WO2017141516A1

WO2017141516A1 - Laminate, polarizing plate and image display device

Info

Publication number: WO2017141516A1
Application number: PCT/JP2016/084963
Authority: WO
Inventors: 佑起中沢; 寛野副; 遊内藤
Original assignee: 富士フイルム株式会社
Priority date: 2016-02-19
Filing date: 2016-11-25
Publication date: 2017-08-24
Also published as: JPWO2017141516A1; JP6734877B2

Abstract

A laminate which comprises a layer containing a cellulose ester and a layer containing an adhesive polymer, and wherein: the layer containing an adhesive polymer is adjacent to at least one surface of the layer containing a cellulose ester; the adhesive polymer has a graft structure, a branched structure or a star structure that is composed of one kind of repeating unit or a block structure, a graft structure, a branched structure or a star structure that is composed of two or more kinds of repeating units; and the repeating units include a repeating unit (a) that has a solubility parameter δt as calculated by a Hoy method of 13.5 or more but less than 20.0. A polarizing plate which uses this laminate; and an image display device.

Description

Laminated body, polarizing plate, and image display device

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

Image display devices represented by an electroluminescence display (ELD) or a liquid crystal display device (LCD) are increasingly required to be thin. In addition, the usage environment of image display devices has been diversified, including outdoor applications, and image display devices have the ability to stably maintain good image quality even in harsh environments (high durability). Is now required.
The decrease in image quality in the image display apparatus is partly caused by moisture entering the polarizing plate and degrading the polarizer. The polarizer is protected by laminating a protective film (optical film) on the surface, but the protective film is also required to be thin. When the protective film is thinned, moisture is more likely to come into contact with the polarizer, and the image quality is likely to deteriorate. In addition, such a decrease in image quality becomes more apparent when used in harsh environments such as outdoor applications.

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

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

As a result of repeated investigations from the viewpoint of suppressing the deterioration of the polarizer, the inventors of the present invention, including the films described in the above-mentioned patent documents, when the film is highly thinned to the above-described required level, It has become clear that it is difficult to sufficiently prevent the penetration of moisture and 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, when the present inventors laminated a hydrophobic resin layer on a layer containing a cellulose ester, it was found that the adhesion at the lamination interface was poor and the layers separated from each other.

The present invention uses a laminate that has high adhesion between layers and is excellent in surface hydrophobicity, and can effectively suppress deterioration of the polarizer when used as a protective film for a polarizer. It is an object to provide a polarizing plate and an image display device using the polarizing plate.

As a result of intensive investigations in view of the above problems, the inventors of the present invention have a contact angle when a polymer having a specific primary structure composed of at least one repeating unit having a solubility parameter within a specific range is formed into a layer. In addition, a layered product of a layer containing the polymer and a layer containing the cellulose ester is used as a protective film for the polarizer. Thus, it has been found that the deterioration of the polarizer can be effectively suppressed. The present invention has been further studied and completed based on these findings.

The above-described 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 side of the layer containing the cellulose ester;
The adhesive polymer has a graft structure, a branch structure or a star structure composed of one type 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 above repeating The unit includes a repeating unit [a] having a solubility parameter δt calculated by the Hoy method of 13.5 or more and less than 20.0,
Laminated body.

<2> The laminate according to <1>, wherein the adhesive polymer has a block structure, a graft structure, a branch structure, or a star structure composed of two or more kinds of repeating units.
<3> The laminate according to <1> or <2>, wherein the adhesive polymer has 2 to 250 ends per molecule.
<4> The laminate according to any one of <1> to <3>, wherein the adhesive polymer has a block structure or a graft structure.
<5> Any one of <1> to <4>, wherein the two or more types of repeating units include the 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 as described in any one.

<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 represents a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
L is a single bond, an alkylene group, an arylene group, a divalent linking group selected from —C (═O) —, —O— and —N (R ⁴ ) —, or two or more of these linking groups. The bivalent coupling group which combines is shown. R ⁴ represents a hydrogen atom or an alkyl group.

<7> The laminate according to any one of <1> to <6>, 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 represents 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 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.
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, halogen atom, hydroxyl group, alkyl group, alkenyl group, aryl group, alkoxy group, acyl group, acyloxy group or alkoxycarbonyl group. To express.

The laminated body as described in <7> whose <8> repeating unit [a] is a repeating unit represented by the said General formula 2.
<9> The laminate according to any one of <1> to <8>, wherein the cellulose ester is cellulose acylate.
<10> A polarizing plate comprising the laminate according to any one of the above items <1> to <9> and a polarizer.
<11> An image display device having the polarizing plate according to <10>.

The laminate of the present invention has high adhesion to a layer containing a cellulose ester and exhibits excellent hydrophobicity on the surface. By superimposing the laminate of the present invention on a polarizer, deterioration of the polarizer can be effectively suppressed even under high temperature and high humidity conditions.
Moreover, the polarizing plate and image display apparatus of this invention can suppress deterioration of a polarizer effectively using the laminated body which has said outstanding effect, and show high durability.
In the present specification, the degree of suppressing the 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 where appropriate to the accompanying drawings.

FIG. 1 is a cross-sectional view showing an embodiment of the laminate of the present invention. FIG. 2 is a schematic diagram showing an outline of an embodiment of a liquid crystal display device including 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 possessed by the adhesive polymer of the present invention. FIG. 3B is a diagram showing an example of a block structure possessed by the adhesive polymer of the present invention. FIG. 3C is a diagram showing an example of a block structure possessed by the adhesive polymer of the present invention. FIG. 3D is a diagram showing an example of a block structure possessed by the adhesive polymer of the present invention. FIG. 3E is a diagram showing an example of a block structure possessed by the adhesive polymer of the present invention. FIG. 4A is a diagram showing an example of a graft structure possessed by the adhesive polymer of the present invention. FIG. 4B is a diagram showing an example of a graft structure possessed by the adhesive polymer of the present invention. FIG. 4C is a diagram showing an example of the graft structure of the adhesive polymer of the present invention. FIG. 4D is a diagram showing an example of a graft structure possessed by the adhesive polymer of the present invention. FIG. 4E is a diagram showing an example of a graft structure possessed by the adhesive polymer of the present invention. FIG. 4F is a diagram illustrating an example of a graft structure included in the adhesive polymer of the present invention. FIG. 4G is a diagram showing an example of a graft structure possessed by the adhesive polymer of the present invention. FIG. 5 is a diagram illustrating a method for synthesizing an adhesive polymer having a graft structure. FIG. 6A is a diagram illustrating an example of a star structure included in the adhesive polymer of the present invention. FIG. 6B is a diagram illustrating an example of a star structure included in the adhesive polymer of the present invention. FIG. 6C is a diagram illustrating an example of a star structure included in the adhesive polymer of the present invention. FIG. 6D is a diagram illustrating an example of a star structure included in the adhesive polymer of the present invention. FIG. 7A is a diagram illustrating an example of a branch structure included in the adhesive polymer of the present invention. FIG. 7B is a diagram showing an example of a branch structure included in the adhesive polymer of the present invention. FIG. 7C is a diagram illustrating an example of a branch structure included in the adhesive polymer of the present invention. FIG. 7D is a diagram illustrating an example of a branch structure included in the adhesive polymer of the present invention. FIG. 7E is a diagram illustrating an example of a branch structure included in the adhesive polymer of the present invention. FIG. 7F is a diagram illustrating an example of a branch structure included in 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 it are included as the lower limit value and the upper limit value.

In this specification, when there are a plurality of substituents or linking groups or the like (hereinafter referred to as substituents or the like) indicated by specific symbols, or when a plurality of substituents or the like are specified simultaneously or alternatively, It means that a substituent etc. may mutually be same or different. The same applies to the definition of the number of substituents and the like. Further, when a plurality of substituents and the like are close (especially adjacent), they may be connected to each other or condensed to form a ring.

In this specification, about the display of a compound, it uses in the meaning containing its salt and its ion other than a compound itself. In addition, it means that a part of the structure is changed as long as the target effect is not impaired. Examples of the salt of the compound include 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. In addition, examples of the ion of the compound include an ion generated by dissolving a salt of the above-described compound in water or a solvent.
In the present specification, a substituent that does not specify substitution or non-substitution (the same applies to a linking group) means that the group may have an arbitrary substituent as long as the desired effect is not impaired. is there. This is synonymous with a compound or repeating unit in which substitution or non-substitution is not specified.
Further, in the present specification, when simply referred to as “substituent”, a group selected from the following substituent group T is mentioned unless otherwise specified. In addition, when only a substituent having a specific range is described (for example, when only “alkyl group” is described), a corresponding group of the following substituent group T (in the above case, an alkyl group) Preferred ranges and specific examples in apply.
In the present specification, when the number of carbon atoms of a certain group is defined, this number of carbons means the total number of carbon atoms in the group. That is, when this group has a further substituent, it means the total number of carbon atoms including this substituent.
In this specification, when a certain group can form an acyclic skeleton and a cyclic skeleton, unless otherwise specified, the certain group includes a group having an acyclic skeleton and a group having a cyclic skeleton. For example, unless otherwise specified, an alkyl group includes a straight chain alkyl group, a branched alkyl group, and a cyclic (cyclo) alkyl group. When a certain 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 certain group.

In this specification, the term “(meth) acrylic acid” is used to include both methacrylic acid and acrylic acid. The same applies to “(meth) acrylamide”. In this specification, the term “acrylic acid” is used in a broader sense than usual. That is, “acrylic acid” is used to include all compounds having the structure of R ^A —C (═CR ^B ₂ ) COOH (R ^A and R ^B each independently represent a hydrogen atom or a substituent, provided that , When R ^A is methyl, means methacrylic acid)). The same applies to “acrylamide”.

Substituent group T:
An alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an n-octyl group, 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, particularly preferably 3 to 8. For example, , A cyclopropyl group, a cyclopentyl group, a cyclohexyl group, etc.), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms such as vinyl Groups, 2-butenyl groups, 3-pentenyl groups, etc.), alkynyl groups (preferably having 2 to 20 carbon atoms, more preferably 2 to 1 carbon atoms). And particularly preferably 2 to 8, for example, propargyl group, 3-pentynyl group, etc.), aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms). For example, a phenyl group, a biphenyl group, a naphthyl group, etc.), an amino group (preferably having 0 to 20, more preferably 0 to 10, particularly preferably 0 to 6 carbon atoms, such as an amino group) , Methylamino group, dimethylamino group, diethylamino group, dibenzylamino group, etc.), alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms). For example, a methoxy group, an ethoxy group, a butoxy group, etc.), an aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16, particularly preferably 6 to 12, and examples thereof include a phenyloxy group and a 2-naphthyloxy group), an acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms). Particularly preferably 1 to 12, for example, acetyl group, benzoyl group, formyl group, pivaloyl group, etc.), alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, especially Preferably, it is 2 to 12, for example, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (preferably having 7 to 20, more preferably 7 to 16, particularly preferably 7 to 10 carbon atoms). Such as a phenyloxycarbonyl group), an acyloxy group (preferably having 2 to 20, more preferably 2 to 16, 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 and particularly preferably 2 to 10 such as acetylamino group and benzoylamino group), alkoxycarbonylamino group ( Preferably it has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group, and an aryloxycarbonylamino group (preferably 7 to 7 carbon atoms). 20, more preferably 7 to 16, particularly preferably 7 to 12, and examples thereof include a phenyloxycarbonylamino group), a sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms). And particularly preferably 1 to 12, for example, methanesulfonylamino group, benzenesulfonate Amino groups, etc.), sulfamoyl groups (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms such as sulfamoyl group, methylsulfamoyl group, dimethylsulfayl group). And a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as a carbamoyl group and a methylcarbamoyl group). , Diethylcarbamoyl group, phenylcarbamoyl group, etc.), alkylthio group (preferably having 1 to 20, more preferably 1 to 16, particularly preferably 1 to 12 carbon atoms, such as methylthio group and ethylthio group) Arylthio group (preferably having 6 to 20 carbon atoms, More preferably, it is 6 to 16, particularly preferably 6 to 12, and examples thereof include a phenylthio group.), A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, and particularly preferably 1 to 1). 12 such as 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, such as a methanesulfinyl group, Benzenesulfinyl group, etc.), urethane group, ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, such as ureido group, methylureido group, phenyl group) Ureido groups, etc.), phosphoric acid amide groups (preferably having 1-20 carbon atoms, more preferably 1-16, 1 to 12 is preferable, and examples thereof include diethyl phosphoric acid amide and phenyl phosphoric acid amide. ), Hydroxy group, mercapto group, halogen atom (eg 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 hetero atom include a nitrogen atom, an oxygen atom and a sulfur atom. A condensed ring is preferable, and specific examples include imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, and the like. A silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms). , For example, a trimethylsilyl group, etc. triphenylsilyl group).
These substituents may further have a substituent. Moreover, when there are two or more substituents, they may be the same or different. Further, adjacent substituents may be connected 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 is laminated adjacent to at least one surface of a layer (also referred to as a cellulose ester layer) 11 containing a cellulose ester and a cellulose ester layer 11. And a layer (also referred to as an adhesive polymer layer) 12 containing an adhesive polymer.
In the present invention, “adjacent lamination” means that both layers are directly laminated without an adhesive layer (adhesive layer) or the like for adhering or adhering both layers between the cellulose ester layer and the adhesive polymer layer. (Superimposed).

