JP2017205941A - Laminate and method for producing the same, molded body, polarizer protective film, and polarizing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate excellent in transparency, excellent in adhesive force when an adherend and the laminate are bonded to each other, and excellent in punching workability and a method for producing the same; and a molded body, a polarizer protective film and a polarizing plate having the laminate.SOLUTION: A laminate has an adhesive auxiliary layer obtained by subjecting a coating film of a resin composition (P) containing a silane coupling agent (A) and a carboxylic acid-modified resin (B) to heating treatment and a base material containing a non-crystalline resin as a main component, where in the resin composition (P), a ratio a/b between an amount a of a substance of an epoxy group which the silane coupling agent (A) has to an amount b of a substance of a carboxylic group which the carboxylic acid-modified resin (B) has is in a range of 0.5-5.0, and the adhesive auxiliary layer has a bond derived from the epoxy group and the carboxylic group.SELECTED DRAWING: None

Description

  The present invention relates to a laminate and a method for producing the same. Moreover, it is related with the molded object, polarizer protective film, and polarizing plate which have the said laminated body.

  For the purpose of enhancing the design property or enhancing the durability, a method of obtaining a molded body by laminating a substrate made of an amorphous resin on the surface of an adherend is known. Such a molded body is usually obtained by joining a base material and an adherend through an adhesive, and then processing into a desired shape by punching. As the non-crystalline resin, for example, a methacrylic resin excellent in transparency, weather resistance, surface hardness and weather resistance is used.

  However, during the punching process, peeling may occur between the adherend and the base material, or cracks and chips may be generated, and foreign matters resulting from these may contaminate the production process. For this reason, in order to prevent a decrease in productivity, vigorous studies have been made on methods for improving the toughness of an adhesive for bonding an adherend and a substrate, and on improving adhesive strength.

  As a method for improving the toughness of the adhesive, a method for controlling the glass transition temperature of the adhesive (Patent Document 1) is known. There is a problem that tends to occur. Moreover, in order to improve the adhesiveness of a base material and a to-be-adhered body, the method of using the laminated body (polarizer protective film) which comprises a base material (polarizer film) and an adhesion adhesion auxiliary layer is known ( However, Patent Document 2) has a problem that the adhesive adhesion layer has insufficient moisture and heat resistance and low durability. In order to improve the durability problem, there is a method of using a resin having a crosslinked structure in the adhesive adhesion promoting layer. However, the anchoring effect of the adhesive on the adhesion promoting layer is lowered by the crosslinked structure, and the laminate. There is a problem that the adhesiveness between the substrate and the adherend is lowered, and a problem that the punching workability of the molded body is lowered.

JP 2010-282161 A JP 2002-328223 A

  As described above, it has been technically difficult to provide a tacky adhesion assisting layer having both durability, punching workability and adhesiveness, and a laminate including the tacky adhesion assisting layer and a substrate.

  The present invention has been made in view of the above problems, and is excellent in transparency, excellent in adhesion and durability when the adherend and the laminate are joined, and further excellent in punching workability and It aims at providing the manufacturing method, the molded object which has this laminated body, a polarizer protective film, and a polarizing plate.

As a result of extensive studies by the present inventors, it has been found that the problems of the present invention can be solved in the following modes, and the present invention has been completed.
[1] a base material mainly composed of an amorphous resin;
An adhesive adhesion layer laminated on at least one surface of the substrate,
The adhesive adhesion promoting layer is a layer obtained by heat-treating a coating film of a resin composition (P) containing a silane coupling agent (A) having an epoxy group and a carboxylic acid-modified resin (B) having a carboxy group. And
The ratio a / b of the substance amount a of the epoxy group and the substance amount b of the carboxy group in the resin composition (P) before the heat treatment is in the range of 0.5 to 5.0,
The laminated body in which the said adhesion promoter layer has the bond derived from the said epoxy group and the said carboxy group.
[2] The laminate according to [1], wherein the silane coupling agent (A) has a hydrolyzable functional group.
[3] The laminate according to [2], wherein the hydrolyzable functional group is an alkoxy group.
[4] At the interface between the adhesive adhesion promoting layer and the substrate, at least a part of the amorphous resin and the silane coupling agent (A) are bonded via a silyloxy group. [3] The laminate according to any one of the above.
[5] The laminate according to any one of [1] to [4], wherein the amorphous resin is a methacrylic resin composition (C) containing a methacrylic resin.
[6] The methacrylic resin contains (i) a resin having 80% by mass or more of a structural unit derived from a methacrylic acid ester, and (ii) a structural unit derived from a methacrylic acid ester and a structural unit having a ring structure. The laminate according to [5], which satisfies any one of the resins.
[7] The laminate according to [5] or [6], wherein the methacrylic resin has a syndiotacticity (rr) of 58% or more.
[8] The laminate according to any one of [1] to [7], wherein the base material has a thickness of 10 to 80 μm.
[9] A molded body obtained by bonding the laminate according to any one of [1] to [8] to an adherend.
[10] A polarizer protective film comprising the laminate according to any one of [1] to [8].
[11] A polarizing plate having a polarizer and the laminate according to any one of [1] to [8].
[12] The polarizing plate according to [11], wherein the polarizer and the adhesion promoting layer of the laminate are bonded via a polyvinyl alcohol-based adhesive layer.
[13] preparing a resin composition (P) comprising a silane coupling agent (A) having an epoxy group and a carboxylic acid-modified resin (B) having a carboxy group;
Applying the resin composition (P) to at least one surface of a base material mainly composed of an amorphous resin to obtain a coating film;
A heat treatment step of heating the coating film,
The resin composition (P) has a ratio a / b between the substance amount a of the epoxy group and the substance amount b of the carboxy group of 0.5 to 5.0 before the heat treatment step,
The manufacturing method of the laminated body which adds and reacts the said epoxy group and the said carboxy group by the said heat processing process, and forms a chemical bond.
[14] The laminate according to [13], wherein a silyloxy group is formed on at least a part of the non-crystalline resin and the silane coupling agent (A) at an interface between the adhesive adhesion promoting layer and the base material. Manufacturing method.

  ADVANTAGE OF THE INVENTION According to this invention, it is excellent in transparency, it is excellent in the adhesive force and durability at the time of joining a to-be-adhered body and a laminated body, and also is excellent in punching workability, its manufacturing method, and this laminated body. It has the outstanding effect that a molded object can be provided.

  Hereinafter, an example of an embodiment to which the present invention is applied will be described. The numerical values specified in this specification are values obtained by the method disclosed in the embodiment or examples. It should be noted that other embodiments are also included in the scope of the present invention as long as they meet the spirit of the present invention.

  The laminated body of this invention has at least the base material which has an amorphous resin as a main component, and the adhesive adhesion auxiliary layer laminated | stacked on the at least one surface of the base material. Here, the “adhesive adhesion assisting layer” is a so-called easy adhesion layer, and is a layer that improves the adhesiveness when the adherend and the substrate are bonded using an adhesive.

  The adhesion promoting layer is a layer obtained by heat-treating a coating film of a resin composition (P) containing a silane coupling agent (A) having an epoxy group and a carboxylic acid-modified resin (B) having a carboxy group. . In the present specification, the “main component” refers to a component that occupies 70% by mass or more of the constituent components. Accordingly, 70% by mass or more of the constituent components of the base material is made of an amorphous resin.

  When the amount of the epoxy group of the silane coupling agent (A) in the resin composition (P) before the heat treatment is a and the amount of the carboxy group of the carboxylic acid-modified resin (B) is b, these ratios a / b is in the range of 0.5 to 5.0. The ratio is preferably in the range of 0.9 to 4.0, more preferably in the range of 1.0 to 3.0. By setting it as the range of 0.5-5.0, lamination | stacking with many types of to-be-adhered bodies is enabled, and the laminated body excellent in punching workability can be provided.

  The adhesion promoting layer has a bond derived from the epoxy group of the silane coupling agent (A) and the carboxy group of the carboxylic acid-modified resin (B). Such a bond has, for example, a structure represented by the general formula (1) when a group bonded to a carbon atom constituting an epoxy group is a hydrogen atom except for a residue of a silane coupling agent. The hydroxyl group in the general formula (1) may further undergo a coupling reaction with another silane coupling agent. The group bonded to the carbon atom constituting the epoxy group is not limited to a hydrogen atom, and can be a substituent such as an alkyl group.

  From the viewpoint of not hindering the formation of a bond between the epoxy group of the silane coupling agent (A) of the resin composition (P) and the carboxy group of the carboxylic acid-modified resin (B), in the resin composition (P), It is preferable that an epoxy group is not contained in a compound other than the silane coupling agent (A). Similarly, in the resin composition (P), it is preferable that the carboxy group is not contained in compounds other than the carboxylic acid-modified resin (B). However, an epoxy group and / or a carboxy group may be contained in other compounds without departing from the spirit of the present invention.

  It is preferable that at least a part of the amorphous resin and the silane coupling agent (A) are bonded via a silyloxy group (—Si—O— group) at the interface between the base material and the adhesion promoting layer. By having a silyloxy group, it is possible to further strengthen the bonding between the base material and the adhesion promoting layer. In order to easily form a silyloxy group, it is preferable that a hydrolyzable functional group is directly bonded to the silicon atom constituting the silane coupling agent (A). Thereby, a silyloxy group can be easily formed with an amorphous resin. Examples of such hydrolyzable functional groups include alkoxy groups, acetoxy groups, and halogen groups.

  From the viewpoint of promoting the formation of the silyloxy group at the interface between the base material and the adhesive adhesion assisting layer, the amorphous resin has a functional group that reacts with the hydrolyzable functional group bonded to the silicon atom of the silane coupling agent (A). It is preferable to have. Such an amorphous resin and a functional group will be described later.

  An example of the bond at the interface between the adhesion promoting layer and the substrate is shown in the following formula (2).

However, R ¹ is independently an organic group derived from a substrate, R ² is independently a hydrogen atom, an organic group derived from a silane coupling agent (A) or another silane coupling agent (A) (another silane coupling agent May be bonded to another silane coupling agent (A)), R ³ is a hydrogen atom, a silicon atom or an organic group, and R ⁴ is a residue of the carboxylic acid-modified resin (B). And Z is a methylene group or polymethylene group derived from the silane coupling agent (A). N is 0, 1, 2, or 3.
Preferable examples of the organic group for R ¹ include an alkoxy group, a substituted amino group, and an ester bond. Preferable examples of the organic group for R ² include an alkoxy group, an ester bond, a hydroxy group and the like including a directly bonded oxygen atom. Preferred examples of Z include an alkylene group having 1 to 10 carbon atoms, and more preferred examples include an alkylene group having 2 to 5 carbon atoms.

<Silane coupling agent (A)>
The silane coupling agent (A) is not particularly limited as long as it has an epoxy group, but preferably has a hydrolyzable functional group directly bonded to a silicon atom from the viewpoint of improving adhesiveness. Examples of hydrolyzable functional groups include alkoxy groups, acetoxy groups, and halogen groups. Among these, an alkoxy group is preferable from the viewpoint of reactivity. As an example of the silane coupling agent (A) having an alkoxy group as a hydrolyzable functional group directly bonded to a silicon atom, a compound represented by the following general formula (3) can be exemplified.

However, R ² and Z are as described in the general formula (2). Instead of the alkoxy group of R 2 ^O, partially or an alkyl group, may or any other organic radical. Substituent X has an epoxy group and is preferably a structure represented by the following formula (4), (5) or (6), and is represented by formula (4) or (5) from the viewpoint of reactivity. More preferably, the structure is

  Examples of the silane coupling agent (A) include 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Examples include trimethoxysilane and 3-glycidoxypropyltriethoxysilane. From the viewpoint of reactivity, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxy Propyltrimethoxysilane, 3-glycol De trimethoxy silane are preferred.

