JP2018119054A - Dispersion liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a dispersion liquid which has excellent antiblocking property and transparency, has excellent adhesion to an active energy ray-curable resin, and further can form a layer which is hardly whitened even when laminated with an active energy ray-curable resin; a laminated body having a layer comprising the liquid dispersion; and a molded body using the same.SOLUTION: Provided is a liquid dispersion containing, as solid components, 0.1 to 10 pts. mass of a multilayer structure polymer relative to 100 pts. mass of a water dispersible resin, where the multilayer structure polymer has an elastomer layer and an outer layer which covers the elastomer layer, where the elastomer layer contains a crosslinked rubber polymer component (I) and the outer layer a rigid polymer component (II) which graft bonded to the crosslinked rubber component (I), and where a ratio (Da/De) of a median size Da of the multilayer structure polymer in acetone and a median size De of the multilayer structure polymer in water satisfies the following formula (1): 1.2<(Da/De)≤2.5 (1). Also provided are: a laminated body having a layer comprising the liquid dispersion; and a molded body using the same.SELECTED DRAWING: None

Description

  The present invention relates to a dispersion in which a solid content is dispersed in a dispersion medium, a laminate having a layer made of the dispersion, and a molded body using the same.

When a film made of a thermoplastic resin or a laminate having a functional layer on the surface of the film has a large surface frictional resistance, the film is stuck (blocking) when the films are stacked or rolled up. By doing so, winding wrinkles are generated, and when the film is unwound from the film roll, damage or breakage occurs.
Therefore, as a method of reducing the frictional resistance on the surface of the film, a method of blending an anti-blocking agent with the resin of the film raw material, or a method of blending an anti-blocking agent into the functional layer to form an anti-blocking layer is performed. As the anti-blocking agent, inorganic fine particles, organic fine particles, organic-inorganic composite fine particles, and the like have been proposed (for example, Patent Document 1, Patent Document 2, etc.).

  Furthermore, in optical applications where high transparency is required, various anti-blocking agents have been proposed to achieve both anti-blocking performance and transparency. For example, a (meth) acryl obtained by subjecting a polymerizable monomer having a (meth) acrylic monomer as a main component to suspension polymerization in the presence of a water-insoluble compound having a specific functional group. (Patent Document 3) using a resin-based resin fine particle, a method of blending colloidal silica of 10 to 200 nm into an easy-adhesion layer (Patent Document 4), an average primary particle diameter exceeding 200 nm, and a particle size distribution of 1.0 to 1.4 And a method using two or more kinds of fine particles having different average particle diameters (Patent Document 5).

JP 59-171623 A JP 2004-75995 A Japanese Patent Laid-Open No. 06-73106 JP 2010-55062 A JP 2012-32768 A Special table 2014-525848 gazette

On the other hand, when a film or a functional layer containing the above-mentioned anti-blocking agent is laminated with an adhesive layer or a further functional layer, the adhesion may be lowered. Further, as an optical application, further improvement in transparency is required. Furthermore, the inventors have intensively studied, and when using a part of the anti-blocking agent, it becomes clear that when the active energy ray-curable resin is laminated, the film and the functional layer are whitened and the optical performance is lowered. It was.
The present invention provides a dispersion capable of forming a layer that is excellent in antiblocking properties and transparency, is excellent in adhesion to an active energy ray-curable resin, and is not easily whitened even when laminated with an active energy ray-curable resin, It aims at providing the laminated body which has a layer which consists of a dispersion liquid, and a molded object using the same.

  As a result of intensive studies, the inventors of the present invention have obtained a dispersion containing a multilayer structure polymer having an elastic layer and an outer layer covering the elastic layer, and the elastic layer is a specific monomer. A cross-linked rubber polymer component having a unit, and the outer layer includes a hard polymer component having a specific monomer unit and graft-bonded to the cross-linked rubber polymer component. It was found that the above problem can be solved by satisfying a specific relationship between the ratio of the median diameter in water and the median diameter in water, and the present invention was completed through further studies based on the findings.

That is, the present invention relates to the following [1] to [17].
[1] A dispersion in which a solid content is dispersed in a dispersion medium,
The solid content includes 100 parts by mass of a water-dispersible resin and 0.1 to 10 parts by mass of a multilayer structure polymer,
The multilayer structure polymer has an elastic body layer and an outer layer covering the elastic body layer,
The elastic body layer is at least one monomer unit selected from the group consisting of units derived from an alkyl acrylate ester having an alkyl group having 1 to 8 carbon atoms and units derived from a conjugated diene monomer ( I-1) containing a crosslinked rubber polymer component (I) having 50% by mass or more,
The outer layer has 75 mass% or more of units derived from methyl methacrylate, and includes a hard polymer component (II) graft-bonded to the crosslinked rubber polymer component (I),
The ratio (Da / De) between the median diameter Da of the multilayer structure polymer in acetone and the median diameter De of the multilayer structure polymer in water measured by a laser diffraction scattering method satisfies the following formula (1). Dispersion.
1.2 <(Da / De) ≦ 2.5 (1)
[2] The dispersion according to [1], wherein the median diameter De is 50 to 350 nm.
[3] The dispersion according to [1] or [2], wherein the ratio of the hard polymer component (II) in the multilayer polymer is 10 to 25% by mass.
[4] The above [1] to [3], wherein the hard polymer component (II) has 80 to 97% by mass of units derived from methyl methacrylate and 3 to 20% by mass of units derived from an acrylate ester. Any dispersion.
[5] The dispersion liquid according to any one of [1] to [4], wherein the crosslinked rubber polymer component (I) further has a unit derived from an aromatic compound.
[6] The dispersion according to any one of [1] to [5], wherein the crosslinked rubber polymer component (I) further includes 1 to 3.5% by mass of a unit derived from a polyfunctional monomer.
[7] The dispersion according to any one of [1] to [6], wherein the hard polymer component (II) further has a unit derived from an aromatic compound.
[8] The above-mentioned [1] to [1], wherein a graft ratio defined by a mass ratio of the hard polymer component (II) grafted to the crosslinked rubber polymer component (I) is 11 to 33% by mass. 7].
[9] The dispersion according to any one of [1] to [8], wherein the number average value of the formula weight of the hard polymer component (II) is 15,000 to 60,000.
[10] The multilayer structure polymer further has an inner layer inside the elastic body layer,
The dispersion liquid according to any one of the above [1] to [9], wherein the inner layer contains a polymer component (i) having 50% by mass or more of units derived from an alkyl methacrylate.
[11] The dispersion according to any one of [1] to [10], including 1 to 20 parts by mass of the solid content with respect to 100 parts by mass of the dispersion.
[12] The dispersion according to any one of [1] to [11], which is a dispersion for an anti-blocking layer.
[13] A laminate having an antiblocking layer made of the dispersion of [12] on at least one surface of a base material made of a thermoplastic resin.
[14] The laminate according to [13], wherein the thermoplastic resin is a (meth) acrylic resin.
[15] The laminate according to [13] or [14], which has an active energy ray-curable resin layer on one side of the anti-blocking layer.
[16] A molded product obtained by bonding the laminate to the adherend via the active energy ray-curable resin layer of the laminate of [15].
[17] The molded body according to [16], wherein the adherend is a polarizer and the molded body is a polarizing plate.

  According to the present invention, the dispersion liquid is excellent in antiblocking property and transparency, has excellent adhesion to the active energy ray curable resin, and can form a layer that is not easily whitened even when laminated with the active energy ray curable resin. A laminate having a layer made of the dispersion, and a molded body using the laminate can be provided.

It is a schematic diagram which shows an example of the multilayer structure polymer which concerns on this invention. It is an example of the photograph which observed the cross section of the laminated body which has an antiblocking layer which consists of a dispersion liquid of this invention with the reflection electron microscope.

  Hereinafter, an example of an embodiment to which the present invention is applied will be described. The numerical value specified in this specification is a value obtained by the method disclosed in the embodiment or the example. 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.