If the laminated body of this invention has the said laminated structure, another structure will not be specifically limited.
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, two or more adhesive polymer layers having different composition ratios may be provided on the cellulose ester layer as the adhesive polymer layer. Furthermore, you may have the various functional layers specialized in the specific function on the surface of the adhesive polymer layer. Examples of such a functional layer include a hard coat layer, an antireflection layer, a light scattering layer, an antifouling layer, and an antistatic layer.

<Layer containing adhesive polymer>
The adhesion polymer layer which comprises the laminated body of this invention is demonstrated.
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, still more preferably 80% by mass or more, and particularly preferably 85% by mass or more. The higher the content of the adhesive polymer, the higher 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, and is 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 can contain various additives described later.
Two or more adhesive polymers may be used in combination. That is, adhesive polymers having different composition ratios and / or molecular weights may be used in combination. 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 be in close contact with the cellulose ester layer, and is merely used to facilitate understanding of the present invention. Such “adhesive polymer” includes all polymers defined in the present invention regardless of the degree of adhesion. That is, in judging the gist and technical scope of the present invention, the term “adhesiveness” is not considered as an invention specific matter for interpreting the present invention in a limited manner.

-Adhesive polymer-
The adhesive polymer constituting the adhesive polymer layer has a primary structure described later.
This 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 is also a star structure.
The adhesive polymer may have one kind of the primary structure or two or more kinds.

First, although the primary structure which an adhesive polymer has is demonstrated with reference to a schematic diagram, this 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 will be described as an example. It is not limited to species. Further, the repeating units A, B, C, and D in the figure can be replaced with different structures (repeating units).

In the present invention, the “main chain direction” means a bonding direction of repeating units forming the partial structure in each partial structure forming the adhesive polymer.
In the present invention, “consisting of repeating units” includes, in addition to an embodiment consisting of only specific repeating units, an embodiment consisting of specific repeating units and one or more other repeating units. . Another 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 constituents described later. It is done.

(Block structure)
In the present invention, the block structure refers to a structure in which the main chain direction of partial structures composed of a single type of repeating unit is a single linear direction in the polymer chain. The block structure consists of two or more types of repeating units.
In the present invention, when one repeating unit is composed of two or more kinds of constituent components, the partial structure composed of a single type of repeating unit is composed of a partial structure formed by combining repeating units having the same constituent components, and a constituent component. At least one of which includes a partial structure comprising different repeating units. For example, when the partial structure is composed of a repeating unit containing an amide bond described later, the partial structure is a portion composed of a single type of repeating unit obtained by co-condensation polymerization of one kind of carboxylic acid compound and one kind of amine compound. In addition to the structure, it includes a partial structure composed of a repeating unit (for example, exemplified repeating unit B-65 described later) obtained by co-condensation polymerization using at least one of a carboxylic acid compound and an amine compound. This also applies to the partial structure composed of a single type of polyester repeating unit.

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

The polymer having a block structure can be obtained by an ordinary polymerization method of a block copolymer. For example, a living radical polymerization method, a living cation polymerization method, or a living anion polymerization method can be used. As an example of living radical polymerization method, living cationic polymerization method, or living anion polymerization method, please refer to “Precise 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 (above)-Radical Polymerization / Cationic Polymerization / Anionic Polymerization", Kodansha, 2010, p60, p105-108, p249- See 259 and p381-386.

The polymer having the block structure shown in FIG. 3B is, for example, as shown below, using an atom transfer radical polymerization (ATRP) method in a living radical polymerization method, with each terminal structure (repeating unit B) as a starting point. It can also be synthesized by extending the repeating unit by reacting the monomer as a unit in order.

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

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

(Graft structure)
In the present invention, the graft structure means a structure that satisfies both of the following conditions (G-1) to (G-3).
(G-1) Another polymer PB ^G1 (also referred to as a branch polymer) consisting of one or more types of repeating units with respect to the polymer PA ^G1 (also referred to as a trunk polymer) consisting of one or more types of repeating units Is a structure in which one or more are bonded.
(G-2) In 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 polymers 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. Good.
Furthermore, the number of polymer PB ^G1 couple | bonded with polymer PA ^G1 should just be one or more, and is suitably determined according to the characteristic etc. of adhesive polymer. For example, it can be 1 or more, and can be 200 or less. Preferably it is 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 described above, and examples thereof include the structures shown in FIGS. 4A to 4G (sometimes referred to as FIG. 4 in combination).
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 polymer PA ^G1 (trunk polymer) composed of repeating units A. The graft structure shown in FIG. 4B is a graft structure in which six polymers PB ^G1 (branched polymer) composed of repeating units A are bonded to polymer PA ^G1 (trunk polymer) composed of repeating units A. The graft structure shown in FIG. 4C is a graft structure in which three polymer PB ^G1 (branch polymer) composed of repeating unit B is bonded to polymer PA ^G1 (trunk polymer) composed of repeating unit A.

The graft structure shown in FIGS. 4D to 4G is a graft structure having a repeating unit C as the third component, the repeating unit C and the repeating unit D as the fourth component.
That is, the graft structure shown in FIG. 4D is a graft in which three polymers PB ^G1 (branched polymer) consisting of repeating units B are bonded to a polymer PA ^G1 (trunk polymer) having a random structure consisting of repeating units A and C. Structure. The graft structure shown in FIG. 4E has two polymers PB ^G1-B consisting of repeating units B and one polymer PB ^G1-C consisting of repeating units C to polymer PA ^G1 (trunk polymer) consisting of repeating units A. This is a combined graft structure. In the graft structure shown in FIG. 4F, three polymers PB ^G1-BC having a block structure (including alternating copolymer structure) consisting of repeating units B and C are bonded to polymer PA ^G1 (trunk polymer) consisting of repeating unit A. The graft structure. The graft structure shown in FIG. 4G is a polymer PB having a block structure (including an alternating copolymer structure) consisting of repeating units C and D with respect to a polymer PA ^G1-AB (trunk polymer) having a random structure consisting of repeating units A and B. It is a graft structure in which three ^G1-CDs are bonded.

The polymer having a graft structure can be obtained by a usual polymerization method of a graft copolymer. For example, a macromonomer (YBBBBBB) having a polymerizable functional group (Y) at the terminal is homopolymerized, or the same monomer (B) as this macromonomer or a different monomer (A ) And the reactive group of the terminal functional polymer (ZBBBBBB) to other polymer chains using the grafting through method (the synthesis method 1 shown in FIG. 5)) The grafting to method (synthesis method 2 shown in FIG. 5)) or the polymer having a polymerization initiation point (X) in the side chain and the monomer (B) are reacted to produce a polymer chain having a repeating unit B from method (synthesis method 3 shown in FIG. 5)). For details, see, for example, Takeshi Endo, Mitsuo Sawamoto et al., “Synthesis of Polymers (above) —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 polymerization reactive groups, and W and Z represent reactive groups. Here, the reactive group represented by Z means a group that forms a partial structure of the polymer by a reaction different from 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 usually used in the synthesis of graft polymers. As the macromonomer, a commercially available product may be used, or an appropriately synthesized monomer may be used. As a method for synthesizing a macromonomer, for example, a method described in JP-A-5-295015, a polymer of a chain transfer agent such as 3-mercapto-1-propanol and a monomer, an isocyanate group, and a polymerizable group For example, there may be mentioned a method of reacting a compound having a compound in the presence of a tin catalyst. Further, as a method for synthesizing a macromonomer, reference can be made to Yuya Yamashita, “Chemistry and Industry of Macromonomer”, IP Publishing Department, 1989.

(Star structure)
In the present invention, the star structure (star structure) means a structure that satisfies both of the following conditions (S-1) to (S-3).
(S-1) It has one nucleus in the polymer.
(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 three or more, and is determined appropriately according to the characteristics of the adhesive polymer. The number of the polymer PA ^S1 is usually the same as the number of end portions described later. A plurality of the polymers PA ^S1 may be the same or different.
The “nucleus” means a multi-branched structure (group) to which the polymer PA ^S1 can be bonded, and becomes 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 possessed by 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 (also referred to as FIG.
The star structure shown in FIG. 6A is a structure in which four polymers PA ^S1 composed of 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 a polymer PA ^S1 having a partial structure consisting of a repeating unit A and a partial structure consisting of a repeating unit B in a block structure is bonded to the nucleus via the repeating unit A. It is. The star structure shown in FIG. 6D is a structure in which eight polymers PA ^S1 composed of the repeating unit A are bonded to the nucleus.

A 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 terminator, and a method using a linking reaction with a divinyl compound, and a method using a polyfunctional initiator is preferred.
For the above-mentioned polymerization method, reference can be made to Takeshi Endo, Mitsuo Sawamoto et al., “Synthesis of Polymers (above) —Radical Polymerization / Cationic Polymerization / Anionic Polymerization”, Kodansha, 2010, p110-113.
Furthermore, anionic polymerization can also be used for the synthesis of a polymer having a star structure. Takeshi Endo, Mitsuo Sawamoto et al., “Synthesis of Polymers (above) —Radical Polymerization / Cationic Polymerization / Anionic Polymerization”, Kodansha, See 2010, p395-402.

As the nucleus forming the star structure, a commonly used compound can be used without any particular limitation. For example, as a core compound, an organic compound (for example, polysubstituted aromatic ring, sugar, calixarene or dendrimer), an inorganic compound (for example, 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 following compounds. Reference can also be made to Takeshi Endo, Mitsuo Sawamoto et al., “Synthesis of Polymers (above) —Radical Polymerization / Cationic Polymerization / Anionic Polymerization”, Kodansha, 2010, p110-113.

(Branch structure)
In the present invention, the branch structure means a structure 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 composed of one type or two 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 condition (B-3) can be satisfied a plurality of times. That is, with respect to the polymer PB ^B1 bonded as described above, another polymer PB ^B1 can be bonded in the prescribed direction to (B-3) (each generation can be repeatedly polymerized). Multi-branched structure). In this case, the number of times satisfying the condition (B-3) may be two or more, and is determined as appropriate according to the characteristics of the adhesive polymer. For example, it can be 2 to 7 times.