  As the silane coupling agent (A), a commercially available product may be used. For example, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403 (all trade names manufactured by Shin-Etsu Chemical Co., Ltd.) SH6040, Z-6040, Z-6042, Z-6043, Z-6044 (all manufactured by Toray Dow Corning Co., Ltd., trade names); A-186, A-187, A-1871 (all momentary performances)・ Materials Japan GK, trade name). A silane coupling agent (A) may be used independently, or may use 2 or more types together.

<Carboxylic acid modified resin (B)>
The carboxylic acid-modified resin (B) is not particularly limited as long as it is a resin having a carboxy group or a resin modified with a carboxylic acid. As the carboxylic acid, for example, succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and the like can be used. These carboxylic acids may be used alone or in combination of two or more. Examples of the resin modified with carboxylic acid include polyester resins and urethane resins. Of these, urethane-based resins are preferable from the viewpoint of the strength of the adhesive adhesion assistant layer. Of these, urethane resins having a carboxy group are preferably used. The urethane resin having a carboxy group can be produced by reacting a polyol (a-1) having a carboxy group, another polyol (a-2) and a polyisocyanate (a-3).

  Examples of the polyol (a-1) having a carboxy group include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, and 2,2′-dimethylolyoshi. And herbic acid. These polyols may be used alone or in combination of two or more. Among these, 2,2'-dimethylolpropionic acid and 2,2'-dimethylolbutanoic acid are preferable from the viewpoint of handleability.

  Examples of the other polyol (a-2) include polyester polyol, polyether polyol, polycarbonate polyol, acrylic polyol, polybutadiene polyol, and low molecular weight polyol. These polyols may be used alone or in combination of two or more. Among these, it is preferable to use a polyester polyol.

  The number average molecular weight of the other polyol (a-2) is preferably in the range of 500 to 50,000, more preferably in the range of 800 to 2,000, from the viewpoint of handleability.

  As a usage-amount of the polyol (a-1) which has a carboxy group, it is a total of 100 mass parts of the said polyol (a-1) and the said other polyol (a-2) from a viewpoint which can further improve stamping workability. On the other hand, the range of 0.1-10 mass parts is preferable, the range of 2.1-6 mass parts is more preferable, and the range of 2.5-5 mass parts is still more preferable.

  The weight average molecular weight of the carboxylic acid-modified resin (B) is preferably in the range of 1,000 to 1,000,000, more preferably in the range of 5,000 to 50,000. If the weight average molecular weight is less than 1,000, burrs are likely to occur during punching, and if it exceeds 1,000,000, it becomes tough and the punching processability tends to decrease.

  The acid value of the carboxylic acid-modified resin (B) is preferably in the range of 10 to 55 mgKOH / g, more preferably in the range of 12 to 42 mgKOH / g, and still more preferably in the range of 14 to 35 mgKOH / g. When the acid value is in the range of 10 to 55 mgKOH / g, the dispersibility of the carboxylic acid-modified resin (B) in the resin composition (P) is good, and the adhesion of the coating film to the substrate is improved.

  The carboxylic acid-modified resin (B) is preferably used as a dispersion composed of a dispersion medium containing water and the carboxylic acid-modified resin (B) from the viewpoints of handleability and environmental properties. At this time, in order to improve the dispersibility in the dispersion medium and the storage stability of the dispersion, it is preferable to add amines such as trimethylamine, triethylamine and triisopropylamine to the dispersion. The amount of amines contained in the dispersion is preferably 0.5 to 2 with respect to the amount of carboxy group substance 1 of the components contained in the dispersion. Moreover, the hydrogen ion index (pH) of the dispersion is preferably in the range of 6 to 8, more preferably in the range of 6.5 to 7.5. When the pH is outside the range of 6 to 8, the dispersibility of the carboxylic acid-modified resin (B) is lowered, and the gelation of the resin composition (P) proceeds, which is not preferable.

  When the dispersion contains alcohols, the proportion of alcohols is preferably less than 60% by mass relative to 100% by mass of water and alcohols in total. If it is 60% by mass or more, the adhesiveness and punching workability tend to decrease. Although such alcohol is not specifically limited, For example, methanol, ethanol, isopropanol etc. are mentioned.

  Examples of commercially available dispersions include Superflex 210, Superflex 460, and Superflex 870 (all are trade names, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

<Base material>
The substrate of the present invention is mainly composed of an amorphous resin and may be either a single layer or a multilayer. The amorphous resin is not particularly limited. For example, cellulose resin, polyester resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, methacrylic resin, cyclic polyolefin resin (norbornene resin), polyarylate Resin, polystyrene resin, polyvinyl alcohol resin, polysulfone resin, phenoxy resin and the like. Among these, a methacrylic resin and a cyclic polyolefin resin (norbornene resin) excellent in transparency are preferable, and a methacrylic resin composition (C) containing a methacrylic resin is more preferable. An amorphous resin is used individually or in mixture of 2 or more types.

  The substrate preferably has a functional group on the surface of the substrate that reacts with the hydrolyzable functional group bonded to the silicon atom of the silane coupling agent (A). As a result, the hydrolyzable functional group bonded to the silicon atom of the silane coupling agent (A) reacts with the functional group on the surface of the non-crystalline resin to chemically bond it, and the bond between the adhesion promoting layer and the substrate is strong. become. The functional group on the surface of the substrate is not particularly limited as long as it can react with a hydrolyzable functional group bonded to a silicon atom to form a chemical bond, and preferred examples include a hydroxy group, a carboxy group, and an amino group. Further, the functional group on the surface of the base material may be originally possessed by the amorphous resin, or may be formed by subjecting the base material to corona treatment or plasma treatment.

  When the substrate is subjected to corona discharge treatment or plasma treatment, the value (discharge amount) obtained by dividing the discharge voltage (W) by the treatment speed (m / min) is preferably in the range of 50 to 300 W / (m / min). More preferably, it is the range of 100-250 W / (m / min), More preferably, it is the range of 150-250 W / (m / min). When the discharge amount is less than 50 W / (m / min), sufficient functional groups are not formed on the surface of the base material. When the discharge amount exceeds 300 W / (m / min), the base material surface deteriorates and adheres to the adhesive adhesion auxiliary layer. Sex is reduced.

  The methacrylic resin mentioned as a suitable example of an amorphous resin includes (i) a resin containing 80% by mass or more of a structural unit derived from a methacrylic acid ester, and (ii) a structural unit and a ring structure derived from a methacrylic acid ester. It is preferably any one of resins containing a structural unit having a methacrylic resin (I), a methacrylic resin (II) or a methacrylic resin (ii) described later, or a mixture thereof. More preferred.

[Methacrylic resin (i)]
[Methacrylic resin (I)]
Methacrylic resin (I) has a syndiotacticity (rr) in the triplet display of 45 to 58%, preferably 49 to 55%. If the syndiotacticity (rr) is 45% or more, the glass transition temperature of the methacrylic resin tends to be high, and if the syndiotacticity (rr) is 58% or less, the molding processability of the methacrylic resin is improved. Tend to. Incidentally, syndiotacticity (rr) is a value measured by method described later using ^{1 H-NMR.}

In the methacrylic resin (I), the polystyrene-equivalent weight average molecular weight Mw ₁ calculated based on the chromatogram obtained by gel permeation chromatography is preferably in the range of 40,000 to 180,000, more preferably. It is in the range of 50,000 to 120,000. When Mw ₁ is 40,000 or more, impact resistance and toughness tend to be improved, and when it is 180,000 or less, fluidity and moldability are improved.

In the methacrylic resin (I), the ratio Mw ₁ / Mn ₁ of the weight average molecular weight Mw _{1 to} the number average molecular weight Mn _{1 in} terms of polystyrene calculated based on a chromatogram obtained by gel permeation chromatography is preferably 1. It is the range of 7-2.6, More preferably, it is the range of 1.7-2.0. When the methacrylic resin (I) having Mw ₁ / Mn ₁ in the range of 1.7 to 2.6 is used, it becomes easy to obtain a molded article having excellent mechanical strength. Mw ₁ and Mn ₁ can be controlled by adjusting the type and amount of the polymerization initiator and chain transfer agent used when producing the methacrylic resin (I), the timing of addition, and the like.

  The glass transition temperature of the methacrylic resin (I) is preferably in the range of 100 to 120 ° C, more preferably in the range of 117 to 120 ° C. The glass transition temperature can be controlled by adjusting the molecular weight or syndiotacticity (rr) of the methacrylic resin (I). When the glass transition temperature of the methacrylic resin (I) is in the range of 100 to 120 ° C., a heat-resistant property is obtained, and a base material that hardly undergoes deformation such as heat shrinkage can be obtained.

  In the methacrylic resin (I), the content of the structural unit derived from the methacrylic acid ester is preferably 90% by mass or more, more preferably 95% by mass or more from the viewpoint of transparency, heat resistance, and mechanical strength. More preferably, it is 100 mass%. Examples of the methacrylic acid ester include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; aryl methacrylates such as phenyl methacrylate; cyclohexane methacrylate such as cyclohexyl methacrylate and norbornyl methacrylate. Alkyl esters; and the like, and these may be used alone or in combination. Among these, it is most preferable to use methyl methacrylate alone.

  Examples of the structural unit other than the structural unit derived from a methacrylic ester that can be contained in the methacrylic resin (I) include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Acrylic acid alkyl esters such as phenyl acrylate; acrylic acid aryl esters such as phenyl acrylate; acrylic acid cycloalkyl esters such as cyclohexyl acrylate and norbornyl acrylate; aromatic vinyl compounds such as styrene and α-methylstyrene; acrylamide; Examples thereof include structural units derived from vinyl monomers having only one polymerizable carbon-carbon double bond in one molecule, such as amide; acrylonitrile; methacrylonitrile;

  The method for producing the methacrylic resin (I) is not particularly limited, but a radical polymerization method is preferable from the viewpoint of productivity.

[Methacrylic resin (II)]
The methacrylic resin (II) has a triplet syndiotacticity (rr) in the range of 58 to 90%, more preferably in the range of 72 to 85%. When the syndiotacticity is 58% or more, the glass transition temperature of the methacrylic resin (II) can be increased, and a substrate having a large surface hardness can be obtained.

In the methacrylic resin (II), the ratio Mw ₂ / Mn ₂ of the weight average molecular weight Mw _{2 to} the number average molecular weight Mn _{2 in} terms of polystyrene calculated based on a chromatogram obtained by gel permeation chromatography is preferably 1. The range is from 01 to 1.80, and more preferably from 1.06 to 1.20. When a methacrylic resin (II) having Mw ₂ / Mn ₂ in such a range is used, a substrate having excellent mechanical strength can be obtained. Mw ₂ and Mn ₂ can be controlled by adjusting the type, amount, timing of addition, and the like of the polymerization initiator and chain transfer agent used in the production of the methacrylic resin (II).

  From the viewpoint of mechanical strength, the methacrylic resin (II) has a proportion of low molecular weight components having a molecular weight in terms of polystyrene of less than 15,000 calculated based on a chromatogram obtained by gel permeation chromatography of 10% by mass. Or less, more preferably 2% by mass or less.