[Dispersion]
The dispersion of the present invention is a dispersion in which a solid content is dispersed in a dispersion medium, and the solid content includes 100 parts by mass of a water-dispersible resin and 0.1 to 10 parts by mass of a multilayer structure polymer. The multilayer structure polymer has an elastic body layer and an outer layer covering the elastic body layer, and the elastic body layer is derived from an acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms. And a crosslinked rubber polymer component (I) having 50% by mass or more of at least one monomer unit (I-1) selected from the group consisting of units derived from conjugated diene monomers, the outer layer comprising In the acetone, which contains a hard polymer component (II) having a unit derived from methyl methacrylate of 75% by mass or more and graft-bonded to the crosslinked rubber polymer component (I), measured by a laser diffraction scattering method The median diameter Da of the multilayer structure polymer (hereinafter referred to as the median diameter Da) The ratio (Da / De) of the multilayer polymer in water (simply referred to as “median diameter Da”) to the median diameter De (hereinafter also simply referred to as “median diameter De”) in water satisfies the following formula (1). .
1.2 <(Da / De) ≦ 2.5 (1)
In this specification, the active energy ray-curable resin for hard coat and the composition thereof, the resin for adhesive and the composition thereof are referred to as “active energy ray-curable resin”. The “adhesiveness between the active energy ray-curable hard coat resin and its composition and the adhesive resin and its composition and the anti-blocking layer” is also simply referred to as “adhesiveness”.
In the present specification, a unit derived from a specific monomer is also simply referred to as a “specific monomer unit”.

The dispersion liquid of the present invention has the above-described configuration, so that it has excellent antiblocking properties and transparency, excellent adhesion to the active energy ray curable resin, and is white even when laminated with the active energy ray curable resin. The effect of the present invention that a layer that is difficult to be formed can be formed is obtained.
Although the reason why such an effect is obtained is not clear, it is presumed as follows.
The dispersion of the present invention includes an elastic layer containing a crosslinked rubber polymer component having a specific monomer unit, and a hard polymer having a specific monomer unit and graft-bonded to the crosslinked rubber polymer component. By including a multilayer structure polymer having an outer layer containing a component, the frictional resistance of the surface is reduced, the anti-blocking property is improved, and the transparency is also excellent.
In addition, when the active energy ray-curable resin is applied as a hard coat or adhesive by setting the ratio of the median diameter in acetone of the multilayer structure polymer to the median diameter in water within a specific range, the active energy ray-curable type is applied. The resin component easily penetrates into the multilayer structure polymer contained in the dispersion, and whitening is also suppressed. It is considered that the anchor effect is produced by irradiating and curing the active energy ray, and strong adhesion is exhibited.

<Multilayer structure polymer>
(Elastic layer)
The multilayer structure polymer according to the present invention has a multilayer particle structure having an elastic body layer and an outer layer covering the elastic body layer. As such a multilayer particle structure, for example, what is shown as a schematic diagram in FIG.
The elastic layer is composed of at least one monomer unit (I-1) selected from the group consisting of an alkyl acrylate ester unit having an alkyl group having 1 to 8 carbon atoms and a conjugated diene monomer unit (hereinafter, It includes a crosslinked rubber polymer component (I) having 50% by mass or more of simply called “monomer unit (I-1)”.
Examples of the crosslinked rubber polymer component (I) include homopolymers of acrylic acid alkyl esters, copolymers having 50% by mass or more of alkyl acrylate units and 50% by mass or less of monomer units other than alkyl acrylate esters. And a homopolymer of a conjugated diene monomer, a copolymer having 50% by mass or more of a conjugated diene monomer unit, and the like. Examples of the copolymer having 50% by mass or more of conjugated diene monomer units include, for example, rubber particles described in JP-A-10-182755, and acrylic graft copolymer described in JP-A-62-151415. Etc. Among these, from the viewpoint of transparency, a copolymer having 50% by mass or more of an alkyl acrylate unit and 50% by mass or less of a monomer unit other than the alkyl acrylate ester is preferable.
The content of the monomer unit (I-1) in the crosslinked rubber polymer component (I) is preferably 60 to 99% by mass, more preferably 70 to 95% by mass, and still more preferably from the viewpoint of adhesion. 80 to 90% by mass.

  As the alkyl acrylate ester, those having 1 to 8 carbon atoms in the alkyl group are used, and those having 4 to 8 carbon atoms are preferred. Specifically, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, etc. Is mentioned. Among these, n-butyl acrylate and 2-ethylhexyl acrylate are preferable, and n-butyl acrylate is more preferable.

The crosslinked rubber polymer component (I) has a crosslinked structure. Such a crosslinked structure may be formed by electron beam irradiation or may be formed by using a polyfunctional monomer as the monomer of the crosslinked rubber polymer component (I). Is preferably used. Thereby, the crosslinked rubber polymer component (I) has a unit derived from a polyfunctional monomer, forms a crosslinked structure and a graft bond in the multilayer structure polymer, and improves blocking prevention and adhesion.
Such polyfunctional monomers include alkenyl esters of unsaturated carboxylic acids such as allyl (meth) acrylate and methallyl (meth) acrylate; dialkenyl esters of dibasic acids such as diallyl maleate; alkylene glycol di (meth) ) Unsaturated carboxylic acid diesters of glycols such as acrylate. Among these, alkenyl ester of unsaturated carboxylic acid is preferable, allyl (meth) acrylate is more preferable, and allyl methacrylate is more preferable. The content of the polyfunctional monomer unit in the crosslinked rubber polymer component (I) is preferably 1% by mass or more, more preferably 1.5% by mass or more, and still more preferably, from the viewpoint of antiblocking properties and adhesion. Is 2% by mass or more, preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 3.5% by mass or less, particularly preferably 3% by mass or less, and most preferably 2.8% by mass or less. It is. Regarding the combination of these upper and lower limits, the polyfunctional monomer unit in the crosslinked rubber polymer component (I) is particularly easy because it is easy to prepare a dispersion having the target ratio (Da / De). The content of is preferably 1 to 3.5% by mass, more preferably 1.5 to 3% by mass, and still more preferably 2 to 2.8% by mass.
In the present specification, “(meth) acryl” means “acryl or methacryl”, and “(meth) acrylate” means “acrylate or methacrylate”.

Moreover, it is preferable that crosslinked rubber polymer component (I) contains the unit derived from monomers other than the acrylic acid alkylester and a polyfunctional monomer. Examples of such monomers include methacrylic acid alkyl esters such as methyl methacrylate and ethyl methacrylate; aromatic group-containing (meth) acrylic esters such as benzyl (meth) acrylate and phenyl (meth) acrylate; styrene, alkyl Examples thereof include styrene monomers such as styrene; unsaturated nitriles such as acrylonitrile and methacrylonitrile.
In view of adjusting the refractive index, the crosslinked rubber polymer component (I) preferably further has a unit derived from an aromatic compound in addition to the monomer unit (I-1). As the aromatic compound, the above-mentioned styrene monomer; the above-mentioned aromatic group-containing (meth) acrylic acid ester is preferable, the styrene monomer is more preferable, and styrene is still more preferable.
The content of the unit derived from the aromatic compound in the crosslinked rubber polymer component (I) is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 10% from the viewpoint of refractive index. 20% by mass.

  The elastic body layer may contain a plurality of cross-linked rubber polymer components having different compositions as the cross-linked rubber polymer component (I), and the elastic body layer contains components other than the cross-linked rubber polymer component (I). You may contain. However, the content of the crosslinked rubber polymer component (I) in the elastic layer is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 100% by mass.

(Inner layer)
The multilayer structure polymer according to the present invention may have a two-layer structure of an elastic layer and an outer layer, or may have a structure of three or more layers having other layers in addition to the elastic layer and the outer layer. From the viewpoint of antiblocking properties, the multilayer structure polymer preferably further has an inner layer containing a polymer component (i) having 50% by mass or more of an alkyl methacrylate unit inside the elastic layer. The polymer component (i) may be covalently bonded to the crosslinked rubber polymer component (I). The content of the methacrylic acid alkyl ester unit in the polymer component (i) is preferably 60 to 99% by mass, more preferably 70 to 99% by mass, still more preferably 80 to 99% by mass, and still more preferably 85 to 99% by mass. It is 98 mass%, Most preferably, it is 90-97 mass%.

Examples of the alkyl methacrylate include methyl methacrylate and ethyl methacrylate. Among these, methyl methacrylate is preferable.
The polymer component (i) preferably has a crosslinked structure in the molecule from the viewpoint of antiblocking properties. Such a crosslinked structure is preferably formed by using a polyfunctional monomer as the monomer of the polymer component (i). As such a polyfunctional monomer, the same thing as the above-mentioned crosslinked rubber polymer component (I) is mentioned. Among these, alkenyl ester of unsaturated carboxylic acid is preferable, allyl (meth) acrylate is more preferable, and allyl methacrylate is still more preferable. The polyfunctional monomer unit in the polymer component (i) is preferably 0.1 to 5% by mass, more preferably 0.15 to 1% by mass, and still more preferably 0.18 from the viewpoint of antiblocking properties. It is -0.5 mass%.