In the branch structure, the polymer PA ^B1 and the polymer PB ^B1 may be the same or different. Moreover, the coupling | bonding mode (structure) of the repeating unit which forms the said polymer PA ^B1 and the said polymer PB ^B1 is not specifically limited, A random structure, a block structure, a graft structure, or a star structure may be sufficient. That is, the branch structure includes, for example, a tree-like multi-branch structure in which a polymer that grows from the nucleus branches one after another according to the terminal direction, and a structure that combines a block structure, a graft structure, and / or a star structure, etc. ,included. In the branch structure, the repeating unit can be changed for each branch.
Furthermore, the number of nuclei in the polymer may be one or more, and is appropriately determined according to the characteristics of the adhesive polymer. For example, it can be 1 or more, and can be 150 or less. In addition, 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. For example, it can be 2 or more, and 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 properties of the adhesive polymer, and can be, for example, 1 or more, and can be 150 or less. . In particular, the number of the polymer PB ^B1 bonded to one polymer PA ^B1 (core) is preferably 2 or more.

The branch structure possessed by 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 (sometimes referred to as FIG. 7 together).
The branch structure shown in FIGS. 7A and 7B has a polymer PB ^B1 further bonded to the polymer PA ^B1 bonded to the nucleus. That is, it is a dendritic multi-branched structure in which repeating units A are branched one after another from the nucleus in the terminal direction. The branch structure shown in FIG. 7C is the same structure as the tree-like multi-branch 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-branch structure shown in FIG. 7B, except that the repeating unit A and the repeating unit B are branched and randomly arranged. The branch structure shown in FIG. 7E has a repeating unit B (second generation) in a branched shape from the end of the branched chain, and further has a repeating unit C (third generation) in a branched shape as a third component from the middle thereof. Except this, it is the same structure as the tree-like multi-branch structure shown in FIG. 7B. The branch structure shown in FIG. 7F is a structure in which two star structures in which five polymer PA ^S1 composed of the repeating unit A are bonded to the nucleus are bonded to each other by one polymer PA ^{S1 of} each star structure.

A polymer having a branch structure can be obtained by an ordinary polymerization method. For example, the divergent method or the convergent method can be mentioned, and the convergent method is preferable. As the polymerization method described above, Macromolecules, 2005, 38 (21), p8701-8711, Macromolecules, 2006, 39 (22), p4361-4365, or Takeshi Endo, Mitsuo Sawamoto et al., “Synthesis of Polymers ( Top)-Radical polymerization / Cation polymerization / Anion polymerization ”, Kodansha, 2010, p402-414.

The nucleus capable of forming the 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 nucleus described in the above star structure. There may be.
Macromolecules, 2005, 38 (21), p8701-8711, Macromolecules, 2006, 39 (22), p4361-4365, or Endo Takeshi, Sawamoto Mitsuo et al., “Synthesis of Polymers (above) ) -Radical polymerization / Cation polymerization / Anion polymerization ”, Kodansha, 2010, p402-414.

Referring to the above primary structure and polymerization method, further reference can be made to Takeshi Endo, Mitsuo Sawamoto et al., “Synthesis of Polymers (above) —Radical Polymerization / Cationic Polymerization / Anionic Polymerization”, Kodansha, 2010.

In the present invention, each primary structure described above can be identified as follows. That is, the graft structure, star structure, and branch structure can be confirmed as the shape of the particle by measuring the mean square turning radius <S ^ 2> from the 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 primary structure, refer to “Organic / Polymer Measurement Lab Guide for Young Researchers”, Kodansha, 2006.

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. It preferably 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 type or two or more types. In the case of a block structure, graft structure, branch structure or star structure composed of two or more kinds of repeating units, the repeating units are preferably 2 to 10 kinds, more preferably 2 to 5 kinds, and further preferably 2 or 3 kinds. . The repeating unit will be described later.

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

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

When the adhesive polymer has a star structure or a branch structure, the number of ends is determined by the nucleus.
For a star structure,
(Number of ends) = (Maximum number of branches of the compound used for the nucleus)
It becomes.
In the case of a branch structure, the calculation is performed 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 for branch point 1) × (maximum number of branches of nucleus used for branch point 2) × ... × (used for branch point n Maximum number of nuclei branches)
Can be calculated as Here, n represents the number of branch points (synonymous with generation number-1).
In the case of the block structure, the number of end portions is two.

Moreover, the number of ends per molecule of the adhesive polymer is based on the results of elemental analysis or X-ray photoelectron spectroscopy (ESCA) analysis and nuclear magnetic resonance (NMR) measurement. It is also possible to identify and calculate an element that is a repeating unit and / or a polymerization initiation point. Examples of the element serving as the polymerization starting point include S atom, halogen atom (Cl, Br), Si atom, N atom, O atom and the like. Examples of the functional group contained in the repeating unit include —SO ₂ — and —SO—.

The repeating unit that forms 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 of only the repeating unit [a]. When there are two or more repeating units forming the adhesive polymer, the adhesive polymer is formed of two or more repeating units including at least one repeating unit [a].

The solubility parameter δt is literature ^{"Properties of Polymers 3 rd, ELSEVIER} , (1990)" The δt obtained for Amorphous Polymers according to the 214-220 pages, "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 according to the above description.
On the other hand, when the repeating unit is a repeating unit composed of two or more kinds of constituents 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 the constituent units 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 sum of these is taken as the solubility parameter δt of the repeating unit.

The repeating unit [a] is not particularly limited as long as the solubility parameter δt is satisfied. As the repeating unit [a], for example, those derived from styrene compounds, those derived from (meth) acrylic acid ester compounds, those derived from (meth) acrylic acid compounds, olefin compounds (in the present specification, when simply referred to as olefin compounds) Means 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 styrenic polymer include [0011] to [0020] in JP-A No. 2004-123965, [0014] to [0016] in JP-A No. 2013-75969, and [0011] in JP-A No. 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 Propene, stilbene, divinylbenzene, di Examples include isopropenylbenzene, 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)), as the structure of such a repeating unit, for example, JP-A-2004-323770 Reference may be made to paragraphs [0021] to [0023] of the publication, paragraphs [0024] to [0059] of JP 2014-185196 A, and the like.
Moreover, when the said 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 preferred. The alkyl group of this (meth) acrylic acid alkyl ester compound may be linear or branched. The alkyl group constituting the (meth) acrylic acid alkyl ester compound preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 18 carbon atoms, and particularly preferably 1 to 16 carbon atoms. The number of carbon atoms of the cycloalkyl group of the (meth) acrylic acid cycloalkyl ester compound is preferably 3 to 30, more preferably 4 to 20, still more preferably 5 to 18, and particularly preferably 6 to 16.
Specific examples of the (meth) acrylic acid ester compound and (meth) acrylic acid cycloalkyl ester compound that lead the repeating unit [a] include, for example, propyl acrylate, iso-propyl acrylate, n-butyl acrylate, 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, iso methacrylate Mention may be made of -propyl, n-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate or dodecyl methacrylate.

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) is (meth) acrylic. There is no particular limitation as long as it is a repeating unit forming an acid polymer. As the structure of such a repeating unit, for example, paragraphs [0020] to [0027] of JP-A No. 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, for example, paragraph [0015] of JP-A No. 2000-159817 as the structure of the repeating unit. Can do.
Specific examples of the olefin compound leading to the repeating unit [a] include, for example, 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 is composed of only a carbon atom and a hydrogen atom, it is classified as an olefin compound instead of 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 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 for deriving the repeating unit [a] include, for example, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, trifluoroethylene chloride, or 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, tetra Mention may be made of cyclododecene and compounds derived therefrom.

The adhesive polymer preferably has a repeating unit derived from a styrene compound or a (meth) acrylate compound as the repeating unit [a], and more preferably has a repeating unit derived from a (meth) acrylate compound. preferable.
The adhesive polymer 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 still more preferably 1 to 3 carbon atoms. The alkyl group is more preferably methyl or ethyl, and still more preferably methyl.
R ⁵ is preferably a hydrogen atom or methyl.

R ⁶ and R ⁷ each independently represents 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 alkyl group described above for R ⁵ , and 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, it is preferable that R ⁵ is a hydrogen atom or an alkyl group, and that R ⁶ and R ⁷ are both 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, preferably an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms. However, when R ⁵ is methyl, R ⁸ can take a hydrogen atom.
The alkyl group having 1 to 20 carbon atoms may be linear or branched. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 12, more preferably 1 to 10, still more preferably 1 to 8, and particularly preferably 1 to 6. Further, 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. The cycloalkyl group having 3 to 20 carbon atoms is preferably in a form in which the substituents of the cycloalkyl group are connected to each other to form a condensed ring (for example, an adamantane ring or an isobornyl ring). Further, 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 preferably an alkyl group having 1 to 4 carbon atoms. Is preferable, and methyl, ethyl or tert-butyl is more preferable.

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 preferred.
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 , and preferred ones are 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 for R ⁶ , and preferred ones are also the same.
R ⁹ , R ¹⁰ and R ¹¹ are each 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. In particular, R ¹⁰ and R ¹¹ are preferably both 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. Preferably, 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 preferred.
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 still 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. The alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, still more preferably 2 or 3. 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, 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 alkoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms. 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 is a corresponding group in the substituent group T. It is synonymous with group, and a preferable thing is also the same.

Two adjacent R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be bonded to each other to form a ring. For example, two adjacent ethenyl groups may be bonded to each other to form a benzene ring (a naphthalene ring as a whole) including the carbon atom to which they are bonded.
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may each further have a substituent selected from the substituent group T described above. For example, the alkyl group which has a substituent is mentioned, Specifically, a trifluoromethyl group is 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) acrylate 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 above repeating unit [a], a repeating unit [b] whose solubility parameter δt calculated by the Hoy method is 20.0 or more and 26.0 or less. As a result, it is possible to obtain a laminate that achieves higher levels of interlayer adhesion and improved contact angle.

The repeating unit [b] is not particularly limited as long as the solubility parameter δt is satisfied. As the repeating unit [b], for example, those derived from (meth) acrylic acid ester compounds, those derived from (meth) acrylic acid compounds, those derived from (meth) acrylamide compounds, those derived from vinyl acetate compounds, vinyl ketone compounds One derived from a maleic anhydride compound, one derived from a styrene compound, one derived from a compound having an ethylenically unsaturated bond other than these repeating units, or a repeating unit containing an amide bond (polyamide repeating unit) 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 ester compound ((meth) acrylic ester repeating unit (b)), as the (meth) acrylic ester repeating unit (b), As long as the repeating unit forms a (meth) acrylic acid ester polymer, it is not particularly limited. As the structure of such a repeating unit, for example, paragraphs [0021] to [0023] in JP-A No. 2004-323770 or [0024] to [0059] in JP-A No. 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, for example, 2-hydroxyethyl acrylate, 2-acetoacetoxyethyl acrylate, 2-isocyanatoethyl acrylate, 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) is (meth) acrylic. There is no particular limitation as long as it is a repeating unit forming an acid polymer. As the structure of such a repeating unit, for example, paragraphs [0020] to [0027] of JP-A No. 2002-212221 can be referred to.
Specific examples of the (meth) acrylic acid compound leading to the repeating unit [b] include acrylic acid and its metal salt, or methacrylic acid and its metal salt.

When the repeating unit [b] is derived from a (meth) acrylamide compound ((meth) acrylamide repeating unit (b)), the (meth) acrylamide repeating unit (b) is 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 later.