  The methacrylic resin (II) preferably has a glass transition temperature in the range of 124 to 140 ° C, more preferably in the range of 128 to 140 ° C. The glass transition temperature can be controlled by adjusting the molecular weight and syndiotacticity (rr). When the glass transition temperature of the methacrylic resin (II) is increased, a base material that hardly undergoes deformation such as heat shrinkage can be obtained.

  The methacrylic resin (II) preferably has a content of structural units derived from methacrylic acid esters of 90% by mass or more, more preferably 95% by mass or more, from the viewpoint of transparency, heat resistance and mechanical strength. Preferably it is 100 mass%.

  Examples of the methacrylic acid esters include methyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; aryl methacrylates such as phenyl methacrylate; cycloalkyl methacrylates such as cyclohexyl methacrylate and norbornyl methacrylate. Ester; etc., and these may be used alone or in combination. Among these, it is preferable to use methyl methacrylate alone from the viewpoints of transparency, heat resistance, and mechanical strength.

  Examples of the structural unit other than the structural unit derived from the methacrylic acid ester that can be contained in the methacrylic resin (II) include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Acrylic acid alkyl esters such as phenyl acrylate; acrylic acid aryl esters such as phenyl acrylate; acrylic acid cycloalkyl esters such as cyclohexyl acrylate and norbornyl acrylate; aromatic vinyl compounds such as styrene and α-methylstyrene; acrylamide; Examples thereof include structural units derived from vinyl monomers having only one polymerizable carbon-carbon double bond in one molecule, such as amide; acrylonitrile; methacrylonitrile;

  The methacrylic resin (II) can be obtained by a known controlled polymerization method such as controlled radical polymerization, anion polymerization, group transfer polymerization, bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like. Among these, anionic polymerization is preferable from the viewpoints of high heat resistance, few foreign substances, few methacrylic ester dimers and trimers, and high productivity of the methacrylic resin (II).

  As anionic polymerization, for example, an organic alkali metal compound is used as a polymerization initiator and anionic polymerization is performed in the presence of a mineral salt such as an alkali metal or alkaline earth metal salt (see Japanese Patent Publication No. 7-25859), organic A method of anionic polymerization using an alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound (see JP-A-11-335432), a method of anionic polymerization using an organic rare earth metal complex as a polymerization initiator (JP-A-6-93060) For example).

  In anionic polymerization, n-butyllithium, sec-butyllithium, and isobutyl are used as polymerization initiators from the viewpoints of high productivity, high heat resistance, few foreign substances, and few methacrylic ester dimers and trimers. Alkyl lithium such as lithium and tert-butyl lithium is preferably used. Moreover, it is preferable to make an organoaluminum compound coexist from a viewpoint of productivity.

[Methacrylic resin (ii)]
The methacrylic resin (ii) is a resin having a structural unit derived from a methacrylic acid ester and a structural unit having a ring structure in the main chain. Examples of the structural unit having a ring structure include a lactone ring unit, a glutaric anhydride unit, and a glutarimide unit. The lactone ring unit, glutaric anhydride unit, and glutarimide unit are structural units similar to the lactone ring, glutaric anhydride, and glutarimide, respectively. The structural unit derived from methyl methacrylate may be simply referred to as methyl methacrylate unit (M) below.

(Lactone ring unit)
The structure of the lactone ring unit is not particularly limited, and one or more known ones can be used. From the viewpoint of ease of production, production yield, structural stability, etc., the number of ring members of the lactone ring unit Is preferably in the range of 4-8, more preferably in the range of 5-6, and even more preferably 6.

  Examples of the 6-membered lactone ring unit include a structure represented by the following formula (7) and a structure described in JP-A No. 2004-168882. Among these, from the viewpoint of raw material availability, cost, heat resistance, and the like, a structure represented by the following formula (7) is preferable, and a structure represented by the following formula (8) is more preferable.

In formula (7), R ^{11 to} R ¹³ are each independently a hydrogen atom or an organic residue having 1 to 20 carbon atoms, preferably a hydrogen atom or an organic residue having 1 to 5 carbon atoms.
Such an organic residue is not particularly limited as long as it has 1 to 20 carbon atoms. For example, a linear or branched alkyl group, a linear or branched alkylene group, an aryl group, an acetyl group, and a cyano group. Groups and the like. The organic residue may contain an oxygen atom.
In the present specification, “Ac” represents an acetyl group.

Me in the formula is a methyl group.

  A method for producing a methacrylic resin having a lactone ring unit is not particularly limited, and a known method can be used. From the viewpoint of raw material availability, cost, heat resistance, and the like, a hydroxy group and an ester group are added to the molecular chain. A method of heat-treating the methacrylic resin having is preferable.

(Glutaric anhydride unit)
The structure of the glutaric anhydride unit is not particularly limited, and one or two or more known ones can be used, and is represented by the following formula (9) from the viewpoint of raw material availability, cost, heat resistance, and the like. A structure is preferable, and a structure represented by the following formula (10) is more preferable.

R ³¹ and R ^{32 in} formula (9) are each independently a hydrogen atom or an organic residue having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Such an organic residue is not particularly limited as long as it has 1 to 20 carbon atoms. For example, a linear or branched alkyl group, a linear or branched alkylene group, an aryl group, an acetyl group, and a cyano group. Groups and the like. The organic residue may contain an oxygen atom.

  A method for producing a methacrylic resin having a glutaric anhydride unit is not particularly limited, and a known method can be used. However, from the viewpoint of raw material availability, cost, heat resistance, etc. A method of dealcoholizing and / or dehydrating a copolymer of a saturated carboxylic acid alkyl ester monomer is preferred.

(Glutarimide unit)
The structure of the glutarimide unit is not particularly limited, and one or more known ones can be used. From the viewpoint of raw material availability, cost, heat resistance, and the like, the structure represented by the following formula (11) Is preferable, and a structure represented by the following formula (12) is more preferable.

In formula (11), R ⁴¹ and R ⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁴³ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 3 to 12 carbon atoms. A cycloalkyl group or an aryl group having 6 to 10 carbon atoms. From the viewpoint of raw material availability, cost, heat resistance, etc., R ⁴¹ and R ⁴² are preferably independently a hydrogen atom or a methyl group, and R ⁴¹ is a methyl group and R ⁴² is a hydrogen atom. More preferred. For the same reason, R ⁴³ is preferably a hydrogen atom, a methyl group, an n-butyl group, a cyclohexyl group, or a benzyl group, and more preferably a methyl group, an n-butyl group, or a cyclohexyl group.

  A method for producing a methacrylic resin having a glutarimide unit is not particularly limited, and a known method can be used.

<Other ingredients>
Other amorphous resins can be blended with the amorphous resin. Examples of other non-crystalline resins include cellulose resins such as triacetyl cellulose, polyester resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, methacrylic resins, and cyclic polyolefin resins (norbornene-based resins). Resin), polyarylate-based resin, polystyrene-based resin, polyvinyl alcohol-based resin, polysulfone-based resin, phenoxy resin, and the like, and one or a combination of two or more thereof may be used.

  Non-crystalline resins are rubber components, fillers, antioxidants, heat stabilizers, UV absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes, pigments, light You may contain additives, such as a spreading | diffusion agent, an organic pigment | dye, a matting agent, an impact modifier, fluorescent substance, and a filler.

  The rubber component is not particularly limited, and examples thereof include diene rubbers, non-diene rubbers, and thermoplastic elastomers. Among these, thermoplastic elastomers, particularly core-shell type graft copolymers, and block copolymers composed of soft blocks and hard blocks are preferable in that they can impart impact resistance and toughness without impairing other physical properties.

  The content of the rubber component in the amorphous resin is preferably in the range of 1 to 30% by mass and more preferably in the range of 5 to 20% by mass from the viewpoint of achieving both heat resistance and toughness. When the rubber component exceeds 30% by mass, the heat resistance decreases, and when it is less than 1% by mass, the toughness tends to decrease.

  Examples of the filler include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, and magnesium carbonate. The filler content in the amorphous resin is preferably 3% by mass or less, more preferably 1.5% by mass or less.

  The antioxidant alone has an effect of preventing oxidative degradation of the resin in the presence of oxygen, and examples thereof include phosphorus antioxidants, hindered phenol antioxidants, and thioether antioxidants. These antioxidants may be used alone or in combination of two or more. Among these, from the viewpoint of preventing deterioration of optical properties due to coloring, a phosphorus-based antioxidant and a hindered phenol-based antioxidant are preferable, and a combination of a phosphorus-based antioxidant and a hindered phenol-based antioxidant is more preferable. When a phosphorus antioxidant and a hindered phenol antioxidant are used in combination, the amount of phosphorus antioxidant used: the amount of hindered phenol antioxidant used ranges from 1: 5 to 2: 1 by mass ratio. Is preferable, and the range of 1: 2 to 1: 1 is more preferable.

  The thermal degradation inhibitor can prevent thermal degradation of the amorphous resin by capturing a polymer radical generated when the amorphous resin is heated to a high temperature in a substantially oxygen-free state. Butyl-6- (3′-tert-butyl-5′-methyl-hydroxybenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumilizer GM), 2,4-di-tert-amyl-6 -(3 ′, 5′-di-tert-amyl-2′-hydroxy-α-methylbenzyl) phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumitizer GS) is preferred.

Ultraviolet absorbers are compounds having the ability to absorb ultraviolet rays, such as benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, succinic anilides, malonic esters, formamidines, etc. Is mentioned. These may be used alone or in combination of two or more. Among them, benzotriazoles, triazines, or ultraviolet absorbers having a maximum molar extinction coefficient ε _max of 1200 dm ³ mol ⁻¹ cm ⁻¹ or less in the wavelength range of 380 to 450 nm are preferable.

  Benzotriazoles are highly effective in suppressing deterioration of optical properties such as coloring of an amorphous resin due to ultraviolet rays, and 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetra Methylbutyl) phenol (manufactured by BASF Japan Ltd .; trade name TINUVIN329), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (BASF Japan Ltd.) Product name: TINUVIN 234) and the like are preferable.

  Triazines have a high absorbance with respect to light having a wavelength near 380 nm. For example, 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine ( Made by ADEKA Corporation; trade name LA-F70), 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2,4-bis-butyloxyphenyl) -1,3,5-triazine (Trade name TINUVIN 460 or TINUVIN 479 manufactured by BASF Japan Ltd.).

The ultraviolet absorber having a maximum value ε _max of the molar extinction coefficient at a wavelength of 380 to 450 nm of 1,200 dm ³ mol ⁻¹ cm ⁻¹ or less can suppress the yellowness of the obtained laminate, for example, 2-ethyl-2 ′ -Ethoxy-oxalanilide (manufactured by Clariant Japan Co., Ltd .; trade name: Sundubore VSU).

  Further, when it is desired to particularly absorb light having a wavelength of 380 nm to 400 nm, for example, WO2011-089794, WO2012-124395, JP2012-012476, JP2013-023461, JP2013-112790. The metal complex containing a hetero complex ring having a specific structure described in JP-A No. 2013-194037, JP-A No. 2014-062223, JP-A No. 2014-088542, JP-A No. 2014-088543, etc. It is preferable to use it as an absorbent. Examples of the heterocyclic complex having a specific structure include 2,2′-iminobisbenzothiazole, 2- (2-benzothiazolylamino) benzoxazole, 2- (2-benzothiazolylamino) benzimidazole, (2 -Benzothiazolyl) (2-benzimidazolyl) methane, bis (2-benzoxazolyl) methane, bis (2-benzothiazolyl) methane, bis [2- (N-substituted) benzimidazolyl] methane and the like and their derivatives. As the central metal of such a metal complex, for example, copper, nickel, cobalt, zinc and the like are preferably used.