The polymer component (i) may have a unit derived from a monomer other than the alkyl methacrylate and the polyfunctional monomer. Examples of such monomers include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate; styrene monomers such as styrene and alkyl styrene; Examples thereof include unsaturated nitriles such as acrylonitrile and methacrylonitrile. Among these, from the viewpoint of adhesion, an alkyl acrylate is preferable, and methyl acrylate is more preferable.
The content of units derived from monomers other than the methacrylic acid alkyl ester in the polymer component (i) is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less. More preferably, it is 15 mass% or less, Most preferably, it is 10 mass% or less.
The inner layer may contain a plurality of polymer components having different compositions as the polymer component (i), and may contain components other than the polymer component (i). However, the content of the polymer component (i) in the inner layer is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 100% by mass.

The mass ratio of the polymer component (i) to the crosslinked rubber polymer component (I) [polymer component (i) / crosslinked rubber polymer component (I)] is preferably 5/95 to 90/10, more preferably It is 10/90 to 70/30, more preferably 20/80 to 60/40, and still more preferably 30/70 to 50/50.
In addition, the said mass ratio is computed from the mass ratio of the monomer mixture of these polymer components.

(Outer layer)
The outer layer constituting the multilayer structure polymer contains a hard polymer component (II) having 75% by mass or more of methyl methacrylate units and graft-bonded to the crosslinked rubber polymer component (I).
The hard polymer component (II) preferably has 75 to 99% by mass of methyl methacrylate units and 1 to 25% by mass of acrylic acid ester units, from the viewpoint of antiblocking properties and adhesion, and 80 to 80 methyl methacrylate units. It is more preferable to have 97% by mass and 3 to 20% by mass of acrylic acid ester units, and it is more preferable to have 90 to 96% by mass of methyl methacrylate units and 4 to 10% by mass of acrylic acid ester units.

Examples of the ester group of the acrylic ester used for the hard polymer component (II) include an alkyl group, a cycloalkyl group, a phenyl group, and derivatives thereof having 1 to 12 carbon atoms. Specific acrylic esters include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, acrylic acid Examples include 2-ethylhexyl, n-octyl acrylate, n-lauryl acrylate, 2-hydroxyethylhexyl acrylate, cyclohexyl acrylate, isobornyl acrylate, tetrahydrofuryl acrylate, benzyl acrylate, and phenyl acrylate. Among these, from the viewpoint of the balance of adhesiveness with active energy ray-curable hard coat and adhesive, heat resistance, handleability, etc., methyl acrylate, n-butyl acrylate, cyclohexyl acrylate, and benzyl acrylate are preferable.
Moreover, when performing a corona treatment before apply | coating an active energy ray hardening-type hard coat and an adhesive agent, a cyclohexyl acrylate and tert-butyl acrylate are preferable.

Moreover, it is preferable that hard polymer component (II) has a unit derived from an aromatic compound further from a viewpoint of the improvement of adhesiveness and adjustment of a refractive index. Examples of such aromatic compounds include aromatic group-containing acrylic esters such as benzyl acrylate and phenyl acrylate. Among these, benzyl acrylate is preferable.
The content of the unit derived from the aromatic compound in the hard polymer component (II) is preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass, further from the viewpoint of refractive index. Preferably it is 0.5-1 mass%.
The outer layer may contain a plurality of hard polymer components having different compositions as the hard polymer component (II), and may contain components other than the hard polymer component (II). However, the content of the hard polymer component (II) in the outer layer is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 100% by mass.

(Graft rate)
In the multilayer structure polymer according to the present invention, the hard polymer component (II) is graft-bonded to the crosslinked rubber polymer component (I). The graft ratio of the multilayer structure polymer is preferably 11 to 33% by mass, more preferably 15 to 30% by mass, and still more preferably 20 to 30% by mass.
The graft ratio is defined by the mass ratio of the hard polymer component (II) grafted to the crosslinked rubber polymer component (I). When the graft ratio is 11% by mass or more, the heat resistance is improved. Adhesiveness with active energy ray hardening-type resin improves that it is below mass%.
The graft ratio is determined by the following formula (2) by measuring the mass of acetone insoluble matter obtained by immersing the multilayer structure polymer in acetone, centrifuging with a centrifuge, removing the acetone soluble matter and drying it. ).
Graft ratio = {[mass of acetone-insoluble matter−mass of crosslinked rubber polymer component (I)] / mass of crosslinked rubber polymer component (I)} × 100 (2)
Here, the mass of the crosslinked rubber polymer component (I) is the total mass of the monomers of the crosslinked rubber polymer component (I) in the polymerization. When the multilayer structure polymer further has the inner layer inside the elastic layer, the mass of the crosslinked rubber polymer component (I) in the above formula (2) is the same as that of the crosslinked rubber polymer component (I) and the polymer component. It is the sum total of the mass of the monomer of (i).

Moreover, in order to improve blocking prevention property, hard polymer component (II) may have a unit derived from a graft-bonding polyfunctional monomer as needed. Further, when the hard polymer component (II) has a unit derived from a graft-bonding polyfunctional monomer, the hard polymer component (II) does not have a unit derived from a graft-bonding polyfunctional monomer. Compared to the case, the amount of the unit derived from the polyfunctional monomer in the crosslinked rubber polymer component (I) can be reduced while maintaining the graft ratio, and such a multilayer structure polymer has a median diameter Da described later. And the median diameter De (Da / De) tend to increase. As such a graft-bonding polyfunctional monomer, for example, alkenyl esters of unsaturated carboxylic acids such as allyl (meth) acrylate and methallyl (meth) acrylate; dialkenyl esters of dibasic acids such as diallyl maleate are preferable. .
From the viewpoint of adhesion, it is preferable that the hard polymer component (II) does not have a unit derived from a graft-bonding polyfunctional monomer.

  The proportion of the hard polymer component (II) in the multilayer structure polymer is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, still more preferably 10 to 25% by mass, and still more preferably 15 ˜20 mass%. By setting the ratio of the hard polymer component (II) in the multilayer polymer to such a range, even when the hard polymer component (II) is 100% by mass grafted to the crosslinked rubber polymer component (I), the multilayer structure The graft ratio of the polymer can be within the above range, and the degree of freedom of the blending amount of the graft-bonding polyfunctional monomer is increased. In addition, the degree of swelling of the multilayer structure polymer by impregnation with the active energy ray-curable resin can be controlled with higher accuracy, and it becomes easy to achieve both adhesion and suppression of whitening.

The number average value of the formula weight of the hard polymer component (II) is preferably 10,000 to 100,000, more preferably 15,000 to 60,000, still more preferably 30,000 to 50, 000. When the number average value of the formula weight is 10,000 or more, the heat resistance is improved, and when it is 100,000 or less, the adhesion is improved.
In addition, the number average value of the formula weight of the hard polymer component (II) is the monomer mixture when the hard polymer component (II) of the multilayer structure polymer is produced, and the crosslinked rubber polymer component (I) is The same conditions as in the case of producing the hard polymer component (II) of the multilayer structure polymer under the conditions that do not exist, the cross-linked rubber polymer component (I) and the polymer component (i) are not present when the inner layer is present. The number average molecular weight of the polymer obtained by polymerization under the conditions. More specifically, it is measured by the method described in the examples. The formula amount can be adjusted by the amount of chain transfer agent such as thiol.

In the multilayer structure polymer, as a more preferable form of the crosslinked rubber polymer component (I), the glass transition temperature is preferably 0 ° C. or less, and the crosslinked rubber polymer component (I) and the hard polymer component (II) The refractive index (nR ₂₃ ) of the crosslinked rubber polymer component (I) at 23 ° C. and the refractive index (nP ₂₃ ) of the hard polymer component (II) at 23 ° C. when the refractive index is measured independently are represented by the following formula (3). And the temperature change of the refractive index of the cross-linked rubber polymer component (I) (dnR / dT) and the temperature of the refractive index of the hard polymer component (II) at 23 to 70 ° C. when measured independently. It is preferable that the amount of change (dnP / dT) satisfies the relationship of the following formula (4).
0.01> nR ₂₃ -nP ₂₃ > 0 (3)
0.00025> | dnR / dT-dnP / dT | (4)
By satisfying the above relationship, the refractive index difference due to the temperature of the crosslinked rubber polymer component (I) and the hard polymer component (II) can be suppressed. As a result, haze is reduced in a wide temperature range, and transparency is improved. improves.