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. It is not limited. As the structure of the vinyl acetate repeating unit (b), reference can be made, for example, to paragraphs [0007] to [0008] of JP-A-2002-338609.
Specific examples of the vinyl acetate compound that leads to the repeating unit [b] include vinyl acetate, vinyl propionate, vinyl pivalate, and isopropenyl acetate. Thus, in the present invention, “vinyl acetate compound” is used to include a compound in which a hydrogen atom of vinyl acetate is substituted.

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. As the structure of such a repeating unit, for example, paragraphs [0010] to [0017] of JP-A-2007-230940 or paragraphs [0009] to [0011] of JP-A-7-291886 can be referred to.
Specific examples of the vinyl ketone compound that leads to the repeating unit [b] include methyl vinyl ketone and ethyl vinyl ketone.

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 that forms a maleic anhydride polymer. If it is, it will not specifically limit. As the structure of such a repeating unit, for example, paragraphs [0027] to [0029] in JP-A-2006-1111710, paragraphs [0013] to [0015] in JP-A-2008-156400, and the like can be referred to. .
Specific examples of the maleic anhydride compound from which the repeating unit [b] is derived include maleic anhydride, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and maleic acid. Thus, in the present invention, “maleic anhydride compound” is used to include 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 that forms a styrene polymer. The preferred structure of such a repeating unit is as shown in the structural formulas exemplified later.

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 unit derived from each compound described above.

In the present invention, the repeating unit [b] includes a repeating unit composed of two or more components. 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 co-condensation polymerization of a polyvalent carboxylic acid compound and a polyvalent amine compound. The carboxylic acid compound and the amine compound are not particularly limited as long as they are compounds that form various polyamides. For example, the valences (carboxy group number and amino group number) of the carboxylic acid compound and the amine compound are not particularly limited, but are preferably divalent.
Examples of carboxylic acid compounds include aliphatic carboxylic acid compounds and aromatic carboxylic acid compounds, and aromatic carboxylic acid compounds are preferred. Aromatic carboxylic acid compounds 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'-stilbene dicarboxylic acid, 4,4'-biphenyldicarboxylic acid or 2,2-bis (4-carboxy) Phenyl) hexafluoropropane and the like. Examples of the aliphatic carboxylic acid compounds include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, decahydro-1,4-naphthalenedicarboxylic acid, decahydro-2,6-naphthalenedicarboxylic acid, sebacic acid, azelaic acid, Examples include suberic acid and pimelic acid.
Examples of the amine compound include aliphatic amine compounds and aromatic amine compounds, and aromatic amine compounds are preferable. Examples of the aliphatic amine compound include 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and the like, in addition to the amine compound that leads to the exemplary repeating unit described later. As the aromatic amine compound, 1,4-phenylenediamine, 1,3-phenylenediamine, 1,5-diaminonaphthalene, 2-chloro-1,4 other than the amine compound that leads to the exemplified 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 combinations shown in the exemplified repeating unit described later.
Here, when two types of at least one of a carboxylic acid compound and an amine compound are used, the obtained polyamide repeating unit is at least two types. For example, exemplified repeating unit B-65 described later 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 co-condensation polymerization 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 (carboxy group number and hydroxyl group number) of the carboxylic acid and alcohol are not particularly limited, but are preferably divalent.
Examples of the carboxylic acid include aliphatic carboxylic acids and aromatic carboxylic acids, and specific examples include carboxylic acids in the polyamide repeating unit.
Examples of the alcohol include aliphatic alcohols and aromatic alcohols. Examples of the aliphatic alcohol include 1,4-cyclohexanediol, 1,3-cyclohexanediol, 4,4′-bicyclohexanol, and the like, in addition to the alcohols shown in the exemplary repeating units described later. As aromatic alcohols (including those having a hydroxyl group bonded to an aliphatic group), resorcinol, 2,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, other than the alcohols shown in the exemplified 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, Examples thereof include methylhydroquinone, 2,3-dimethylhydroquinone, 2,2-bis (4-hydroxyphenyl) propane, and 4,4′-ethylidenebisphenol.
In the polyester repeating unit, the combination of the carboxylic acid and the alcohol is not particularly limited, and examples thereof include combinations shown in the exemplified repeating unit described later.
The polyester repeating unit can be obtained in the same manner as in the polyester synthesis method.
In this invention, the partial structure or polymer which consists of a polyester repeating unit may have another repeating unit similarly to the said 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, the alkyl group has the same meaning as R ⁵ in General Formula 2 above.
R ² and R ³ each independently represents a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group. R ² and R ³ are each 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 an alkyl group, an aryl group, and R ⁶ and R ⁷ in General Formula 2 above. It is synonymous with an alkoxycarbonyl group, and a preferable thing is also the same.

L is a single bond, a divalent linking group selected from an alkylene group, an arylene group, —C (═O) —, —O— and —N (R ⁴ ) —, or a linking group thereof. A divalent linking group formed by combining two or more types is shown. R ⁴ represents a hydrogen atom or an alkyl group, and has the same meaning as R ⁵ described above, and preferred ones are also the same.
When L is an alkylene group, the alkylene group is preferably linear. The alkylene group preferably has 1 to 5 carbon atoms, more preferably 1 to 4, more preferably 1 to 3, and particularly preferably 2. 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 each may have a substituent. Examples of the substituent include the groups in the substituent group T described above.
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 is preferably 2 to 9, and more preferably 2 or 3. The combination of the linking groups is not particularly limited, and for example, a combination of —C (═O) — and —O— or a combination including —C (═O) — and —O— is preferable. The combination including —C (═O) — and —O— includes a combination of —C (═O) —, —O— and an alkylene group, or —C (═O) —, —O— and an arylene group. A combination of —C (═O) —, —O— and an alkylene group is more preferred. In particular, it is more preferable that —C (═O) — is included in the linking group, and —C (═O) — is bonded to the main chain (the carbon atom to which R ¹ is bonded).

The adhesive polymer further preferably has a repeating unit represented by the following general formula 1-2 as the repeating unit [b].

In general formula 1-2, R ^1A represents a hydrogen atom or an alkyl group. R ^1A has the same meaning as R ^{1 in} formula 1 above, 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 group of these linking groups. A divalent linking group formed by combining two or more types is shown. R ^4A represents a hydrogen atom or an alkyl group, and has the same meaning as R ⁴ described above, and 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 preferred ones are also the same.
In the repeating units represented by formula 1 and formula 1-2, the acetoacetoxy group in each repeating unit may be substituted with a substituent.

The adhesive polymer includes, 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 preferred combination) or a polyamide repeating unit. It is preferable to have a repeating unit derived from an acrylate 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 (meth) acrylic acid ester compounds. 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) acrylamides. B-15 to A-17 are repeating units derived from a vinyl acetate compound, B-19 is a vinyl ketone compound, and B-38 to B-46 are repeating units derived from a maleic anhydride compound. B-47 to B-65 are polyamide repeating units, B-66 to B-75 are polyester repeating units, and B-81 is a repeating unit derived from a styrene compound.

In the adhesive polymer, the repeating unit 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 repeating units [a], but a partial structure consisting of repeating units [a] and a repeating unit A block structure having a partial structure consisting of [b] is preferred.
When the adhesive polymer has a graft structure, the graft chain may have either one 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 a polymer P B ^G1 (branched polymer) containing a repeating unit [a] is bonded to a polymer PA ^G1 (trunk polymer) containing a repeating unit [b] 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 another repeating unit (also referred to as other repeating unit). Also 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 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 should be 5 mol% or more. Is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, particularly preferably 40 mol% or more, and 50 mol%. % Or more is most preferable. 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, and more preferably 90 mol% or less. In the above adhesive polymer, the molar amount of the repeating unit [a] in the total molar amount of the monomer component constituting the adhesive polymer is preferably 100 mol% or less, and is included in the adhesive polymer. It is also preferred that all of the above repeating units are the above repeating unit [a].

Further, from the viewpoint of obtaining a laminate having both higher contact angle maintenance and adhesion, the moles of the repeating unit [b] in the total molar amount of the monomer components constituting the adhesive polymer. The amount is preferably 5 mol% or more, and more preferably 10 mol% or more. The molar amount of the repeating unit [b] in the total molar amount of the monomer component 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 as follows: [Repeating unit [a]] / [Repeating unit [b]] = 95/5 to 10/90 is preferably satisfied, and [Repeating unit [a]] / [Repeating unit [b]] = 95 / It is more preferable to satisfy 5 to 30/70, and it is more preferable to satisfy [Repeating unit [a]] / [Repeating unit [b]] = 92/8 to 50/50, and [Repeating unit [a]] / It is more preferable to satisfy [Repeating unit [b]] = 90/10 to 60/40, and it is particularly preferable to satisfy [Repeating unit [a]] / [Repeating unit [b]] = 90/10 to 75/25. 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. More preferably, it is more preferably 80 mol% or more, and particularly preferably 90 mol% or more. Further, 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 preferred 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 preferably 80 mol% or more, and particularly preferably 90 mol% or more. Further, 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 100 mol% or less. It is also preferred that all of the above repeating units [b] contained in are repeating units represented by the above 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. More preferably, it is more preferably 80 mol% or more, and particularly preferably 90 mol% or more. Further, 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 100% by mole or less. It is also preferred 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 other repeating units in addition to the repeating unit [a] and the repeating unit [b]. This other repeating unit may be present in any of the chains forming the polymer. In the total molar amount of the monomer components constituting the adhesive polymer, the content of the repeating unit [a] and the content of the repeating unit [b] are preferably 50% by mass or more in total, and 70% by mass. % Or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more. In the adhesive polymer, the molar amount of the repeating unit [a] and the repeating unit [b] is preferably 100 mol% or less in total, and from the repeating unit [a] and the repeating unit [b]. It is also preferable that it is the form which becomes.

The reason why the layer containing the above-mentioned repeating unit [a] and containing the above-mentioned adhesive polymer having the primary structure is excellent in adhesion to the cellulose ester layer and 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 the cellulose ester. Therefore, the polymer having the repeating unit [a] usually has low affinity with the cellulose ester and does not exhibit sufficient adhesion. However, the adhesive polymer of the present invention has the primary structure described above. Therefore, it is considered that the adhesive polymer of the present invention can partially enter the cellulose ester layer. That is, the adhesive polymer of the present invention can serve as an anchor layer for the cellulose ester layer while maintaining hydrophobicity.

Moreover, the adhesive polymer of the present invention has the primary structure described above. In particular, when it has a graft structure, a branch structure or a star structure, the number of ends of the polymer chain is large, and the interaction with the cellulose ester becomes large. Accordingly, 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, for example, a repeating unit [b] as another repeating unit, 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 separation. That is, the structure that maintains the hydrophobicity derived from the repeating unit [a] and the structure that partially enters the cellulose ester layer derived from the repeating unit [b] are arranged in a balanced manner in the same polymer. Thus, since partial structures that contribute to hydrophobicity and adhesion are present in various places in the same polymer, it is considered that excellent hydrophobicity and adhesion with the cellulose ester layer are expressed.

In particular, when the adhesive polymer of the present invention has the repeating unit [b] in addition to the repeating unit [a], strong adhesion to the cellulose ester layer is expressed. The repeating unit [b] has a solubility parameter δt close to that of the cellulose ester, and has a high affinity for the cellulose ester. In addition, when the repeating unit [b] is formed in the form of a layer adjacent to the cellulose ester layer due to the structure described above, the repeating unit [b] tends to be unevenly distributed near the surface on the cellulose ester layer side (the repeating unit [b] is near the surface). Adhesive polymer is arranged to be located in Or, as described above, it partially enters the cellulose ester layer. Accordingly, 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 damaging the function of the repeating unit [a], even if it has the repeating unit [b]. Adhesion and contact angle can be achieved at a higher level. The reason for this is not clear, but is considered to be due to having the primary structure described above. In particular, when the above repeating unit [a] and the above repeating unit [b] are balanced in the above-mentioned preferred composition ratio (molar ratio), the properties 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 15,000 or more from the viewpoint of the film surface shape. More preferably it is. 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, from the viewpoint of film forming properties, and 500 It is more preferable that it is 1,000 or less, it is especially preferable that it is 200,000 or less, and it is most preferable that it is 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) used 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, 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 which comprises the laminated body of this invention is a layer which contains 50 mass% or more of cellulose esters in a layer. 60 mass% or more is preferable, as for content of the cellulose ester in a cellulose-ester layer, 70 mass% or more is more preferable, 80 mass% or more is further more preferable, and 85 mass% or more is especially preferable. The upper limit of the content of the 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 remainder excluding the cellulose ester includes, for example, additives described later.

