figure can be replaced by different structures (repeating units).

In the present invention, the “main chain direction” means, in each partial structure forming the adhesive polymer, the bonding direction of the repeating unit forming this partial structure.
In addition, in the present invention, the term “consisting of repeating units” includes not only an aspect consisting of a specific repeating unit but also an aspect consisting of a specific repeating unit and one or more repeating units different from this. .. The other repeating unit is not particularly limited, and examples thereof include a repeating unit derived from a compound having a polymerizable group for introducing a graft chain, or a repeating unit composed of two or more constituent components described below. To be

(Block structure)
In the present invention, the block structure means a structure in which the main chain directions of the partial structures composed of a single type of repeating unit are a single linear direction in the polymer chain. The block structure is composed of two or more kinds of repeating units.
In the present invention, when one repeating unit is composed of two or more kinds of constituent components, the partial structure consisting of a single kind of repeating unit is a partial structure in which repeating units each having the same constituent component are bonded, and a constituent component. At least one of the substructures comprises different repeating units. For example, when the partial structure is composed of a repeating unit containing an amide bond described below, the partial structure is a part composed of a single repeating unit obtained by copolycondensation of one carboxylic acid compound and one amine compound. In addition to the structure, a partial structure including a repeating unit (for example, an exemplary repeating unit B-65 described later) obtained by copolycondensation of at least one of a carboxylic acid compound and an amine compound is included. The same applies to the partial structure composed of a single type of polyester repeating unit.

The block structure of the adhesive polymer of the present invention is not particularly limited as long as it is one described above, and examples thereof include the structures shown in FIGS. 3A to 3E (may be collectively referred to as FIG. 3). In FIG. 3, A to D represent different repeating units (the same in FIGS. 4 to 7).
The block structure shown in FIG. 3A is a block structure (AB type) in which a partial structure consisting of the repeating unit A and a partial structure consisting of the repeating unit B are bonded in a single linear direction within the polymer chain. .. The block structure shown in FIG. 3B is a block structure (B-A-B type) in which the partial structure of the repeating unit B is bonded to a single linear direction in the polymer chain to both ends of the partial structure of the repeating unit A. ). In the block structure shown in FIG. 3C, a partial structure consisting of the repeating unit B, a partial structure consisting of the repeating unit A, and a partial structure consisting of the repeating unit C as the third component are formed in this order in the polymer chain. It is a block structure connected in one linear direction. In the block structure shown in FIG. 3D, in the block structure shown in FIG. 3C, a partial structure consisting of repeating unit C and a partial structure consisting of repeating unit D as a fourth component are bonded in a single linear direction in the polymer chain. It has a block structure. The block structure shown in FIG. 3E is a block structure in which a partial structure consisting of the repeating unit A and a partial structure consisting of the repeating unit B are alternately repeated (bonded) twice in a single linear direction within the polymer chain. Is.

The polymer having a block structure can be obtained by a usual method for polymerizing a block copolymer. For example, a living radical polymerization method, a living cationic polymerization method, or a living anionic polymerization method can be mentioned. As an example of living radical polymerization method, living cationic polymerization method, or living anionic polymerization method, "Precision Radical Polymerization Guidebook (Aldrich)" (URL: http://www.sigmaaldrich.com/japan/materialscience/polymer-science/ crp-guide.html) or Takeshi Endo, Mitsuo Sawamoto et al., "Synthesis of polymers (top)-radical polymerization/cationic polymerization/anionic polymerization", Kodansha, 2010, p60, p105-108, p249- 259 and p381-386.

Ｒは、末端基を示し、後述する末端構造の末端基と同義である。The polymer having the block structure shown in FIG. 3B can be obtained by repeating, for example, the terminal structure (repeating unit B) as a starting point using an atom transfer radical polymerization (ATRP) method in a living radical polymerization method as shown below. It is also possible to extend the repeating unit by sequentially reacting the monomers to be a unit to synthesize.

R represents a terminal group and has the same meaning as the terminal group of the terminal structure described later.

Further, the polymer having the block structure shown in FIG. 3B is synthesized, for example, by using a bromo compound or the like as a chain transfer agent and extending a repeating unit on both sides of the chain transfer agent as a center point as shown below. You can do it. In this case, the residue of the chain transfer agent is interposed between the two partial structures of the repeating unit A as described below.

(Graft structure)
In the present invention, the graft structure means one that satisfies both of the following conditions (G-1) to (G-3).
(G-1) Polymer P A ^G1 (also referred to as a trunk polymer) composed of one or more types of repeating units, while another polymer P B ^G1 (also referred to as a branch polymer) composed of one or more types of repeating units Is a structure in which one or more are bonded.
(G-2) Within the polymer chain, the main chain direction of the polymer PB ^G1 is different from the main chain direction of the polymer PA ^G1 .
(G-3) to the polymer ^{PB G1,} polymer ^{PB G2} having a main chain direction different from the main chain direction of the polymer ^{PB G1} is not bound.

In the graft structure, the polymer PA ^G1 and the polymer PB ^G1 may be the same or different, and when a plurality of the polymer PB ^G1 are present, they may be the same or different. The bonding mode (structure) of the repeating units forming the polymer PA ^G1 and the polymer PB ^G1 is not particularly limited as long as they are bonded in a single linear direction in each polymer, and may be a block structure or a random structure. Good.
Further, the number of the polymer PB ^G1 bonded to the polymer PA ^G1 may be one or more, and is appropriately determined according to the properties of the adhesive polymer and the like. For example, the number may be one or more, and may be 200 or less. The number is preferably 100 or less, more preferably 50 or less.

The graft structure of the adhesive polymer of the present invention is not particularly limited as long as it is as described above, and examples thereof include the structures shown in FIGS. 4A to 4G (may be collectively referred to as FIG. 4).
The graft structure shown in FIG. 4A is a graft structure in which three polymers PB ^G1 (branch polymer) composed of repeating units A are bonded to a polymer PA ^G1 (stem polymer) composed of repeating units A. The graft structure shown in FIG. 4B is a graft structure in which 6 polymers PB ^G1 (branch polymer) composed of repeating units A are bonded to polymer PA ^G1 (stem polymer) composed of repeating units A. The graft structure shown in FIG. 4C is a graft structure in which three polymers PB ^G1 (branch polymer) composed of repeating units B are bonded to a polymer PA ^G1 (stem polymer) composed of repeating units A.

The graft structure shown in FIGS. 4D to 4G is a graft structure further having a repeating unit C as a third component, the repeating unit C described above and a repeating unit D as a fourth component.
That is, the graft structure shown in FIG. 4D is a graft in which three polymers P B ^G1 (branch polymer) composed of repeating units B are bonded to a polymer PA ^G1 (stem polymer) having a random structure composed of repeating units A and C. The structure. The graft structure shown in FIG. 4E has two polymers PB ^G1-B composed of repeating units B and one polymer PB ^G1-C composed of repeating units C with respect to the polymer PA ^G1 (stem polymer) composed of repeating units A. This is a fully bonded graft structure. In the graft structure shown in FIG. 4F, three polymers PB ^G1-BC having a block structure (including an alternating copolymer structure) composed of repeating units B and C are bonded to a polymer PA ^G1 (a backbone polymer) composed of repeating units A. It is a graft structure. The graft structure shown in FIG. 4G is a polymer P ^G1-AB (stem polymer) having a random structure composed of repeating units A and B, and a polymer PB having a block structure (including an alternating copolymer structure) composed of repeating units C and D. It is a graft structure in which three ^G1-CD are linked.

The polymer having a graft structure can be obtained by a usual method for polymerizing a graft copolymer. For example, a macromonomer (YBBBBBB) having a polymerizable functional group (Y) at the terminal is homopolymerized, or the same monomer (B) or a different monomer (A) as the macromonomer. )), a grafting through method (synthesis method 1 shown in FIG. 5)), which utilizes a reactive group of a terminal functional polymer (ZBBBBBBB) to form another polymer chain. Grafting to method (Synthesis method 2 shown in FIG. 5)) or a polymer having a polymerization initiation point (X) in a side chain and a monomer (B) are reacted to form a polymer chain having a repeating unit B. From method (synthesis method 3 shown in FIG. 5)). Details of these are described in, for example, Takeshi Endo, Mitsuo Sawamoto et al., “Synthesis of polymers (top)-radical polymerization/cationic polymerization/anionic polymerization”, Kodansha, 2010, p60, p108-110 and p387-393. Can be referred to.
In FIG. 5, X and Y represent a polymerization reactive group, and W and Z represent a reactive group. Here, the reactive group represented by Z means a group which forms a partial structure of the polymer by a reaction different from the polymerization with respect to the reactive group W.

The macromonomer used in the grafting through method is not particularly limited as long as it is one that is usually used in the synthesis of a graft polymer. As the macromonomer, a commercially available product may be used, or an appropriately synthesized product may be used. As a method for synthesizing a macromonomer, for example, the method described in JP-A-5-295015, or a polymer of a chain transfer agent such as 3-mercapto-1-propanol and a monomer, an isocyanate group and a polymerizable group Examples of the method include a method of reacting with a compound having As a method for synthesizing a macromonomer, Yuya Yamashita, "Chemistry and Industry of Macromonomer", IPC Publishing, 1989 can be referred to.

(Star structure)
In the present invention, the star structure (star structure) means one satisfying the following conditions (S-1) to (S-3).
(S-1) The polymer has one nucleus.
(S-2) Three or more polymers PA ^S1 composed of one type or two or more types of repeating units are bonded to the nucleus.
To (S-3) The polymer ^{PA S1,} having a backbone direction different from the main chain direction of the polymer ^{PA S1,} and one or polymer ^{PB S1} composed of two or more kinds of repeating units is not bound ..

In the star structure, the number of the polymer PA ^S1 bonded to the nucleus may be 3 or more, and is appropriately determined according to the characteristics of the adhesive polymer and the like. The number of polymers PA ^S1 is usually the same as the number of edges described below. The plurality of polymers PA ^S1 may be the same or different.
Further, the “nucleus” means a multi-branched structure (group) to which the polymer PA ^S1 can be bonded, and serves as a central point where a large number (for example, 2 to 12) of polymers are grown.
In the star structure, the bonding mode (structure) of the repeating units forming the polymer PA ^S1 is not particularly limited, and may be a block structure or a random structure.

The star structure of the adhesive polymer of the present invention is not particularly limited as long as it is as described above, and examples thereof include the structures shown in FIGS. 6A to 6D (may be collectively referred to as FIG. 6).
The star structure shown in FIG. 6A is a structure in which four polymers PA ^S1 including the repeating unit A are bonded to the nucleus. The star structure shown in FIG. 6B is a structure in which four polymers PA ^S1 having repeating units A and B in a random structure are bonded to the nucleus. The star structure shown in FIG. 6C has a structure in which four polymers PA ^S1 having a block structure of a partial structure consisting of repeating units A and a partial structure consisting of repeating units B are bonded to the nucleus via the repeating units A. Is. The star structure shown in FIG. 6D is a structure in which eight polymer PA ^S1 composed of the repeating unit A is bonded to the nucleus.

The polymer having a star structure can be obtained by an ordinary polymerization method of a star copolymer. Examples thereof include a method using a polyfunctional initiator, a method using a polyfunctional terminating agent, and a method using a linking reaction with a divinyl compound, and a method using a polyfunctional initiator is preferable.
Regarding the above-mentioned polymerization method, reference may be made to Takeshi Endo, Mitsuo Sawamoto et al., “Synthesis of Polymer (Upper)—Radical Polymerization/Cationic Polymerization/Anionic Polymerization”, Kodansha, 2010, p110-113.
Furthermore, anionic polymerization can also be used for synthesizing a polymer having a star structure. Takeshi Endo, Mitsuo Sawamoto et al., “Synthesis of Polymer (Upper)—Radical Polymerization/Cationic Polymerization/Anionic Polymerization”, Kodansha, 2010, reference can be made to p395-402.

As the nucleus forming the star structure, a commonly used compound can be used without particular limitation. For example, as the compound serving as a nucleus, an organic compound (for example, a polysubstituted aromatic ring, sugar, calixarene or dendrimer), an inorganic compound (for example, a cyclic siloxane or phosphorus amide), or a polydentate metal complex having a metal at the center, etc. Is mentioned.
Examples of the nucleus described above include the compounds described below. Also, reference can be made to “End Polymerization (Upper)—Radical Polymerization/Cationic Polymerization/Anionic Polymerization”, edited by Takeshi Endo, Mitsuo Sawamoto et al., Kodansha, 2010, p110-113.

(Branch structure)
In the present invention, the term “branch structure” means one that satisfies both of the following conditions (B-1) to (B-3).
(B-1) The polymer has one or more nuclei.
(B-2) Two or more polymers PA ^B1 each composed of one or more types of repeating units are bonded to the nucleus.
To (B-3) The polymer ^{PA B1,} has a main chain direction different from the main chain direction of the polymer ^{PA B1,} and one or polymer ^{PB B1} consisting of two or more kinds of the repeating units (generation) of ( (Via the nucleus).
The above condition (B-3) can be satisfied multiple times. That is, with respect to the polymer PB ^B1 bonded as described above, another polymer PB ^B1 can bond (B-3) in a prescribed direction (each generation repeatedly polymerizes). Multi-branch structure). In this case, the number of times satisfying the condition (B-3) may be two or more, and is appropriately determined according to the properties of the adhesive polymer and the like. For example, it can be set to 2 to 7 times.

In the branch structure, the polymer PA ^B1 and the polymer PB ^B1 may be the same or different. The bonding mode (structure) of the repeating units forming the polymer PA ^B1 and the polymer PB ^B1 is not particularly limited and may be a random structure, a block structure, a graft structure or a star structure. That is, the branch structure includes, for example, a dendritic multi-branched structure in which a polymer growing from the nucleus is branched one after another in accordance with the end direction, and also a structure in which a block structure, a graft structure and/or a star structure are combined. ,included. In the branch structure, the repeating unit can be changed for each branch.
Further, the number of cores contained in the polymer may be one or more, and is appropriately determined according to the characteristics of the adhesive polymer and the like. For example, the number may be one or more, and may be 150 or less. Further, the number of the polymer PA ^B1 bonded to the nucleus may be two or more, and is appropriately determined according to the characteristics of the adhesive polymer and the like. For example, the number can be two or more, and the number can be 20 or less. Furthermore, the number of the polymer PB ^B1 bonded to the polymer PA ^B1 is appropriately determined according to the characteristics of the adhesive polymer, and can be, for example, 1 or more, and 150 or less. .. In particular, the number of polymers PB ^B1 bonded to one polymer PA ^B1 (nucleus) is preferably 2 or more.

The branch structure of the adhesive polymer of the present invention is not particularly limited as long as it is as described above, and examples thereof include the structures shown in FIGS. 7A to 7E (may be collectively referred to as FIG. 7).
The branch structure shown in FIGS. 7A and 7B has the polymer P ^{B B1} further bound to the polymer PA ^B1 bound to the nucleus. That is, it is a tree-like multi-branched structure in which repeating units A are branched one after another from the nucleus toward the end. The branch structure shown in FIG. 7C is the same structure as the tree-like multibranched structure shown in FIG. 7B except that the repeating unit B is branched from the end of the branched chain. The branch structure shown in FIG. 7D is the same structure as the tree-like multi-branched structure shown in FIG. 7B except that it has repeating units A and repeating units B in a branched random arrangement. The branch structure shown in FIG. 7E has a repeating unit B (second generation) in a branched form from the end of the branched chain, and further has a repeating unit C (third generation) in a branched form as a third component in the middle thereof. Other than that, the structure is the same as the tree-like multi-branched structure shown in FIG. 7B. The branch structure illustrated in FIG. 7F is a structure in which two star structures in which five polymers PA ^S1 including the repeating unit A are bonded to the nucleus are bonded to one polymer PA ^S1 in each star structure.

The polymer having a branch structure can be obtained by a usual polymerization method. For example, the divergent method or the convergent method can be mentioned, and the convergent method is preferable. As the above-mentioned polymerization method, Macromolecules, 2005, 38(21), p8701-8711, Macromolecules, 2006, 39(22), p4361-4365, or Takeshi Endo, Mitsuo Sawamoto et al., “Polymer Synthesis ( Top)-Radical polymerization/cationic polymerization/anionic polymerization", Kodansha, 2010, p402-414.

The core capable of forming a branch structure is a polymer or macromonomer having at least one structure selected from the group consisting of a block structure, a graft structure and a star structure, in addition to the core described in the above star structure. It may be.
As the above-mentioned nucleus, Macromolecules, 2005, 38(21), p8701-8711, Macromolecules, 2006, 39(22), p4361-4365, or Takeshi Endo, Mitsuo Sawamoto et al., “Synthesis of Polymers (above )-Radical polymerization/cationic polymerization/anionic polymerization", Kodansha, 2010, p402-414.