(Median diameter De)
The median diameter De (unit: nm) of the multilayered structure polymer in water, measured by laser diffraction scattering method, is preferably 50 nm or more, more preferably the antiblocking property and transparency are further improved. 100 nm or more, more preferably 150 nm or more, particularly preferably 200 nm or more, and preferably 350 nm or less, more preferably 300 nm or less.
The median diameter De of the multilayer polymer is determined by diluting the emulsion obtained when the polymerization of the monomer of the hard polymer component (II) is stopped 200 times with water in the production of the multilayer polymer. It is a value obtained by measuring the diluted solution at 25 ° C. using a diffraction scattering type particle size distribution measuring apparatus. At this time, the absolute refractive indexes of the multilayer structure polymer and water are 1.4900 and 1.3333, respectively. More specifically, it is measured by the method described in the examples.

(Median diameter Da)
The median diameter Da (unit: nm) of the multilayer structure polymer in acetone, measured by a laser diffraction scattering method, is preferably 200 to 500 nm, more preferably 250 to 470 nm, still more preferably 280 to 450 nm. And more preferably 300 to 400 nm.
The median diameter Da is an index indicating the degree of swelling of the multilayer structure polymer due to the penetration of the active energy ray-curable resin component into the layer made of the dispersion. The degree of swelling of the multilayer structure polymer is considered to contribute to improvement of adhesion and suppression of whitening. When the median diameter Da is 200 nm or more, the adhesion is improved, and when it is 500 nm or less, whitening when the active energy ray-curable resin is applied is suppressed.
The median diameter Da of the multilayer structure polymer is 25 ° C. using a laser diffraction scattering type particle size distribution measuring apparatus for the acetone solution after the multilayer structure polymer is immersed in acetone and left at 25 ° C. for 24 hours. It is a value obtained by measuring with. At this time, the absolute refractive indexes of the multilayer structure polymer and acetone are 1.4900 and 1.3591, respectively. More specifically, it is measured by the method described in the examples.

In the multilayer polymer, the ratio (Da / De) of the median diameter Da to the median diameter De satisfies the following formula (1).
1.2 <(Da / De) ≦ 2.5 (1)
The ratio (Da / De) is preferably 1.25 or more, more preferably 1.3 or more, and preferably 2.0 or less, more preferably 1.8 or less, still more preferably 1.6 or less, More preferably, it is 1.5 or less. When the ratio (Da / De) is 1.2 or less, the adhesiveness with the active energy ray-curable resin is lowered, and when it is greater than 2.5, the anti-blocking formed of the dispersion liquid when laminated with the active energy ray-curable resin. The layer turns white.

(Manufacture of multilayer structure polymer)
The multilayer structure polymer is preferably produced by an emulsion polymerization method. The type and amount of the emulsifier used in the emulsion polymerization is selected depending on the stability of the polymerization system, the target particle size, and the like, but known emulsifiers such as an anionic surfactant, a cationic surfactant, and a nonionic surfactant. Can be used alone or in combination of two or more. Among these, an anionic surfactant is particularly preferable.

  Examples of such anionic surfactants include carboxylic acid salts such as sodium stearate, sodium myristate, and sodium N-lauroyl sarcosinate; sulfonates such as sodium dioctyl sulfosuccinate and sodium dodecylbenzene sulfonate; and sodium lauryl sulfate. Sulfate ester salt; phosphate ester salt such as sodium mono-n-butylphenylpentaoxyethylene phosphate; polyoxyethylene alkyl ether carboxylate such as sodium polyoxyethylene tridecyl ether acetate and sodium polyoxyethylene didecyl ether acetate A polyoxyethylene alkylphenyl ether phosphate such as sodium polyoxyethylene alkylphenyl ether phosphate; Among these, carboxylates or phosphates having a polyoxyethylene alkyl ether group or a polyoxyethylene alkyl phenyl ether group have good compatibility with acrylic acid esters and methacrylic acid esters, and the active energy ray-curable resin. It is preferable because the adhesion can be improved. Specific examples of such an emulsifier include sodium polyoxyethylene tridecyl ether acetate, sodium polyoxyethylene alkylphenyl ether phosphate, and the like.

  In the production of the multilayer structure polymer, the proportion of the monomer forming the hard polymer component (II) grafted to the crosslinked rubber polymer component (I) is 85 to 100% by mass, preferably 90 to 90% by mass. It is 100 mass%, More preferably, it is 95-100 mass%. Such a ratio can be controlled by the amount of the polyfunctional monomer blended in the monomer mixture forming the crosslinked rubber polymer component (I) or the hard polymer component (II).

The content of the multilayer structure polymer in the solid content of the dispersion liquid of the present invention is 0.1 parts by mass or more, preferably 0.2 parts by mass or more, more preferably with respect to 100 parts by mass of the water-dispersible resin. 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, and 10 parts by mass or less, preferably 7 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less. It is. When the content of the multilayer structure polymer is less than 0.1 parts by mass, the anti-blocking property is lowered, and when it is more than 10 parts by mass, the haze increases and the transparency is lowered.
In the dispersion of the present invention, the total amount of the multilayer structure polymer and the water-dispersible resin in the solid content is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 100% by mass.

<Water dispersible resin>
The dispersion of the present invention further contains a water-dispersible resin in addition to the multilayer structure polymer as a solid content. By containing a water-dispersible resin as a solid content, even when using a base material made of a material with low solvent resistance such as an acrylic resin, the mechanical properties and surface defects of the base material due to solvent erosion are reduced. And a uniform coating of the dispersion is possible.
The water-dispersible resin preferably has a hydrophilic functional group, and examples of the hydrophilic functional group include a carboxyl group, a sulfonic acid group, a sulfuric acid group, and a quaternary ammonium group. These hydrophilic functional groups may be used alone or in combination of two or more.
Examples of the water dispersible resin include a water dispersible polyurethane resin, a water dispersible acrylic resin, or a combination thereof. Among these, a water-dispersible polyurethane resin is preferable from the viewpoint of adhesion.

(Water-dispersible polyurethane resin)
Hereinafter, as a preferable form of the water-dispersible resin, a water-dispersible polyurethane resin will be described in detail as an example.
The water-dispersible polyurethane resin preferably contains a carboxyl group. When the polyurethane-based resin contains a carboxyl group, dispersibility of the polyurethane-based resin in a dispersion medium is improved, and adhesion between a base material and an active energy ray-curable resin described later is improved.
The polyurethane resin can be obtained, for example, by reacting a polyol and polyisocyanate with a chain extender having a carboxyl group.
Examples of the chain extender having a carboxyl group include dihydroxycarboxylic acid and dihydroxysuccinic acid. Examples of the dihydroxy carboxylic acid include dialkylol alkanoic acid including dimethylol alkanoic acid such as dimethylol acetic acid, dimethylol butanoic acid, dimethylol propionic acid, dimethylol butyric acid, dimethylol pentanoic acid and the like. These can be used alone or in combination of two or more.

  The polyol is not particularly limited as long as it has two or more hydroxy groups in the molecule, and is preferably polyester polyol, polycarbonate polyol, or polyether polyol. These can be used alone or in combination of two or more.

The polyester polyol is obtained by reacting a polybasic acid component and a polyol component.
Examples of such polybasic acid components include orthophthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and tetrahydrophthalic acid. Aromatic dicarboxylic acids such as oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, tartaric acid, alkylsuccinic acid Aliphatic dicarboxylic acids such as acid, linolenic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid; hexahydrophthalic acid, tetrahydrophthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid Alicyclic dicals such as Phosphate; or acid anhydrides thereof, alkyl esters, reactive derivatives such as acid halides and the like. These can be used alone or in combination of two or more.
Examples of the polyol component include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 1,6- Hexanediol, 1,8-octanediol, 1,10-decanediol, 4,4'-dihydroxyphenylpropane, 4,4'-dihydroxymethylmethane, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, bisphenol A, bisphenol F, glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexatriol, pentaerythritol Lumpur, glucose, sucrose and sorbitol, and the like. These can be used alone or in combination of two or more.

Examples of the polycarbonate polyol include polytetramethylene carbonate diol, polyhexamethylene carbonate diol, poly-1,4-cyclohexanedimethylene carbonate diol, and 1,6-hexanediol polycarbonate polyol.
Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol homopolymer, block copolymer, random copolymer, ethylene oxide and propylene oxide, ethylene oxide and butylene oxide random copolymer, and block copolymer. A polymer etc. are mentioned. These can be used alone or in combination of two or more.

  The polyisocyanate is not limited as long as it is a compound having two or more isocyanate groups in the molecule. For example, 1,4-phenylene diisocyanate, toluene diisocyanate (TDI), xylylene diisocyanate (XDI), 4,4′-diphenylmethane. Aromatic diisocyanate compounds such as diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), and tolidine diisocyanate (TODI); Aliphatic diisocyanate compounds such as hexamethylene diisocyanate (HMDI); Cycloaliphatic such as isophorone diisocyanate (IPDI) At least one selected from the group consisting of: a diisocyanate compound can be used.