<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 the production of a cellulose ester film.
The β-1,4-bonded glucose unit constituting cellulose has free hydroxy groups at the 2nd, 3rd and 6th positions. The cellulose ester is a polymer (polymer) obtained by esterifying a part of these hydroxy groups with an esterifying agent or the like.
Examples of cellulose include cotton linter or wood pulp (hardwood pulp, softwood pulp) and the like. Any cellulose obtained from any raw material cellulose can be used, and in some cases, it may be mixed and used. The raw material cellulose is, for example, Marusawa, Uda, “Plastic Materials Course (17) Fibrous Resin”, Nikkan Kogyo Shimbun (published in 1970), or Japan Institute of Invention and Technology Publication No. 2001-1745 (page 7). To page 8) can be used.
As a cellulose ester, the well-known cellulose ester used for manufacture of a cellulose-ester film can be used without a restriction | limiting at all. Of these, cellulose acylate is preferably used.

(Cellulose acylate)
As the cellulose acylate used in the present invention, a known cellulose acylate used for producing a cellulose acylate film can be used without any limitation.
The acyl substitution degree (hereinafter, sometimes simply referred to as “substitution degree”) indicates the degree of acylation of the hydroxy group of cellulose located at the 2-position, 3-position and 6-position, and is 2 for all glucose units. When the hydroxy groups at the 3rd, 6th and 6th positions are all acylated, the total degree of acyl substitution is 3. For example, if all glucose units are all acylated at position 6, the total degree of acyl substitution is 1. Similarly, the total acyl substitution degree is 1 when all of any one of the 6-position and 2-position is acylated in each glucose unit in all hydroxy groups of all glucose.
That is, the degree of substitution indicates the degree of acylation, assuming that 3 is when all the hydroxy groups in the glucose molecule are all acylated.
The degree of substitution of cellulose acylate is described in Tezuka et al., Carbohydrate. Res. , 273, 83-91 (1995), or according to the method prescribed 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, from the viewpoint of moisture permeability, and 2.30 or more. More preferably, it is less than 2.97, and 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 acyl group or may have two or more 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 Examples include carbonyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like. 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 the acyl group of cellulose acylate can be suitably 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 properties. 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. A range of 2.30 to 2.95 is particularly preferable.

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

In the present invention, two types of cellulose esters or cellulose acylates having one or both of an ester group and a degree of substitution can be used in combination. In this case, you may form as a laminated structure which consists of a different cellulose ester by the co-casting method etc. which are mentioned 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 40000 to 230,000, more preferably 60000 to 230,000, and most preferably 75,000 to 200000.
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 (acetic acid, propionic acid, butyric acid, etc.) corresponding to the desired acyl group or an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride, etc.) of cellulose is used. Is used to esterify the hydroxy group.
For example, cotton linter or cellulose derived from cellulose pulp is used as a raw material, and this is activated with an organic acid such as acetic acid, and then esterified with an organic acid having a desired structure in the presence of a sulfuric acid catalyst. Cellulose acylate can be obtained. When an organic acid anhydride is used as the acylating agent, cellulose is generally esterified using an excess amount of the organic acid anhydride relative to the amount of hydroxy groups present in the cellulose.
Cellulose acylate can also be synthesized, for example, by the method described in JP-A-10-45804.

Further, in the cellulose ester layer of the present invention, other resins (for example, (meth) acrylic resin etc.) can be used in combination with the cellulose ester within a range not impairing 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, still more preferably 20% by mass or less, and particularly preferably 15% by mass or less in the cellulose ester layer. 10 mass% or less is the most preferable.

<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. For example, the cellulose ester layer is preferably formed by a melt casting method or a solution casting method (solvent casting method). More preferably, it is formed by the method. Examples of polymer film production using the solvent cast method are described in US Pat. Nos. 2,336,310, 2,367,603, 2,492,078, and 2,492,977. 2,492,978, 2,607,704, 2,739,069 and 2,739,070, British Patent Nos. 640731 and 736892. Nos. 45-4554, 49-5614, JP-A-60-176834, JP-A-60-203430, and JP-A-62-115035 can be referred to. . The cellulose ester layer may be subjected to a stretching treatment. For the stretching method and conditions, refer to, for example, JP-A-62-115035, JP-A-4-152125, 4-284221, 4-298310, and 11-48271. can do.

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

The cellulose ester layer may be a single layer or multiple layers, and in the case of multiple layers, it is preferable to use a lamination casting method such as a co-casting method, a sequential casting method or a coating method, 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 production cost reduction.
When producing a cellulose ester layer 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 for each layer (which may be three layers or more) is provided on a 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 cast simultaneously. 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, a total of three layers: a surface layer two layers formed from a surface layer dope on a casting support, and a core layer composed of a core layer dope sandwiched between these surface layers. It can be extruded and cast simultaneously on a support.

In the sequential casting method, a casting dope for the first layer is first extruded from a casting die on a casting support, cast, and dried or dried without being dried. The dope for casting for two layers is extruded from a casting die, and if necessary, the dope is sequentially cast and laminated to the third layer or more, and peeled off from the support after an appropriate time. And dried to form a cellulose ester layer.
In the coating method, generally, a core layer is formed into a film by a solution casting method, and a coating solution that is a target cellulose ester solution is applied to the surface layer, followed by drying to form a cellulose ester having a laminated structure. Form a layer.

(Stretching)
The cellulose ester layer is preferably stretched after casting and drying. The stretching direction of the cellulose ester layer may be either a film transport direction (MD (Machine Direction) direction) or a direction (TD (Transverse Direction) direction) orthogonal to the transport direction. Considering the subsequent polarizing plate processing process, the TD direction is preferable. The stretching process may be performed a plurality of times in two or more stages.

Methods for stretching in the TD direction are described in, for example, JP-A-62-115035, JP-A-4-152125, JP-A-2842211, JP-A-298310, and JP-A-11-48271. Yes. In the case of stretching in the TD direction, the film can be stretched by conveying the film while holding the film with a tenter and gradually widening the width of the tenter. Further, after the polymer film is dried, it can be stretched using a stretching machine (preferably uniaxial stretching using a long stretching machine).
In the case of stretching in the MD direction, for example, it can be performed by adjusting the speed of the film transport roller to make the winding speed 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 the cellulose ester An embodiment in which the slow axes in the plane of the layer are arranged in parallel is preferable. Since the transmission axis of the roll film polarizer produced continuously is generally parallel to the width direction of the roll film, the protection comprising the roll film polarizer and the roll film cellulose ester layer is used. In order to continuously bond the films, the in-plane slow axis of the roll film-like 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 process may be performed in the middle of the film forming process, or the original fabric that has been 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 stretching is 0%. The stretching process may be performed in the middle of the film forming process, or the original fabric that has been formed and wound may be stretched. In the former case, stretching may be performed in a state including the residual solvent amount, 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%. It is preferable to do. It is more preferable to stretch 5 to 80% in a state where the residual solvent amount is 0.05 to 5%.

<Additives>
The said cellulose-ester layer may contain the additive in the range which does not impair the effect of this invention. Examples of the additive include known plasticizers, organic acids, dyes, polymers, retardation adjusting agents, ultraviolet absorbers, antioxidants, and matting agents. Regarding these, the description of paragraph numbers [0062] to [0097] of JP2012-155287A can be referred to, and the contents thereof are incorporated in the present specification. Examples of the additive include a peeling accelerator, an organic acid, and a polyvalent carboxylic acid derivative. Regarding these, the description 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. Furthermore, examples of the additive include a radical scavenger, a deterioration inhibitor, and a barbituric acid compound, which will be described later.
The content of the additive (when the cellulose ester layer contains two or more 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, and further preferably 5 to 30 parts by mass.

(Plasticizer)
One preferred additive is a plasticizer. By adding a plasticizer to the cellulose ester layer, the hydrophobicity of the cellulose ester layer can be increased. 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 the 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 hardly generated. .

Although it does not specifically limit as a plasticizer, The polyvalent ester compound (henceforth "polyhydric alcohol ester plasticizer") of a polyhydric alcohol, and a polycondensation ester compound (henceforth "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 International Publication No. 2015/005398, and for polycondensed ester plasticizers, paragraphs [0099] to [0122] of the same publication, Regarding the agent, paragraphs [0123] to [0140] of the same publication can be referred to, and the contents thereof are incorporated in the present specification.
The molecular weight of the plasticizer is preferably 3000 or less, more preferably 1500 or less, and still more preferably 1000 or less, from the viewpoint of obtaining the above-described effect by adding it satisfactorily. The molecular weight of the plasticizer is, for example, 300 or more, preferably 350 or more, from the viewpoint of low volatility. In the case of multimeric plasticizers, the molecular weight is the 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 suppressing the precipitation of the plasticizer. It is preferably 2 to 15 parts by mass, more preferably 5 to 15 parts by mass.
Two or more plasticizers may be used in combination. Also when using 2 or more types together, the specific example and preferable range of content are the same as the above.

(Antioxidant)
One preferable additive may include an antioxidant. Regarding the antioxidant, reference can be made to the description of paragraphs [0143] to [0165] of International Publication No. 2015/005398, the contents of which are incorporated herein.

(Radical scavenger)
One preferred additive may include a radical scavenger. Regarding the radical scavenger, the description in paragraphs [0166] to [0199] of International Publication No. 2015/005398 can be referred to, and the contents thereof are incorporated in the present specification.

(Deterioration inhibitor)
As one of preferable additives, a deterioration preventing agent can be mentioned. As for the deterioration preventing agent, the description in paragraphs [0205] to [0206] of International Publication No. 2015/005398 can be referred to, and the contents thereof are incorporated in the present specification.

(Barbituric acid compound)
The cellulose ester layer may also contain a compound having a barbituric acid structure (barbituric acid compound). A barbituric acid compound is a compound which can express various functions in a cellulose-ester layer by adding this compound. For example, the barbituric acid compound is effective for improving the hardness of the cellulose ester layer. The barbituric acid compound is also effective in improving the durability of a polarizing plate having a cellulose ester layer containing this compound against light, heat or humidity. As for the barbituric acid compound that can be used in the cellulose ester layer, for example, the description 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 cellulose ester layer can be improved in adhesion to a polarizer material such as polyvinyl alcohol by alkali saponification treatment.
Regarding the saponification method, the methods described in paragraph No. [0211] and paragraph No. [0212] of JP-A No. 2007-86748 can be used.

For example, the alkali saponification treatment for the cellulose ester layer is preferably performed in a cycle in which the film surface is immersed in an alkali solution, neutralized with an acidic solution, washed with water and dried. Examples of the alkaline solution include potassium hydroxide solution and sodium hydroxide solution. The concentration of hydroxide ions is preferably in the range of 0.1 to 5.0 mol / L, and more preferably in the range of 0.5 to 4.0 mol / L. The alkaline solution temperature is preferably in the range of room temperature to 90 ° C, and more preferably in the range of 40 to 70 ° C.