Regarding the above-mentioned primary structure and polymerization method, reference may be made to Takeshi Endo, Mitsuo Sawamoto et al., “Synthesis of Polymer (Upper)—Radical Polymerization/Cationic Polymerization/Anionic Polymerization”, Kodansha, 2010.

In the present invention, each of the above-mentioned primary structures can be identified as follows. That is, the graft structure, star structure, and branch structure can be confirmed as the particle shape by measuring the mean square radius of gyration <S^2> from static light scattering measurement. The presence or absence of the block structure can be confirmed by nuclear magnetic resonance (NMR) measurement.
For the identification of the above primary structure, "Organic/Polymer Measurement Lab Guide for Young Researchers", Kodansha, 2006 can be referred to.

In the present invention, the adhesive polymer preferably has a block structure, a graft structure, a branch structure or a star structure composed of two or more kinds of repeating units in terms of contact angle and adhesion, and two or more kinds of repeating units. Preferably, it has a block structure or a graft structure.
The repeating unit forming the adhesive polymer is not particularly limited as long as it is one kind or two or more kinds. In the case of a block structure, a graft structure, a branch structure or a star structure composed of two or more types of repeating units, the number of repeating units is preferably 2 to 10 types, more preferably 2 to 5 types, even more preferably 2 or 3 types. .. The repeating unit will be described later.

The adhesive polymer preferably has 2 to 250 end portions per molecule, more preferably 2 to 100 end portions, still more preferably 2 to 80 end portions, and more preferably 2 to 80 end portions. It is especially preferred to have ~50 ends. In the present invention, the end portion of the adhesive polymer means the maximum number of terminals that can be taken in the adhesive polymer having a certain molecular weight.

The number of edges of the adhesive polymer can be calculated by the following calculation method.
When the adhesive polymer has a graft structure, the number of end portions can be determined using the number average molecular weight (Mn).
For example, when a copolymer having a graft structure (Mn=100,000) is synthesized by copolymerizing a monomer A and a macromonomer AA-1 (Mn=5,000),
(Number of ends)=(Number average molecular weight of copolymer)/(Number average molecular weight of macromonomer)+(Number of end of trunk)
Than,
(Number of ends)=100,000/5,000+2
=22 (pieces)
Can be calculated as
Here, the number average molecular weights of the copolymer and the macromonomer can be measured by the method described in Examples below.

When the adhesive polymer has a star structure or a branch structure, the number of ends is determined by the nucleus.
In case of star structure,
(Number of edges) = (Maximum number of branches of compound used as nucleus)
Becomes
In the case of a branch structure, it is calculated by multiplying the number of branches of the nucleus by the maximum number of branches of the nucleus used at each branch point. That is,
(Number of ends)=maximum number of branches of nucleus×(maximum number of branches of nucleus used at branch point 1)×(maximum number of branches of nucleus used at branch point 2)×...×(used at branch point n Maximum number of branches in the nucleus)
Can be calculated as Here, n represents the number of branch points (synonymous with the number of generations-1).
In the case of the block structure, the number of end portions is 2.

In addition, the number of end portions per molecule of the adhesive polymer is determined from the analysis results of elemental analysis or X-ray photoelectron spectroscopy (ESCA; Electron Spectroscopy for Chemical Analysis) and nuclear magnetic resonance (NMR) measurements. It is also possible to identify and calculate the repeating unit and/or the element serving as the polymerization initiation point. Examples of the element serving as the polymerization initiation point include S atom, halogen atom (Cl, Br), Si atom, N atom, O atom and the like. In addition, examples of the functional group contained in the repeating unit include —SO ₂ — and —SO—.

The repeating unit forming the adhesive polymer will be described.
The repeating unit includes at least a repeating unit [a] having a solubility parameter δt calculated by the Hoy method of 13.5 or more and less than 20.0.
When the repeating unit forming the adhesive polymer is one kind, the adhesive polymer is formed only by the repeating unit [a]. When the repeating unit forming the adhesive polymer is two or more kinds, the adhesive polymer is formed by two or more kinds of repeating units containing at least one kind of repeating unit [a].

The solubility parameter δt is literature ^{"Properties of Polymers 3 rd, ELSEVIER} , (1990)" The δt obtained for Amorphous Polymers of pp 214-220, "2) Method of Hoy (1985,1989)" column of Meaning and calculated according to the description in the above column of the above document. In the present invention, the unit of the solubility parameter δt is “(cal/cm ³ ) ^1/2 ”.
Here, when the repeating unit is derived from a single compound, it is calculated as described above.
On the other hand, when the repeating unit is a repeating unit composed of two or more kinds of constituent components described later, for example, a repeating unit containing an amide bond described later, the solubility parameter δt is calculated as follows. That is, in the repeating unit, the mass ratio W of each structural unit after polymerization forming the repeating unit is calculated. Next, the solubility parameter δtr in each structural unit is calculated according to the above description. For each structural unit, the product of the solubility parameter δtr and the mass ratio W is calculated, and the value obtained by summing these is taken as the solubility parameter δt of the repeating unit.

The repeating unit [a] is not particularly limited as long as it satisfies the solubility parameter δt. As the repeating unit [a], for example, one derived from a styrene compound, one derived from a (meth)acrylic acid ester compound, one derived from a (meth)acrylic acid compound, an olefin compound (in the present specification, when simply referred to as an olefin compound, A non-cyclic olefin compound), a vinylidene compound, or a cyclic olefin compound.

When the repeating unit [a] is derived from a styrene compound (styrene repeating unit (a)), the styrene repeating unit (a) is not particularly limited as long as it is a repeating unit forming a styrene polymer. Examples of the styrene-based polymer include [0011] to [0020] in JP-A-2004-123965, [0014] to [0016] in JP-A-2013-75969, and [0011] in JP-A-7-3094. ] Etc. can be referred to.
Specific examples of the styrene compound leading to the repeating unit [a] include, for example, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 4-chloromethylstyrene, 2,6-dimethylstyrene, 2,6-dichlorostyrene, 2,6-difluorostyrene, pentafluorostyrene, 4-ethylstyrene, 4-butylstyrene, 4-tert-butylstyrene, 4- Methoxystyrene, 4-trifluoromethylstyrene, 4-acetoxystyrene, 4-phenylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylanthracene, α-methylstyrene, β-methylstyrene, 2-methyl-1-phenyl Examples thereof include propene, stilbene, divinylbenzene, diisopropenylbenzene, 4-isopropenyltoluene, cinnamonitrile, and 1,1-diphenylethylene.

When the repeating unit [a] is a repeating unit derived from a (meth)acrylic acid ester compound ((meth)acrylic acid ester repeating unit (a)), the structure of the repeating unit is described in, for example, JP-A 2004-323770. Reference can be made to paragraphs [0021] to [0023] of the publication, paragraphs [0024] to [0059] of JP-A-2014-185196, and the like.
When the repeating unit [a] is a repeating unit derived from a (meth)acrylic acid ester compound, it may be a repeating unit derived from a (meth)acrylic acid alkyl ester compound or a (meth)acrylic acid cycloalkyl ester compound. More preferable. The alkyl group of this (meth)acrylic acid alkyl ester compound may be linear or branched. 1-30 are preferable, as for carbon number of the alkyl group which comprises a (meth)acrylic-acid alkylester compound, 1-20 are more preferable, 1-18 are more preferable, and 1-16 are especially preferable. 3-30 are preferable, as for carbon number of the cycloalkyl group of a (meth)acrylic acid cycloalkyl ester compound, 4-20 are more preferable, 5-18 are more preferable, and 6-16 are especially preferable.
Specific examples of the (meth)acrylic acid ester compound and the (meth)acrylic acid cycloalkyl ester compound that lead to the repeating unit [a] include, for example, propyl acrylate, iso-propyl acrylate, n-butyl acrylate, and acrylic. Iso-butyl acid, sec-butyl acrylate, tert-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isomethacrylate. -Propyl, n-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate or dodecyl methacrylate can be mentioned.

When the repeating unit [a] is derived from a (meth)acrylic acid compound ((meth)acrylic acid repeating unit (a)), the (meth)acrylic acid repeating unit (a) may be (meth)acrylic. The repeating unit is not particularly limited as long as it is a repeating unit forming an acid polymer. For the structure of such a repeating unit, for example, paragraphs [0020] to [0027] of JP-A-2002-212221 can be referred to.
Specific examples of the (meth)acrylic acid compound leading to the repeating unit [a] include acrylic acid and its metal salt, or methacrylic acid and its metal salt.

When the repeating unit [a] is derived from an olefin compound (olefin repeating unit (a)), see paragraph [0015] of JP-A-2000-159817 for the structure of the repeating unit. You can
Specific examples of the olefin compound that leads to the repeating unit [a] include ethylene, propylene, isoprene, butadiene, isobutene, and vinyl chloride.
In the present invention, even if the olefin compound can be interpreted as a vinylidene compound, when the structure thereof is composed of only carbon atoms and hydrogen atoms, it is classified as an olefin compound rather than a vinylidene compound.

When the repeating unit [a] is derived from a vinylidene compound (vinylidene repeating unit (a)), examples of the structure of the repeating unit include, for example, paragraphs [0032] to [0041] of JP-A-2015-44967 or Reference can be made to paragraphs [0008] to [0009] of JP-A-8-67793.
Specific examples of the vinylidene compound that leads to the repeating unit [a] include vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, trifluoroethylene chloride, and perfluoroalkoxytrifluoroethylene.

When the repeating unit [a] is derived from a cyclic olefin compound (cyclic olefin repeating unit (a)), specific examples of the cyclic olefin compound leading to the repeating unit [a] include, for example, cyclohexene, norbornene and tetra. Mention may be made of cyclododecene and the compounds derived therefrom.

The adhesive polymer preferably has a repeating unit derived from a styrene compound or a (meth)acrylic acid ester compound as the repeating unit [a], and more preferably has a repeating unit derived from a (meth)acrylic acid ester compound. preferable.
The adhesive polymer more preferably has a repeating unit represented by the following general formula 2 or 3 as the repeating unit [a], and particularly preferably has a repeating unit represented by the following general formula 2.

In General Formula 2, R ⁵ represents a hydrogen atom or an alkyl group.
When R ⁵ is an alkyl group, the alkyl group may be linear, branched or cyclic. When the alkyl group is linear or branched, the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms. The alkyl group is more preferably methyl or ethyl, and further preferably methyl.
R ⁵ is preferably a hydrogen atom or methyl.

R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
When R ⁶ or R ⁷ is an alkyl group, the alkyl group has the same meaning as the above alkyl group for R ⁵ , and the preferred ones are also the same.
When R ⁶ or R ⁷ is an aryl group, the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, particularly preferably 6 to 12 carbon atoms, and particularly preferably phenyl.
When R ⁶ or R ⁷ is an alkoxycarbonyl group, the alkoxycarbonyl group preferably has 2 to 10 carbon atoms, and more preferably 2 to 5 carbon atoms. The alkoxycarbonyl group is more preferably methoxycarbonyl, ethoxycarbonyl or propoxycarbonyl.

In the repeating unit represented by the general formula 2, R ⁵ is preferably a hydrogen atom or an alkyl group, and R ⁶ and R ⁷ are preferably hydrogen atoms.

R ⁸ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms is preferable. However, when R ⁵ is methyl, R ⁸ may be a hydrogen atom.
The alkyl group having 1 to 20 carbon atoms may be linear or branched. 1-15 are preferable, as for carbon number of this alkyl group, 1-12 are more preferable, 1-10 are more preferable, 1-8 are more preferable, 1-6 are especially preferable. When the alkyl group having 1 to 20 carbon atoms has a substituent, a halogen atom is preferable, and a fluorine atom is more preferable.
The cycloalkyl group having 3 to 20 carbon atoms preferably has 4 to 15 carbon atoms, and more preferably 5 to 12 carbon atoms. It is also preferable that the cycloalkyl group having 3 to 20 carbon atoms has a form in which the substituents of the cycloalkyl group are linked to each other to form a condensed ring (eg, adamantane ring, isobornyl ring). When the cycloalkyl group having 3 to 20 carbon atoms has a substituent, it is preferably an alkyl group (which may be linear or branched), and is an alkyl group having 1 to 4 carbon atoms. Is preferred, and more preferably methyl, ethyl or tert-butyl.

In general formula 3, R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group.
When R ⁹ , R ¹⁰ or R ¹¹ is a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom is preferable.
When R ^{9, R 10} or ^{R 11} is an alkyl group, the alkyl group has the same meaning as the alkyl group of ^{R 5,} it is preferable also the same.
When R ⁹ , R ¹⁰ or R ¹¹ is an aryl group, the aryl group has the same meaning as the aryl group of R ⁶ , and the preferred ones are also the same.
Each of R ⁹ , R ¹⁰ and R ¹¹ is preferably a hydrogen atom, a halogen atom or an alkyl group, more preferably a hydrogen atom or a halogen atom, and even more preferably a hydrogen atom. Particularly, it is preferable that both R ¹⁰ and R ¹¹ are hydrogen atoms.

R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an acyl group, an acyloxy group or an alkoxycarbonyl group. R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxyl group, an acyloxy group or an alkoxy group, more preferably a hydrogen atom, a halogen atom or an alkyl group. A hydrogen atom is more preferable.

When R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ or R ¹⁶ is a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom is preferable.
When R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ or R ¹⁶ is an alkyl group, the alkyl group may be linear, branched or cyclic. When the alkyl group is linear or branched, the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms. The alkyl group is preferably methyl, ethyl or butyl, more preferably methyl.
When R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ or R ¹⁶ is an alkenyl group, the alkenyl group may be linear, branched or cyclic. 2-10 are preferable, as for carbon number of this alkenyl group, 2-5 are more preferable, and 2 or 3 is still more preferable. The alkenyl group is more preferably ethenyl or propenyl, and even more preferably ethenyl.
When R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ or R ¹⁶ is an aryl group, the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, particularly preferably 6 to 12 carbon atoms, and particularly preferably Phenyl is preferred.

When R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ or R ¹⁶ is an alkoxy group, the alkoxy group may be linear, branched or cyclic. When the alkoxy group is linear or branched, the number of carbon atoms in the alkoxy group is preferably 1-10, more preferably 1-5, and even more preferably 1-3. The alkoxy group is more preferably methoxy or ethoxy.
When R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ or R ¹⁶ is an acyl group, an acyloxy group or an alkoxycarbonyl group, the acyl group, the acyloxy group or the alkoxycarbonyl group respectively corresponds to the corresponding substituent in the substituent group T. It has the same meaning as the group, and the preferred ones are also the same.

Two adjacent R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may combine with each other to form a ring. For example, two adjacent ethenyl groups may be bonded to each other to form a benzene ring containing the carbon atoms to which they are bonded (naphthalene ring as a whole).
Each of R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may further have a substituent selected from the above substituent group T. For example, an alkyl group having a substituent may be mentioned, and specifically, a trifluoromethyl group may be mentioned.

Preferred examples of the repeating unit [a] are shown below as structural formulas, but the present invention is not limited to these specific examples.
In the following specific examples, A-1 to A-9, A-17 to A-21 and A-24 to A-35 are (meth)acrylic acid ester repeating units (a), and A-22 and A-23. Is a (meth)acrylic acid repeating unit (a), A-10 to A-15 are styrene repeating units (a), and A-16 and A-44 to A-48 are vinylidene repeating units (a). A-36 to A-43 are olefin repeating units (a), and A-49 to A-63 are cyclic olefin repeating units (a).

The adhesive polymer preferably contains, in addition to the repeating unit [a], a repeating unit [b] having a solubility parameter δt calculated by the Hoy method of 20.0 or more and 26.0 or less. As a result, it is possible to obtain a laminate in which the interlayer adhesion and the improvement of the contact angle are compatible with each other at a higher level.

The repeating unit [b] is not particularly limited as long as it satisfies the solubility parameter δt. Examples of the repeating unit [b] include those derived from a (meth)acrylic acid ester compound, those derived from a (meth)acrylic acid compound, those derived from a (meth)acrylamide compound, those derived from a vinyl acetate compound, and those derived from a vinyl ketone compound. Those derived from maleic anhydride compounds, those derived from styrene compounds, or those derived from compounds having an ethylenically unsaturated bond other than these repeating units, or repeating units containing amide bonds (polyamide repeating units), or Examples thereof include a repeating unit containing an ester bond (polyester repeating unit).