  The light stabilizer is a compound having a function of trapping radicals generated mainly by oxidation by light, and examples thereof include hindered amines such as a compound having a 2,2,6,6-tetraalkylpiperidine skeleton.

  Examples of the lubricant include stearic acid, behenic acid, stearamide, methylene bisstearamide, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octyl alcohol, and hardened oil.

  Examples of the mold release agent include higher alcohols such as 1-hexadecanol and stearyl alcohol; glycerin fatty acid ester composed of glycerin and higher fatty acid such as glyceryl stearate and glyceryl distearate; and the like. It is preferable to use a fatty acid monoester in combination. When higher alcohols and glycerin fatty acid monoester are used in combination, the ratio is not particularly limited, but from the viewpoint of releasability and bleed out, the amount of higher alcohol used: the amount of glycerin fatty acid monoester used is 2 by mass. The range of 5: 1 to 3.5: 1 is preferred, and the range of 2.8: 1 to 3.2: 1 is more preferred.

  The polymer processing aid may be a single layer particle composed of a polymer having a single composition and a single intrinsic viscosity, or a multilayer particle composed of two or more kinds of polymers having different composition ratios or intrinsic viscosities. However, a two-layered particle having a layer made of a polymer having an intrinsic viscosity of less than 5 in the inner layer and a layer made of a polymer having an intrinsic viscosity of 5 to 10 dL / g in the outer layer is preferable. The intrinsic viscosity of the polymer processing aid is preferably in the range of 3 to 6 dL / g. If the intrinsic viscosity is small, the effect of improving the moldability of the substrate tends to be low, and if the intrinsic viscosity is large, the moldability of the amorphous resin tends to be lowered. Examples of commercially available products include Paraloid 125 or Paraloid 125P (both manufactured by Dow Chemical Co., Ltd., trade names); Metabrene P-530A or P-550A (both manufactured by Mitsubishi Rayon Co., Ltd., trade names); Kane Ace PA20 or PA30 (Both manufactured by Kaneka Corporation, trade names).

As the organic dye, a compound having a function of converting ultraviolet light into visible light is preferably used.
Examples of the light diffusing agent and matting agent include glass fine particles, polysiloxane-based crosslinked fine particles, crosslinked polymer fine particles, talc, calcium carbonate, and barium sulfate.
Examples of the phosphor include fluorescent pigments, fluorescent dyes, fluorescent white dyes, fluorescent brighteners, and fluorescent bleaches.

  The compounding amount of the additive excluding the rubber component is preferably 7% by mass or less, more preferably 4% by mass or less so as not to impair the physical properties of the substrate.

<Manufacturing method of substrate>
The substrate can be produced by a solution casting method, a melt casting method, an extrusion molding method, an inflation molding method, a blow molding method, or the like. Among these, the extrusion molding method is preferable in order to obtain a substrate excellent in balance of transparency, toughness, handleability, surface hardness, and rigidity. The temperature of the amorphous resin discharged from the extruder is preferably in the range of 160 to 270 ° C, more preferably in the range of 220 to 260 ° C.

  In the extrusion molding method, from the viewpoint of obtaining a substrate having good surface smoothness and specular gloss and having a low haze, the non-crystalline resin is passed through a filter in a molten state to remove foreign matters, extruded from a T-die, and then It is more preferable to use a method of sandwiching and molding two or more mirror rolls or mirror belts or a combination thereof.

  The mirror roll is preferably a metal rigid roll or a metal elastic roll having a mirror-like metal thin film on an outer cylinder. The linear pressure between the pair of mirror rolls or the mirror belt is preferably in the range of 10 to 100 N / mm, more preferably in the range of 20 to 60 N / mm, and still more preferably in the range of 25 to 45 N / mm. . If it is less than 10 N / mm, the specular gloss of the substrate tends to decrease. If it exceeds 100 N / mm, the strain remaining on the substrate is large, and the substrate tends to shrink when heated.

  The surface temperature of the pair of mirror rolls or mirror belts is preferably 130 ° C. or lower and at least one of the surface temperatures is preferably 60 ° C. or higher. When such a surface temperature is set, a substrate having excellent surface smoothness and low haze can be produced. The haze of the substrate is preferably 1.0% or less, more preferably 0.5% or less, and still more preferably 0.3% or less.

  The thickness of the base material is preferably in the range of 10 to 300 μm, more preferably in the range of 10 to 80 μm, and in the range of 20 to 60 μm, from the viewpoint of handleability and gas barrier properties against water vapor and the like. Is more preferable.

  The base material may be subjected to stretching treatment. The toughness is increased by the stretching treatment, and a base material that is difficult to break can be obtained. The stretching method is not particularly limited, and examples thereof include a simultaneous biaxial stretching method, a sequential biaxial stretching method, and a tuber stretching method. Among these, the biaxial stretching method is preferable and the simultaneous biaxial stretching method is more preferable from the viewpoint that a highly strong base material that can be uniformly stretched can be obtained.

  The temperature of the base material during stretching is preferably in a range from a temperature 10 ° C. higher than the glass transition temperature of the amorphous resin to a temperature 40 ° C. higher than the glass transition temperature of the amorphous resin. Moreover, it is preferable that extending | stretching is performed in 100-5000% / min. After stretching, heat fixing is performed to obtain a substrate with little heat shrinkage. The thickness of the substrate after stretching is preferably in the range of 10 to 200 μm from the viewpoints of handleability, gas barrier properties against water vapor and the like and toughness.

  Biaxial stretching is a preheating step for preheating an unstretched substrate; a stretching step for biaxial stretching while heating the substrate; a temperature lowering step for cooling the substrate after biaxial stretching; and biaxial stretching. It is preferable to have a relaxation step of relaxing the base material in this order. In the preheating step, preheating is performed until the unstretched substrate reaches the temperature of the rubber-like flat region in the storage modulus curve of the nonpolar resin. In the stretching step, the preheated substrate is biaxially stretched at the temperature of the rubber-like flat region.

<Preparation of resin composition (P)>
The silane coupling agent (A) is preferably used as an aqueous solution, and the weight ratio of the silane coupling agent (A) / water in the aqueous solution is preferably in the range of 0.5 / 99.5 to 5/95, more preferably. Is in the range of 1/99 to 3/97, more preferably in the range of 1.5 / 98.5 to 2/98. When the silane coupling agent (A) is less than 0.5, the adhesiveness tends to be lowered, and when it is more than 5, the handleability tends to be lowered.

  Such an aqueous solution may contain alcohols. In this case, when the total amount of water and alcohol is 100% by mass, the proportion of alcohols is preferably less than 60% by mass. If it is 60% by mass or more, the adhesiveness and punching processability tend to decrease. Although alcohol which can be used is not specifically limited, For example, methanol, ethanol, isopropanol etc. are mentioned.

  Such an aqueous solution is preferably stirred for 1 to 5 hours at a temperature of 10 to 40 ° C. and then mixed with a dispersion of the carboxylic acid-modified resin (B).

  The resin composition (P) is preferably prepared by stirring at 20 ° C. The solid content concentration in the resin composition (P) is preferably in the range of 1 to 30% by mass, more preferably in the range of 2 to 20% by mass, and still more preferably in the range of 3 to 10% by mass. . If it is less than 1% by mass, the adhesion promoting layer becomes thin, and if it exceeds 30% by mass, the surface property of the adhesion promoting layer tends to be lowered. The solid content means components other than water in the resin composition (P) and alcohols generated by hydrolysis, such as silane coupling agent (A), carboxylic acid-modified resin (B), and additives. Mean total.

<Formation of adhesive adhesion auxiliary layer>
Although the application method to the base material of resin composition (P) is not limited, For example, well-known methods, such as a bar coat, a gravure, a die coat, a spray coat, can be illustrated. The coating speed is preferably in the range of 15 to 150 m / min, and more preferably in the range of 50 to 100 m / min.

  The resin composition (P) applied to the substrate is used to react the epoxy group of the silane coupling agent (A) with the carboxy group of the carboxylic acid-modified resin (B) and to dry the resin composition (P). Heat treatment. The temperature of the heat treatment is preferably in the range of 80 to 200 ° C., more preferably in the range of 80 to 100 ° C., from the viewpoint of the adhesiveness between the base material and the adhesion promoting layer.

  The application, drying, and heat treatment of the resin composition (P) can be performed separately, or can be incorporated into the production process when biaxial stretching is performed. In this case, the application of the resin composition (P) is preferably performed before the preheating step of biaxial stretching, the drying is performed in the preheating step to the stretching step, and the heat treatment is preferably performed in the stretching step to the relaxation step.

  The thickness of the adhesion promoting layer is not particularly limited and can be appropriately determined according to the surface properties and purpose of the adherend to be laminated, but is preferably in the range of 30 to 10,000 nm, more preferably from the viewpoint of handleability. Is in the range of 50 to 5,000 nm, more preferably in the range of 100 to 1,000 nm.

The water vapor permeability of the laminate of the present invention is preferably in the range of 150 to 400 g / m ² · day, more preferably in the range of 200 to 350 g / m ² · day under the conditions of 70 ° C. and 90% RH. is there. If it is less than 150 g / m ² · day, the adhesive is difficult to dry when bonded to an aqueous adhesive such as a polyvinyl alcohol-based adhesive or an emulsion-based adhesive. On the other hand, if it exceeds 400 g / m ² · day, it is not preferable from the viewpoint of the protection performance of the adherend. The term “adhesive” as used herein means an adhesive in a broad sense including a pressure-sensitive adhesive and / or an adhesive having adhesiveness and / or adhesiveness.

<Molded body>
The molded body of the present invention is formed by joining the laminate of the present invention to an adherend. Examples of the adherend include synthetic resin, wood, metal, and ceramics. Examples of the synthetic resin include polyolefin resins, polycarbonate resins, methacrylic resins, polystyrene resins, polyester resins, polyvinyl alcohol resins, polyvinyl acetal resins, and cellulose resins. Among these, methacrylic resins, polyvinyl alcohol (PVA) resins, polyvinyl acetal resins, and cellulose resins are preferable from the viewpoints of transparency and adhesiveness.
<Adhesive>

  As a method of adhering the laminate to the adherend, there is a method using an adhesive, that is, a method of bonding via an adhesive layer. Moreover, after laminating | stacking a laminated body and a to-be-adhered body, well-known methods, such as the method of heat-fusing and joining these, can be illustrated. From the viewpoint of adhesiveness, a method using an adhesive is preferably used.

  Examples of the adhesive used for bonding to the adherend include an emulsion-based adhesive, a solvent-based adhesive, and a solventless adhesive. Examples of the emulsion-based adhesive or solvent-based adhesive include organic resin or synthetic resin solutions, dispersions, and emulsions using water as a solvent. The synthetic resin is preferably a thermoplastic resin and / or a thermosetting resin. Examples of the solventless adhesive include a thermosetting adhesive and an active energy ray-curable adhesive. From the viewpoint of environmental load, an adhesive using a water-based solvent or a solventless adhesive is preferable. A joining method is appropriately selected according to the type of adherend.

  As a preferable example of the adhesive using an aqueous solvent, an adhesive containing a PVA resin will be described.