Instead of 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 skin layer A and skin layer B is preferably 0.5 to 20 μm, more preferably 0.5 to 10 μm, and still more preferably 0.5 to 3 μm. The core layer is a layer located inside in the laminated structure, and in the case of a three-layer structure, the core layer is an intermediate layer, and the skin layers A and B are layers located outside in the laminated structure or three-layer structure. Say.

[Manufacturing method of laminate]
The manufacturing method of the laminated body of this invention is demonstrated.
The laminated body of this invention is not specifically limited, A well-known method is employable. In addition to the melt film forming method or the solution film forming method, after the cellulose ester layer is produced by the above-described method, an adhesive polymer layer can be formed by various known coating methods to produce a laminate. Although there is no restriction | limiting in particular as such a coating method, A micro gravure coating system can be used preferably. Note that, regardless of which application method is used, the coating solution is not particularly limited as long as the adhesive polymer is dissolved in an appropriate solvent at an appropriate concentration. There is no particular limitation.
In addition, from the viewpoint of suitability for mass production, it can be produced by a melt casting method or a solution casting 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 coextrusion method. As the solution casting method, a lamination casting method such as the above co-casting method, sequential casting method or coating method is preferably used, and a simultaneous co-casting method (also referred to as simultaneous multi-layer co-casting) method is particularly used. Is particularly preferable from the viewpoints of stable production and production cost reduction.

<Physical properties or characteristics of the 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 surface of the adhesive polymer layer, 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 exhibiting such a contact angle, the surface of the adhesive polymer layer exhibits high hydrophobicity, and water adhesion to the surface of the adhesive polymer layer can be prevented. Therefore, the moisture permeability in the adhesive polymer layer is reduced, and deterioration of the polarizer can be effectively suppressed by superimposing 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 column.

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

(Film thickness)
The film thickness of the laminate of the present invention can be appropriately determined according to the application, but can be set to, for example, 5 to 100 μm. When the thickness is 5 μm or more, the handling property when producing a web-like film is improved, which is preferable. Moreover, by setting it as 100 micrometers or less, it becomes easy to respond to a humidity change and it becomes easy to maintain an optical characteristic. The film thickness of the laminate is more preferably 8 to 80 μm, still more preferably 10 to 70 μm.
In order to meet the above-described demand for thinning of the image display device, the laminate is preferably thinned. In this case, the thickness of the laminate is preferably 8 to 80 μm, for example, and 10 to 70 μm. Is more preferable.

(Moisture permeability)
The moisture permeability of the laminate is measured under the conditions of 40 ° C. and relative humidity of 90% based on the description of JIS Z 0208.
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 Particularly preferably, it is less than 250 g / m ² / day. By controlling the moisture permeability of the laminated body within the above range, the liquid crystal display device mounted with the laminated body of the present invention is warped or displayed during black display after normal temperature, high humidity and high temperature and high humidity environments. Unevenness can be suppressed.

(Moisture content)
The moisture content of the laminate (equilibrium moisture content) is 25 ° C., regardless of the film thickness, so as not to impair the adhesion 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% by mass. The water content is more preferably 0 to 2.5% by mass, and still more preferably 0 to 1.5% by mass. If the equilibrium moisture content is 4% by mass or less, the dependency of retardation on humidity change does not become too large, and the liquid crystal display device displays black at a normal temperature in a high humidity environment and in a high temperature and high humidity environment. It is also preferable from the viewpoint of suppressing unevenness.
The moisture content can be measured by a Karl Fischer method using a film sample 7 mm × 35 mm using a moisture measuring device and sample drying apparatuses “CA-03” and “VA-05” (both manufactured by Mitsubishi Chemical Corporation). . The moisture content can be calculated by dividing the moisture 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. In general, a polarizing plate in which both surfaces of a polarizer are sandwiched between polarizing plate protective films to protect both surfaces is widely used.

As the polarizer, for example, a film obtained by immersing and stretching a polyvinyl alcohol film in an iodine solution can be used. When using a polarizer obtained by immersing and stretching a polyvinyl alcohol film in an iodine solution, for example, the saponification surface of the cellulose ester layer in the laminate is bonded to at least one surface of the polarizer using an adhesive. Can do.

The laminate of the present invention can be used as a polarizing plate protective film. When using as a polarizing plate protective film, the preparation method of the polarizing plate of this invention is not specifically limited, It can produce according to a general method. For example, there is a method in which the laminate of the present invention is treated with an alkali and bonded to both surfaces of a polarizer produced by immersing and stretching a polyvinyl alcohol film in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. Instead of alkali treatment, easy adhesion processing as described in JP-A-6-94915 or JP-A-6-118232 may be applied. 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 is in a form in which an adhesive polymer layer is provided on one side of the cellulose ester layer, the laminate surface of the laminate with the polarizer may be on the adhesive polymer layer side or on the cellulose ester layer side. But you can. 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 is preferably bonded to the polarizer so 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, using a birefringence meter (KOBRADH, manufactured by Oji Scientific Instruments).
Here, parallel, orthogonal, or 45 ° includes a range of errors allowed in the technical field to which the present invention belongs. For example, it means that it is within the range of ± 10 ° from the strict angle with respect to parallel, orthogonal and 45 °, respectively, and the error from the strict angle is preferably within the range of ± 5 °, and within the range of ± 3 ° Is more preferable.
The parallel of 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 °. Means that This angle is preferably within a range of ± 5 °, more preferably within a range of ± 3 °, further preferably within a range of ± 1 °, and most preferably within a range of ± 0.5 °.
Further, the orthogonality of 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 °. It means that they intersect at an angle within the range of. 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 °. Within range. If it is the above ranges, the fall of the polarization degree performance under polarizing plate cross Nicol will be suppressed, and light omission is reduced and it is preferable.

Although it does not specifically limit as an adhesive agent used for bonding a polarizing plate protective film and a polarizer, For example, the aqueous solution of polyvinyl alcohol or polyvinyl acetal (for example, polyvinyl butyral), vinyl polymer (for example, polybutyl) Acrylate) latex, UV curable adhesive, and the like. Particularly preferred adhesives are aqueous solutions of fully saponified polyvinyl alcohol or UV curable adhesives.

The polarizing plate is composed of a polarizer and protective films protecting both surfaces thereof, and at least one of the protective films is preferably a laminate of the present invention. As a protective film other than the laminate of the present invention, a known film can be used without any 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. Furthermore, 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 to be bonded to the liquid crystal plate, and is used on the surface side of the polarizing plate to be bonded to the liquid crystal plate.

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

In the present invention, the degree of polarization 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 column.

<Change in polarization degree>
The polarizing plate of the present invention is excellent in durability under wet heat aging conditions. For this reason, the amount of change in the degree of polarization before and after the polarizing plate durability test described later is small.
The polarizing plate of the present invention measures orthogonal transmittance and parallel transmittance using an automatic polarizing film measuring device VAP-7070 manufactured by JASCO Corporation, and calculates the degree of polarization according to 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 of the polarizing plate of the present invention are described in paragraphs [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 for 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, for example, it is used for antireflection applications. Especially, the polarizing plate of this invention is used suitably for a liquid crystal display device.
<Liquid crystal display device>
The liquid crystal display device which is one embodiment as the image display device of the present invention includes a liquid crystal cell and the polarizing plate of the present invention disposed in at least one of the liquid crystal cells.

A liquid crystal display device as an embodiment of the image display device of the present invention includes a liquid crystal cell in which liquid crystal is supported between two electrode substrates, two polarizing plates disposed on both sides thereof, and 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. In FIG. 2, the liquid crystal display device 20 includes a liquid crystal layer 24 and a first (upper liquid crystal cell) electrode substrate 23 and a second (lower liquid crystal cell) electrode substrate 25 arranged on both surface sides (referred to as upper and lower sides in FIG. 2). A first (upper) polarizing plate 21 and a second (lower) polarizing plate 26 disposed on both sides of the liquid crystal cell. A color filter may be disposed between the liquid crystal cell and each polarizing plate. When the liquid crystal display device 20 is used as a transmission type, a cold cathode or hot cathode fluorescent tube, or a backlight having a light emitting diode, field emission element, or electroluminescent element as a light source is disposed 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 configuration in which a polarizer is sandwiched between two polarizing plate protective films. In the liquid crystal display device 20 of the present invention, it is preferable that at least one polarizing plate is the polarizing plate of the present invention. Moreover, after arrange | positioning the laminated body of this invention as a polarizing plate protective film of the 1st polarizing plate 21 (viewing side polarizing plate) among two polarizing plates, it is further the 2nd polarizing plate 26 (backlight side polarizing plate). It is also preferable to arrange the laminate of the present invention as a polarizing plate protective film. Thereby, expansion / contraction of the polarizer contained in two polarizing plates can be suppressed, and the curvature of a panel can be prevented. The liquid crystal display device 20 of the present invention is preferably laminated in the order of the laminate of the present invention as a polarizing plate protective film, a polarizer, and a general transparent protective film 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 sealing 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 substance. Thereby, it becomes an electrode substrate provided with the substrate and the transparent electrode layer. The liquid crystal cell may further be provided with a gas barrier layer, a hard coat layer, or an undercoat layer (undercoat layer) (used for adhesion of the transparent electrode 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 liquid crystal display devices. In this case, the liquid crystal display device has a liquid crystal cell in which liquid crystal is supported between two electrode substrates, two polarizers disposed on both sides thereof, and at least between the liquid crystal cell and the polarizer described above. It is more preferable that the laminate of the present invention is arranged as an optical compensation film.

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

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 the repeating unit 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 (compound preA-1 leading to repeating unit A-1; hereinafter, a compound leading to repeating unit XY may be referred to as preXY), dimethyl- Weigh out 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. The 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. in a nitrogen stream. The monomer composition P1 was dropped into the methyl ethyl ketone at a rate of 0.31 mL / min. A chemical pump was used for dripping. The reaction solution after completion of the dropwise addition was further reacted at 80 ° C. for 2 hours, 0.02 g of dimethyl-2,2′-azobisisobutyrate was further added, and the resulting mixture was further stirred for 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 methanol 1.4 L and water 0.4 L to obtain a white precipitate. The resulting white precipitate was filtered off and dried at 50 ° C. overnight to obtain 22.5 g of the target P-1.
The obtained polymer P-1 is shown below. In the following structure, 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 is thoroughly dried, and 150 mL of benzene is added and stirred at −78 ° C. to stir at n-BuLi (n-butyllithium, 0.16 M hexane solution) 12.5 mL was added. 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 and the above reaction mixture were mixed. To this, 1.26 mL of s-BuLi (s-butyllithium, 0.53M hexane solution) was added, and 4.66 g of methyl methacrylate preA-1 was further added. After stirring for 1 hour, 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 obtained white precipitate was filtered off and dried at 50 ° C. overnight to obtain 10.7 g of the target branch polymer polymer P-2.
The obtained polymer P-2 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.
The polymer P-2 has the structure shown in FIG. 7A, specifically, three polymers PA ^B1 are bonded with the Si atom at the upper right of the following polymer P-2 as a nucleus, and further to the polymer PA ^B1. Thus, the polymer had a branch structure in which two polymers PB ^B1 were bonded through the diphenylethylene-derived nucleus.