A known method can be adopted for the production of the water-dispersible polyurethane resin, and examples thereof include a one-shot method in which the above components are reacted at once and a multi-stage method in which the components are reacted in stages. When manufacturing the water-dispersible polyurethane-type resin which has a carboxyl group, it is preferable to manufacture by a multistage method from a reactive viewpoint. Any appropriate urethane reaction catalyst may be used during the production of the polyurethane resin.
In the production of the water-dispersible polyurethane resin, it is preferable to use an organic solvent that is inactive with respect to the polyisocyanate and is compatible with water. Examples of the organic solvent include ester solvents such as ethyl acetate and ethyl cellosolve acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether solvents such as dioxane tetrahydrofuran and the like. Two or more kinds can be used in combination.
The water-dispersible polyurethane resin preferably has a weight average molecular weight of 10,000 to 1,000,000. When the weight average molecular weight is 10,000 or more, adhesion is improved, and when it is 1,000,000 or less, production of a water-dispersible polyurethane resin is facilitated.

(Water-dispersible acrylic resin)
The water-dispersible acrylic resin can be produced by polymerizing an acrylic monomer. As the acrylic monomer, it is preferable to use a monomer that gives a homopolymer having a glass transition temperature higher than room temperature, such as methyl (meth) acrylate, ethyl (meth) acrylate, iso-butyl (meth) acrylate, or these. And the like.
The acrylic monomer forming the water-dispersible acrylic resin can further contain at least one acrylic monomer that gives a homopolymer having a glass transition temperature lower than room temperature. Thereby, the physical property of adhesiveness and an antiblocking layer can be improved. Examples of the acrylic monomer that gives a homopolymer having a glass transition temperature lower than room temperature include 2-methoxyethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, and mixtures thereof. It is done.
The acrylic monomer forming the water-dispersible acrylic resin can further contain at least one water-soluble acrylic monomer. Thereby, the storage stability of the acrylic monomer is improved. Examples of the water-soluble acrylic monomer include 2-hydroxyhexyl acrylate, 2-hydroxyethyl acrylamide, (meth) acrylic acid, or a mixture thereof.
The water-dispersible acrylic resin preferably has a weight average molecular weight of 10,000 to 1,000,000. When the weight average molecular weight is 10,000 or more, adhesion is improved, and when it is 1,000,000 or less, production of a water-dispersible acrylic resin is facilitated.

  The dispersion of the present invention may contain optional components such as an antistatic agent, a flame retardant, fine particles, a pigment, and a dye as long as the effects of the present invention are not impaired. The fine particles may be inorganic fine particles or organic fine particles. Examples of the inorganic fine particles include calcium carbonate, magnesium carbonate, barium sulfate, titanium oxide, magnesium oxide, zinc oxide, zirconium oxide, aluminum oxide, aluminum hydroxide, silica (silicon dioxide), calcined calcium silicate, calcined kaolin, and hydrated silicic acid. Examples include calcium, aluminum silicate, magnesium silicate, calcium phosphate, glass, talc, clay, mica, carbon black, and white carbon. Examples of the organic fine particles include crosslinked styrene resin particles, high molecular weight styrene resin particles, and crosslinked siloxane resin particles. The fine particles may be fine particles that have been surface-treated with a fatty acid or the like. The mica may be either synthetic mica or natural mica.

(Preparation of dispersion)
The dispersion of the present invention can be produced by mixing the above-described water-dispersible resin, multilayer structure polymer, dispersion medium and, if necessary, further optional components, followed by stirring. Each of the water-dispersible resin and the multilayer structure polymer may be mixed in a solid state, or may be mixed in the state of an emulsion dispersed in a dispersion medium. In the latter case, it may be prepared by dispersing a solid water-dispersible resin or a multilayer structure polymer in a dispersion medium, or the emulsion obtained in the production process may be used as it is or after being concentrated or diluted. Also good.
The dispersion medium is a liquid, and a dispersion medium mainly containing water is preferable from the viewpoint of handleability. In addition, when the dispersion medium contains water as a main component, the environmental load is small and no special exposure equipment is required. Therefore, the dispersion liquid is applied to the substrate in-line at the time of manufacturing the substrate. Can do. Although the ratio of the solid content in a dispersion liquid is not specifically limited, Preferably it is 1-20 mass parts with respect to 100 mass parts of dispersion liquid, More preferably, it is 5-15 mass parts. When the solid content is 1 part by mass or more, anti-blocking properties and adhesion are improved, and when it is 20 parts by mass or less, handleability is easy.
The dispersion medium may contain alcohols. In this case, the ratio of the alcohols with the total amount of water and alcohols being 100% by mass is preferably less than 50% by mass, more preferably less than 30% by mass, and even more preferably less than 10% by mass. . If it is less than 50% by mass, adhesion and punching workability are improved. The alcohol to be used is not particularly limited, and examples thereof include methanol, ethanol, isopropanol and the like.

The dispersion of the present invention preferably has a low content of the emulsifier used in the production of the multilayer structure polymer from the viewpoint of adhesion. When at least one selected from the group consisting of carboxylic acid, phosphoric acid, and salts thereof having a polyoxyethylene alkyl ether group or a polyoxyethylene alkyl phenyl ether group is used as the emulsifier, the content thereof Is preferably 5 to 50 ppm by mass, more preferably 10 to 30 ppm by mass, and still more preferably 15 to 25 ppm by mass with respect to the mass of the solid content of the dispersion. Specifically, the content of the emulsifier in the dispersion is measured by the method described in Examples.
The dispersion of the present invention is excellent in antiblocking property and transparency, has excellent adhesion to the active energy ray curable resin, and can form a layer that is not easily whitened even when laminated with the active energy ray curable resin. It can be suitably used as a dispersion for an anti-blocking layer (dispersion for forming an anti-blocking layer).

[Laminate]
The laminate of the present invention has an anti-blocking layer made of the dispersion of the present invention on at least one surface of a base material made of a thermoplastic resin. Thereby, the laminated body from which winding defects, such as winding wrinkles and blocking, were improved effectively is obtained.

<Base material>
The base material is made of a thermoplastic resin. Examples of the thermoplastic resin include norbornene resins, polyester resins, polyolefin resins, polycarbonate resins, polysulfone resins, polyethersulfone resins, and (meth) acrylic resins. , Polyarylate resin, polystyrene resin, polyvinyl chloride resin and the like. Among these, a (meth) acrylic resin is preferable from the viewpoint of transparency. In addition, the base material may contain only 1 type of the above resins, and may contain 2 or more types. Moreover, the base material may consist only of a thermoplastic polymer, and may contain other components (other polymers, additives, etc.) other than a thermoplastic polymer.

  The (meth) acrylic resin is mainly composed of a resin containing at least one selected from an acrylic ester unit and a methacrylic ester unit, and only a homopolymer composed of an acrylic ester unit or a methacrylic ester unit. In addition, at least one selected from acrylic acid ester units and methacrylic acid ester units, and copolymers obtained by copolymerizing other monomer units other than these, and these (meth) acrylic resins It may be a blended resin in which other resins are blended. Examples of (meth) acrylic resins include copolymers containing alkyl (meth) acrylate units and N-cycloalkylmaleimide units; copolymers containing alkyl (meth) acrylate units and styrene monomer units; Examples thereof include a copolymer containing an alkyl (meth) acrylate unit, an N-cycloalkylmaleimide unit and a styrene monomer unit. Moreover, the blend resin containing the above copolymers and the aromatic group containing polycarbonate-type resin which has a carbonate part in a principal chain may be sufficient.

The alkyl group of the alkyl (meth) acrylate unit preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
The N-cycloalkyl group of the N-cycloalkylmaleimide unit preferably has 4 to 12 carbon atoms, and more preferably 5 to 8 carbon atoms.
The (meth) acrylic resin may be a (meth) acrylic resin having a lactone ring structure. Examples of the (meth) acrylic resin include those described in JP 2000-230016 A, JP 2001-151814 A, JP 2002-120326 A, and the like.
The (meth) acrylic resin may be a (meth) acrylic resin having an aromatic ring. Examples of the (meth) acrylic resin include those described in JP-T-2011-519389.

The method for producing the substrate (preferably a film) is not particularly limited. For example, after a thermoplastic resin and other polymers, additives and the like are sufficiently mixed by a known mixing method to produce a thermoplastic resin composition, This can be molded and manufactured. Examples of the base material molding method include a solution casting method (solution casting method), a melt extrusion method, a calender method, a compression molding method, and an injection molding method, and the melt extrusion method is particularly preferable.
The melt extrusion method is not particularly limited, and can be performed by a known melt extrusion method. For example, a T-die method or an inflation method can be used. At this time, molding temperature becomes like this. Preferably it is 150-350 degreeC, More preferably, it is 200-300 degreeC.