  PVA-based resins include, for example, saponified products of polyvinyl acetate and derivatives thereof; saponified products of copolymers of vinyl acetate and other monomers; acetalization, urethanization, etherification, grafting or phosphoric acid of PVA Examples thereof include esterified modified PVA. Examples of the other monomers include unsaturated carboxylic acids such as (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid and (meth) acrylic acid and esters thereof; α-olefins such as ethylene and propylene; Meta) allylsulfonic acid (soda), sulfonic acid soda (monoalkylmalate), disulfonic acid soda alkylmalate, N-methylolacrylamide, acrylamide alkylsulfonic acid alkali salt, N-vinylpyrrolidone, N-vinylpyrrolidone derivative . In the molded body of the present invention, when the amorphous resin is a methacrylic resin and the adherend is a polyvinyl alcohol resin, the adhesion between the adherend and the laminate is improved, and the durability of the polarizing plate It is preferable that PVA-type resin contains acetoacetyl group containing PVA from the point which improves.

  The average degree of polymerization of the PVA-based resin is preferably about 100 to 5,000, more preferably 1,000 to 4,000, from the viewpoint of adhesiveness of the adhesive composition. The average saponification degree of the PVA-based resin is preferably about 85 to 100 mol%, more preferably 90 to 100 mol%, from the viewpoint of the adhesiveness of the adhesive composition.

  The acetoacetyl group-containing PVA can be obtained, for example, by reacting PVA and diketene by an arbitrary method. A specific example is a method of adding diketene to a dispersion in which PVA is dispersed in a solvent such as acetic acid; a method of adding diketene to a solution in which PVA is dissolved in a solvent such as dimethylformamide or dioxane; and diketene gas to PVA. Or it is the method of making liquid diketene contact directly.

  The degree of acetoacetyl group modification in the acetoacetyl group-containing PVA is typically 0.1 mol% or more, preferably 0.1 to 40 mol%, more preferably 1 to 20 mol%, and still more preferably 2 mol%. ~ 7 mol%. When the degree of modification is less than 0.1 mol%, the effect of modification (for example, improvement in water resistance) may be insufficient. If the degree of modification exceeds 40 mol%, the water resistance is not improved further. The degree of acetoacetyl group modification of PVA can be measured, for example, by NMR.

  The adhesive composition may contain a crosslinking agent. Although a crosslinking agent is not limited, It is a compound which has at least two functional groups which show the reactivity with respect to PVA-type resin. Crosslinking agents include, for example, ethylenediamine, triethylenediamine, hexamethylenediamine and other alkylenediamines having an alkylene group and two amino groups; tolylene diisocyanate, hydrogenated tolylene diisocyanate, trimethylolpropane tolylene diisocyanate adduct, triphenylmethane Isocyanates such as triisocyanate, methylenebis (4-phenylmethane triisocyanate), isophorone diisocyanate, and ketoxime block or phenol block thereof; ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin Triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylo Epoxy such as rupropane triglycidyl ether, diglycidyl aniline, diglycidyl amine; monoaldehyde such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde; glyoxal, malondialdehyde, succindialdehyde, glutardialdehyde, maleindialdehyde, phthalate Dialdehydes such as dialdehyde; amino-formaldehyde resins such as methylol urea, methylol melamine, alkylated methylol urea, alkylated methylol melamine, acetoguanamine, condensate of benzoguanamine and formaldehyde; sodium, potassium, magnesium, calcium, aluminum, Salts and oxides of monovalent to trivalent metals such as iron and nickel. Of these, amino-formaldehyde resin and dialdehyde are preferable as the crosslinking agent. The amino-formaldehyde resin preferably has a methylol group, and methylol melamine is preferred. The dialdehyde is preferably glyoxal.

  The compounding quantity of the crosslinking agent in an adhesive composition can be suitably set according to the kind of PVA-type resin. Typically, it is about 10 to 60 parts by weight with respect to 100 parts by weight of the PVA resin, and preferably 20 to 50 parts by weight. In this range, good adhesion can be obtained. When the amount of the crosslinking agent is excessively large, the reaction via the crosslinking agent proceeds in a short time, so that the adhesive composition tends to gel. For this reason, the pot life (pot life) as an adhesive composition becomes extremely short, and industrial use may be difficult.

An active energy ray-curable adhesive is described as a preferred example of the solventless adhesive.
The main component of the active energy ray-curable adhesive is an active energy ray-curable compound. Examples of such compounds include photo radical polymerizable compounds and photo cation polymerizable compounds. The radical photopolymerizable compound is cured by causing radical polymerization by active energy rays. Examples of such compounds are compounds having a functional group such as acryloyl group, methacryloyl group, and allyl group. The photocationically polymerizable compound is cured by causing a photocationic reaction with active energy rays. Examples of such compounds are compounds having a functional group such as an epoxy group, an oxetane group, a hydroxyl group, a vinyl ether group, an episulfide group, and an ethyleneimine group.

  Examples of the photo-radical polymerizable compound include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; hydroxyaryl acrylates such as 2-hydroxy-3-phenoxypropyl acrylate; 2-acryloyloxyethyl succinic acid, 2 -Acrylic modified carboxylic acid such as acryloyloxyethylphthalic acid; Polyethylene glycol diacrylate such as triethylene glycol diacrylate and tetraethylene glycol diacrylate; Polypropylene glycol diacrylate such as dipropylene glycol diacrylate and tripropylene glycol diacrylate; Others, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanegio Diacrylate, bisphenol A ethylene oxide modified diacrylate, bisphenol A propylene oxide modified diacrylate, dimethylol tricyclodecane diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc. Other functional acrylates such as polyfunctional acrylates; epoxy acrylates, urethane acrylates, neopentyl glycol acrylic acid benzoic acid mixed esters, and the like, and methacrylates thereof.

  Examples of the photocationically polymerizable compound include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin; compounds classified into novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin; Group epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, polyfunctional epoxy resin, biphenyl type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin; hydrogenated bisphenol A Compounds classified into alcohol-type epoxy resins such as epoxy resins; halogenated epoxy resins such as brominated epoxy resins; rubber-modified epoxy resins, urethane-modified epoxy resins, epoxidized polybutadiene, Compounds having an epoxy group such as xylized styrene-butadiene-styrene block copolymer, epoxy group-containing polyester resin, epoxy group-containing polyurethane resin, epoxy group-containing acrylic resin; phenoxymethyl oxetane, 3,3-bis (methoxymethyl) Oxetane, 3,3-bis (phenoxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-{[3 -(Triethoxysilyl) propoxy] methyl} oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, oxetanylsilsesquioxane, phenol novolac oxetane, 1,4-bis {[(3-ethyl-3- Oxetanyl) methoxy] methyl} benzene It includes compounds having an oxetanyl group.

  A compound that is a photoradical polymerizable compound and a photocationic polymerizable compound is also referred to as a radical / cationic amphoteric monomer. Examples of such amphoteric monomers include (3-ethyloxetane-3-yl) methyl acrylate. These active energy ray-curable compounds may be used alone or in combination.

  By mix | blending a polymerization initiator with an active energy ray hardening adhesive, the curing reaction efficiency of this adhesive can be improved. The polymerization initiator is selected according to the type of active energy ray used. Examples of the polymerization initiator include photo radical polymerization initiators such as acetophenone series, benzophenone series, thioxanthone series, benzoin series, benzoin alkyl ether series; aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metathelone compounds, benzoin Photocationic polymerization initiators such as sulfonic acid esters; and the like. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the acetophenone photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- [ 4- (2-hydroxyethyl) -phenyl] -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone and the like.

  Examples of the benzoin alkyl ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexyl phenyl ketone, and the like.

  The cationic photopolymerization initiator can effectively initiate and advance the cationic photopolymerization of the cationic photopolymerizable compound. For this reason, it is preferable that a photocationic polymerization initiator is activated by the light of wavelength 300nm or more. The cationic photopolymerization initiator may be an ionic photoacid generator or a nonionic photoacid generator.

  The ionic photoacid generator is not particularly limited. Examples of such photoacid generators include onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts; organometallic complexes such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes; tetrakis (penta And agents having a bulky counter anion such as fluorophenyl) borate. These ionic agents may be used alone or in combination of two or more.

  Examples of the ionic photoacid generator include “Adekaoptomer” series such as “Adekaoptomer SP150” and “Adekaoptomer SP170” manufactured by Asahi Denka Kogyo Co., Ltd., and a product name of General Electronics Co., Ltd. “UVE-1014”, trade name “CD-1012” manufactured by Sartomer, and trade name “Photoinitiator 2074” manufactured by Rhodia may be used.

  The nonionic photoacid generator is not particularly limited. For example, nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenolsulfonic acid ester, diazonaphthoquinone, N-hydroxyimidophosphonate and the like can be mentioned. These nonionic photoacid generators may be used alone or in combination of two or more.

  The preferable compounding quantity of a polymerization initiator is 0.5-20 mass parts of polymerization initiators with respect to 100 mass parts of active energy ray-curable compounds. The blending amount is preferably 1 part by mass or more, and preferably 10 parts by mass or less. When the active energy ray-curable compound is an epoxy resin, the adhesive can be sufficiently cured when the blending amount is 0.5 parts by mass or more. For this reason, the mechanical strength of a laminated body and the adhesiveness between a laminated body and a to-be-adhered body can be improved. Moreover, when the polymerization initiator is ionic, the content of the ionic substance is increased in the adhesive after curing because the blending amount is 20 parts by mass or less, and the durability of the adhesive is increased. The decline in sex can be suppressed.

  The adherend is a three-dimensional object having an arbitrary structure having a functional layer such as a film or a sheet, a flat surface, or a curved surface. Examples of the functional layer include a hard coat, an antiglare layer, an antireflection layer, and a combination of these. The method for producing the functional layer is not limited, and for example, it can be produced by a known method such as a method of forming a layer by curing with heat or ionizing radiation, or a method of depositing or sputtering a metal or metal oxide.

<Polarizer protective film, polarizing plate>
A suitable example of the molded article of the present invention is a polarizing plate. The laminated body in this case is a polarizer protective film, and the polarizer is an adherend. As a suitable example of the adherend, a display device-related member such as a front plate or a retardation film having a polarizer is also suitable. Furthermore, the laminate is also suitable for, for example, a decorative film, a metallic decorative film, a hard coat film, or an antiglare film. Preferable examples of the molded article of the present invention include sashes, entrance doors, kitchen doors, vehicle interior and exterior panels, and solar panels.

  According to the laminate of the present invention, in the adhesive adhesion auxiliary layer that functions as an easy-adhesion layer, by building a crosslinked structure with a carboxy group and an epoxy group, the durability of the laminate is enhanced and the adherend is bonded. The laminated body which can implement | achieve the outstanding adhesiveness at the time and the outstanding punching workability can be provided. In addition, by bonding the base material layer and the adhesion promoting layer with a silyloxy group, the adhesive force between the adhesion promoting layer and the substrate can be effectively increased, and the durability of the laminate can be further enhanced.

  Further, by forming a cross-linked structure in the adhesion promoting layer and forming a bond with the substrate, it is possible to suppress a decrease in the anchor effect with the adherend to the adhesion promoting layer. As a result, the adhesive force between the laminate and the adherend can be increased, and the punching processability of the molded body can be improved. That is, by using the laminate of the present invention, it is possible to provide a laminate having both durability, punching workability and adhesiveness.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to the following Example. The physical property values and the like were measured by the following method.