When the repeating unit satisfying the above [b] is derived from a (meth)acrylic acid ester compound ((meth)acrylic acid ester repeating unit (b)), the (meth)acrylic acid ester repeating unit (b) is There is no particular limitation as long as it is a repeating unit forming a (meth)acrylic acid ester polymer. For the structure of such a repeating unit, for example, paragraphs [0021] to [0023] of JP-A-2004-323770 or [0024] to [0059] of JP-A-2014-185196 can be referred to.
The (meth)acrylic acid ester repeating unit (b) is preferably derived from a (meth)acrylic acid (cyclo)alkyl ester compound.
Specific examples of the (meth)acrylic acid ester compound leading to the repeating unit [b] include 2-hydroxyethyl acrylate, 2-acetoacetoxyethyl acrylate, 2-isocyanatoethyl acrylate, and methacrylic acid 2 -Hydroxyethyl, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate or 2-isocyanatoethyl methacrylate.

When the repeating unit [b] is derived from a (meth)acrylic acid compound ((meth)acrylic acid repeating unit (b)), the (meth)acrylic acid repeating unit (b) may be (meth)acrylic. The repeating unit is not particularly limited as long as it is a repeating unit that forms an acid polymer. For the structure of such a repeating unit, for example, paragraphs [0020] to [0027] of JP-A-2002-212221 can be referred to.
Specific examples of the (meth)acrylic acid compound leading to the repeating unit [b] include acrylic acid and a metal salt thereof, or methacrylic acid and a metal salt thereof.

When the repeating unit [b] is derived from a (meth)acrylamide compound ((meth)acrylamide repeating unit (b)), the (meth)acrylamide repeating unit (b) may be a (meth)acrylamide polymer. There is no particular limitation as long as it is a repeating unit to be formed. The preferred structure of such a repeating unit is as shown in the structural formulas exemplified below.

When the repeating unit [b] is derived from a vinyl acetate compound (vinyl acetate repeating unit (b)), the vinyl acetate repeating unit (b) is particularly a repeating unit that forms a vinyl acetate polymer. Not limited. For the structure of the vinyl acetate repeating unit (b), reference can be made to, for example, paragraphs [0007] to [0008] of JP-A-2002-338609.
Specific examples of the vinyl acetate compound leading to the repeating unit [b] include vinyl acetate, vinyl propionate, vinyl pivalate, isopropenyl acetate and the like. Thus, in the present invention, the “vinyl acetate compound” is used to include a compound in which the hydrogen atom of vinyl acetate is replaced.

When the repeating unit [b] is derived from a vinyl ketone compound (vinyl ketone repeating unit (b)), the vinyl ketone repeating unit (b) is not particularly limited as long as it is a repeating unit forming a vinyl ketone polymer. For the structure of the repeating unit, reference can be made to paragraphs [0010] to [0017] of JP-A 2007-230940, paragraphs [0009] to [0011] of JP-A 7-291886, and the like.
Specific examples of the vinyl ketone compound leading to the repeating unit [b] include methyl vinyl ketone, ethyl vinyl ketone and the like.

When the repeating unit [b] is derived from a maleic anhydride compound (maleic anhydride repeating unit (b)), the maleic anhydride repeating unit (b) is a repeating unit forming a maleic anhydride polymer. If it is, it will not be limited in particular. For the structure of the repeating unit, reference can be made to paragraphs [0027] to [0029] of JP 2006-111710 A, paragraphs [0013] to [0015] of JP 2008-156400 A, and the like. ..
Specific examples of the maleic anhydride compound leading to the repeating unit [b] include maleic anhydride, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, maleic acid and the like. Thus, in the present invention, the term "maleic anhydride compound" is used to mean a compound derived from maleic anhydride.

When the repeating unit [b] is derived from a styrene compound (styrene repeating unit (b)), the styrene repeating unit (b) is not particularly limited as long as it is a repeating unit forming a styrene polymer. The preferred structure of such a repeating unit is as shown in the structural formulas exemplified below.

Further, the repeating unit [b] may be a repeating unit derived from a compound having an ethylenically unsaturated bond (carbon-carbon double bond) other than the repeating units derived from the above-mentioned compounds.

In the present invention, the repeating unit [b] also includes a repeating unit composed of two or more kinds of constituent components. Examples of such repeating units include polyamide repeating units and polyester repeating units.
The polyamide repeating unit is not particularly limited as long as it has an amide bond, and usually includes a unit constituting a polyamide obtained by copolycondensation of a polyvalent carboxylic acid compound and a polyvalent amine compound. The carboxylic acid compound and amine compound are not particularly limited as long as they are compounds that form various polyamides. For example, the valence numbers (the number of carboxy groups and the number of amino groups) of the carboxylic acid compound and the amine compound are not particularly limited, but are preferably divalent.
Examples of the carboxylic acid compound include an aliphatic carboxylic acid compound and an aromatic carboxylic acid compound, and the aromatic carboxylic acid compound is preferable. Examples of the aromatic carboxylic acid compound include terephthalic acid, isophthalic acid, 4,4′-dicarboxydiphenyl ether, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, benzophenone-4,4′-dicarboxylic acid, 5 -Tert-butylisophthalic acid, 2,5-dimethylterephthalic acid, 4,6-dimethylisophthalic acid, 4,4'-stilbenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid or 2,2-bis(4-carboxy) Phenyl)hexafluoropropane and the like. As the aliphatic carboxylic acid compound, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, decahydro-1,4-naphthalenedicarboxylic acid, decahydro-2,6-naphthalenedicarboxylic acid, sebacic acid, azelaic acid, Examples thereof include suberic acid and pimelic acid.
Examples of amine compounds include aliphatic amine compounds and aromatic amine compounds, with aromatic amine compounds being preferred. Examples of the aliphatic amine compound include 1,4-cyclohexanediamine and 1,3-cyclohexanediamine, in addition to the amine compound that leads to the exemplary repeating unit described below. Further, as the aromatic amine compound, 1,4-phenylenediamine, 1,3-phenylenediamine, 1,5-diaminonaphthalene, 2-chloro-1,4, in addition to the amine compound leading to an exemplary repeating unit described later, -Phenylenediamine, 4-chloro-1,3-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminotoluene, 2,5-dichloro-1,4-phenylenediamine or 2,5-diaminotoluene Can be mentioned.
In the polyamide repeating unit, the combination of the carboxylic acid compound and the amine compound is not particularly limited, and examples thereof include the combinations shown in the exemplary repeating units described below.
Here, when two kinds of at least one of the carboxylic acid compound and the amine compound are used, the obtained polyamide repeating unit is at least two kinds. For example, the following exemplary repeating unit B-65 formed by using two kinds of carboxylic acids can be mentioned.
The polyamide repeating unit can be obtained in the same manner as in the polyamide synthesis method.

The polyester repeating unit is not particularly limited as long as it has an ester bond, and usually includes a unit constituting a polyester obtained by copolycondensation of a polyvalent carboxylic acid and a polyvalent alcohol. The carboxylic acid and alcohol are not particularly limited as long as they are compounds that form various polyesters. For example, the valences of the carboxylic acid and the alcohol (the number of carboxy groups and the number of hydroxyl groups) are not particularly limited, but are preferably divalent.
Examples of the carboxylic acid include an aliphatic carboxylic acid and an aromatic carboxylic acid, and specific examples include the carboxylic acid in the polyamide repeating unit.
Examples of alcohols include aliphatic alcohols and aromatic alcohols. Examples of the aliphatic alcohol include 1,4-cyclohexanediol, 1,3-cyclohexanediol, and 4,4′-bicyclohexanol, in addition to the alcohols shown in the exemplary repeating units described below. As the aromatic alcohol (including those having a hydroxyl group bonded to an aliphatic group), resorcinol, 2,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, in addition to the alcohols shown in the exemplary repeating units described later, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl ether, 2-methylresorcinol, chlorohydroquinone, 1,3-bis(4-hydroxyphenoxy)benzene, 4-chlororesorcinol, Methylhydroquinone, 2,3-dimethylhydroquinone, 2,2-bis(4-hydroxyphenyl)propane, 4,4′-ethylidene bisphenol and the like can be mentioned.
In the polyester repeating unit, the combination of carboxylic acid and alcohol is not particularly limited, and examples thereof include the combinations shown in the exemplary repeating units described below.
The polyester repeating unit can be obtained in the same manner as in the polyester synthesis method.
In the present invention, the partial structure comprising the polyester repeating unit or the polymer may have another repeating unit, like the polyamide repeating unit.

The adhesive polymer preferably has a repeating unit represented by the following general formula 1 as the repeating unit [b].

In General Formula 1, R ¹ represents a hydrogen atom or an alkyl group, and preferably a hydrogen atom or methyl. When R ¹ is an alkyl group, each alkyl group has the same meaning as R ⁵ in the above general formula 2.
R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group. Each of R ² and R ³ is preferably a hydrogen atom.
When R ² or R ³ is an alkyl group, an aryl group and an alkoxycarbonyl group, the alkyl group, the aryl group and the alkoxycarbonyl group are respectively the alkyl group, the aryl group and the R ⁶ and R ⁷ in the above general formula 2. It has the same meaning as the alkoxycarbonyl group, and the preferred ones are also the same.

L is either a single bond or an alkylene group, an arylene group, -C (= O) -, - O- and -N ^{(R 4)} - from the divalent linking group or linking group of these selected A divalent linking group formed by combining two or more kinds is shown. R ⁴ represents a hydrogen atom or an alkyl group, has the same meaning as R ⁵ described above, and the preferred ones are also the same.
When L is an alkylene group, the alkylene group is preferably linear. Moreover, 1-5 are preferable, as for carbon number of this alkylene group, 1-4 are more preferable, 1-3 are more preferable, and 2 is especially preferable. When L is an arylene group, the arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, particularly preferably 6 to 12 carbon atoms, and particularly preferably phenylene. The alkylene group and the arylene group may each have a substituent, and examples of the substituent include the groups of the above-mentioned substituent group T.
In the divalent linking group formed by combining two or more linking groups, the number of the linking groups to be combined is not particularly limited, but for example, 2 to 9 are preferable, and 2 or 3 is more preferable. The combination of linking groups is not particularly limited, and for example, a combination of -C(=O)- and -O- or a combination containing -C(=O)- and -O- is preferable. Examples of the combination containing -C(=O)- and -O- include a combination of -C(=O)-, -O- and an alkylene group, or -C(=O)-, -O- and an arylene group. Is preferred, and a combination of -C(=O)-, -O- and an alkylene group is more preferred. In particular, it is more preferable that -C(=O)- is contained in the linking group, and -C(=O)- is bonded to the main chain (carbon atom to which R ¹ is bonded).

It is more preferable that the adhesive polymer has a repeating unit represented by the following general formula 1-2 as the repeating unit [b].

In Formula 1-2, R ^1A represents a hydrogen atom or an alkyl group. R ^1A has the same meaning as R ¹ in the above general formula 1, and preferred ones are also the same.
L is a single bond, or a divalent linking group selected from an alkylene group, an arylene group, —C(═O)—, —O— and —N(R ^4A )— or a linking group thereof. A divalent linking group formed by combining two or more kinds is shown. R ^4A represents a hydrogen atom or an alkyl group, has the same meaning as R ⁴ described above, and the preferred ones are also the same.
L in the general formula 1-2 has the same meaning as L in the general formula 1, and preferable ones are also the same.
In the repeating units represented by the general formulas 1 and 1-2, the acetoacetoxy group in each repeating unit may be substituted with a substituent.

In the adhesive polymer, as the repeating unit [b], a repeating unit derived from an acrylate compound (in the compounds represented by the general formulas 1 and 1-2, L is the above preferable combination) or a polyamide repeating unit is used. It is preferable to have a repeating unit derived from an acrylic acid ester compound (in the compounds represented by the general formulas 1 and 1-2, L is a preferable combination).

Preferred examples of the repeating unit [b] are shown below as structural formulas, but the present invention is not limited to these examples.
In the following specific examples, B-1 to B-9, B-14, B-18, B-20 to B-33, B-76, B-77 and B-80 are derived from a (meth)acrylic acid ester compound. A repeating unit, B-10 is a repeating unit derived from a (meth)acrylic acid compound, and B-11 to B-13, B-34 to B-37, B-78 and B-79 are (meth)acrylamide. Compound-derived repeating units, B-15 to A-17 are vinyl acetate compound-derived repeating units, B-19 is a vinyl ketone compound, and B-38 to B-46 are maleic anhydride compound-derived repeating units. B-47 to B-65 are polyamide repeating units, B-66 to B-75 are polyester repeating units, and B-81 is a styrene compound-derived repeating unit.

The repeating unit of the adhesive polymer is appropriately selected according to each primary structure and the like, and preferably has at least one repeating unit [a] and at least one repeating unit [b].
When the adhesive polymer has a block structure, this block structure may be a block structure having two partial structures consisting of the repeating unit [a], but a partial structure consisting of the repeating unit [a] and a repeating unit A block structure having a partial structure consisting of [b] is preferable.
When the adhesive polymer has a graft structure, the graft chain may have either or both of the repeating unit [a] and the repeating unit [b]. Preferably, the graft chain has a repeating unit [a]. That is, a graft structure in which the polymer PA ^G1 (trunk polymer) containing the repeating unit [b] is bonded to the polymer PB ^G1 (branching polymer) containing the repeating unit [a] is preferable. Here, the polymer containing a repeating unit may be a polymer composed of only a specific repeating unit, or a polymer containing a specific repeating unit and a repeating unit other than this (also referred to as another repeating unit), Good.

In the above adhesive polymer, the content of each repeating unit is not particularly limited.

From the viewpoint of obtaining a laminate having both a contact angle and adhesiveness, the molar amount of the repeating unit [a] in the total molar amount of the monomer components constituting the adhesive polymer is 5 mol% or more. Is preferable, 10 mol% or more is more preferable, 20 mol% or more is still more preferable, 30 mol% or more is further preferable, 40 mol% or more is particularly preferable, 50 mol% It is most preferable that the content be at least %. The molar amount of the repeating unit [a] in the total molar amount of the monomer components constituting the adhesive polymer is preferably 95 mol% or less, more preferably 90 mol% or less. In the above-mentioned adhesive polymer, the molar amount of the repeating unit [a] in the total molar amount of the monomer components constituting the adhesive polymer is preferably 100 mol% or less, and is contained in the adhesive polymer. It is also preferable that all of the repeating units described above are the repeating unit [a].

Further, from the viewpoint of obtaining a laminate having a higher contact angle and adhesiveness at a higher level, the number of moles of the repeating unit [b] in the total molar amount of the monomer components constituting the adhesive polymer is high. The amount is preferably 5 mol% or more, more preferably 10 mol% or more. The molar amount of the repeating unit [b] in the total molar amount of the monomer components constituting the adhesive polymer is preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 80 mol% or less, 15 mol% or less is particularly preferable, and 10 mol% or less is most preferable.

When the adhesive polymer has the repeating unit [a] and the repeating unit [b], the content of the repeating unit [a] and the content of the repeating unit [b] in the adhesive polymer are mols. The ratio preferably satisfies [repeat unit [a]]/[repeat unit [b]]=95/5 to 10/90, and [repeat unit [a]]/[repeat unit [b]]=95/ 5 to 30/70 is more preferable, and [repeating unit [a]]/[repeating unit [b]]=92/8 to 50/50 is further preferable, and [repeating unit [a]]/ [Repeating unit [b]]=90/10 to 60/40 is more preferable, and [repeating unit [a]]/[repeating unit [b]]=90/10 to 75/25 is particularly preferable. preferable.

In the adhesive polymer, the molar amount of the repeating unit represented by the general formula 2 or 3 in the total molar amount of the repeating unit [a] is preferably 50 mol% or more, and 70 mol% or more. It is more preferable that the amount is 80 mol% or more, further preferably 90 mol% or more, and particularly preferably 90 mol% or more. The adhesive polymer preferably has a molar amount of the repeating unit represented by the general formula 2 or 3 in the total molar amount of the repeating unit [a] of 100 mol% or less. It is also preferable that all of the repeating units [a] contained in the polymer are repeating units represented by the above general formula 2 or 3.

In the adhesive polymer, the molar amount of the repeating unit represented by the general formula 1 in the total molar amount of the repeating unit [b] is preferably 50 mol% or more, and 70 mol% or more. Is more preferable, 80 mol% or more is still more preferable, and 90 mol% or more is particularly preferable. The adhesive polymer preferably has a molar amount of the repeating unit represented by the general formula 1 in the total molar amount of the repeating unit [b] of 100 mol% or less. It is also preferred that all of the repeating units [b] contained in are repeating units represented by the general formula 1.