The substrate may be unstretched or stretched. In the case of a stretched film, it may be a uniaxially stretched film or a biaxially stretched film. In the case of a biaxially stretched film, it may be a simultaneous biaxially stretched film or a sequential biaxially stretched film. When biaxially stretched, the mechanical strength is improved and the film performance is improved. Stretching can be carried out by stretching in the extrusion direction using a stretching roll at an appropriate temperature, or stretching the substrate in a direction perpendicular to the extrusion direction using a transverse stretching machine such as a tenter.
When the substrate is stretched after the dispersion is applied to the substrate, the dispersion can be dried and the substrate can be stretched at the same time. At this time, the stretching temperature is not less than the glass transition temperature (Tg) of the thermoplastic resin forming the substrate, and is preferably not more than 30 ° C. higher than the glass transition temperature (Tg + 30 ° C.), and is 2 below the glass transition temperature. It is more preferable that the temperature is higher than the temperature (Tg + 2 ° C.) and not higher than the glass transition temperature (Tg + 20 ° C.). When the stretching temperature is Tg or higher, the substrate can be stretched without breaking, and when the temperature is 30 ° C. higher than the glass transition temperature (Tg + 30 ° C.) or lower, the dispersion does not flow and the substrate is stabilized. Can be stretched.

(Manufacture of laminates)
The laminate of the present invention can be produced by applying the dispersion of the present invention to the surface of a substrate and drying it. Thereby, the laminated body by which the antiblocking layer which consists of a dispersion liquid was formed in the surface of the base material is obtained.
In order to improve the adhesion between the substrate and the dispersion, the substrate may be subjected to surface treatment such as corona treatment or plasma treatment on the surface to which the dispersion is applied before applying the dispersion.

The method for applying the dispersion liquid to the substrate is not particularly limited, and examples thereof include known methods such as bar coating, gravure, die coating, spray coating and the like. 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.
From the viewpoint of adhesion between the substrate and the anti-blocking layer, the dispersion applied to the substrate is preferably dried at 80 to 200 ° C, more preferably 80 to 150 ° C, and 80 to 100. It may be dried at ° C. The application and drying of the dispersion liquid can be performed separately, or can be incorporated into a process of biaxially stretching the substrate. In this case, the dispersion is preferably applied before the biaxial stretching preheating step, and the drying is preferably performed between the preheating step and the relaxation step.

The thickness of the anti-blocking layer made of the dispersion is preferably 50 to 10,000 nm, more preferably 100 to 5,000 nm, and still more preferably 500 to 2,000 nm. When the thickness of the layer is 50 nm or more, the anti-blocking property and adhesion are improved, and when it is 10,000 nm or less, the layer can be sufficiently dried, and good anti-blocking property is obtained.
The thickness of the substrate is preferably 10 to 1,000 μm, more preferably 20 to 500 μm, still more preferably 20 to 300 μm, still more preferably 30 to 200 μm, and 30 to 100 μm. May be.

The laminate of the present invention preferably has a surface friction coefficient of 0.50 or less, more preferably 0.45 or less, still more preferably 0.40 or less, still more preferably 0.35 or less, and particularly preferably 0.33 or less. It is. When the surface friction coefficient is within the range, winding defects such as winding wrinkles and blocking can be effectively improved.
In the laminate, the anti-blocking layer preferably has easy adhesion and transparency from the viewpoint of effective use in optical applications.
The laminate preferably has a haze of 1.0% or less, more preferably 0.5% or less, still more preferably 0.3% or less, and still more preferably 0.2% or less, as an index of transparency. is there. When the haze is 1.0% or less, a favorable contrast ratio can be obtained when the laminate is used for optical purposes.
In addition, the surface friction coefficient and haze of a laminated body are measured by the method as described in an Example.

The laminate of the present invention may further have an active energy ray-curable resin layer on one side of the anti-blocking layer.
The active energy ray-curable resin preferably has a solvent content of 0 to 2% by mass from the viewpoint of suppressing warpage of the laminate. The content of the solvent can be measured by gas chromatography or the like. Examples of the solvent include aliphatic hydrocarbons such as n-hexane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, propanol, isopropanol and n-butanol; acetone, butanone and methyl ethyl ketone. Ketones such as methyl isobutyl ketone and cyclohexanone; esters such as methyl acetate, ethyl acetate and butyl acetate; cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; halogenated hydrocarbons such as methylene chloride and chloroform It is done.
From the viewpoint of applicability, the active energy ray-curable resin preferably has a viscosity measured by a B-type viscometer of 50 to 2,000 mPa · s at 23 ° C. Any known active energy ray-curable resin can be used without particular limitation as long as it is colorless and transparent.

  Examples of the active energy ray-curable compound that is the main component of the active energy ray-curable resin include a compound that is cured by radical polymerization with active energy rays such as a compound having an acryloyl group, a methacryloyl group, an allyl group or the like as a functional group. (Hereinafter, also simply referred to as “photo radical polymerizable compound”); a photocation reaction is caused by an active energy ray of a compound 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. And a compound that is cured (hereinafter also simply referred to as “photocationically polymerizable compound”). These active energy ray-curable compounds may be used alone or in combination of two or more.

  Examples of radically polymerizable compounds include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; hydroxyaryls such as 2-hydroxy-3-phenoxypropyl (meth) acrylate (Meth) acrylates; (meth) acryl-modified carboxylic acids such as 2- (meth) acryloyloxyethyl succinic acid and 2- (meth) acryloyloxyethylphthalic acid; triethylene glycol diacrylate, tetraethylene glycol diacrylate, etc. Polyethylene glycol di (meth) acrylate; polypropylene glycol di (meth) acrylate such as dipropylene glycol di (meth) acrylate and tripropylene glycol di (meth) acrylate; Diglycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, bisphenol A propylene oxide modified di ( Such as (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Other (meth) such as polyfunctional acrylate; epoxy (meth) acrylate, urethane (meth) acrylate, (meth) acrylic acid benzoic acid mixed ester of neopentyl glycol Acrylate and the like.

Examples of the photocationically polymerizable compound include a compound having an epoxy group and a compound having an oxetanyl group.
Examples of the compound having an epoxy group include bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins; novolak type epoxy resins such as phenol novolac type epoxy resins and cresol novolak type epoxy resins; aliphatic epoxy resins, 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 type epoxy resin, etc. Alcohol-type epoxy resins; Halogenated epoxy resins such as brominated epoxy resins; Rubber-modified epoxy resins, urethane-modified epoxy resins, epoxidized polybutadiene, epoxidized styrene-butadienes Ren block copolymer, epoxy group-containing polyester resin, epoxy group-containing polyurethane resins, epoxy group-containing acrylic resins.

  Examples of the compound having an oxetanyl group include phenoxymethyl oxetane, 3,3-bis (methoxymethyl) oxetane, 3,3-bis (phenoxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, and 3-ethyl. -3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, oxetanylsilsesqui Oxane, phenol novolac oxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene and the like.

  A polymerization initiator can be blended with the active energy ray-curable resin for the purpose of increasing the curing reaction efficiency. 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, benzophenone, thioxanthone, benzoin, and benzoin alkyl ether; aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, benzoin Examples include photocationic polymerization initiators such as sulfonic acid esters. These can be used alone or in combination of two or more.

  As the acetophenone photopolymerization initiator, for example, 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, polyvinyl benzophenone, α-hydroxycyclohexyl phenyl ketone, and the like.

  The cationic photopolymerization initiator may be an ionic photoacid-generating photocationic polymerization initiator or a nonionic photoacid-generating photocationic polymerization initiator. The photocationic polymerization initiator is a photocationic polymerization initiator that is activated by light having a wavelength of 300 nm or more because it can effectively initiate and advance the photocationic polymerization of the photocationic polymerizable compound. Is preferred.

The ionic photoacid-generating photocationic polymerization initiator is not particularly limited. For example, onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts; iron-allene complexes, titanocene complexes, arylsilanols— Organometallic complexes such as aluminum complexes; and photocationic polymerization initiators having bulky counter anions such as tetrakis (pentafluorophenyl) borate. These ionic photoacid-generating photocationic polymerization initiators may be used alone or in combination of two or more.
Examples of commercially available ionic photoacid-generating photocationic polymerization initiators include “Adekaoptomer” series such as “Adekaoptomer SP150” and “Adekaoptomer SP170” manufactured by Asahi Denka Kogyo Co., Ltd. Examples include the product name “UVE-1014” manufactured by General Electronics Co., Ltd., the product name “CD-1012” manufactured by Sartomer, and the product name “Photoinitiator 2074” manufactured by Rhodia.