The compounds used in the examples are shown below.
Ultraviolet absorber [U-1]: manufactured by ADEKA Corporation; trade name LA-31
Ultraviolet absorber [U-2]: manufactured by ADEKA Corporation; trade name LA-F70
Polycarbonate resin: Sumitomo Chemical scan Tyrone polycarbonate Co., Ltd., trade name Caliber 301-40 (temperature 300 ℃, MVR is 40cm ^3/10 minutes in load 1.2kg)
Phenoxy resin: manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; trade name YP-50S
Polymer processing aid: Rohm and Haas Japan Co., Ltd .; Paraloid K125P
Silane coupling agent [A-1]: manufactured by Toray Dow Corning Co., Ltd .; trade name Z-6040 (3-glycidoxypropyltrimethoxysilane)
Silane coupling agent [A-2]: manufactured by Toray Dow Corning Co., Ltd .; trade name Z-6044 (3-glycidoxypropylmethyldimethoxysilane)
Silane coupling agent [A-3]: manufactured by Toray Dow Corning Co., Ltd .; trade name Z-6043 (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane)
Silane coupling agent [A-4]: manufactured by Toray Dow Corning Co., Ltd .; trade name Z-6030 (3-methacryloxypropyltrimethoxysilane)
Carboxylic acid-modified resin [B-1]: manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; trade name Superflex 210 (non-volatile 35% aqueous dispersion)
Carboxylic acid modified resin [B-2]: manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; trade name Superflex 460 (non-volatile content 38% aqueous dispersion)
Carboxylic acid modified resin [B-3]: manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; trade name Superflex 870 (non-volatile content 30% aqueous dispersion)

(Polymerization conversion)
A gas chromatograph (manufactured by Shimadzu Corporation; GC-14A) is connected to a column (GL ScIcens Inc .; InertCap 1 (df = 0.4 μm, 0.25 mm ID × 60 m)), and the injection temperature is 180 ° C. In addition, the measurement was performed under the condition that the detector temperature was 180 ° C., the column temperature was increased from 60 ° C. (held for 5 minutes) to 200 ° C. at a rate of temperature increase of 10 ° C./minute, and held for 10 minutes. The polymerization conversion was calculated.

(Measurement of chromatogram by GPC and determination of molecular weight distribution based on chromatogram)
A 5 mL tetrahydrofuran solution containing 4 mg of the resin material to be tested was filtered through a 0.1 μm filter to prepare a test solution.
A GPC device (manufactured by Tosoh Corporation; HLC-8320) having two detectors as a differential refractive index detector and two columns (manufactured by Tosoh Corporation; TSKgel SuperMultiIpore HZM-M) and one column (manufactured by Tosoh Corporation; Super HZ4000) Were connected in series, tetrahydrofuran as an eluent was allowed to flow at a flow rate of 0.35 mL / min, the column temperature was set to 40 ° C., 20 μL of the test solution was injected, and the chromatogram was measured.
A calibration curve was prepared using data of 10 standard polystyrene points. A standard polystyrene having a molecular weight in the range of 400 to 5,000,000 was measured by gel permeation chromatography, and a calibration curve showing the relationship between retention time and molecular weight was prepared. The baseline connecting the point where the slope on the high molecular weight side of the chromatogram changes from zero to positive and the point where the slope of the peak on the low molecular weight side changes from negative to zero was taken as the baseline. If the chromatogram shows multiple peaks, connect the line connecting the point where the slope of the highest molecular weight peak changes from zero to positive and the point where the slope of the lowest molecular weight peak changes from negative to zero. Baseline.
The molecular weight was the weight average molecular weight, and the weight average molecular weight / number average molecular weight was the molecular weight distribution.

(Syndiotacticity (rr) in triplet display)
¹ H-NMR measurement was performed on the resin sample. The area (X) of the region of 0.60 to 0.95 ppm and the area (Y) of the region of 0.60 to 1.35 ppm when TMS was set to 0 ppm were measured, and the formula: (X / Y) × 100 The value calculated in this way was defined as syndiotacticity (rr) (%) in triplet display.
Equipment: Nuclear magnetic resonance equipment (Bruker ULTRA SHIELD 400 PLUS)
Solvent: Deuterated chloroform Measurement nuclide: ¹ H
Measurement temperature: 20 ° C
Integration count: 64 times

(Glass transition temperature (Tg))
In accordance with JIS K7121, the resin material to be tested was heated up to 150 ° C. at 10 ° C./min (first time) using a differential scanning calorimeter (manufactured by Shimadzu Corporation; DSC-50), and then In the DSC curve obtained by cooling to 20 ° C. and then increasing the temperature from 20 ° C. to 200 ° C. at a rate of 10 ° C./min (second time), the glass transition temperature obtained from the second temperature increase result is the glass transition temperature. Defined as temperature.

(Average particle diameter of graft copolymer)
The resin material was diluted 500 times with water, dropped on a glass preparation with a dropper, and then water was evaporated. After platinum palladium was vapor-deposited on such a preparation, it was observed using a reflection electron microscope (manufactured by JEOL Ltd .; JSM-7600F), and the average particle diameter of 10 graft copolymers was defined as the average particle diameter.

(Haze)
Based on JIS K7136, the haze was measured using a haze / transmittance meter (manufactured by Murakami Color Research Laboratory; HM-150).

(Total light transmittance)
Based on JIS K7361-1, the total light transmittance was measured using a haze / transmittance meter (manufactured by Murakami Color Research Laboratory; HM-150).

(Amount of unit epoxy group substance of silane coupling agent (A))
Epoxy equivalent EE (g / equivalent) was calculated based on JIS K7236, and the amount of epoxy group substance (unit epoxy group substance amount) contained in 1 g of silane coupling agent (A) was determined by the following formula.
Unit epoxy group substance amount (mmol / g) = 1000 / EE

(Unit carboxy group substance amount of carboxylic acid-modified resin (B))
The dispersion liquid of the carboxylic acid-modified resin (B) is dried to remove the amine as a cap agent, 1.0 g of the obtained sample is dissolved in 10 g of methyl ethyl ketone, and a mixed solvent of toluene and methanol (toluene: methanol = 7 : 3) After adding to 40 mL, neutralization titration was performed using a methanol solution of 0.1 mol / L normal potassium hydroxide and phenolphthalein to obtain an acid value (mgKOH / g). ) To determine the amount of carboxy group substances (unit carboxy group substance amount) contained in 1 g of the carboxylic acid-modified resin (B).
Unit carboxy group substance amount = acid value / 56.1
However, the unit of the amount of the unit carboxy group substance is mmol / g, and the unit of oxidation is mgKOH / g.

(Ratio of substance amount of epoxy group and carboxy group in resin composition (P))
The substance amount ratio of the epoxy group and the carboxy group in the resin composition (P) depends on the compounding amount of the silane coupling agent (A) and the carboxylic acid-modified resin (B) in the resin composition (P). Multiply the substance amount (mmol / g) or unit carboxy group substance amount (mmol / g) to calculate the epoxy group substance amount (a (mmol)) and the carboxy group substance amount (b (mmol)), and a and b The ratio a / b was determined.

(Adhesive adhesion auxiliary layer film formability)
The film formability when the resin composition (P) was applied to the substrate was evaluated as follows.
A ⁺ : The resin composition (P) spread uniformly and a coating film was formed.
B: The resin composition (P) did not spread and a coating film could not be formed.

(Punching workability)
A Thomson blade (dumbbell made; SSK-1000-D) with both teeth of 40 mm x 40 mm is attached to an SD-type lever type sample cutter (made by dumbbell; SDL-200), and a punching test is performed with a molded body of 100 mm x 100 mm. The fracture surface was observed and evaluated as follows.
A ⁺ : Good (no chipping, cracking or peeling).
A: Slight chipping, cracking or peeling occurs.
B: Clear chipping, cracking or peeling occurs.

(Adhesive strength)
The molded body was cut into a size of 150 mm × 25 mm, a slight cut was made in the adhesive part in the molded body, and the base material in the molded body was attached to a stainless steel test plate with a double-sided tape. A test plate according to a small tabletop testing machine (manufactured by Shimadzu Corporation; EZ-SX) is fixed, and the adherend side of the notched molded body is sandwiched between film chucks, under the conditions of a load cell 100N and a tensile speed of 300 mm / min. The laminate of the molded body and the adherend were peeled off, and a 90 ° peel test between the laminate and the adherend was performed. The measurement value was not taken into consideration until the first 25 mm peeled after the start of measurement, and the stress during the subsequent 25 mm peeling was averaged to obtain the adhesive force (unit: gf / 25 mm).
In addition, it was described as “material breakage” when the adhesive strength was strong, the laminate or the adherend was destroyed, and the accurate stress could not be measured. In this case, the adhesive force was 1,000 gf / 25 mm or more.

(durability)
The molded body was cut into a size of 100 mm × 100 mm, and left to stand in an environment of 85 ° C. and 85% RH for 500 hours using a small environmental tester (manufactured by ESPEC Corporation; SH-241), and the appearance was observed. The evaluation was as follows.
A ⁺ : Good with no occurrence of peeling or the like.
B: Peeling occurs at the end, which is defective.

(Production Example 1) (Production of methacrylic resin [M-1])
The inside of the autoclave equipped with the stirrer and the sampling tube was replaced with nitrogen. To this, 100 parts by mass of purified methyl methacrylate, 0.002 parts by mass of 2,2′-azobis (2-methylpropionitrile (hydrogen abstraction ability: 1%, 1 hour half-life temperature: 83 ° C.), and n -0.203 parts by mass of octyl mercaptan was added and stirred to obtain a raw material liquid, and nitrogen was fed into the raw material liquid to remove dissolved oxygen in the raw material liquid.
The raw material liquid was put to 2/3 of the capacity in a tank reactor connected to the autoclave by piping. First, the polymerization reaction was started in a batch mode while maintaining the temperature at 140 ° C. When the polymerization conversion rate reaches 55%, the raw material liquid is supplied from the autoclave to the tank reactor at a flow rate of an average residence time of 150 minutes, and the reaction liquid is reacted at a flow rate corresponding to the supply flow rate of the raw material liquid. It was extracted from the vessel, the temperature was maintained at 140 ° C., and the polymerization reaction was switched to a continuous flow type polymerization reaction. After switching, the polymerization conversion in the steady state was 48%.
The reaction liquid withdrawn from the tank reactor in a steady state was heated by supplying it to a multi-tubular heat exchanger having an internal temperature of 230 ° C. at a flow rate with an average residence time of 2 minutes. Next, the heated reaction solution was introduced into a flash evaporator, and volatile components mainly composed of unreacted monomers were removed to obtain a molten resin. The molten resin from which volatile components have been removed is supplied to a twin-screw extruder having an internal temperature of 260 ° C., discharged into a strand, cut with a pelletizer, Mw is 101,000, molecular weight distribution is 1.87, and syndiotactic A pellet of methacrylic resin [M-1] having a city (rr) of 52%, a glass transition temperature of 120 ° C., and a content of a structural unit derived from methyl methacrylate of 100% by mass was obtained.

(Production Example 2) (Production of methacrylic resin [M-2])
The inside of the autoclave equipped with the stirrer and the sampling tube was replaced with nitrogen. 100 parts by mass of purified methyl methacrylate, 0.002 parts by mass of 2,2′-azobis (2-methylpropionitrile (hydrogen abstraction ability: 1%, 1 hour half-life temperature: 83 ° C.), and n- 0.28 parts by mass of octyl mercaptan was added and stirred to obtain a raw material liquid, and nitrogen was fed into the raw material liquid to remove dissolved oxygen in the raw material liquid.
The raw material liquid was put to 2/3 of the capacity in a tank reactor connected to the autoclave by piping. First, the polymerization reaction was started in a batch mode while maintaining the temperature at 140 ° C. When the polymerization conversion rate becomes 55%, the flow rate becomes an average residence time of 150 minutes, the raw material liquid is supplied from the autoclave to the tank reactor, and the reaction liquid is reacted at the flow rate corresponding to the supply flow rate of the raw material liquid. It was extracted from the vessel, the temperature was maintained at 140 ° C., and the polymerization reaction was switched to a continuous flow type polymerization reaction. After switching, the polymerization conversion in the steady state was 52%.
The reaction liquid withdrawn from the tank reactor in a steady state was heated by supplying it to a multi-tubular heat exchanger having an internal temperature of 230 ° C. at a flow rate with an average residence time of 2 minutes. Next, the heated reaction solution was introduced into a flash evaporator, and volatile components mainly composed of unreacted monomers were removed to obtain a molten resin. The molten resin from which volatile components have been removed is supplied to a twin-screw extruder having an internal temperature of 260 ° C., discharged into a strand, cut with a pelletizer, Mw is 82,000, molecular weight distribution is 1.92, and syndiotactic A pellet of methacrylic resin [M-2] having a city (rr) of 51%, a glass transition temperature of 120 ° C., and a content of structural units derived from methyl methacrylate of 100% by mass was obtained.