<Synthesis Example 3: Synthesis of Polymer P-3>
To a 10 mL vial, add 0.22 mg of copper (I) bromide, 0.17 mg of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, and 1 mL of toluene to obtain a homogeneous catalyst solution 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, 0.17 g of dimethyl-2,2′-azobisisobutyrate, and 2 -6.7 mg of ethyl bromoisobutyrate was weighed, the catalyst solution was added, and the mixture was stirred at 70 ° C for 20 hours under a nitrogen stream.
Next, a mixed solution of 3.73 g of cyclohexyl methacrylate preA-2 and toluene 2 mL was added to the reaction solution obtained above after purging with nitrogen, and the mixture was stirred at 70 ° C. After completion of the reaction, 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 resulting white precipitate was filtered off and dried at 50 ° C. overnight to obtain 21.3 g of the target P-3.
The obtained polymer P-3 is shown below. This polymer P-3 has a structure shown in FIG. 3A composed of two types of repeating units [a], specifically, a partial structure composed of the repeating unit A-2 and a partial structure composed of the repeating unit A-1. It was a block structure (AB type) bonded in a single linear direction within the polymer chain.

<Synthesis Example 4: Synthesis of Polymer P-4>
In a 100 mL Erlenmeyer flask, 22.53 g of methyl methacrylate preA-1, 5.36 g of acetoacetoxyethyl methacrylate preB-1, 0.069 g of dimethyl-2,2′-azobisisobutyrate 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 and mixed to prepare a monomer composition P4.
Next, 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. in a nitrogen stream. The monomer composition P4 was dropped into the methyl ethyl ketone at a rate of 0.31 mL / min. A chemical pump was used for dripping. The reaction solution after completion of the dropwise addition was further reacted at 80 ° C. for 2 hours, 0.02 g of dimethyl-2,2′-azobisisobutyrate was further added, and the resulting mixture was further stirred for 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 methanol 1.4 L and water 0.4 L 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 obtained polymer P-4 is shown below. This polymer P-4 has the structure shown in FIG. 6B, specifically, a star structure in which four polymers PA ^S1 having a repeating unit 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 methyl methacrylate preA-1 macromonomer AA-6 (manufactured by Toagosei Co., Ltd., number average molecular weight 6,000, average degree of polymerization about 60), dimethyl-2,2′-azobis A monomer composition P5-1 was prepared by measuring 0.41 g of isobutyrate and 23.0 g of methyl ethyl ketone and mixing and dissolving them.
Separately from this, 8.7 g of methyl methacrylate preA-1 and 7.7 g of methyl ethyl ketone were weighed and mixed to prepare a monomer composition P5-2.
Next, 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. in a nitrogen stream. Into this 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 individually dropped at a rate of 0.13 mL / min. A chemical pump was used for dripping. The reaction solution after completion of the addition was further reacted at 80 ° C. for 3 hours. After completion of the reaction, the reaction solution was 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-5.
The obtained polymer P-5 is shown below. In the following structure, the number attached to each repeating unit in the trunk polymer represents a 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 the 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, weigh 19.5 g of methyl monomer AA-6 of methyl methacrylate preA-1, 0.12 g of dimethyl-2,2′-azobisisobutyrate, and 20.0 g of methyl ethyl ketone. Were mixed and dissolved to prepare a monomer composition P6-1.
Separately from this, 8.7 g of acrylic ester compound preB-6 and 7.7 g of methyl ethyl ketone were weighed and mixed to prepare 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, a stirring blade and a reflux ring, and stirred at 80 ° C. in 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 simultaneously dropped at a rate of 0.13 mL / min. A chemical pump was used for dripping. The reaction solution after completion of the addition was further reacted at 80 ° C. for 3 hours. After completion of the reaction, the reaction solution was 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 25.8 g of the intended P-6.
The obtained polymer P-6 is shown below. This polymer P-6 has the structure shown in FIG. 4C, specifically, a graft structure in which the branch polymer PB ^G1 composed of the repeating unit A-1 is bonded to the trunk polymer PA ^G1 including the repeating unit B-6. 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 A monomer composition P7-1 was prepared by measuring 0.17 g of the rate and 20.0 g of methyl ethyl ketone, and mixing and dissolving them.
Separately, 4.69 g of acetoacetoxyethyl methacrylate preB-1 and 4.6 g of methyl ethyl ketone were weighed and mixed to prepare a monomer composition P7-2.
Next, 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. in a nitrogen stream. Into this 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 simultaneously dropped at a rate of 0.07 mL / min. A chemical pump was used for dripping. The reaction solution after completion of the addition was further reacted at 80 ° C. for 3 hours. After completion of the reaction, the reaction solution was 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 20.8 g of the intended P-7.
The obtained polymer P-7 is shown below. This polymer P-7 has the structure shown in FIG. 4C, specifically, a graft structure in which the branch polymer PB ^G1 composed of the repeating unit A-10 is bonded to the trunk polymer PA ^G1 including the repeating unit B-1. Was.

<Synthesis Example 8: Synthesis of polymer P-8>
To a 10 mL vial, add 0.22 mg of copper (I) bromide, 0.17 mg of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, and 1 mL of toluene to obtain a homogeneous catalyst solution 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, 0.17 g of dimethyl-2,2′-azobisisobutyrate, and 2 -6.7 mg of ethyl bromoisobutyrate was weighed, the catalyst solution was added, and the mixture was stirred at 70 ° C for 20 hours under a nitrogen stream.
Next, 5.0 g of a mixed solution of acetoacetoxyethyl methacrylate preB-1 and 2 mL of toluene was added to the obtained reaction solution after nitrogen substitution, and the mixture was stirred at 70 ° C. After completion of the reaction, 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 resulting white precipitate was filtered off and dried at 50 ° C. overnight to obtain 22.3 g of the target P-8.
The obtained polymer P-8 is shown below. This polymer P-8 has a structure shown in FIG. 3A, specifically, a partial structure consisting of the repeating unit B-1 and a partial structure consisting of the repeating unit A-1 in a single linear direction within the polymer chain. It was a combined block structure (AB type).

<Synthesis Example 9: Synthesis of Polymer P-9>
In a 100 mL Erlenmeyer flask, weigh 23.4 g of methyl methacrylate preA-1 macromonomer AA-6, 0.21 g of dimethyl-2,2′-azobisisobutyrate, and 25.4 g of methyl ethyl ketone. 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 and mixed 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 dripping. The reaction solution after completion of the addition was further reacted at 80 ° C. for 3 hours. After completion of the reaction, the reaction solution was 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 intended P-9.
The obtained polymer P-9 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>
In Synthesis Example 9, the procedure was similar to that of Synthesis Example 9, except that the amounts used of the macromonomer AA-6 and acetoacetoxyethyl methacrylate preB-1 were changed to the molar ratios (composition ratios) shown in Table 1, respectively. 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 30.0 g was weighed, and these were mixed and dissolved to prepare monomer composition P11.
Next, 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. in a nitrogen stream. The monomer composition P11 was dropped into this methyl ethyl ketone at a rate of 0.62 mL / min. A chemical pump was used for dripping. The reaction solution after completion of the dropwise addition was further reacted at 80 ° C. for 2 hours, 0.02 g of dimethyl-2,2′-azobisisobutyrate was further added, and the resulting mixture was further stirred for 3 hours. After completion of the reaction, 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 desired diol compound DA-11. The weight average molecular weight of the diol compound DA-11 thus obtained was 7,000.

Next, 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, 2,2′-bis (trifluoromethyl) 3.9 g of benzidine preB-55-1 and 0.2 g of triethylamine were charged and stirred at 40 ° C. in a nitrogen stream to completely dissolve. 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 stirred at room temperature for 4 hours. After completion of the reaction, the internal temperature was heated to 40 ° C., 35 μL of acetyl 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 obtained white precipitate was filtered off and dried at 190 ° C. to obtain 10.2 g of the target P-11.
The obtained polymer P-11 is shown below. This polymer P-11 has a structure shown in FIG. 4C, 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 B-55. 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, 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 isophthalic acid chloride preB-53-2 was added in portions (10 times) and stirred at room temperature for 4 hours. After completion of the reaction, the internal temperature was adjusted to 40 ° C., 35 μL of acetyl 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 obtained white precipitate was filtered off and dried at 190 ° C. to obtain 10.5 g of the intended P-12.
The obtained polymer P-12 is shown below. This polymer P-12 has a structure shown in FIG. 4C, 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 B-53. 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 these were 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, a stirring blade and a reflux ring, and stirred at 70 ° C. in a nitrogen stream. The monomer composition P13 was dropped into 1-methoxy-2-propanol at a rate of 0.62 mL / min. A chemical pump was used for dripping. 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 resulting mixture was further stirred for 3 hours. After completion of the reaction, 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 amine compound AM-13 thus obtained had a weight average molecular weight of 6,000.

Next, polymer P-13 was synthesized as follows.
In a 500 mL three-necked flask equipped with a thermometer, stirring blades and reflux ring, 115 g of N-methylpyrrolidone, 11.0 g of amine compound AM-13 synthesized above, 2,2′-bis (trifluoromethyl) 3.9 g of benzidine preB-55-1 and 0.2 g of triethylamine were charged and stirred at 40 ° C. in a nitrogen stream to completely dissolve. 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 stirred at room temperature for 4 hours. After completion of the reaction, the internal temperature was heated to 40 ° C., 35 μL of acetyl 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 resulting white precipitate was filtered off and dried at 190 ° C. to obtain 10.8 g of the intended P-13.
The obtained polymer P-13 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 is single in the polymer chain at both ends of the partial structure consisting of the repeating unit B-55. It had a block structure (BAB 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, 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. in a nitrogen stream to be completely dissolved. 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 stirred at room temperature for 4 hours. After completion of the reaction, the internal temperature was heated to 40 ° C., 35 μL of acetyl 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 obtained white precipitate was filtered off and dried at 190 ° C. to obtain 10.0 g of the intended P-14.
The obtained polymer P-14 is shown below. This polymer P-14 has the structure shown in FIG. 3B, specifically, the partial structure consisting of the repeating unit A-1 is single in the polymer chain at both ends of the partial structure consisting of the repeating unit B-51. It had a block structure (BAB 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 amine compound AM-13 synthesized in Synthesis Example 13 above, 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 stirred at room temperature for 4 hours. After completion of the reaction, the internal temperature was heated to 40 ° C., 35 μL of acetyl 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 resulting white precipitate was filtered off and dried at 190 ° C. to obtain 9.9 g of the target P-15.
The obtained polymer P-15 is shown below. This polymer P-15 has the structure shown in FIG. 3B, specifically, the partial structure consisting of the repeating unit A-1 is single in the polymer chain at both ends of the partial structure consisting of the repeating unit B-53. It had a block structure (BAB 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 these were 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, a stirring blade and a reflux ring, and stirred at 70 ° C. in a nitrogen stream. The monomer composition P16 was dropped into 1-methoxy-2-propanol at a rate of 0.62 mL / min. A chemical pump was used for dripping. After completion of the dropwise addition, the reaction solution was further reacted at 80 ° C. for 2 hours, then 0.02 g of dimethyl-2,2′-azobisisobutyrate was further added, and the resulting mixture was further stirred for 3 hours. After completion of the reaction, 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 resulting white precipitate was filtered off and dried at 50 ° C. overnight to obtain 80.3 g of the target amine compound AM-16. The amine compound AM-16 thus obtained had a weight average molecular weight of 7,000.

Next, 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, 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 stirred at room temperature for 4 hours. After completion of the reaction, the internal temperature was heated to 40 ° C., 35 μL of acetyl 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 resulting white precipitate was filtered off and dried at 190 ° C. to obtain 7.8 g of the intended P-16.
The obtained polymer P-16 is shown below. This polymer P-16 has a structure shown in FIG. 3B, specifically, a partial structure consisting of the repeating unit A-2 is single in the polymer chain at both ends of the partial structure consisting of the repeating unit B-53. It had a block structure (BAB type) bonded in a linear direction.