The nonionic photoacid-generating photocationic polymerization initiator is not particularly limited, and examples thereof include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenolsulfonic acid ester, diazonaphthoquinone, N-hydroxyimide phosphonate, and the like. It is done. These nonionic photoacid-generating photocationic polymerization initiators may be used alone or in combination of two or more.
Examples of commercially available nonionic photoacid-generating photocationic polymerization initiators include trade name “UVI-6992” manufactured by Dow Chemical Co., Ltd.

  The blending amount of the polymerization initiator is preferably 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the active energy ray-curable compound. When the blending amount is 0.5 parts by mass or more, curing is sufficient, and when it is 20 parts by mass or less, durability is improved.

  The active energy ray curable resin includes optional components such as a photosensitizer, an antistatic agent, an infrared absorber, an ultraviolet absorber, an antioxidant, organic particles, inorganic oxide particles, metal powder, a pigment, and a dye. It may be blended.

The active energy ray is not particularly limited, and examples thereof include microwaves, infrared rays, visible light, ultraviolet rays, X-rays, and γ rays. Ultraviolet rays are preferably used because of excellent handleability and relatively high energy. That is, the active energy ray curable resin layer is preferably an ultraviolet curable resin layer.
An ultraviolet ray that is preferable among the active energy rays will be described in detail as an example. The light source used for irradiating ultraviolet rays is not particularly limited, and examples thereof include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, and a metal halide lamp. The irradiation intensity is not particularly limited, but the irradiation intensity in the wavelength region effective for activating the polymerization initiator is preferably 0.1 to 100 mW / cm ² . When the light irradiation intensity is 0.1 mW / cm ² or more, the reaction time is shortened and the productivity is improved. When the light irradiation intensity is 100 mW / cm ² or less, the active energy ray curable type is generated by radiant heat from the lamp or heat of polymerization reaction. It is possible to suppress yellowing of the resin and suppress deterioration of the substrate and the adherend. The light irradiation time is appropriately selected according to the curing situation and is not particularly limited, but the integrated light amount expressed as the product of the irradiation intensity and the irradiation time is 10 to 5,000 mJ / cm ^2. It is preferably set.

[Molded body]
The laminate of the present invention can be formed into a molded body in which the above-mentioned active energy ray-curable resin is used as an adhesive and the laminate is bonded to an adherend via an active energy ray-curable resin layer. .
The use of the laminate and the molded body of the present invention is not particularly limited. For example, vehicle decorative parts such as vehicle exteriors and interiors; building material parts such as wall materials, window films and bathroom wall materials; tableware, toys, musical instruments, etc. Household items; home appliance decoration parts such as vacuum cleaner housing, television housing, and air conditioner housing; interior materials such as kitchen door cover materials; ship members; electronic communication devices such as touch panel cover materials, personal computer housings, mobile phone housings; Optical components such as protective plates, light guide plates, light guide films, polarizer protective films, polarizing plate protective films, retardation films, polarizing plates, front plates and cover materials of various displays, diffusion plates, solar cells or solar power generation Solar power generation members such as panel cover materials for panels, etc. Also, such laminates and molded bodies can be used by being incorporated into an image display device. Yes. Examples of the image display device include a liquid crystal display (LCD), a cathode ray tube display device (CRT), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (FED), a touch panel, a tablet PC, electronic paper, and a head. An up display (HUD) etc. are mentioned.

(Polarizer)
A suitable example of such a molded body is a polarizing plate. Hereinafter, a molded body using the laminate of the present invention will be specifically described with reference to a polarizing plate.
For the polarizing plate, the laminate of the present invention is used as a polarizer protective film, the adherend is used as a polarizer, and the polarizer protective film is bonded to at least one surface of the polarizer via an active energy ray-curable resin. It is obtained by.

  The polarizing plate is formed by laminating a polarizer protective film on at least one surface of the polarizer, and the polarizer protective film may be laminated on both sides of the polarizer. Further, a polarizer protective film may be laminated on one surface of the polarizer, and another polarizer protective film may be laminated on the other surface, or a polarizer protective film may be laminated on one surface of the polarizer. The polarizer protective film may not be laminated on the other surface.

The polarizer is not particularly limited, but a stretched film obtained by dyeing a polyvinyl alcohol (PVA) resin film with iodine is preferable. The polyvinyl alcohol resin can be obtained by saponifying a polyvinyl acetate resin. As the polyvinyl acetate resin, there is polyvinyl acetate which is a homopolymer of vinyl acetate. Another example is a copolymer of vinyl acetate and other monomers copolymerizable therewith. Examples of other monomers include unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, vinyl ethers, and acrylamides having an ammonium group.
The thickness of the polarizer is preferably 5 to 40 μm, more preferably 10 to 35 μm.

The method of bonding the laminate of the present invention to the polarizer is not particularly limited, and a method of bonding a laminate having an active energy ray-curable resin layer on one side of the anti-blocking layer to the polarizer is active as an adhesive to the polarizer. Examples include a method of applying an energy ray curable resin and bonding the surface of the anti-blocking layer to the surface of the active energy ray curable resin layer formed on the polarizer.
The method for applying the active energy ray-curable resin to the polarizer is not limited. For example, various coating apparatuses such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used. Before adhering the laminate to the polarizer, the surface of the polarizer may be subjected to easy adhesion treatment such as saponification treatment, corona treatment, primer treatment, anchor coating treatment and the like.
Since the polarizing plate using the laminate of the present invention is excellent in adhesion and transparency, its application is extended to devices with severe use environments of liquid crystal displays, for example, large televisions, car navigation systems, Examples include smart phones, tablet-type and mobile-type personal computers, wearable displays, and the like.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, this invention is not restrict | limited by a following example. Moreover, this invention includes all the aspects which combine arbitrarily the matter showing technical characteristics, such as a characteristic value, a form, a manufacturing method, a use which are described in the said embodiment and the following Example.

The measurement of physical property values in Examples and Comparative Examples was performed by the following method. In addition, abbreviations such as monomers used in Examples and Comparative Examples are as follows.
MMA: methyl methacrylate ALMA: allyl methacrylate MA: methyl acrylate BA: n-butyl acrylate BzA: benzyl acrylate St: styrene n-OM: n-octyl mercaptan 3NEX: polyoxyethylene (ethylene oxide average added mole number = 3) Sodium tridecyl ether acetate (Nikko Chemicals "Nikkor 3NEX", solid content 99 mass% or more)
G25: Sodium dodecylbenzenesulfonate aqueous solution (“Neopelex G25” manufactured by Kao Corporation, solid content: 26% by mass)

[Number average value of formula weight of hard polymer component (II)]
The number average value of the formula weight of the hard polymer component (II) was determined in terms of polystyrene equivalent by GPC (gel permeation chromatography) with the following apparatus and measurement conditions.
Equipment: Tosoh GPC equipment "HLC-8320"
Separation column: “TSKguardcolum SuperHZ-H”, “TSKgel HZM-M” and “TSKgel SuperHZ4000” manufactured by Tosoh Corporation are connected in series Eluent: Tetrahydrofuran Eluent flow rate: 0.35 ml / min Column temperature: 40 ° C.
Detection method: differential refractive index (RI)

[Median diameter De of multilayer structure polymer in water]
The emulsion obtained after polymerizing the hard polymer component (II) is diluted 200 times with water and 25 using a laser diffraction scattering type particle size distribution measuring device (manufactured by Horiba, Ltd., device name “LA-950V2”). The diluted solution was analyzed at 0 ° C., and the median diameter De was calculated. At this time, the absolute refractive indexes of the multilayer structure polymer and water were 1.4900 and 1.3333, respectively.

[Median diameter Da of multilayer structure polymer in acetone]
0.2 g of the multilayer structure polymer obtained in Examples and Comparative Examples was immersed in 10 g of acetone, left to stand at 25 ° C. for 24 hours to dissolve and swell, and a laser diffraction scattering type particle size distribution measuring apparatus (manufactured by Horiba, Ltd.) Then, the acetone dispersion was analyzed using an apparatus name “LA-950V2”), and the median diameter Da was calculated. At this time, the absolute refractive indexes of the multilayer structure polymer and acetone were 1.4900 and 1.3591, respectively.