(Production Example 3) (Production of methacrylic resin [M-3])
First, the inside of a 5 L glass reaction vessel equipped with a stirring blade and a three-way cock was replaced with nitrogen. To this, at 20 ° C., toluene 1600 g, 1,1,4,7,10,10-hexamethyltriethylenetetramine 2.49 g (10.8 mmol), 0.45 M isobutyl bis (2,6-dioxy) 5. 53.5 g (30.9 mmol) of a toluene solution of tert-butyl-4-methylphenoxy) aluminum and a solution of sec-butyllithium having a concentration of 1.3 M (solvent: cyclohexane 95%, n-hexane 5%) 17 g (10.3 mmol) was charged. While stirring, 550 g of methyl methacrylate distilled and purified was added dropwise at 20 ° C. over 30 minutes. After completion of dropping, the mixture was stirred at 20 ° C. for 90 minutes. At this time, the polymerization conversion rate of methyl methacrylate was 100%.
The resulting solution was diluted by adding 1,500 g of toluene. Next, the diluted solution was poured into 100 kg of methanol to obtain a precipitate. The obtained precipitate was dried at 80 ° C. and 140 Pa for 24 hours, Mw was 81,400, molecular weight distribution was 1.08, syndiotacticity (rr) was 73%, glass transition temperature was 131 ° C., and A methacrylic resin [M-3 ′] having a content of structural units derived from methyl methacrylate of 100% by mass was obtained.
Next, the inside of the autoclave equipped with the stirrer and the sampling tube was replaced with nitrogen. To this, 100 parts by mass of purified methyl methacrylate, 0.002 parts by mass of 2,2′-azobis (2-methylpropionitrile (hydrogen abstraction capacity: 1%, 1 hour half-life temperature: 83 ° C.), and n -0.225 parts by mass of octyl mercaptan was added and stirred to obtain a raw material liquid, and nitrogen was fed into the raw material liquid to remove dissolved oxygen in the raw material liquid.
The raw material liquid was put to 2/3 of the capacity in a tank reactor connected to the autoclave by piping. First, the polymerization reaction was started in a batch mode while maintaining the temperature at 140 ° C. When the polymerization conversion rate reaches 55%, the raw material liquid is supplied from the autoclave to the tank reactor at a flow rate of an average residence time of 150 minutes, and the reaction liquid is supplied to the tank at a flow rate corresponding to the supply flow rate of the raw material liquid. The reactor was extracted from the mold reactor and the temperature was maintained at 140 ° C., and the polymerization reaction was switched to a continuous flow polymerization reaction. After switching, the polymerization conversion in the steady state was 55%.
The reaction liquid withdrawn from the tank reactor in a steady state was heated by supplying it to a multi-tubular heat exchanger having an internal temperature of 230 ° C. at a flow rate with an average residence time of 2 minutes. Next, the heated reaction solution was introduced into a flash evaporator, and volatile components mainly composed of unreacted monomers were removed to obtain a molten resin. The molten resin from which volatile components have been removed is supplied to a twin-screw extruder having an internal temperature of 260 ° C., discharged into a strand, cut with a pelletizer, Mw of 103,600, molecular weight distribution of 1.81, and syndiotacticity A pellet of methacrylic resin [M-3 ″] having a city (rr) of 52%, a glass transition temperature of 120 ° C., and a content of structural units derived from methyl methacrylate of 100% by mass was obtained.
57 parts by mass of methacrylic resin [M-3 ′] and 43 parts by mass of methacrylic resin [M-3 ″] are mixed, and a twin-screw extruder (manufactured by Technobel Co., Ltd .; KZW20TW-45MG-NH-600) is used. And kneaded and extruded at 250 ° C. to produce a methacrylic resin [M-3].

(Production Example 4) (Production of methacrylic resin [M-4])
A twin screw extruder (manufactured by Technobel Co., Ltd .; KZW20TW-45MG-NH-600) equipped with a screw having a kneading block and a reverse flight and a nozzle is set at a screw rotation speed of 120 rpm and a temperature of 250 ° C. A methacrylic resin [M-1] was supplied from a hopper at 2 kg / hr, and 2 parts by mass of monomethylamine (Mitsubishi Gas Chemical Co., Ltd.) was injected from a nozzle with respect to 100 parts by mass of the resin. By-products and excess monomethylamine after the reaction were discharged from a vent port whose pressure was reduced to 20 Torr. The resin discharged in a strand form from a die provided at the exit of the extruder was cooled in a water tank and then pelletized with a pelletizer to obtain a methacrylic resin [M-4 ′].
Next, a twin screw extruder of the same type as the twin screw extruder is set to a screw rotation speed of 100 rpm and a temperature of 230 ° C., and a methacrylic resin [M-4 ′] is supplied from the hopper at 1 kg / hr, and the resin is 100 mass. A mixed solution of 0.8 parts by mass of dimethyl carbonate and 0.2 parts by mass of triethylamine was injected from a nozzle. The by-product after reaction and excess dimethyl carbonate were discharged from the vent port whose pressure was reduced to 20 Torr. The resin discharged in the form of a strand from the die provided at the outlet of the extruder is cooled in a water tank, then pelletized with a pelletizer, and a methacrylic resin [M-4 "having an acid value smaller than that of the methacrylic resin [M-4 '] ] Was obtained.
Furthermore, a twin-screw extruder of the same type as the twin-screw extruder is set at a screw rotation speed of 100 rpm and a temperature of 230 ° C., and methacrylic resin [M-4 ”] is supplied at 1 kg / hr, and the pressure at the vent port is set. Volatile components including unreacted auxiliary materials were removed by setting to 20 Torr, by cooling the resin discharged in a strand form from a die provided at the exit of the extruder in a water tank, and then pelletizing with a pelletizer, A methacrylic resin [M-4] was obtained.
The methacrylic resin [M-4] had an imidization ratio of 3.6 mol%, Mw of 82,000, Mw / Mn of 1.95, a glass transition temperature of 124 ° C., and an acid value of 0.27 mmol / g. It was.

(Production Example 5) (Production of methacrylic resin [M-5])
A methacrylic resin [M-5] was obtained by the same method as the method for producing the copolymer (A-1) described in the examples of WO2014 / 021264.
^{According to 13} C-NMR analysis, the methacrylic resin [M-5] is derived from methyl methacrylate, 26 mass% of structural units, 18 mass% of structural units derived from maleic anhydride having a cyclic structure, and derived from styrene. The Mw was 169,000, the molecular weight distribution was 2.47, and the Tg was 137 ° C.

Table 1 shows the contents of the structural units derived from methyl methacrylate of the methacrylic resins obtained in Production Examples 1 to 5, weight average molecular weight, molecular weight distribution, syndiotacticity, and glass transition temperature.

(Production Example 6) (Production of core-shell type graft copolymer [G-1])
In a reactor equipped with a stirrer, thermometer, nitrogen gas introduction tube, monomer introduction tube and reflux condenser, 1,050 parts by mass of ion exchange water, 1.0 part by mass of sodium polyoxyethylene tridecyl ether acetate and carbonic acid 0.7 parts by mass of sodium was charged, and the inside of the reactor was sufficiently replaced with nitrogen gas. The internal temperature was then 80 ° C. Thereto was added 0.25 part by mass of potassium persulfate, and the mixture was stirred for 5 minutes. To this, 445 parts by mass of a monomer mixture consisting of 95.4% by mass of methyl methacrylate, 4.4% by mass of methyl acrylate and 0.2% by mass of allyl methacrylate was continuously added dropwise over 60 minutes. After completion of the dropping, a polymerization reaction was further performed for 30 minutes.
Next, 0.32 parts by mass of potassium persulfate was charged into the reactor and stirred for 5 minutes. Thereafter, 115 parts by mass of a monomer mixture consisting of 80.5% by mass of butyl acrylate, 17.5% by mass of styrene and 2% by mass of allyl methacrylate was continuously dropped over 60 minutes. After completion of the dropping, a polymerization reaction was further performed for 30 minutes.
Next, 0.14 parts by mass of potassium persulfate was charged into the reactor and stirred for 5 minutes. Thereafter, 140 parts by mass of a monomer mixture consisting of 95.2% by mass of methyl methacrylate, 4.4% by mass of methyl acrylate and 0.4% by mass of n-octyl mercaptan was continuously added dropwise over 30 minutes. After completion of the dropping, a polymerization reaction was further performed for 60 minutes. Through the above operation, a latex containing crosslinked rubber particles [G-1 ′] was obtained. The latex containing the crosslinked rubber particles [G-1 ′] was frozen and coagulated, then washed with water and dried to obtain a core-shell type graft copolymer [G-1]. The average particle size of the graft copolymer [G-1] was 0.09 μm, and the acrylate content was 17%.

(Production Example 7) (Production of diblock copolymer [D-1])
Into a three-necked flask deaerated inside and purged with nitrogen, 735 kg of dry toluene, 36.75 kg of 1,2-dimethoxyethane, isobutylbis (2,6-di-tert-butyl-4-methyl) at 20 ° C. Phenoxy) 39.4 kg of toluene solution containing 20 mol of aluminum was added. To this, 1.17 mol of sec-butyllithium and 39.0 kg of methyl methacrylate were added and reacted at 20 ° C. for 1 hour to obtain a methyl methacrylate polymer [d11]. The methyl methacrylate polymer [d11] contained in the reaction solution had a weight average molecular weight Mw _d11 of 45,800.
Next, the reaction solution was brought to −25 ° C., and a mixed solution of 29.0 kg of n-butyl acrylate and 10.0 kg of benzyl acrylate was added dropwise over 0.5 hour to form a methyl methacrylate polymer block [d11] and A diblock copolymer [D-1] composed of an acrylate polymer block [d2] composed of n-butyl acrylate and benzyl acrylate was obtained. The diblock copolymer [D-1] contained in the reaction solution had a weight average molecular weight Mw _D-1 of 92,000 and a weight average molecular weight Mw _D-1 / number average molecular weight Mn _D-1 of 1.06. Therefore, the weight average molecular weight of the acrylate polymer block [d2] composed of n-butyl acrylate and benzyl acrylate was determined to be 46,200. The proportion of benzyl acrylate contained in the acrylate polymer block [d2] was 25.6% by mass.
Subsequently, 4 kg of methanol was added to the reaction solution to stop the polymerization. Thereafter, the reaction solution was poured into a large amount of methanol to precipitate the diblock copolymer [D-1], and the precipitate was filtered and dried at 80 ° C. and 1 torr (about 133 Pa) for 12 hours. The ratio of the mass of the methacrylic ester polymer block [d11] to the mass of the acrylate polymer block [d2] was 50/50.