In the adhesive polymer, the molar amount of the repeating unit represented by the general formula 1-2 in the total molar amount of the repeating unit [b] is preferably 50 mol% or more, and 70 mol% or more. It is more preferable that the amount is 80 mol% or more, further preferably 90 mol% or more, and particularly preferably 90 mol% or more. The adhesive polymer preferably has a molar amount of the repeating unit represented by the general formula 1-2 in the total molar amount of the repeating unit [b] of 100 mol% or less. It is also preferable that all of the repeating units [b] contained in the polymer are repeating units represented by the general formula 1-2.

The adhesive polymer may have another repeating unit in addition to the repeating unit [a] and the repeating unit [b]. The other repeating unit may be contained in any of the chains forming the polymer. The total content of the repeating unit [a] and the repeating unit [b] in the total molar amount of the monomer components constituting the adhesive polymer is preferably 50% by mass or more, and 70% by mass. % Or more, more preferably 80% by mass or more, still more preferably 90% by mass or more. The adhesive polymer preferably has a total molar amount of the repeating unit [a] and the repeating unit [b] of 100 mol% or less, and is composed of the repeating unit [a] and the repeating unit [b]. It is also preferable that the form is

The reason why the layer containing the above-mentioned repeating unit [a] and containing the adhesive polymer having the above-mentioned primary structure is excellent in the adhesiveness to the cellulose ester layer and the hydrophobicity is not clear, but the present inventor Estimated as follows. However, the following reasons do not limit the present invention.
The solubility parameter δt of the repeating unit [a] is not close to the solubility parameter δt of cellulose ester. Therefore, the polymer having the repeating unit [a] usually has a low affinity for cellulose ester and does not exhibit sufficient adhesion. However, the adhesive polymer of the present invention has the above-mentioned primary structure. Therefore, it is considered that the adhesive polymer of the present invention can partially penetrate inside the cellulose ester layer. That is, the adhesive polymer of the present invention can function as an anchor layer for the cellulose ester layer while maintaining its hydrophobicity.

Moreover, the adhesive polymer of the present invention has the above primary structure. In particular, in the case of having a graft structure, a branch structure or a star structure, the number of end portions of the polymer chain is large and the interaction with the cellulose ester becomes large. From these, it is considered that the layer containing the adhesive polymer of the present invention exhibits excellent hydrophobicity (large contact angle) and further exhibits strong adhesiveness with the cellulose ester layer. On the other hand, in the case of a block structure having a repeating unit [a] and another repeating unit, for example, a repeating unit [b], the repeating unit [a] and the repeating unit [b] are made the same polymer by controlling the structure of the block structure. It can be introduced with some space inside. That is, the structure of maintaining the hydrophobicity derived from the repeating unit [a] and the structure of partially entering inside the cellulose ester layer derived from the repeating unit [b] are arranged in a good balance in the same polymer. As described above, since partial structures that contribute to the hydrophobicity and the adhesiveness are present everywhere in the same polymer, it is considered that excellent hydrophobicity and adhesiveness to the cellulose ester layer are exhibited.

In particular, when the adhesive polymer of the present invention has the repeating unit [b] in addition to the repeating unit [a], it exhibits strong adhesiveness with the cellulose ester layer. The solubility parameter δt of the repeating unit [b] is similar to that of cellulose ester, and has a high affinity for cellulose ester. In addition, the above-mentioned structure makes it easy for the repeating unit [b] to be unevenly distributed in the vicinity of the surface on the cellulose ester layer side when the layer is formed adjacent to the cellulose ester layer (the repeating unit [b] is near the surface The adhesive polymer is placed so that it is located at). Alternatively, as described above, it partially penetrates inside the cellulose ester layer. From these, it is considered that the adhesive polymer of the present invention having the repeating unit [b] effectively exhibits the interaction with the cellulose ester layer.

Moreover, the adhesive polymer of the present invention exhibits the function of the repeating unit [b] without impairing the function of the repeating unit [a] even if it has the repeating unit [b], The adhesion and the contact angle can be compatible at a higher level. The reason for this is not clear, but it is considered to be due to the fact that it has the above-mentioned primary structure. In particular, if the repeating unit [a] and the repeating unit [b] have the above-mentioned suitable composition ratio (molar ratio) in a well-balanced manner, the characteristics of each repeating unit can be made compatible at a higher level. it can.

The lower limit of the weight average molecular weight of the adhesive polymer used in the present invention is preferably 5,000 or more, more preferably 10,000 or more, and more preferably 15,000 or more from the viewpoint of the film surface state. More preferably, On the other hand, the upper limit of the weight average molecular weight of the adhesive polymer used in the present invention is preferably 1,000,000 or less, more preferably 800,000 or less, and 500 from the viewpoint of film-forming property. It is more preferably 5,000 or less, particularly preferably 200,000 or less, most preferably 100,000 or less.
The molecular weight can be measured by the method described in Examples described later.

The terminal structure of the adhesive polymer is not particularly limited, but is not uniquely determined by the presence or absence of other repeating units, the type of substrate used during synthesis, or the type of quenching agent (reaction terminator) during synthesis. .. Examples of the terminal group forming the terminal structure include a hydrogen atom, a halogen atom, a hydroxy group, an ethylenically unsaturated group, an alkyl group, an acyl group, an aromatic heterocyclic group or an aromatic hydrocarbon group.

The film thickness of the adhesive polymer layer is not particularly limited and is preferably 1 to 25 μm, more preferably 1 to 20 μm, and particularly preferably 1 to 15 μm.

[Cellulose ester layer]
The cellulose ester layer constituting the laminate of the present invention is a layer containing 50% by mass or more of cellulose ester in the layer. The content of the cellulose ester in the cellulose ester layer is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 85% by mass or more. The upper limit of the content of cellulose ester in the cellulose ester layer is usually 96% by mass or less, preferably 95% by mass or less, and more preferably 92% by mass or less. In this case, the balance excluding the cellulose ester contains, for example, additives described below.

<Cellulose ester>
The cellulose ester used as a raw material in the production of the cellulose ester layer of the present invention will be described.
The cellulose ester can be used without particular limitation as long as it is a cellulose ester used for producing a cellulose ester film.
The β-1,4-bonded glucose unit constituting cellulose has a free hydroxy group at the 2-position, 3-position and 6-position. Cellulose ester is a polymer obtained by esterifying a part of these hydroxy groups with an esterifying agent or the like.
Examples of the cellulose include cotton linter and wood pulp (hardwood pulp, softwood pulp), etc. Cellulose obtained from any raw material cellulose can be used, and may be mixed and used depending on the case. The raw material cellulose is, for example, by Marusawa and Uda, “Plastic Material Course (17) Fiber-Based Resin”, Nikkan Kogyo Shimbun (issued in 1970), or the Institute of Invention and Innovation Public Technical Report No. 2001-1745 (page 7). ~ Page 8) can be used.
As the cellulose ester, a known cellulose ester used for producing a cellulose ester film can be used without any limitation. Of these, it is preferable to use cellulose acylate.

(Cellulose acylate)
As the cellulose acylate used in the present invention, any known cellulose acylate used for producing a cellulose acylate film can be used without any limitation.
The degree of acyl substitution (hereinafter sometimes simply referred to as “degree of substitution”) indicates the degree of acylation of the hydroxy groups of cellulose at the 2-position, 3-position and 6-position, and is 2% of all glucose units. When all the hydroxy groups at the 3-, 3- and 6-positions are acylated, the total degree of acyl substitution is 3. For example, in all glucose units, when only the 6-position is all acylated, the total degree of acyl substitution is 1. Similarly, in all the hydroxy groups of all glucose, the total degree of acyl substitution is 1 when all of the 6-position or the 2-position is acylated in each glucose unit.
That is, the degree of substitution indicates the degree of acylation, where the case where all the hydroxy groups in the glucose molecule are all acylated is 3.
The degree of substitution of cellulose acylate is described in Tezuka et al., Carbohydrate. Res. , 273, 83-91 (1995) or the method defined in ASTM-D817-96.

The total acyl substitution degree of the cellulose acylate used in the present invention is preferably 1.50 or more and 3.00 or less, more preferably 2.00 to 2.97, and more preferably 2.30 or more from the viewpoint of moisture permeability. It is more preferably less than 2.97, particularly preferably 2.30 to 2.95.

The acyl group of the cellulose acylate used in the present invention is not particularly limited, and may have one type of acyl group or two or more types of acyl groups. The cellulose acylate that can be used in the present invention preferably has an acyl group having 2 or more carbon atoms as a substituent. The acyl group having 2 or more carbon atoms is not particularly limited, and may be an aliphatic acyl group or an aromatic acyl group. Specific examples of the acyl group having 2 or more carbon atoms include acetyl, propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, isobutanoyl, tert-butanoyl, cyclohexane. Carbonyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like can be mentioned. Among these, acetyl, propionyl, butanoyl, dodecanoyl, octadecanoyl, tert-butanoyl, oleoyl, benzoyl, naphthylcarbonyl and cinnamoyl are preferable, and acetyl, propionyl and butanoyl are more preferable.

Cellulose acetate using only an acetyl group as an acyl group of cellulose acylate can be preferably used in the present invention. The total acyl substitution degree of this cellulose acetate is 2.00 or more from the viewpoint of moisture permeability and optical characteristics. It is preferably 3.00 or less, more preferably 2.20 to 3.00, further preferably 2.30 to 3.00, and further preferably 2.30 to 2.97. It is preferably 2.30 to 2.95, and particularly preferably 2.30 to 2.95.

A mixed fatty acid ester having two or more kinds of acyl groups can also be preferably used as the cellulose acylate in the invention. Among them, the acyl group of the mixed fatty acid ester preferably contains an acetyl group and an acyl group having 3 to 4 carbon atoms. When the mixed fatty acid ester contains an acetyl group as an acyl group, its acetyl substitution degree is preferably less than 2.5, more preferably less than 1.9. On the other hand, when the acyl group having 3 to 4 carbon atoms is contained, the substitution degree of the acyl group having 3 to 4 carbon atoms is preferably 0.1 to 1.5, and is 0.2 to 1.2. It is more preferable, and it is especially preferable that it is 0.5 to 1.1.
Further, the mixed acid ester having a fatty acid acyl group and a substituted or unsubstituted aromatic acyl group described in paragraphs [0023] to [0038] of JP-A-2008-20896 can also be preferably used.

In the present invention, two types of cellulose ester or cellulose acylate having different ester groups and/or substitution degrees may be used in combination. In this case, it may be formed as a laminated structure made of different cellulose esters by a co-casting method described later.

The degree of polymerization of the cellulose ester or cellulose acylate used in the present invention is preferably 250 to 800, more preferably 300 to 600. The number average molecular weight of the cellulose ester or cellulose acylate used in the present invention is preferably 40,000 to 230,000, more preferably 60,000 to 230,000, and most preferably 75,000 to 200,000.
The degree of polymerization can be determined by dividing the number average molecular weight measured in terms of polystyrene by gel permeation chromatography (GPC) by the molecular weight of the glucopyranose unit of cellulose ester or cellulose acylate.

The cellulose ester used in the present invention can be synthesized by a conventional method. For example, cellulose acylate can be synthesized using an acid anhydride or acid chloride as an acylating agent. When the acylating agent is an acid anhydride, an organic acid (for example, acetic acid) or methylene chloride is used as a reaction solvent. Further, a protic catalyst such as sulfuric acid can be used as the catalyst. When the acylating agent is an acid chloride, a basic compound can be used as a catalyst. In general industrial production of cellulose acylate, an organic acid corresponding to the target acyl group of cellulose (acetic acid, propionic acid, butyric acid, etc.) or an acid anhydride thereof (acetic anhydride, propionic acid anhydride, butyric acid anhydride, etc.) Is used to esterify the hydroxy group.
For example, using cotton linter or cellulose derived from wood pulp as a raw material, after activation treatment of this with an organic acid such as acetic acid, in the presence of a sulfuric acid catalyst, by esterification with an organic acid having a desired structure, Cellulose acylate can be obtained. When an organic acid anhydride is used as the acylating agent, the organic acid anhydride is generally used in excess with respect to the amount of hydroxy groups present in the cellulose to esterify the cellulose.
Cellulose acylate can also be synthesized by the method described in JP-A-10-45804.

Further, in the cellulose ester layer of the present invention, other resin (for example, (meth)acrylic resin or the like) may be used in combination in addition to the cellulose ester within a range that does not impair the effects of the present invention. The content of the other resin in the cellulose ester layer is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, particularly preferably 15% by mass or less, in the cellulose ester layer. Most preferably, it is 10% by mass or less.

<Formation of cellulose ester layer>
Next, the formation of the cellulose ester layer will be described.
The formation of the cellulose ester layer is not particularly limited, and it is preferably formed by, for example, a melt film forming method or a solution film forming method (solvent casting method), and in consideration of volatilization or decomposition of the additive, the solution film forming is performed. More preferably, it is formed by a method. For examples of polymer film production using the solvent cast method, US Pat. Nos. 2,336,310, 2,367,603, 2,492,078, and 2,492,977 are described. Nos. 2,492,978, 2,607,704, 2,739,069 and 2,739,070, British Patents 640731 and 736892. Reference can be made to the respective specifications of JP-B Nos. 45-4554 and 49-5614, JP-A-60-176834, 60-203430, and 62-115035. .. The cellulose ester layer may be stretched. For the stretching method and conditions, refer to, for example, JP-A-62-115035, JP-A-4-152125, JP-A-4-284221, JP-A-4-298310, and JP-A-11-48271. can do.

(Casting)
As a method for casting a solution, a method for uniformly extruding the prepared dope from a pressure die onto a metal support, a doctor for once adjusting the film thickness with a blade of the dope once cast on a support such as a metal There are a method using a blade, a method using a reverse roll coater which adjusts with a reverse rotating roll, and the like, and a method using a pressure die is preferable. The pressure die includes a coat hanger type and a T-die type, and any of them can be preferably used. Further, in addition to the method mentioned here, it can be carried out by various methods for casting a conventionally known cellulose ester solution into a film, and set each condition in consideration of the difference in the boiling point of the solvent to be used. can do.

The cellulose ester layer may be a single layer or a multi-layer, and in the case of a multi-layer, it is preferable to use a co-casting method, a sequential casting method or a laminated casting method such as a coating method, In particular, it is particularly preferable to use the simultaneous co-casting (also referred to as simultaneous multi-layer co-casting) method from the viewpoint of stable production and reduction of production cost.
When the cellulose ester layer is produced by the co-casting method and the sequential casting method, first, a cellulose ester solution (also referred to as a dope) for each layer is prepared, and this solution is cast on a support.
In the co-casting method (multi-layer simultaneous casting), first, the casting dope of each layer (three layers or more) may be formed on the casting support (band or drum) from separate slits or the like. The dope is extruded using a casting die that can be extruded at the same time, and the layers are simultaneously cast. It is a casting method in which after casting, the film is peeled off from the support after an appropriate time and dried to form a film. By using a co-casting die, for example, two surface layers formed from the dope for the surface layer on the casting support and three core layers composed of the dope for the core layer sandwiched between the surface layers are provided. , Can be simultaneously extruded and cast on a support.

In the sequential casting method, first, a casting dope for the first layer is extruded from a casting die on a casting support, cast, and dried or dried without drying. The dope for casting for two layers is cast from a casting die and cast, and if necessary, the dope is cast and laminated in succession up to the third layer and peeled from the support after an appropriate time. And dried to form a cellulose ester layer.
In addition, in the coating method, generally, the core layer is formed into a film by a solution film-forming method, and the surface layer thereof is coated with a coating solution which is a target cellulose ester solution, and dried to form a cellulose ester having a laminated structure. Form the layers.

(Stretch)
It is also preferable that the above-mentioned cellulose ester layer is stretched after the above casting and drying. The stretching direction of the cellulose ester layer may be either the film transport direction (MD (Machine Direction) direction) or the direction orthogonal to the transport direction (TD (Transverse Direction) direction). Considering the subsequent polarizing plate processing process, the TD direction is preferable. The stretching treatment may be carried out multiple times in two or more stages.

The method of stretching in the TD direction is described in, for example, JP-A-62-115035, JP-A-4-152125, JP-A-4-284421, JP-A-4-298310, and JP-A-11-48271. There is. In the case of stretching in the TD direction, the film can be stretched while being conveyed while holding the width of the film with a tenter and gradually widening the width of the tenter. After the polymer film is dried, it may be stretched by using a stretching machine (preferably uniaxial stretching using a long stretching machine).
Stretching in the MD direction can be performed, for example, by adjusting the speed of the film transport roller so that the winding speed is faster than the film peeling speed.