<Comparative Synthesis Example 1: Synthesis of Comparative Polymer HP-1>
In a 300 mL Erlenmeyer flask, weigh 133.5 g of methyl methacrylate preA-1, 0.1 g of dimethyl-2,2′-azobisisobutyrate and 75.0 g of methyl ethyl ketone, and mix and dissolve them. 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 monomer composition HP1 was dropped into this methyl ethyl ketone at a rate of 1.1 mL / min. A chemical pump was used for dripping. The reaction solution after completion of the dropwise addition was further reacted at 85 ° C. for 6 hours. After completion of the reaction, 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 resulting white precipitate was filtered off, 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>
In Comparative Synthesis Example 1, the procedure was the same as Comparative Synthesis Example 1, 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 consisting of repeating unit B-1.

The solubility parameter δt calculated by the Hoy method of the repeating units constituting the polymers obtained in the above synthesis examples and comparative synthesis examples is shown in Table 1 below.
The primary structures of the polymers obtained in the above synthesis examples and comparative synthesis examples, and the molar amount (mol%) of each repeating unit in each polymer are also shown in Table 1 below. Here, the primary structure of the polymer was confirmed by the method described above. In addition, the mol% of the repeating unit in the polymer is the integral in the chart obtained by measuring ¹ H-NMR of each polymer using a nuclear magnetic resonance (NMR) spectrum measuring apparatus (manufactured by BRUKER, 300 MHz). It was calculated (identified) from the value.
Furthermore, depending on the number of ends per molecule of each polymer obtained, 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. Table 1 shows the results obtained by the above method. 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 the above synthesis examples and comparative synthesis examples. As the weight average molecular weight of the polymer, a weight average molecular weight measured in terms of polystyrene by gel permeation chromatography (GPC) was adopted. Specific measurement conditions are shown below.
GPC equipment: GPC equipment manufactured by Tosoh Corporation (HLC-8320GPC, Ecosec)
Column: TSK gel SuperHZM-H, TSK gel SuperHZ4000, TSK gel SuperHZ2000 combined use (manufactured by Tosoh, 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

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

――――――――――――――――――――――――――――――――――
Composition of cellulose acetate solution (Dope A) ――――――――――――――――――――――――――――――――――
Cellulose acetate with an acetyl substitution degree of 2.86 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Ultraviolet absorber (manufactured by Tinuvin 328 Ciba Japan) 0. 9 parts by weight UV absorber (manufactured by Tinuvin 326 Ciba Japan) 0.2 parts by weight Methylene chloride (first solvent) 336 parts by weight Methanol (second solvent) 29 parts by weight 1-butanol (third solvent) 11 parts by weight ――――――――――――――――――――――――――――――――――

Using a band casting apparatus, the prepared dope A was uniformly cast from a casting die onto a stainless steel endless band (casting support) having a width of 2000 mm. When the amount of residual solvent in the dope A reaches 40% by mass, it is peeled off as a polymer film from the casting support, and is conveyed without being actively stretched by a tenter and dried at 130 ° C. in a drying zone. went. The thickness of the obtained cellulose ester layer (cellulose ester film) was 55 μm.

<Preparation of laminate S-1>
The polymer P-1 was mixed with methyl ethyl ketone so as to have 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 filtered through a polypropylene depth filter having a pore size of 5 μm. Thus, an adhesive polymer layer forming composition (coating solution) was obtained. Next, the adhesive polymer layer forming composition was applied onto the cellulose ester layer prepared above using a gravure coater. Next, the applied composition for forming an adhesive polymer layer was dried at 25 ° C. for 1 minute, and further dried at 120 ° C. for about 5 minutes to obtain a laminate S-1 having a thickness of 60 μm (the thickness of the adhesive polymer layer). Was 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, except that the polymer P-1 used in the composition for forming an adhesive polymer layer was changed as shown in Table 2 below, Laminated bodies S-2 to S-16 and comparative laminated bodies HS-1 and HS-2 were produced.
The thicknesses of the obtained laminates were all 60 μm.

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

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

(Adhesion test of laminate)
As a method for evaluating the adhesion 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 intervals of 1 mm on the surface on the adhesive polymer layer side using a cutter knife and a cutter guide to produce 100 grids. A cellophane tape (registered trademark) was strongly pressed onto the grid, and the end of the tape was peeled off at an angle of 45 ° with respect to the surface. The cellophane tape (registered trademark) was applied and peeled off five times in succession. A new cellophane tape (registered trademark) was used each time.
Thereafter, the state of the grids (the state of peeling of the grids constituting the grids) was observed, and the number of grids (residual number) that was in close contact with the cellulose acetate layer without peeling was counted.
In this test, the adhesiveness is an acceptable level when the remaining number is 70 or more, preferably 95 or more, and particularly preferably 100.

From the results shown in Table 2, all of the laminates S-1 to S-16 including the above-mentioned repeating unit [a] and including the above-described adhesive polymer having the primary structure contain the adhesive polymer. It was shown that the contact angle of the layer to be used was high and the laminate had excellent adhesion between layers.
In particular, each of the laminates S-4 and S-6 to S-16 in which the adhesive polymer having the primary structure described above has the repeating unit [a] and the repeating unit [b] maintains the contact angle. However, it showed strong adhesion.
On the other hand, the laminate HS-1 having a layer containing the homopolymer HS-1 composed only of the above repeating unit [a] has all the lattices peeled off, and the adhesion between the layers is extremely inferior. there were. On the other hand, the laminate HS-2 having a layer containing the homopolymer HS-2 consisting only of the above repeating unit [b] had a poor contact angle.

[Production Example 2: Production of polarizing plates PL-1 to PL-15 and comparative polarizing plates HPL-1 and HPL-2]
As described below, polarizing plates PL-1 to PL-15 and comparative polarizing plates HPL-1 and HPL-2 were produced.

<Production of polarizer>
According to Example 1 of Japanese Patent Laid-Open No. 2001-141926, iodine was adsorbed to a stretched polyvinyl alcohol film to prepare a polarizer having a thickness of 27 μm.

<Preparation of active energy ray-curable adhesive composition>
Each component was mixed by the composition shown below, and it stirred at 50 degreeC for 1 hour, and obtained the active energy ray hardening-type adhesive composition.

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

<Preparation 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 the corona treatment, the active energy ray-curable adhesive composition prepared above is applied to an MCD coater (manufactured by Fuji Machine Co., Ltd., cell shape: honeycomb, number of gravure roll wires: 1000 / INCH, rotation speed 140% / vs. 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) was prepared, and the surface thereof was subjected to corona treatment. The active energy ray-curable adhesive composition was applied to the corona-treated surface so as to have a thickness of 0.5 μm in the same manner as described above.
Subsequently, the surface of each laminate applied with the active energy ray-curable adhesive composition and the surface of the cycloolefin-based film applied with the active energy ray-curable adhesive composition of the polarizer produced above were used. A polarizing plate precursor was prepared by bonding to both sides. Under the present circumstances, it arrange | positioned so that the longitudinal direction of the roll of the produced polarizer and the longitudinal direction of the roll of the cellulose-ester layer in each laminated body might become parallel. Moreover, it arrange | positioned so that the longitudinal direction of the roll of a polarizer and the longitudinal direction of the said cycloolefin type film might become parallel.

Then, it heated at 50 degreeC using IR heater from both surfaces of this polarizing plate precursor. Subsequently, the active energy ray shown below was irradiated to both surfaces of the polarizing plate precursor, and the said active energy ray hardening-type adhesive composition was hardened. Then, it heated-air-dried at 70 degreeC for 3 minute (s), and each polarizing plate was obtained.
(Active energy rays)
As active energy rays, ultraviolet rays (gallium filled metal halide lamp), irradiation device: Fusion UV Systems, Inc. Light HAMMER10, bulb: V bulb, peak illuminance: 1600 mW / cm ² , integrated irradiation amount 1000 / mJ / cm ² (wavelength) 380-440 nm) was used. 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 peeled off 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 a form in which the polarizing plate was attached to glass via an adhesive.
Two samples (about 5 cm × 5 cm) in which a polarizing plate was pasted on a glass plate so that the side of the laminate was on the air interface side (side away from the glass plate) were prepared. About these samples, the glass plate side was set toward the light source, and the degree of polarization was measured. Each of the two samples was measured and the arithmetic average value was taken as the polarization degree of the polarizing plate.
The degree of polarization was calculated by the following formula.

Polarization degree (%) = [(parallel transmittance−orthogonal transmittance) / (orthogonal transmittance + parallel transmittance)] ^1/2 × 100

The degree of polarization was measured in the range of 380 to 780 nm using an automatic polarizing film measuring device VAP-7070 manufactured by JASCO Corporation, and the measured value at a wavelength of 410 nm at which the degree of deterioration is more noticeable than other wavelengths was adopted.
Thereafter, it was stored for 500 hours in a high temperature and high humidity environment at a temperature of 85 ° C. and a relative humidity of 85%. Subsequently, the polarization degree was measured about two samples like the above, the measured value of two samples was arithmetically averaged, and it was set as the polarization degree of the polarizing plate after a preservation | save.
Based on the amount of change in the degree of polarization before and after storage, the polarizing plate durability was evaluated based on the following evaluation criteria. In this test, evaluations A to C are acceptable levels among the following four grades. Evaluations A and B are preferable, and evaluation A is particularly preferable.
Here, the amount of change in polarization degree is calculated by the following equation.

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 More than 3.0% change

From the results shown in Table 3, all of the polarizing plates HPL-1 to 15 provided with the laminate of the present invention showed a small change in the degree of polarization and 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.
In contrast, the comparative polarizing plate HPL-1 using the comparative laminate HS-1 as a protective film has a poor interlayer adhesion of the protective film, and the cellulose ester layer and the polymer layer are peeled off. It was not possible to produce a polarizing plate capable of performing the above. Further, the comparative polarizing plate HPL-2 using the comparative laminate HS-2 as a protective film resulted in a greatly inferior polarizer durability.

While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.

This 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 hereby incorporated herein by reference as if fully set forth herein.

10 Laminate (laminate)
DESCRIPTION OF SYMBOLS 11 Cellulose ester layer 12 Adhesive polymer layer 20 Liquid crystal display device 21 1st (upper side) polarizing plate 22 Direction of 1st polarizing plate absorption axis 23 1st (on liquid crystal cell) electrode substrate 24 Liquid crystal layer 25 2nd (under liquid crystal cell) ) Electrode substrate 26 Second (lower) polarizing plate 27 Second polarizing plate absorption axis direction

Claims

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 type of repeating unit, or a block structure, a graft structure, a branch structure or a star structure composed of two or more types of repeating units, The unit includes a repeating unit [a] having a solubility parameter δt calculated by the Hoy method of 13.5 or more and less than 20.0,
Laminated body.
The laminate according to claim 1, wherein the adhesive polymer has a block structure, a graft structure, a branch structure, or a star structure 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 any one of claims 1 to 4, wherein the two or more kinds of 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 represents a hydrogen atom, an alkyl group, an aryl group or an alkoxycarbonyl group.
L is a single bond, an alkylene group, an arylene group, a divalent linking group selected from —C (═O) —, —O— and —N (R 4 ) —, or two or more of these linking groups. The bivalent coupling group which combines is shown. R 4 represents a hydrogen atom or an alkyl group.
The laminate according to any one of claims 1 to 6, 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 represents 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 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.
R 12 , R 13 , R 14 , R 15 and R 16 are each independently a hydrogen atom, halogen atom, hydroxyl group, alkyl group, alkenyl group, aryl group, alkoxy group, acyl group, acyloxy group or alkoxycarbonyl group. To express.
The laminate according to claim 7, wherein the repeating unit [a] is a repeating unit represented by the general formula 2.
The laminate according to any one of claims 1 to 8, wherein the cellulose ester is cellulose acylate.
A polarizing plate comprising the laminate according to any one of claims 1 to 9 and a polarizer.
An image display device having the polarizing plate according to claim 10.