(Production Example 8) (Production of triblock copolymer [D-2])
Into a three-necked flask deaerated inside and purged with nitrogen, 2,003 kg of dry toluene, 100.15 kg of 1,2-dimethoxyethane, and isobutylbis (2,6-di-tert-butyl-4 -Methylphenoxy) 51.5 kg of toluene solution containing 20 mol of aluminum was added. To this, 1.13 mol of sec-butyllithium and 34.3 kg of methyl methacrylate were added and reacted at 20 ° C. for 1 hour to obtain a methyl methacrylate polymer block [d11]. The weight average molecular weight Mw _d11 of the methyl methacrylate polymer block [d11] contained in the reaction solution was 6,000.
Next, the reaction solution was brought to −30 ° C., 266.3 kg of n-butyl acrylate was added dropwise over 0.5 hour, and an acrylic ester polymer consisting of a methyl methacrylate polymer block [d11] and n-butyl acrylate was added. A diblock copolymer consisting of the combined block [d2] was obtained. Since the weight average molecular weight of the diblock polymer contained in the reaction solution was 53,000, the weight average molecular weight of the acrylate polymer block [d2] composed of n-butyl acrylate was determined to be 47,000. The proportion of benzyl acrylate contained in the acrylate polymer [d2] was 0% by mass.
Subsequently, 297.3 kg of methyl methacrylate was added, the reaction solution was returned to 20 ° C., and stirred for 8 hours, whereby an acrylic ester ester consisting of a methyl methacrylate polymer block [d11] and n-butyl acrylate was added. A triblock copolymer [D-2] consisting of a combined block [d2] and a methyl methacrylate polymer block [d12] was obtained.
Thereafter, 4 kg of methanol was added to the reaction solution to stop the polymerization, and the mixture was poured into a large amount of methanol to precipitate a triblock copolymer [D-2]. The precipitate was filtered and collected at 80 ° C., 1 torr (about 133 Pa). And dried for 12 hours. Since the triblock copolymer [D-2] had a weight average molecular weight Mw _D-2 of 105,000 and Mw _D-2 / Mn _D-2 of 1.08, the methyl methacrylate polymer block [d12] Was determined to have a weight average molecular weight of 52,000. The ratio of the total mass of the methacrylic ester polymer blocks [d11] and [d12] to the mass of the acrylate polymer block [d2] was 45/55.

Table 2 shows the average molecular weight of each block of the block copolymers obtained in Production Examples 7 and 8.

(Production Example 9) (Production of methacrylic resin composition [C-1] and substrate [F-1])
76 parts by mass of methacrylic resin [M-1] obtained in Production Example 1, 1.8 parts by mass of UV absorber [U-1], core-shell type graft copolymer [G-1] 24 obtained in Production Example 6 The methacrylic resin composition [C-1] was manufactured by mixing and extruding with a twin screw extruder (manufactured by Technobel Co., Ltd .; KZW20TW-45MG-NH-600) set at 250 ° C.
The methacrylic resin composition [C-1] was hot press molded at 220 ° C. to form a plate-like substrate of 50 mm × 50 mm × 3.2 mm, and the total light transmittance, haze and glass transition temperature were measured. Table 3 shows the physical properties of the methacrylic resin composition [C-1].
After the methacrylic resin composition [C-1] was dried at 80 ° C. for 12 hours, the methacrylic resin composition [C-1] was extruded from a T-die having a width of 150 mm using a 20 mmφ single screw extruder at 260 ° C. The substrate was sandwiched between a metal rigid roll and a metal elastic roll having a surface temperature of 85 ° C. to obtain a substrate [F-1] having a width of 110 mm and a thickness of 60 μm.

(Production Example 10) (Production of methacrylic resin composition [C-2] and substrate [F-2])
In Production Example 9, a methacrylic resin composition [C-2] and a substrate [F-2] were obtained in the same manner as in Production Example 9 except that the formulation shown in Table 3 was used.

(Production Example 11) (Production of substrate [F-3])
In Production Example 9, a base material [F-3 ′] having a thickness of 160 μm was obtained in the same manner as in Production Example 9 except that the composition shown in Table 3 was used.
The base material [F-3 ′] is cut into a 100 mm × 100 mm square so that the two sides are parallel to the extrusion direction, and 10% from the glass transition temperature by a pantograph biaxial stretching tester (manufactured by Toyo Seiki Co., Ltd.). Continuous biaxial stretching in this order in the direction parallel to the extrusion direction and in the direction perpendicular to the extrusion direction under the stretching conditions of a high stretching temperature, a stretching rate of 150% / min per direction, and a stretching ratio of 2 times per direction. (4 times in area ratio), left for 10 seconds, and then rapidly cooled by taking it out in an environment of 20 ° C. to obtain a stretched base material [F-3] having a thickness of 40 μm. Table 3 shows the measurement results of the total light transmittance, light transmittance at a wavelength of 380 nm, haze, and stretchability of the obtained substrate [F-3].

(Production Examples 12 to 16)
In Production Example 11, methacrylic resin compositions [C-4] to [C-8] and base materials [F-4] to [F-8] were prepared in the same manner as in Production Example 11 except that the composition shown in Table 3 was used. Got.

Table 3 shows the blending compositions, blending amounts, and unstretched film evaluation results of Production Examples 9-16.

(Production Example 17) (Preparation of adhesive)
Acetacetyl group-containing polyvinyl alcohol resin (average polymerization degree: 1,200, saponification degree: 98.5 mol%, acetoacetyl group modification degree: 5 mol%) 100 parts by mass and 4,6-diamino-2- ( Hydroxymethylamino) hexahydro-1,3,5-triazine (20 parts by mass) was dissolved in pure water at a temperature of 30 ° C. to obtain an adhesive having a concentration of 0.5%.

Example 1
(Preparation of resin composition (P-1))
The flask was charged with 0.62 parts by mass of a silane coupling agent [A-1] and 72 parts by mass of ion-exchanged water and stirred at 20 ° C. for 4 hours. Then, carboxylic acid-modified resin [B-1] was added and stirred at 20 ° C. for 1 hour to obtain a resin composition (P-1).

(Formation of adhesive adhesion layer)
On the surface of the base material [F-1] obtained in Production Example 9, a corona with a discharge amount of 77 W / (m ² / min) using a corona surface treatment apparatus (made by Kasuga Electric, ceramic electrode, discharge distance 1 mm). A discharge treatment was performed, and the resin composition (P-1) was applied to the surface with a liquid thickness of 18.3 μm. Next, the substrate coated with the resin composition (P-1) was heated in a hot air oven set at 90 ° C. for 30 seconds, taken out from the oven, and allowed to stand at 20 ° C. for 15 minutes to obtain a laminate [J-1]. It was. The evaluation results are shown in Table 4.

(Formation of molded body)
As the adherend, a stretched film having a thickness of 60 μm in which a polyvinyl alcohol film is doped with iodine is used, and on one side, the adhesive adhesion layer is opposed to the adherend side through the adhesive obtained in Production Example 17. The laminated body was bonded together. The adhesive layer obtained in Production Example 17 was applied to the other surface of the adherend, and a saponified triacetyl cellulose film (manufactured by Fuji Photo Film Co., Ltd .; trade name Fuji Tac UV80) was bonded to the surface. And dried for 10 minutes to obtain a molded body. The obtained molded body could be used as a polarizing plate. Table 4 shows the results of evaluation of the punching workability and durability of the obtained molded body.

(Examples 2-5, Comparative Examples 1-8)
A laminate [J-2] was prepared in the same manner as in Example 1 except that the resin compositions (P-2) to (P-14) having the compositions shown in Tables 4 and 5 were prepared and an adhesive adhesion auxiliary layer was formed. ] To [J-5] and [J-13] to [J-20] and molded articles were produced. The evaluation results are shown in Tables 4 and 5.

(Examples 6 to 12)
The laminates [J-6] to [J-12] were used in the same manner as in Example 1 except that the base material shown in Table 4 was used and the temperature of the hot air oven was set to 130 ° C. in the formation of the adhesion promoting layer. And the molded object was produced. These evaluation results are shown in Table 4.

  From Tables 4 and 5, the resin composition (P) prepared in the examples of the present invention is excellent in film formability, the laminate of the present invention is excellent in adhesiveness, and the molded body having such a laminate is durable. And it was proved that it was excellent in punching workability. On the other hand, in Comparative Example 3, the resin composition (P) did not spread and a coating film could not be formed. Other Comparative Examples 1, 2, 4 to 8 had good film forming properties, but the adhesive strength was inferior to that of the Examples. Regarding punching workability, Comparative Examples 1 and 2 were good, but Comparative Examples 4 to 8 had at least one of obvious chipping, cracking and peeling.

Claims (14)

A base material mainly composed of an amorphous resin;
An adhesive adhesion layer laminated on at least one surface of the substrate,
The adhesive adhesion promoting layer is a layer obtained by heat-treating a coating film of a resin composition (P) containing a silane coupling agent (A) having an epoxy group and a carboxylic acid-modified resin (B) having a carboxy group. And
The ratio a / b of the substance amount a of the epoxy group and the substance amount b of the carboxy group in the resin composition (P) before the heat treatment is in the range of 0.5 to 5.0,
The laminated body in which the said adhesion promoter layer has the bond derived from the said epoxy group and the said carboxy group.   The laminate according to claim 1, wherein the silane coupling agent (A) has a hydrolyzable functional group.   The laminate according to claim 2, wherein the hydrolyzable functional group is an alkoxy group.   The interface according to any one of claims 1 to 3, wherein at least a part of the non-crystalline resin and the silane coupling agent (A) is bonded via a silyloxy group at the interface between the adhesive adhesion promoting layer and the substrate. The laminated body of crab.   The laminate according to any one of claims 1 to 4, wherein the amorphous resin is a methacrylic resin composition (C) containing a methacrylic resin.   The methacrylic resin is any one of (i) a resin having 80% by mass or more of a structural unit derived from a methacrylic acid ester, and (ii) a resin containing a structural unit derived from a methacrylic acid ester and a structural unit having a ring structure. The laminated body of Claim 5 which satisfy | fills either.   The laminate according to claim 5 or 6, wherein the methacrylic resin has a syndiotacticity (rr) of 58% or more.   The laminated body in any one of Claims 1-7 whose thickness of the said base material is the range of 10-80 micrometers.   The molded object formed by joining the laminated body in any one of Claims 1-8 to a to-be-adhered body.   The polarizer protective film which comprises the laminated body in any one of Claims 1-8.   A polarizing plate comprising a polarizer and the laminate according to claim 1.   The polarizing plate according to claim 11, wherein the polarizer and the adhesion promoting layer of the laminate are bonded via a polyvinyl alcohol-based adhesive layer. Preparing a resin composition (P) comprising a silane coupling agent (A) having an epoxy group and a carboxylic acid-modified resin (B) having a carboxy group;
Applying the resin composition (P) to at least one surface of a base material mainly composed of an amorphous resin to obtain a coating film;
A heat treatment step of heating the coating film,
The resin composition (P) has a ratio a / b between the substance amount a of the epoxy group and the substance amount b of the carboxy group of 0.5 to 5.0 before the heat treatment step,
The manufacturing method of the laminated body which adds and reacts the said epoxy group and the said carboxy group by the said heat processing process, and forms a chemical bond.   The manufacturing method of the laminated body of Claim 13 which forms a silyloxy group in at least one part of the said non-crystalline resin and the said silane coupling agent (A) in the interface of the said adhesive adhesion auxiliary layer and the said base material. .