When the laminate of the present invention is used as a protective film for a polarizer (also referred to as a polarizing plate protective film), in order to suppress light leakage when the polarizing plate is viewed obliquely, the transmission axis of the polarizer and cellulose ester are used. A preferred mode is one in which the slow axes in the plane of the layers are arranged in parallel. The transmission axis of the roll film-shaped polarizer that is continuously produced is generally parallel to the width direction of the roll film, and thus the protection is formed from the roll film-shaped polarizer and the roll film-shaped cellulose ester layer. In order to continuously bond the films, the in-plane slow axis of the roll film-shaped protective film needs to be parallel to the width direction of the cellulose ester layer. Therefore, it is preferable to stretch more in the TD direction. The stretching treatment may be performed in the middle of the film-forming step, or the raw material film-formed and wound may be stretched.

The stretching in the TD direction is preferably 5 to 100%, more preferably 5 to 80%, and particularly preferably 5 to 40%. In the case of unstretched, the stretch is 0%. The stretching treatment may be performed in the middle of the film-forming step, or the raw material film-formed and wound may be stretched. In the former case, the stretching may be carried out in a state where the residual solvent amount is included, and the residual solvent amount=(residual volatile matter mass/film mass after heat treatment)×100% is stretched in a state of 0.05 to 50%. Preferably. It is more preferable to stretch 5 to 80% with the residual solvent amount being 0.05 to 5%.

<Additive>
The cellulose ester layer may contain an additive as long as the effect of the present invention is not impaired. Examples of the additives include known plasticizers, organic acids, dyes, polymers, retardation adjusters, ultraviolet absorbers, antioxidants and matting agents. Regarding these, the description in paragraph numbers [0062] to [0097] of JP 2012-155287 A can be referred to, and the contents thereof are incorporated in the present specification. Further, examples of the additive include a peeling accelerator, an organic acid, and a polycarboxylic acid derivative. Regarding these, the descriptions in paragraphs [0212] to [0219] of International Publication No. 2015/005398 can be referred to, and the contents thereof are incorporated in the present specification. Further, as an additive, a radical scavenger, a deterioration inhibitor, a barbituric acid compound, and the like, which will be described later, can be mentioned.
The content of the additive (when the cellulose ester layer contains two or more kinds of additives, the total content thereof) is preferably 50 parts by mass or less with respect to 100 parts by mass of the cellulose ester, The amount is more preferably 30 parts by mass or less, further preferably 5 to 30 parts by mass.

(Plasticizer)
A plasticizer can be mentioned as one of the preferable additives. The hydrophobicity of the cellulose ester layer can be increased by adding the plasticizer to the cellulose ester layer. This point is preferable from the viewpoint of reducing the water content of the cellulose ester layer. It is preferable to use such a plasticizer because when a laminate having a cellulose ester layer is used as a polarizing plate protective film, display unevenness of the image display device due to humidity can be less likely to occur. ..

The plasticizer is not particularly limited, but may be a polyvalent ester compound of a polyhydric alcohol (hereinafter, also referred to as “polyhydric alcohol ester plasticizer”), a polycondensation ester compound (hereinafter, also referred to as “polycondensation ester plasticizer”). Or a carbohydrate compound (hereinafter, also referred to as “carbohydrate derivative plasticizer”). Regarding polyhydric alcohol ester plasticizers, paragraphs [0081] to [0098] of WO 2015/005398, and regarding polycondensation ester plasticizers, paragraphs [0099] to [0122] of the same publication, carbohydrate derivative plasticizers. Regarding the agent, reference can be made to paragraphs [0123] to [0140] of the publication, the contents of which are incorporated in the present specification.
The molecular weight of the plasticizer is preferably 3000 or less, more preferably 1500 or less, and even more preferably 1000 or less, from the viewpoint of obtaining the above effects by addition. The molecular weight of the plasticizer is, for example, 300 or more, preferably 350 or more, from the viewpoint of low volatility. In addition, regarding a plasticizer of a multimer, the molecular weight means a number average molecular weight.

The content of the plasticizer is 1 to 20 parts by mass with respect to 100 parts by mass of the resin (cellulose ester) of the layer to which the plasticizer is added, from the viewpoint of achieving both the effect of adding the plasticizer and the suppression of precipitation of the plasticizer. It is preferable that the amount is 2 to 15 parts by mass, more preferably 5 to 15 parts by mass.
Two or more plasticizers may be used in combination. When two or more kinds are used in combination, the specific examples of the content and the preferable range are the same as above.

(Antioxidant)
An antioxidant can also be mentioned as one of the preferable additives. Regarding the antioxidant, the description in paragraphs [0143] to [0165] of WO 2015/005398 can be referred to, and the contents thereof are incorporated in the present specification.

(Radical scavenger)
A radical scavenger can also be mentioned as one of the preferable additives. Regarding the radical scavenger, the description in paragraphs [0166] to [0199] of WO 2015/005398 can be referred to, and the contents thereof are incorporated in the present specification.

(Deterioration preventive agent)
As one of the preferable additives, a deterioration inhibitor can also be mentioned. Regarding the deterioration inhibitor, the description in paragraphs [0205] to [0206] of WO 2015/005398 can be referred to, and the contents thereof are incorporated in the present specification.

(Barbituric acid compound)
The cellulose ester layer may contain a compound having a barbituric acid structure (barbituric acid compound). The barbituric acid compound is a compound capable of exhibiting various functions in the cellulose ester layer by adding this compound. For example, the barbituric acid compound is effective in improving the hardness of the cellulose ester layer. Further, the barbituric acid compound is also effective for improving the durability of a polarizing plate provided with a cellulose ester layer containing this compound against light, heat or humidity. Regarding the barbituric acid compound that can be used in the cellulose ester layer, for example, the descriptions in paragraphs [0029] to [0060] of International Publication No. 2015/005398 can be referred to, and the contents thereof are incorporated in the present specification. ..

<Saponification treatment>
The above-mentioned cellulose ester layer can be improved in adhesiveness with a material of a polarizer such as polyvinyl alcohol by performing an alkali saponification treatment.
As the saponification method, the methods described in paragraph Nos. [0211] and [0212] of JP2007-86748A can be used.

For example, the alkali saponification treatment of the cellulose ester layer is preferably performed by a cycle of immersing the film surface in an alkali solution, neutralizing the film with an acidic solution, washing with water and drying. Examples of the alkaline solution include potassium hydroxide solution and sodium hydroxide solution. The hydroxide ion concentration is preferably in the range of 0.1 to 5.0 mol/L, more preferably in the range of 0.5 to 4.0 mol/L. The temperature of the alkaline solution is preferably room temperature to 90°C, more preferably 40 to 70°C.

Instead of the alkali saponification treatment, easy adhesion processing as described in JP-A-6-94915 or JP-A-6-118232 may be performed.

The film thickness of the cellulose ester layer is preferably 1 to 80 μm, more preferably 1 to 60 μm, still more preferably 3 to 60 μm.
When the cellulose ester layer has a laminated structure of three or more layers, the thickness of the core layer is preferably 3 to 70 μm, more preferably 5 to 60 μm. In the case of a three-layer structure, the thickness of both the skin layer A and the skin layer B is preferably 0.5 to 20 μm, more preferably 0.5 to 10 μm, and further preferably 0.5 to 3 μm. The core layer means an inner layer in the laminated structure and an intermediate layer in the case of a three-layer structure, and the skin layers A and B are outer layers in the laminated structure or the three-layer structure. Say.

[Method for manufacturing laminated body]
The method for manufacturing the laminate of the present invention will be described.
The laminate of the present invention is not particularly limited, and a known method can be adopted. In addition to the melt film-forming method or the solution film-forming method, after producing the cellulose ester layer by the above-mentioned method, the adhesive polymer layer may be formed by various known coating methods to produce a laminate. The coating method is not particularly limited, but the microgravure coating method can be preferably used. Note that, whichever coating method is used, the coating liquid is not particularly limited as long as the adhesive polymer is dissolved in an appropriate solvent at an appropriate concentration, and the coating conditions and the film forming conditions are also set. There is no particular limitation.
From the viewpoint of suitability for mass production, it can be manufactured by a melt film forming method or a solution film forming method. As the melt film forming method, it is preferable to use a manufacturing method such as a T-die method, and it is particularly preferable to use a simultaneous co-extrusion method. As the solution film-forming method, it is preferable to use the above-mentioned co-casting method, sequential casting method, coating method or other laminated casting method, and in particular, simultaneous co-casting method (also referred to as simultaneous multi-layer co-casting method) is used. Is particularly preferable from the viewpoint of stable manufacturing and reduction of production cost.

<Physical properties or characteristics of laminate>
The laminate of the present invention preferably has the following physical properties or characteristics.
(Contact angle)
In the laminate of the present invention, the contact angle of the adhesive polymer layer surface measured by the following method is preferably 64° or more, more preferably 65° or more, and particularly preferably 70° or more. preferable. In the laminate having such a contact angle, the surface of the adhesive polymer layer exhibits high hydrophobicity and water can be prevented from adhering to the surface of the adhesive polymer layer. Therefore, the moisture permeability in the adhesive polymer layer becomes small, and deterioration of the polarizer can be effectively suppressed by stacking the laminate of the present invention on the polarizer.
The contact angle on the surface of the adhesive polymer layer can be measured by the method described in the Example section.

(Haze)
The laminate of the present invention has a haze measured by the following method of preferably 1% or less, more preferably 0.7% or less, and particularly preferably 0.5% or less. The laminate showing such haze has excellent transparency and is suitable as a film member of a liquid crystal display device. The lower limit of haze is, for example, 0.001% or more, but is not particularly limited.
Haze is measured according to JIS K7136 (2000) using a haze meter (HGM-2DP, Suga Tester) in an environment of 25° C. and 60% relative humidity using a laminated body of 40 mm×80 mm.

(Film thickness)
The film thickness of the laminate of the present invention can be appropriately determined depending on the application, but can be, for example, 5 to 100 μm. When the thickness is 5 μm or more, the handling property when producing a web-shaped film is improved, which is preferable. Further, when the thickness is 100 μm or less, it is easy to cope with a change in humidity and it is easy to maintain the optical characteristics. The film thickness of the laminate is more preferably 8 to 80 μm, further preferably 10 to 70 μm.
In order to meet the above-mentioned demand for thinning of the image display device, the laminated body is preferably thinned, and the thickness of the laminated body in this case is, for example, preferably 8 to 80 μm, and 10 to 70 μm. Is more preferable.

(Moisture permeability)
The moisture permeability of the laminate is measured based on the description of JIS Z 0208 under the conditions of 40° C. and relative humidity of 90%.
Moisture permeability of the laminate of the present invention is preferably less than 1600g ^/ m 2 ^/ day, more preferably less than 1000g ^/ m 2 ^/ day, more preferably less than 500g ^/ m 2 ^/ day , 250 g/m ² /day is particularly preferable. By controlling the water vapor transmission rate of the laminate within the above range, the liquid crystal display device equipped with the laminate of the present invention has a warp of the liquid crystal cell after normal temperature, high humidity and high temperature and high humidity environment aging, and a display during black display. Unevenness can be suppressed.

(Moisture content)
The water content (equilibrium water content) of the laminate is 25° C. regardless of the film thickness so as not to impair the adhesiveness with a hydrophilic thermoplastic resin such as polyvinyl alcohol when used as a protective film for a polarizing plate. The water content at a relative humidity of 80% is preferably 0 to 4 mass %. The water content is more preferably 0 to 2.5% by mass, further preferably 0 to 1.5% by mass. When the equilibrium water content is 4% by mass or less, the dependence of the retardation on the humidity change does not become too large, and the display at the time of black display after aging in the normal temperature and high humidity environment and the high temperature and high humidity environment of the liquid crystal display device It is also preferable in terms of suppressing unevenness.
As a method for measuring the water content, a film sample of 7 mm×35 mm can be measured by the Karl Fischer method using a moisture meter and a sample drying device “CA-03” and “VA-05” (both manufactured by Mitsubishi Chemical Corporation). .. The water content can be calculated by dividing the water content (g) by the sample mass (g).

[Polarizer]
The polarizing plate of the present invention includes a polarizer and at least one laminate of the present invention as a protective film for the polarizer. Generally, a polarizing plate in which both sides of a polarizer are sandwiched between polarizing plate protective films to protect both sides is widely used.

As the polarizer, for example, a polyvinyl alcohol film which is immersed in an iodine solution and stretched can be used. When a polarizer obtained by immersing a polyvinyl alcohol film in an iodine solution and stretching is used, for example, an adhesive is used to attach at least one surface of the polarizer to the saponified surface of the cellulose ester layer in the laminate. You can

The laminate of the present invention can be used as a polarizing plate protective film. When used as a polarizing plate protective film, the method for producing the polarizing plate of the present invention is not particularly limited, and it can be produced according to a general method. For example, there is a method in which the laminate of the present invention is subjected to alkali treatment, and a polyvinyl alcohol film is immersed and stretched in an iodine solution to be laminated on both surfaces of the polarizer using a completely saponified polyvinyl alcohol aqueous solution. Instead of the alkali treatment, easy adhesion processing as described in JP-A-6-94915 or JP-A-6-118232 may be performed. Other surface treatments can also be performed. Examples of other surface treatments include methods such as corona discharge, glow discharge, ultraviolet (UV) irradiation, and flame treatment.
When the laminate has a form in which the adhesive polymer layer is provided on one surface of the cellulose ester layer, the surface of the laminate to be attached to the polarizer may be the adhesive polymer layer side or the cellulose ester layer side. But it's okay. From the viewpoint of further enhancing the effect of the present invention, it is preferable to directly bond the adhesive polymer layer side to the polarizer.

The lamination of the laminate of the present invention to the polarizer is preferably such that the transmission axis of the polarizer and the slow axis of the laminate of the present invention are parallel, orthogonal or 45°. The slow axis can be measured by various known methods, for example, a birefringence meter (KOBRADH, manufactured by Oji Scientific Instruments Co., Ltd.).
Here, parallel, orthogonal, or 45° includes an error range allowable in the technical field to which the present invention belongs. For example, it means within ±10° from a strict angle with respect to parallel, orthogonal, and 45°, respectively, and the error from the strict angle is preferably within ±5°, and within ±3°. Is more preferable.
The parallel to the transmission axis of the polarizer and the slow axis of the laminate of the present invention means that the direction of the main refractive index nx of the laminate of the present invention and the direction of the transmission axis of the polarizer intersect at an angle of ±10°. It means that This angle is preferably within ±5°, more preferably within ±3°, even more preferably within ±1°, and most preferably within ±0.5°.
Further, the orthogonality between the transmission axis of the polarizer and the slow axis of the laminate of the present invention means that the direction of the main refractive index nx of the laminate of the present invention and the direction of the transmission axis of the polarizer are 90°±10°. Means that they intersect at an angle within the range. This angle is preferably in the range of 90°±5°, more preferably in the range of 90°±3°, even more preferably in the range of 90°±1°, most preferably 90°±0.1°. It is within the range. Within the above range, deterioration of the polarization degree performance under the polarizing plate crossed Nicols is suppressed, and light leakage is reduced, which is preferable.

The adhesive used for bonding the polarizing plate protective film and the polarizer is not particularly limited, and examples thereof include an aqueous solution of polyvinyl alcohol or polyvinyl acetal (for example, polyvinyl butyral), a vinyl polymer (for example, polybutyl). Acrylate) latex, UV-curable adhesive, and the like. A particularly preferred adhesive is an aqueous solution of completely saponified polyvinyl alcohol or an ultraviolet curable adhesive.

The polarizing plate is composed of a polarizer and a protective film that protects both surfaces thereof, and at least one of the protective films is preferably the laminate of the present invention. As the protective film other than the laminate of the present invention, known films can be used without particular limitation. The polarizing plate of the present invention includes the laminate of the present invention as a polarizing plate protective film. Therefore, deterioration of the polarizer is effectively prevented, and high polarizer durability is exhibited. Further, it is also preferable that this polarizing plate is constituted by laminating a separate film on the surface. The separate film is used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection. The separate film is used for the purpose of covering the adhesive layer that is stuck to the liquid crystal plate, and is used on the surface side where the polarizing plate is stuck to the liquid crystal plate.

[Optical characteristics of polarizing plate]
<Degree of polarization>
The polarization degree of the polarizing plate of the present invention is preferably 95.0% or more, more preferably 98% or more, and most preferably 99.5% or more.

In the present invention, the polarization degree of the polarizing plate can be measured using an automatic polarizing film measuring device VAP-7070 manufactured by JASCO Corporation. More specifically, it can be measured by the method described in the Example section.

<Change in polarization degree>
The polarizing plate of the present invention is excellent in durability under heat and humidity aging conditions. Therefore, the amount of change in the degree of polarization before and after the polarizing plate durability test described below is small.
The polarizing plate of the present invention measures the orthogonal transmittance and the parallel transmittance using an automatic polarizing film measuring device VAP-7070 manufactured by JASCO Corporation, and calculates the degree of polarization by the formula described below. The amount of change in polarization degree when stored for 500 hours in an environment of 85% humidity is preferably less than 3%.

<Other characteristics>
Other preferable optical characteristics and the like of the polarizing plate of the present invention are described in paragraph numbers [0238] to [0255] of JP-A-2007-086748, and it is preferable to satisfy these characteristics.

[Image display device]
The polarizing plate of the present invention is preferably used as an image display device. Examples of such an image display device include a liquid crystal display device and an organic electroluminescence display device. When used for an organic electroluminescence display device, it is used for antireflection applications, for example. Above all, the polarizing plate of the present invention is suitably used for a liquid crystal display device.
<Liquid crystal display>
A liquid crystal display device, which is one embodiment of the image display device of the present invention, includes a liquid crystal cell and the polarizing plate of the present invention arranged in at least one of the liquid crystal cells.

A liquid crystal display device, which is an embodiment of the image display device of the present invention, requires a liquid crystal cell in which liquid crystal is carried between two electrode substrates, and two polarizing plates arranged on both sides thereof. Accordingly, at least one optical compensation film is provided between the liquid crystal cell and the polarizing plate.
A preferred embodiment of the liquid crystal display device will be described.

FIG. 2 is a schematic view showing an embodiment of the liquid crystal display device. 2, the liquid crystal display device 20 includes a liquid crystal layer 24, a first (upper liquid crystal cell) electrode substrate 23 and a second (lower liquid crystal cell) electrode substrate 25 disposed on both surface sides (referred to as upper and lower sides in FIG. 2). And a first (upper) polarizing plate 21 and a second (lower) polarizing plate 26 arranged on both sides of the liquid crystal cell. A color filter may be arranged between the liquid crystal cell and each polarizing plate. When the liquid crystal display device 20 is used as a transmissive type, a cold cathode or a hot cathode fluorescent tube, or a backlight having a light emitting diode, a field emission element, or an electroluminescent element as a light source is arranged on the back surface. The substrate of the liquid crystal cell generally has a thickness of 50 μm to 2 mm.
Although not shown, the first polarizing plate 21 and the second polarizing plate 26 usually have a structure in which two polarizing plate protective films are laminated so as to sandwich the polarizer. In the liquid crystal display device 20 of the present invention, at least one polarizing plate is preferably the polarizing plate of the present invention. Further, of the two polarizing plates, the laminate of the present invention is arranged as a polarizing plate protective film of the first polarizing plate 21 (viewing side polarizing plate), and then the second polarizing plate 26 (backlight side polarizing plate). It is also preferable to dispose the laminate of the present invention as the polarizing plate protective film of (1). Thereby, the expansion and contraction of the polarizer included in the two polarizing plates can be suppressed, and the warp of the panel can be prevented. In the liquid crystal display device 20 of the present invention, it is also preferable to laminate the laminate of the present invention as a polarizing plate protective film, a polarizer, and a general transparent protective film in this order from the outside of the device (the side far from the liquid crystal cell).

The liquid crystal layer 24 of the liquid crystal cell is usually formed by enclosing a liquid crystal in a space formed by sandwiching a spacer between two substrates. The transparent electrode layer is formed on the substrate as a transparent film containing a conductive material. Thereby, an electrode substrate including the substrate and the transparent electrode layer is obtained. The liquid crystal cell may be further provided with a gas barrier layer, a hard coat layer or an undercoat layer (used for adhesion of the transparent electrode layer) (undercoat layer). These layers are usually provided on the substrate.

The laminate of the present invention can also be preferably used as an optical compensation film for a liquid crystal display device. In this case, the liquid crystal display device is a liquid crystal cell in which liquid crystal is carried between two electrode substrates, two polarizers arranged on both sides of the liquid crystal cell, and at least between the above liquid crystal cell and the polarizer. It is more preferable that one laminate of the present invention is arranged as an optical compensation film.

(Type of liquid crystal display device)
The laminate of the present invention can be used in liquid crystal cells of various display modes. TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-ferroelectric Liquid Nested, CB) Various display modes such as ECB (Electrically Controlled Birefringence) or HAN (Hybrid Aligned Nematic) have been proposed. Further, a display mode in which the above-mentioned display mode is orientation-divided is also proposed. The cellulose ester of the present invention can be suitably used for liquid crystal display devices of any display mode. Further, it can be suitably used for any of a transmissive type, a reflective type, and a transflective type liquid crystal display device.

The present invention will be described in more detail based on examples, but the present invention is not limited to the following examples.
In the following examples, the number of repeating units is a value calculated from the molecular weight of repeating units and the number average molecular weight of the polymer.

[Synthesis example]
<Synthesis Example 1: Synthesis of polymer P-1>
In a 100 mL Erlenmeyer flask, 25.0 g of methyl methacrylate (a compound preA-1 that leads to the repeating unit A-1; hereinafter, a compound that leads to the repeating unit XY may be referred to as preX-Y), and dimethyl-as a polymerization initiator. 0.16 g of 2,2′-azobisisobutyrate, 0.86 g of tetrakis(3-mercaptopropionic acid)pentaerythritol I-4 as a core compound, and 15.0 g of methyl ethyl ketone were weighed out, and these were taken. A monomer composition P1 was prepared by mixing and dissolving.
Next, 10.0 g of methyl ethyl ketone was charged into a 300 mL three-necked flask equipped with a thermometer, a stirring blade and a reflux ring, and stirred at 80° C. under a nitrogen stream. The monomer composition P1 was added dropwise to the methyl ethyl ketone at a rate of 0.31 mL/min. A chemical pump was used for dropping. The reaction solution after completion of the dropwise addition was further reacted at 80° C. for 2 hours, then 0.02 g of dimethyl-2,2′-azobisisobutyrate was further added, and the obtained mixture was stirred for another 3 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature (30° C.), diluted with 70 g of methyl ethyl ketone, and reprecipitated with a mixed solution of 1.4 L of methanol and 0.4 L of water to obtain a white precipitate. The white precipitate obtained was filtered off and dried at 50° C. overnight to obtain 22.5 g of the target P-1.
The polymer P-1 obtained is shown below. In the structure below, the number (40) attached to the repeating unit represented by R represents the number of repeating units in the polymer PA ^S1 .
This polymer P-1 had a structure shown in FIG. 6A, specifically, a star structure in which four polymers PA ^S1 having a repeating unit A-1 were bonded to the nucleus.

<Synthesis Example 2: Synthesis of polymer P-2>
Polymer P-2 was synthesized with reference to Macromolecules, 2006, 39(22), 4361.
A 500 mL three-necked flask equipped with a thermometer, a stirring blade, and a reflux ring was thoroughly dried, 150 mL of benzene was added, and the mixture was stirred at -78°C to n-BuLi (n-butyllithium, 0.16 M hexane solution). ) Was added in an amount of 12.5 mL. 10.1 g of methyl methacrylate preA-1 was added and stirred for 1 hour. In a 500 mL three-necked flask equipped with a thermometer, a stirring blade and a reflux ring, 196 mg of 4-(dichloromethylsilyl)diphenylethylene was mixed with the above reaction solution. To this, 1.26 mL of s-BuLi (s-butyllithium, 0.53 M hexane solution) was added, and 4.66 g of methyl methacrylate preA-1 was further added, followed by stirring for 1 hour, and then trichloromethylsilane 33. 2 mg was added and stirred. After completion of the reaction, a small amount of methanol was added, the reaction solution was allowed to cool to room temperature, diluted with 30 g of methyl ethyl ketone, and reprecipitated with 500 mL of methanol to obtain a white precipitate. The white precipitate obtained was filtered off and dried overnight at 50° C. to obtain 10.7 g of the target branch polymer polymer P-2.
The polymer P-2 obtained is shown below. In the following structure, the numbers (50 and 70) attached to the repeating units represented by R represent the number of repeating units.
This polymer P-2 has the structure shown in FIG. 7A, specifically, the upper right Si atom of the following polymer P-2 serves as a nucleus to bond three polymers PA ^B1 , and further, to this polymer PA ^B1. It had a branched structure in which two polymers PB ^B1 were bonded via the diphenylethylene-derived nucleus.

<Synthesis Example 3: Synthesis of polymer P-3>
To a 10 mL vial, 0.22 mg of copper(I) bromide, 0.17 mg of N,N,N′,N″,N″-pentamethyldiethylenetriamine, and 1 mL of toluene were added, and a homogeneous catalyst solution was added. Got In a 200 mL three-necked flask equipped with a thermometer, a stirring blade, and a reflux ring, 20.0 g of methyl methacrylate preA-1 and 0.17 g of dimethyl-2,2′-azobisisobutyrate, and 2 Ethyl bromoisobutyrate was weighed in an amount of 6.7 mg, the catalyst solution was added, and the mixture was stirred at 70° C. for 20 hours under a nitrogen stream.
Then, a mixed solution of 3.73 g of cyclohexyl methacrylate preA-2 and 2 mL of toluene was added to the obtained reaction solution after purging with nitrogen, and the mixture was stirred at 70°C. After the reaction was completed, the reaction solution was allowed to cool to room temperature, diluted with 70 g of methyl ethyl ketone, and reprecipitated with a mixed solution of 1.2 L of methanol and 0.5 L of water to obtain a white precipitate. The obtained white precipitate was filtered off and dried at 50° C. overnight to obtain 21.3 g of the target P-3.
The polymer P-3 obtained is shown below. This polymer P-3 has a structure shown in FIG. 3A composed of two kinds of repeating units [a], specifically, a partial structure composed of repeating unit A-2 and a partial structure composed of repeating unit A-1. It was a block structure (AB type) in which a single linear direction was bonded in the polymer chain.

<Synthesis Example 4: Synthesis of polymer P-4>
In a 100 mL Erlenmeyer flask, methyl methacrylate preA-1 22.53 g, acetoacetoxyethyl methacrylate preB-1 5.36 g, dimethyl-2,2'-azobisisobutyrate 0.069 g as a polymerization initiator, As a core compound, 0.367 g of tetrakis(3-mercaptopropionic acid)pentaerythritol and 16.73 g of methyl ethyl ketone were weighed out and mixed and dissolved to prepare a monomer composition P4.
Then, 11.15 g of methyl ethyl ketone was charged into a 300 mL three-necked flask equipped with a thermometer, a stirring blade and a reflux ring, and stirred at 80° C. under a nitrogen stream. The monomer composition P4 was added dropwise to the methyl ethyl ketone at a rate of 0.31 mL/min. A chemical pump was used for dropping. The reaction solution after completion of the dropwise addition was further reacted at 80° C. for 2 hours, then 0.02 g of dimethyl-2,2′-azobisisobutyrate was further added, and the obtained mixture was stirred for another 3 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature (30° C.), diluted with 70 g of methyl ethyl ketone, and reprecipitated with a mixed solution of 1.4 L of methanol and 0.4 L of water to obtain a white precipitate. The obtained white precipitate was filtered off and dried at 50° C. overnight to obtain 25.5 g of the target P-4.
The polymer P-4 obtained is shown below. This polymer P-4 has a structure shown in FIG. 6B, specifically, a star structure in which four polymers PA ^S1 having a repeating structure A-1 and a repeating unit B-1 in a random structure are bonded to the nucleus. Had.

<Synthesis Example 5: Synthesis of polymer P-5>
In a 100 mL Erlenmeyer flask, 20.5 g of macromonomer AA-6 of methyl methacrylate preA-1 (manufactured by Toagosei Co., Ltd., number average molecular weight 6,000, average degree of polymerization about 60), dimethyl-2,2'-azobis. 0.41 g of isobutyrate and 23.0 g of methyl ethyl ketone were weighed out and mixed and dissolved to prepare a monomer composition P5-1.
Separately, 8.7 g of methyl methacrylate preA-1 and 7.7 g of methyl ethyl ketone were weighed and mixed and dissolved to prepare a monomer composition P5-2.
Then, 13.1 g of methyl ethyl ketone was charged into a 300 mL three-necked flask equipped with a thermometer, a stirring blade and a reflux ring, and stirred at 80° C. under a nitrogen stream. Into the methyl ethyl ketone, the monomer composition P5-1 was dropped simultaneously at a rate of 0.32 mL/min, and the monomer composition P5-2 was dropped simultaneously at a rate of 0.13 mL/min. A chemical pump was used for dropping. After completion of the dropping, the reaction solution is further reacted at 80° C. for 3 hours, and after the reaction is completed, the reaction solution is allowed to cool to room temperature, diluted with 70 g of methyl ethyl ketone, and mixed with 1.2 L of methanol and 0.5 L of water. Reprecipitation gave a white precipitate. The obtained white precipitate was separated by filtration and dried at 50° C. overnight to obtain 25.8 g of the target P-5.
The polymer P-5 thus obtained is shown below. In the structure below, the number attached to each repeating unit in the trunk polymer represents the molar ratio, and the number attached to the repeating unit in the branch polymer (graft chain) represents the number of repeating units (degree of polymerization). This also applies to polymers P-6 to P-9 described later.
This polymer P-5 has a structure shown in FIG. 4A, specifically, a graft structure in which a branch polymer PB ^G1 containing a repeating unit A-1 is bonded to a trunk polymer PA ^G1 containing a repeating unit A-1. Was.

<Synthesis Example 6: Synthesis of polymer P-6>
In a 100 mL Erlenmeyer flask, 19.5 g of macromonomer AA-6 of methyl methacrylate preA-1, 0.12 g of dimethyl-2,2′-azobisisobutyrate, and 20.0 g of methyl ethyl ketone were weighed, and Were mixed and dissolved to prepare a monomer composition P6-1.
Separately, 8.7 g of acrylic acid ester compound preB-6 and 7.7 g of methyl ethyl ketone were weighed out and mixed and dissolved to prepare a monomer composition P6-2.
Next, 11.2 g of methyl ethyl ketone was charged into a 300 mL three-necked flask equipped with a thermometer, stirring blades and a reflux ring, and stirred at 80° C. under a nitrogen stream. Into this methyl ethyl ketone, the monomer composition P6-1 was dropped simultaneously at a rate of 0.32 mL/min, and the monomer composition P6-2 was dropped simultaneously at a rate of 0.13 mL/min. A chemical pump was used for dropping. After completion of the dropping, the reaction solution is further reacted at 80° C. for 3 hours, and after the reaction is completed, the reaction solution is allowed to cool to room temperature, diluted with 70 g of methyl ethyl ketone, and mixed with 1.2 L of methanol and 0.5 L of water. Reprecipitation gave a white precipitate. The obtained white precipitate was filtered off and dried at 50° C. overnight to obtain 25.8 g of the target P-6.
The polymer P-6 thus obtained is shown below. The polymer P-6, the structure shown in FIG. 4C, specifically, with respect to the trunk polymer ^{PA G1} comprising repeating units B-6, have a graft structure branch polymer ^{PB G1} is bonded to a repeating unit A-1 Was.

<Synthesis Example 7: Synthesis of polymer P-7>
In a 100 mL Erlenmeyer flask, 18.8 g of styrene preA-10 macromonomer AS-6 (manufactured by Toagosei Co., Ltd., number average molecular weight 6,000, average degree of polymerization about 60), dimethyl-2,2′-azobisisobutyrate. 0.17 g of the rate and 20.0 g of methyl ethyl ketone were weighed out, and these were mixed and dissolved to prepare a monomer composition P7-1.
Separately, 4.69 g of acetoacetoxyethyl methacrylate preB-1 and 4.6 g of methyl ethyl ketone were weighed out and mixed and dissolved to prepare a monomer composition P7-2.
Then, 10.6 g of methyl ethyl ketone was charged into a 200 mL three-necked flask equipped with a thermometer, a stirring blade and a reflux ring, and stirred at 80° C. under a nitrogen stream. Into the methyl ethyl ketone, the monomer composition P7-1 was dropped simultaneously at a rate of 0.32 mL/min, and the monomer composition P7-2 was dropped simultaneously at a rate of 0.07 mL/min. A chemical pump was used for dropping. After completion of the dropping, the reaction solution is further reacted at 80° C. for 3 hours, and after the reaction is completed, the reaction solution is allowed to cool to room temperature, diluted with 70 g of methyl ethyl ketone, and mixed with 1.2 L of methanol and 0.5 L of water. Reprecipitation gave a white precipitate. The obtained white precipitate was filtered off and dried at 50° C. overnight to obtain 20.8 g of the target P-7.
The polymer P-7 obtained is shown below. The polymer P-7, a structure shown in FIG. 4C, specifically, with respect to the trunk polymer ^{PA G1} comprising repeating units B-1, have a graft structure branch polymer ^{PB G1} comprising repeating units A-10 bound Was.

<Synthesis Example 8: Synthesis of polymer P-8>
To a 10 mL vial, 0.22 mg of copper(I) bromide, 0.17 mg of N,N,N′,N″,N″-pentamethyldiethylenetriamine, and 1 mL of toluene were added, and a homogeneous catalyst solution was added. Got In a 200 mL three-necked flask equipped with a thermometer, a stirring blade, and a reflux ring, 20.0 g of methyl methacrylate preA-1 and 0.17 g of dimethyl-2,2′-azobisisobutyrate, and 2 Ethyl bromoisobutyrate was weighed in an amount of 6.7 mg, the catalyst solution was added, and the mixture was stirred at 70° C. for 20 hours under a nitrogen stream.
Then, to the obtained reaction solution was added a mixed solution of 5.0 g of acetoacetoxyethyl methacrylate preB-1 and 2 mL of toluene after nitrogen substitution, and the mixture was stirred at 70°C. After the reaction was completed, the reaction solution was allowed to cool to room temperature, diluted with 70 g of methyl ethyl ketone, and reprecipitated with a mixed solution of 1.2 L of methanol and 0.5 L of water to obtain a white precipitate. The obtained white precipitate was filtered off and dried at 50° C. overnight to obtain 22.3 g of the target P-8.
The polymer P-8 thus obtained is shown below. This polymer P-8 has a structure shown in FIG. 3A, specifically, a partial structure composed of the repeating unit B-1 and a partial structure composed of the repeating unit A-1 in a single linear direction in the polymer chain. It was a linked block structure (AB type).

<Synthesis Example 9: Synthesis of polymer P-9>
In a 100 mL Erlenmeyer flask, 23.4 g of macromonomer AA-6 of methyl methacrylate preA-1, 0.21 g of dimethyl-2,2′-azobisisobutyrate, and 25.4 g of methyl ethyl ketone were weighed. Were mixed and dissolved to prepare a monomer composition P9-1.
Separately, 5.59 g of acetoacetoxyethyl methacrylate preB-1 and 5.0 g of methyl ethyl ketone were weighed out and mixed and dissolved to prepare a monomer composition P9-2.
Next, 13.1 g of methyl ethyl ketone was charged into a 200 mL three-necked flask equipped with a thermometer, a stirring blade and a reflux ring, and stirred at 80° C. under a nitrogen stream. Into this methyl ethyl ketone, the monomer composition P9-1 was dropped simultaneously at a rate of 0.32 mL/min, and the monomer composition P9-2 was dropped simultaneously at a rate of 0.07 mL/min. A chemical pump was used for dropping. After completion of the dropping, the reaction solution is further reacted at 80° C. for 3 hours, and after the reaction is completed, the reaction solution is allowed to cool to room temperature, diluted with 70 g of methyl ethyl ketone, and mixed with 1.2 L of methanol and 0.5 L of water. Reprecipitation gave a white precipitate. The resulting white precipitate was filtered off and dried at 50° C. overnight to obtain 23.3 g of the target P-9.
The polymer P-9 thus obtained is shown below. The polymer P-9, the structure shown in FIG. 4C, specifically, with respect to the trunk polymer ^{PA G1} comprising repeating units B-1, have a graft structure branch polymer ^{PB G1} is bound comprising repeating units A-1 Was.

<Synthesis Example 10: Synthesis of polymer P-10>
The same procedure as in Synthesis Example 9 was repeated except that the amounts of the macromonomer AA-6 and acetoacetoxyethyl methacrylate preB-1 used in Synthesis Example 9 were changed to the molar ratios (composition ratios) shown in Table 1. Thus, polymer P-10 was synthesized.

<Synthesis Example 11: Synthesis of polymer P-11>
First, the following diol compound DA-11 was synthesized as follows.
In a 100 mL Erlenmeyer flask, 50.1 g of methyl methacrylate preA-1, 0.230 g of dimethyl-2,2′-azobisisobutyrate, 1.08 g of 3-mercapto-1,2-propanediol, and methyl ethyl ketone. Was weighed in an amount of 30.0 g and mixed and dissolved to prepare a monomer composition P11.
Then, 20.0 g of methyl ethyl ketone was charged into a 500 mL three-necked flask equipped with a thermometer, a stirring blade and a reflux ring, and stirred at 70° C. under a nitrogen stream. The monomer composition P11 was added dropwise to the methyl ethyl ketone at a rate of 0.62 mL/min. A chemical pump was used for dropping. The reaction solution after completion of the dropwise addition was further reacted at 80° C. for 2 hours, then 0.02 g of dimethyl-2,2′-azobisisobutyrate was further added, and the obtained mixture was stirred for another 3 hours. After the reaction was completed, the reaction solution was allowed to cool to room temperature, diluted with 170 g of methyl ethyl ketone, and reprecipitated with a mixed solution of 2.5 L of methanol and 1.3 L of water to obtain a white precipitate. The obtained white precipitate was filtered off and dried at 50° C. overnight to obtain 46.2 g of the target diol compound DA-11. The diol compound DA-11 thus obtained had a weight average molecular weight of 7,000.

Then, the polymer P-11 was synthesized as follows.
In a 500 mL three-necked flask equipped with a thermometer, a stirring blade and a reflux ring, 115 g of N-methylpyrrolidone, 11.0 g of the diol compound DA-11 synthesized above, and 2,2'-bis(trifluoromethyl). 3.9 g of benzidine preB-55-1 and 0.2 g of triethylamine were charged, and the mixture was stirred at 40° C. under a nitrogen stream to completely dissolve it. After returning the internal temperature to room temperature, 2.80 g of isophthalic acid chloride preB-55-2 was added in portions (10 times), and the mixture was stirred at room temperature for 4 hours. After the reaction was completed, the internal temperature was heated to 40° C., 35 μL of acetyl acid chloride was added thereto, and the mixture was stirred at 60° C. for 1 hour. The reaction solution was allowed to cool to room temperature and reprecipitated with a mixed solution of 2.2 L of methanol and 0.6 L of water to obtain a white precipitate. The white precipitate obtained was filtered off and dried at 190° C. to obtain 10.2 g of the target P-11.
The polymer P-11 obtained is shown below. The polymer P-11, the structure shown in FIG. 4C, specifically, with respect to the trunk polymer ^{PA G1} comprising repeating units B-55, have a graft structure branch polymer ^{PB G1} is bound comprising repeating units A-1 Was.

<Synthesis Example 12: Synthesis of polymer P-12>
In a 500 mL three-necked flask equipped with a thermometer, a stirring blade and a reflux ring, 115 g of N-methylpyrrolidone, 11.0 g of the diol compound DA-11 synthesized in Synthesis Example 11 above, and 1,1-bis(4- Aminophenyl)cyclohexane preB-53-1 (3.25 g) and triethylamine (0.2 g) were charged, and the mixture was stirred at 40° C. under a nitrogen stream to completely dissolve it. After returning the internal temperature to room temperature, 2.80 g of isophthaloyl chloride preB-53-2 was added in portions (10 times), and the mixture was stirred at room temperature for 4 hours. After the reaction was completed, the internal temperature was adjusted to 40° C., 35 μL of acetyl acid chloride was added, and the mixture was stirred at 60° C. for 1 hour. The reaction solution was allowed to cool to room temperature, and then reprecipitated with a mixed solution of 2.2 L of methanol and 0.6 L of water to obtain a white precipitate. The white precipitate obtained was filtered off and dried at 190° C. to obtain 10.5 g of the target P-12.
The polymer P-12 thus obtained is shown below. The polymer P-12, the structure shown in FIG. 4C, specifically, with respect to the trunk polymer ^{PA G1} comprising repeating units B-53, have a graft structure branch polymer ^{PB G1} is bound comprising repeating units A-1 Was.

<Synthesis Example 13: Synthesis of polymer P-13>
First, the following amine compound AM-13 was synthesized as follows.
In a 100 mL Erlenmeyer flask, 50.1 g of methyl methacrylate preA-1, 0.230 g of dimethyl-2,2′-azobisisobutyrate, 0.772 g of 2-aminoethanethiol, and 1-methoxy-2- 30.0 g of propanol was weighed and mixed and dissolved to prepare a monomer composition P13.
Next, 20.0 g of 1-methoxy-2-propanol was charged into a 500 mL three-necked flask equipped with a thermometer, stirring blades and a reflux ring, and stirred at 70° C. under a nitrogen stream. The monomer composition P13 was added dropwise to the 1-methoxy-2-propanol at a rate of 0.62 mL/min. A chemical pump was used for dropping. The reaction solution after completion of the dropping was further reacted at 80° C. for 2 hours, then 0.02 g of dimethyl-2,2′-azobisisobutyrate was further added, and the obtained mixture was stirred for another 3 hours. After the reaction was completed, the reaction solution was allowed to cool to room temperature, diluted with 170 g of 1-methoxy-2-propanol, and reprecipitated with a mixed solution of 2.5 L of methanol and 1.3 L of water to obtain a white precipitate. The obtained white precipitate was filtered off and dried at 50° C. overnight to obtain 42.1 g of the target amine compound AM-13. The weight average molecular weight of the amine compound AM-13 thus obtained was 6,000.

Then, the polymer P-13 was synthesized as follows.
In a 500 mL three-necked flask equipped with a thermometer, a stirring blade, and a reflux ring, 115 g of N-methylpyrrolidone, 11.0 g of the amine compound AM-13 synthesized above, and 2,2'-bis(trifluoromethyl). 3.9 g of benzidine preB-55-1 and 0.2 g of triethylamine were charged, and the mixture was stirred at 40° C. under a nitrogen stream to completely dissolve it. After returning the internal temperature to room temperature, 2.66 g of isophthalic acid chloride preB-55-2 was added in portions (10 times), and the mixture was stirred at room temperature for 4 hours. After the reaction was completed, the internal temperature was heated to 40° C., 35 μL of acetyl acid chloride was added thereto, and the mixture was stirred at 60° C. for 1 hour. The reaction solution was allowed to cool to room temperature and reprecipitated with a mixed solution of 2.2 L of methanol and 0.6 L of water to obtain a white precipitate. The white precipitate obtained was filtered off and dried at 190° C. to obtain 10.8 g of the target P-13.
The polymer P-13 obtained is shown below. This polymer P-13 has a structure shown in FIG. 3B, specifically, a partial structure consisting of the repeating unit A-1 in which both ends of the partial structure consisting of the repeating unit B-55 have a single structure in the polymer chain. It had a block structure (B-A-B type) bonded in a linear direction.

<Synthesis Example 14: Synthesis of polymer P-14>
In a 500 mL three-necked flask equipped with a thermometer, a stirring blade and a reflux ring, 115 g of N-methylpyrrolidone, 11.0 g of the amine compound AM-13 synthesized in Synthesis Example 13 above, and 4,4′-methylenebis(2 -Methylcyclohexylamine) preB-51-1 (2.91 g) and triethylamine (1.42 g) were charged, and the mixture was stirred at 40°C under a nitrogen stream to completely dissolve it. After returning the internal temperature to room temperature, 2.66 g of isophthalic acid chloride preB-51-2 was added in portions (10 times), and the mixture was stirred at room temperature for 4 hours. After the reaction was completed, the internal temperature was heated to 40° C., 35 μL of acetyl acid chloride was added thereto, and the mixture was stirred at 60° C. for 1 hour. The reaction solution was allowed to cool to room temperature and reprecipitated with a mixed solution of 2.2 L of methanol and 0.6 L of water to obtain a white precipitate. The white precipitate obtained was filtered off and dried at 190° C. to obtain 10.0 g of the target P-14.
The polymer P-14 obtained is shown below. This polymer P-14 has a structure shown in FIG. 3B, specifically, a partial structure consisting of the repeating unit A-1 in which both ends of the partial structure consisting of the repeating unit B-51 have a single structure in the polymer chain. It had a block structure (B-A-B type) bonded in a linear direction.

<Synthesis Example 15: Synthesis of polymer P-15>
In a 500 mL three-necked flask equipped with a thermometer, a stirring blade and a reflux ring, 115 g of N-methylpyrrolidone, 11.0 g of the amine compound AM-13 synthesized in Synthesis Example 13 above, and 1,1-bis(4- Aminophenyl)cyclohexane preB-53-1 (3.25 g) and triethylamine (0.2 g) were charged, and the mixture was stirred at 40° C. under a nitrogen stream to completely dissolve it. After returning the internal temperature to room temperature, 2.66 g of isophthalic acid chloride preB-53-2 was added in portions (10 times), and the mixture was stirred at room temperature for 4 hours. After the reaction was completed, the internal temperature was heated to 40° C., 35 μL of acetyl acid chloride was added thereto, and the mixture was stirred at 60° C. for 1 hour. The reaction solution was allowed to cool to room temperature and reprecipitated with a mixed solution of 2.2 L of methanol and 0.6 L of water to obtain a white precipitate. The white precipitate obtained was filtered off and dried at 190° C. to obtain 9.9 g of the target P-15.
The polymer P-15 obtained is shown below. In this polymer P-15, the structure shown in FIG. 3B, specifically, the both ends of the partial structure consisting of the repeating unit B-53 has a single partial structure consisting of the repeating unit A-1 within the polymer chain. It had a block structure (B-A-B type) bonded in a linear direction.

<Synthesis Example 16: Synthesis of polymer P-16>
First, the following amine compound AM-16 was synthesized as follows.
In a 100 mL Erlenmeyer flask, 84.1 g of cyclohexyl methacrylate preA-2, 0.230 g of dimethyl-2,2'-azobisisobutyrate, 0.772 g of 2-aminoethanethiol, and 1-methoxy-2-. 30.0 g of propanol was weighed and mixed and dissolved to prepare a monomer composition P16.
Next, 20.0 g of 1-methoxy-2-propanol was charged into a 500 mL three-necked flask equipped with a thermometer, stirring blades and a reflux ring, and stirred at 70° C. under a nitrogen stream. The monomer composition P16 was dropped into the 1-methoxy-2-propanol at a rate of 0.62 mL/min. A chemical pump was used for dropping. The reaction solution after completion of the dropwise addition was further reacted at 80° C. for 2 hours, then 0.02 g of dimethyl-2,2′-azobisisobutyrate was further added, and the obtained mixture was stirred for another 3 hours. After the reaction was completed, the reaction solution was allowed to cool to room temperature, diluted with 170 g of 1-methoxy-2-propanol, and reprecipitated with a mixed solution of 3 L of methanol and 1.5 L of water to obtain a white precipitate. The obtained white precipitate was filtered off and dried overnight at 50° C. to obtain 80.3 g of the target amine compound AM-16. The weight average molecular weight of the amine compound AM-16 thus obtained was 7,000.

Then, the polymer P-16 was synthesized as follows.
In a 300 mL three-necked flask equipped with a thermometer, a stirring blade and a reflux ring, 88 g of N-methylpyrrolidone, 10.0 g of the amine compound AM-16 synthesized above, and 1,1-bis(4-aminophenyl) 1.76 g of cyclohexane preB-53-1 and 0.2 g of triethylamine were charged, and the mixture was stirred at 40° C. under a nitrogen stream to completely dissolve it. After returning the internal temperature to room temperature, 1.49 g of isophthalic acid chloride preB-53-2 was added in portions (10 times), and the mixture was stirred at room temperature for 4 hours. After the reaction was completed, the internal temperature was heated to 40° C., 35 μL of acetyl acid chloride was added thereto, and the mixture was stirred at 60° C. for 1 hour. The reaction solution was allowed to cool to room temperature and reprecipitated with a mixed solution of 1.1 L of methanol and 0.3 L of water to obtain a white precipitate. The white precipitate obtained was filtered off and dried at 190° C. to obtain 7.8 g of the target P-16.
The polymer P-16 obtained is shown below. In this polymer P-16, the structure shown in FIG. 3B, specifically, the both ends of the partial structure composed of the repeating unit B-53 has a single partial structure composed of the repeating unit A-2 in the polymer chain. It had a block structure (B-A-B type) bonded in a linear direction.

<Comparative Synthesis Example 1: Synthesis of Comparative Polymer HP-1>
In a 300 mL Erlenmeyer flask, 133.5 g of methyl methacrylate preA-1 and 0.1 g of dimethyl-2,2′-azobisisobutyrate and 75.0 g of methyl ethyl ketone are weighed, and these are mixed and dissolved. A monomer composition HP1 was prepared.
Next, 75.0 g of methyl ethyl ketone was charged into a 1 L three-necked flask equipped with a thermometer, a stirring blade and a reflux ring, and stirred at 85° C. under a nitrogen stream. The above monomer composition HP1 was dropped into this methyl ethyl ketone at a rate of 1.1 mL/min. A chemical pump was used for dropping. The reaction solution after completion of the dropping was further reacted at 85° C. for 6 hours, and after the reaction was completed, the reaction solution was allowed to cool to room temperature, diluted with 500 mL of methyl ethyl ketone, and reprecipitated with 5 L of methanol to obtain a white precipitate. The obtained white precipitate was filtered off, and then redispersed and washed with 2 L of methanol three times, and dried at 60° C. overnight to obtain 91.0 g of polymer HP-1.
This polymer HP-1 was a homopolymer composed of the repeating unit A-1.

<Comparative Synthesis Example 2: Synthesis of Comparative Polymer HP-2>
Comparative Synthesis Example 1 was repeated except that 274.6 g of acetoacetoxyethyl methacrylate preB-1 was used instead of 133.5 g of methyl methacrylate preA-1. , Polymer HP-2 was synthesized.
This polymer HP-2 was a homopolymer composed of the repeating unit B-1.

Table 1 below shows the solubility parameter δt calculated by the Hoy method for the repeating units constituting the polymers obtained in each of the above-mentioned Synthesis Examples and Comparative Synthesis Examples.
Table 1 below also shows the primary structures of the polymers obtained in each of the above Synthesis Examples and Comparative Synthesis Examples, and the molar amount (mol %) of each repeating unit in each polymer. Here, the primary structure of the polymer was confirmed by the method described above. Further, the mol% of the repeating unit in the polymer is an integral in a chart obtained by measuring ¹ H-NMR of each polymer using a nuclear magnetic resonance (NMR) spectrum measuring device (manufactured by BRUKER, 300 MHz). The value was calculated (identified).
Further, depending on the number of end portions per molecule of each obtained polymer, the above method using the number average molecular weight when the polymer has a graft structure, and the number of nuclei when the polymer has a star structure or a branch structure. The results are shown in Table 1. At this time, the number average molecular weights of the synthesized polymers, macromonomers AA-6 and AS-6, and diol compound DA-11, amine compounds AM-13 and AM-16 were measured under the following weight average molecular weight measurement conditions: It was measured.
Furthermore, Table 1 below shows the weight average molecular weights of the polymers obtained in each of the above Synthesis Examples and Comparative Synthesis Examples. As the weight average molecular weight of the polymer, the weight average molecular weight measured in terms of polystyrene by gel permeation chromatography (GPC) was adopted. The specific measurement conditions are shown below.
GPC device: Tosoh GPC device (HLC-8320GPC, Ecosec)
Column: TSK gel SuperHZM-H, TSK gel SuperHZ4000, TSK gel SuperHZ2000 combined use (Tosoh's 4.6 mm ID (inner diameter) x 15.0 cm)
Eluent: Tetrahydrofuran (THF)
Measurement temperature: 40°C
Carrier flow rate: 1.0 mL/min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector

[Manufacturing Example 1: Preparation of Laminates S-1 to S-16 and HS-1 and HS-2]
<Preparation of cellulose ester layer>
The following composition was put into a mixing tank and stirred with heating to dissolve each component to prepare a cellulose acetate solution (dope A) having a solid content concentration of 22% by mass.

――――――――――――――――――――――――――――――――――
Composition of cellulose acetate solution (dope A)――――――――――――――――――――――――――――――――――
Cellulose acetate having an acetyl substitution degree of 2.86 100 parts by mass Triphenyl phosphate (plasticizer) 7.8 parts by mass Biphenyldiphenyl phosphate (plasticizer) 3.9 parts by mass Ultraviolet absorber (Tinuvin 328 manufactured by Ciba Japan Co., Ltd.) 9 parts by mass UV absorber (Tinuvin 326 manufactured by Ciba Japan Co., Ltd.) 0.2 parts by mass Methylene chloride (first solvent) 336 parts by mass Methanol (second solvent) 29 parts by mass 1-butanol (third solvent) 11 parts by mass ――――――――――――――――――――――――――――――――――

The dope A prepared above was uniformly cast on a stainless steel endless band (casting support) with a width of 2000 mm from a casting die using a band casting device. When the amount of the residual solvent in the dope A reached 40% by mass, it was peeled off from the casting support as a polymer film, conveyed by a tenter without positive stretching, and dried at 130° C. in a drying zone. went. The thickness of the obtained cellulose ester layer (cellulose ester film) was 55 μm.

<Production of laminated body S-1>
The above polymer P-1 was mixed with methyl ethyl ketone to a solid content of 15% by mass, charged into a glass separable flask equipped with a stirrer, stirred at room temperature for 5 hours, and then filtered with a polypropylene depth filter having a pore size of 5 μm. Then, an adhesive polymer layer forming composition (coating liquid) was obtained. Next, the composition for forming an adhesive polymer layer was applied onto the cellulose ester layer produced above using a gravure coater. Then, the applied adhesive polymer layer-forming composition is dried at 25° C. for 1 minute and further at 120° C. for about 5 minutes to obtain a laminate S-1 having a thickness of 60 μm (thickness of the adhesive polymer layer). Is 5 μm).

<Production of Laminates S-2 to S-16 and Comparative Laminates HS-1 and HS-2>
In the production of the laminate S-1, the same procedure as the production of the laminate S-1 was performed except that the polymer P-1 used in the composition for forming an adhesive polymer layer was changed as shown in Table 2 below. Laminates S-2 to S-16 and comparative laminates HS-1 and HS-2 were produced.
The thickness of each of the obtained laminated bodies was 60 μm.

<Evaluation of laminated body>
The contact angle of the adhesive polymer layer surface and the adhesiveness of each produced laminate were evaluated by the following methods. The results are shown in Table 2.

(Measurement of contact angle on surface of adhesive polymer layer)
The contact angle was measured and evaluated according to JIS R 3257 (1999). However, the image used for the measurement was taken 30 seconds after water was dropped on the coated surface of the adhesive polymer, and the angle formed by the dropped water droplet and the surface of the adhesive polymer was used as the image. It was calculated based on
In this test, a contact angle of 64° or more is a pass level, 65° or more is more preferable, and 70° or more is still more preferable.

(Adhesion test of laminate)
As a method for evaluating the adhesiveness between the adhesive polymer layer and the cellulose acetate layer, a cross-cut test (cross-cut method) according to JIS K 5400 was applied. The specific procedure is shown below.
In each of the produced laminates, 11 cuts were made at 1 mm intervals on the surface of the adhesive polymer layer side using a cutter knife and a cutter guide to produce 100 cross-cuts. Cellophane tape (registered trademark) was strongly pressure-bonded onto the cross-cut, and the end of the tape was peeled off at an angle of 45° to the surface. This cellophane tape (registered trademark) sticking and peeling operation was continuously performed 5 times. A new cellophane tape (registered trademark) was used each time.
After that, the state of the grid (the state of peeling of the grid forming the grid) was observed, and the number of the grids (the number of remaining grids) that were in close contact with the cellulose acetate layer without peeling was counted.
In this test, the adhesiveness is a pass level when the remaining number is 70 or more, preferably 95 or more, and particularly preferably 100.

From the results of Table 2, all of the laminates S-1 to S-16 including the layer containing the repeating unit [a] and containing the adhesive polymer having the above-mentioned primary structure all contain the adhesive polymer. It was shown that the contact angle of the layer was high and the adhesion between the layers was excellent as a laminate.
In particular, the laminates S-4 and S-6 to S-16 in which the adhesive polymer having the above-mentioned primary structure has the repeating unit [a] and the repeating unit [b] all maintain the contact angle. However, it showed strong adhesion.
On the other hand, the laminated body HS-1 provided with the layer containing the homopolymer HS-1 consisting only of the repeating unit [a] has peeled off all the lattice openings, and the adhesiveness between the layers is significantly poor. there were. On the other hand, the laminate HS-2 provided with the layer containing the homopolymer HS-2 consisting only of the repeating unit [b] had a poor contact angle.

[Production Example 2: Preparation of Polarizing Plates PL-1 to PL-15 and Comparative Polarizing Plates HPL-1 and HPL-2]
Polarizing plates PL-1 to PL-15 and comparative polarizing plates HPL-1 and HPL-2 were produced as described below.

<Production of polarizer>
According to Example 1 of JP 2001-141926 A, a stretched polyvinyl alcohol film was caused to adsorb iodine to prepare a polarizer having a film thickness of 27 μm.

<Preparation of active energy ray-curable adhesive composition>
Each component was mixed with the composition shown below and stirred at 50° C. for 1 hour to obtain an active energy ray-curable adhesive composition.

――――――――――――――――――――――――――――――――――
Composition of active energy ray-curable adhesive composition――――――――――――――――――――――――――――――――――
Radical heavy synthetic compound: Aronix M-220 manufactured by Toagosei Co., Ltd.
20.0 parts by mass Kojin's N-hydroxylacrylamide 40.0 parts by mass Kojin's acroylmorpholine 40.0 parts by mass Radical polymerization initiator: Nippon Kayaku's KAYACURE DETX-S
0.5 parts by mass Radical polymerization initiator: IRGACURE907 manufactured by BASF
1.5 parts by mass――――――――――――――――――――――――――――――――――

<Production of polarizing plate>
Corona treatment was applied to the adhesive polymer layer side of each laminate produced above. On the surface of the laminate subjected to corona treatment, the active energy ray-curable adhesive composition prepared above was coated with an MCD coater (manufactured by Fuji Kikai Co., Ltd., cell shape: honeycomb, number of gravure roll lines: 1000/INCH, rotation speed (140%/line speed) was applied to a thickness of 0.5 μm.
Separately, a cycloolefin film having a thickness of 40 μm (Arton G7810 manufactured by JSR Corporation) was prepared, and the surface thereof was subjected to corona treatment. The active energy ray-curable adhesive composition was applied to the surface subjected to the corona treatment in the same manner as described above so as to have a thickness of 0.5 μm.
Subsequently, the surface of each laminate coated with the active energy ray-curable adhesive composition and the surface of the cycloolefin-based film coated with the active energy ray-curable adhesive composition were treated with the polarizer prepared above. A polarizing plate precursor was prepared by bonding the both surfaces to each other. At this time, it was arranged so that the longitudinal direction of the roll of the produced polarizer and the longitudinal direction of the roll of the cellulose ester layer in each laminate were parallel to each other. Moreover, the longitudinal direction of the roll of the polarizer and the longitudinal direction of the cycloolefin-based film were arranged so as to be parallel to each other.

Then, from both sides of this polarizing plate precursor, it heated at 50 degreeC using the IR heater. Next, the active energy rays shown below were applied to both surfaces of the polarizing plate precursor to cure the active energy ray-curable adhesive composition. Then, each polarizing plate was obtained by drying with hot air at 70° C. for 3 minutes.
(Active energy ray)
As active energy rays, ultraviolet rays (gallium-encapsulated metal halide lamp), irradiation device: Fusion UV Systems, Inc. Light HAMMER 10, bulb: V bulb, peak illuminance: 1600 mW/cm ² , integrated irradiation dose 1000/mJ/cm ² (wavelength) 380-440 nm) was used. In addition, the illuminance of ultraviolet rays was measured using a Sola-Check system manufactured by Solatell.

The comparative polarizing plate HPL-1 could not be produced because the cellulose ester layer and the polymer layer were separated during the production of the polarizing plate. In the "Durability" column of Table 3, "-" is shown.

<Evaluation of polarizer durability of polarizing plate>
For the durability of the polarizing plate, the degree of polarization was measured in the following manner in the form in which the polarizing plate was attached to glass via an adhesive.
Two samples (about 5 cm×5 cm) were prepared by sticking a polarizing plate on a glass plate such that the laminate side was the air interface side (the side away from the glass plate). For these samples, the glass plate side was set to face the light source and the degree of polarization was measured. Each of the two samples was measured, and the arithmetically averaged value was used as the polarization degree of the polarizing plate.
The degree of polarization was calculated by the following formula.

Degree of polarization (%)=[(parallel transmittance-orthogonal transmittance)/(orthogonal transmittance+parallel transmittance)] ^1/2 ×100

The polarization degree was measured in the range of 380 to 780 nm using an automatic polarizing film measuring device VAP-7070 manufactured by JASCO Corporation, and a measurement value at a wavelength of 410 nm at which the degree of deterioration was more remarkable than other wavelengths was adopted.
Then, it was stored for 500 hours in a high temperature and high humidity environment where the temperature was 85°C and the relative humidity was 85%. Then, the polarization degree of the two samples was measured in the same manner as above, and the measured values of the two samples were arithmetically averaged to obtain the polarization degree of the polarizing plate after storage.
The durability of the polarizing plate was evaluated based on the change amount of polarization degree before and after storage based on the following evaluation criteria. In this test, the evaluations A to C are the passing levels among the following four-level evaluation. Evaluations A and B are preferable, and evaluation A is particularly preferable.
Here, the polarization degree change amount is calculated by the following formula.

Polarization degree change (%)=[polarization degree before storage (%)-polarization degree after storage (%)]

A: Polarization degree change amount is less than 0.05% B: Polarization degree change amount is 0.05% or more and less than 2.0% C: Polarization degree change amount is 2.0% or more and less than 3.0% D: Polarization degree Change amount is 3.0% or more

From the results in Table 3, all of the polarizing plates HPL-1 to 15 provided with the laminate of the invention showed a small amount of change in polarization degree and showed excellent polarizer durability. That is, it can be seen that by incorporating a polarizing plate using the laminate of the present invention as a protective film for a polarizer into an image display device, deterioration of image quality can be effectively suppressed even under high temperature and high humidity conditions.
On the other hand, in the comparative polarizing plate HPL-1 using the comparative laminate HS-1 as the protective film, the interlayer adhesion of the protective film was poor and the cellulose ester layer and the polymer layer were peeled off, and the durability was evaluated. It was not possible to produce a polarizing plate capable of carrying out. In addition, the comparative polarizing plate HPL-2 using the comparative laminate HS-2 as a protective film resulted in a significantly poor polarizer durability.

Although the present invention has been described in conjunction with its embodiments, it is not intended to limit our invention to any details of the description, unless otherwise indicated, contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted broadly without.

The present application claims priority based on Japanese Patent Application No. 2016-030028 filed in Japan on February 19, 2016 and Japanese Patent Application No. 2016-149498 filed on July 29, 2016 in Japan. All of which are incorporated herein by reference in their entirety.

10 Laminate (Laminate)
11 Cellulose Ester Layer 12 Adhesive Polymer Layer 20 Liquid Crystal Display Device 21 First (Upper) Polarizer 22 Direction of Absorption Axis of First Polarizer 23 First (Upper Liquid Crystal Cell) Electrode Substrate 24 Liquid Crystal Layer 25 Second (Lower Liquid Crystal Cell) ) Electrode substrate 26 Second (lower) polarizing plate 27 Second polarizing plate Absorption axis direction

Claims (10)

A laminate having a layer containing a cellulose ester and a layer containing an adhesive polymer,
The layer containing the adhesive polymer is adjacent to at least one surface of the layer containing the cellulose ester,
The adhesive polymer has a graft structure, a branch structure or a star structure composed of one kind of repeating unit, or a block structure, a graft structure, a branch structure or a star structure composed of two or more kinds of repeating units, and the repeating structure units see contains recurring units [a] solubility parameter δt is calculated is less than 13.5 or 20.0 by Hoy method,
A laminate, wherein the repeating unit [a] is a repeating unit represented by the following general formula 2 or 3 .

In General Formula 2, R ⁵ represents a hydrogen atom or an alkyl group.
R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
R ⁸ represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.

In formula 3, R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group.
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an acyl group, an acyloxy group or an alkoxycarbonyl group. Represent The laminate according to claim 1, wherein the adhesive polymer has a block structure, a graft structure, a branch structure or a star structure, which is composed of two or more kinds of repeating units. The laminate according to claim 1 or 2, wherein the adhesive polymer has 2 to 250 ends per molecule. The laminate according to any one of claims 1 to 3, wherein the adhesive polymer has the block structure or the graft structure. The laminate according to claim 1, wherein the two or more repeating units include a repeating unit [b] having a solubility parameter δt calculated by the Hoy method of 20.0 or more and 26.0 or less. body. The laminate according to claim 5, wherein the repeating unit [b] is a repeating unit represented by the following general formula 1.

In General Formula 1, R ¹ represents a hydrogen atom or an alkyl group.
R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
L is a single bond or a divalent linking group selected from an alkylene group, an arylene group, —C(═O)—, —O— and —N(R ⁴ )— or two or more of these linking groups. A divalent linking group formed by combining R ⁴ represents a hydrogen atom or an alkyl group. The laminate according to claim 1, wherein the repeating unit [a] is a repeating unit represented by the general formula 2. The cellulose ester is laminate according to any one of claims 1 to 7, which is a cellulose acylate. Polarizer having a laminate according, a polarizer to any one of claims 1-8. An image display device comprising the polarizing plate according to claim 9 .

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