[Graft ratio of multilayer polymer]
(1) Preparation of preparation liquid The emulsion of a multilayer structure polymer was frozen and dried, and the powder of the multilayer structure polymer was obtained. 2 g of the powder was precisely weighed, and this was used as the mass (W) of the sample. The powder was immersed in 118 g of acetone at 25 ° C. for 24 hours. Thereafter, the powder and acetone were stirred to uniformly disperse the multilayer structure polymer in acetone, thereby preparing a preparation solution.
(2) Calculation of graft ratio Next, 30 g of the prepared solution was dispensed into four stainless centrifuge tubes that were weighed in advance. The centrifuge tube was centrifuged using a high-speed cooling centrifuge (manufactured by Hitachi, Ltd., model name “CR22GIII”) at 0 ° C., 20,000 rpm for 60 minutes. The supernatant liquid from each centrifuge tube was removed by decantation.
Thereafter, 30 g of acetone was newly added to each centrifuge tube. The precipitate and acetone were stirred. The centrifuge tubes were again centrifuged under the same conditions as described above, and then the supernatant was removed from each centrifuge tube. Stirring, centrifugation and supernatant removal were repeated a total of 4 times. As described above, acetone-soluble components were sufficiently removed.
Thereafter, the precipitate was dried together with the centrifuge tube by vacuum drying. The mass of acetone insoluble matter was calculated | required by weighing a deposit after drying. The graft ratio of the multilayer structure polymer was calculated based on the following formula.
Graft ratio = {[mass of acetone insoluble matter−mass of crosslinked rubber polymer component (I)] / mass of crosslinked rubber polymer component (I)} × 100
Here, the mass of the crosslinked rubber polymer component (I) is the total mass of the monomers used for synthesizing the crosslinked rubber polymer component (I) contained in the sample of mass (W).
When the multilayer structure polymer further has the inner layer inside the elastic layer, the mass of the crosslinked rubber polymer component (I) in the above formula is the weight of the crosslinked rubber contained in the sample of mass (W). This is the total mass of monomers used to synthesize the polymer component (I) and the polymer component (i).

[Emulsifier content in dispersion]
(Preparation of standard solution)
A methanol standard solution was prepared by dissolving the emulsifier used in the production of the multilayer structure polymer in methanol.
(Preparation of sample solution)
100 mL of methanol was added to 20 g of the dispersions obtained in Examples and Comparative Examples, and after suction filtration using filter paper (Advantech, JIS P 3801, 2 types), the methanol was distilled off with an evaporator. Next, 5 mL of methanol was added to the residue after the methanol was distilled off, the residue was dissolved, and filtered through a syringe filter (Advantech, pore size 5 μm) to prepare a sample solution.
(Measurement of emulsifier content)
Using the standard solution obtained above, an analytical curve was prepared by HPLC analysis using the following apparatus and conditions. The baseline was the line connecting the peak start and peak end. The peak start is the point where the slope of the peak on the high molecular weight side of the HPLC chart changes from zero to positive when viewed from the earlier retention time, and the peak end is the peak slope of the low molecular weight side of the HPLC chart. The point that changes from minus to zero when viewed from the earlier side.
Subsequently, the sample solution obtained above was analyzed by HPLC with the following apparatus and conditions, and the emulsifier content in the dispersion was measured.
Apparatus: Shiseido's HPLC system "NANOSPACE SI-2"
Column: Shiseido Capsule Pack C18 (AG120, inner diameter 4.6 mm × length 250 mm, particle diameter 5 μm)
Eluent: methanol / water = 90/10 (volume ratio)
Eluent flow rate: 0.5 ml / min Column temperature: 40 ° C
Detection method: differential refractive index (RI)

[Haze]
The laminates obtained in Examples and Comparative Examples were cut out to 50 mm × 50 mm to obtain test pieces, and a haze meter (Murakami Color Research Laboratory, apparatus name “HM-150”) was used according to JIS K7105: 2008. The haze was measured at 23 ° C.

[Surface friction coefficient]
The laminates obtained in the examples and comparative examples were cut into 70 mm × 80 mm to obtain test pieces. Two test pieces are prepared, the anti-blocking layer side of one test piece and the base material side of the other test piece face each other, and a small tabletop testing machine (manufactured by Shimadzu Corporation, model name “EZ-SX”) Was used to measure the dynamic frictional force (N) between the two test pieces under the condition that a 220 g load was applied, and the dynamic friction coefficient μ was calculated by the following equation, which was used as the surface friction coefficient. The moving speed was 200 mm / min.
Coefficient of dynamic friction μ = F / N
Here, F is the dynamic friction force (N), and N is the vertical effect (N).

(Anti-blocking property)
The laminates obtained in the examples and comparative examples were cut into 50 mm × 50 mm to obtain test pieces. Two test pieces were prepared, the anti-blocking layer side of one test piece and the base material side of the other test piece faced each other, and a pressure of 35 g / cm ² was applied at 60 ° C. The specimen was left for 24 hours, and then the blocking state of the two test pieces was evaluated according to the following criteria A to C. If it is B or more in the following classification, it can be put to practical use.
A: Not blocking, and two test pieces can be easily peeled off by hand.
B: Although it blocks slightly, two test pieces can be peeled off by hand.
C: Strongly blocked and the two test pieces cannot be peeled off by hand.

[Section observation of the laminate]
The laminates obtained in the examples and comparative examples were hardened with an epoxy resin, and a thin film section for observing the cross section of the laminate using a microtome (Leica Microsystems, product name “LEICA EM UC6 / FC6”) Produced. The thin film sections were immersed in a 15% by mass phosphotungstic acid aqueous solution for 15 minutes for staining and observed with a reflection electron microscope (manufactured by JEOL, product name “JSM-7600F”).

[Adhesion]
Using the laminate of the present invention as a polarizer protective film, the adhesion between the active energy ray-curable resin layer and the anti-blocking layer was evaluated as follows. Ten samples having a length of 50 mm and a width of 25 mm were randomly cut out from the molded bodies obtained in Examples and Comparative Examples. The active energy ray-curable resin layer was cut with a cutter, and the sample was peeled by hand so as to be separated into a polarizer protective film and a polarizer. These adhesion properties were evaluated according to the following criteria A to C. If it is B or more according to the following classification, it can be put to practical use.
A: Adhesive strength was strong, and any film was damaged in all samples, and the polarizer and the polarizer protective film could not be separated in all samples.
B: Nine out of 10 samples were damaged in either the polarizer or the polarizer protective film. That is, there was material destruction. Both the polarizer and the polarizer protective film could be separated from each other with the interface between the active energy ray-curable resin layer and the substrate without damaging both the polarizer and the polarizer protective film. That is, interfacial peeling was possible.
C: The number of samples in which material destruction occurred was 8 or less. In addition, interfacial peeling was achieved with two or more samples. In all samples, comparative examples in which interfacial peeling between both films can be classified.

[Evaluation of whitening]
From the molded bodies obtained in Examples and Comparative Examples, 10 samples of 50 mm length × 25 mm width were randomly cut out and the appearance was observed, and the degree of whitening of the polarizer protective film was evaluated according to the following criteria A to C. did. Since the polarizer is black, the appearance of the sample becomes white when the anti-blocking layer is whitened. If it is B or more in the following classification, it can be put to practical use.
A: All of 10 samples were not whitened.
B: One sample out of 10 was whitened. The other samples were not whitened.
C: Two or more of the ten samples were whitened.

(Production Example 1) [Production of Multilayer Polymer (A1)]
(1) In a reactor equipped with a stirrer, a thermometer, a nitrogen gas introduction pipe, a monomer introduction pipe and a reflux condenser, 1,050 parts by mass of ion-exchanged water, polyoxyethylene (average number of moles of added ethylene oxide = 3) Sodium tridecyl ether acetate (manufactured by Nikko Chemicals, trade name “Nikkor 3NEX”, solid content 99% by mass or more) 0.13 part by mass and sodium carbonate 0.7 part by mass were charged with nitrogen gas in the reactor. Fully replaced. Next, after raising the internal temperature to 80 ° C., 0.25 part by mass of potassium persulfate was added to the reactor and stirred for 5 minutes. Furthermore, the solution which melt | dissolved 1.75 mass parts of said polyoxyethylene tridecyl ether sodium acetate in 245 mass parts of monomer mixtures which form the polymer component (i) shown in Table 1 in the reactor for 60 minutes. It was dripped continuously over time. After completion of dropping, a polymerization reaction was further performed for 30 minutes to obtain an emulsion of polymer component (i) corresponding to the inner layer.
(2) Next, with the internal temperature maintained at 80 ° C., 0.32 parts by mass of potassium persulfate was added to the reactor and stirred for 5 minutes. Next, in the same reactor, a solution obtained by dissolving 0.85 parts by mass of sodium polyoxyethylene tridecyl ether acetate in 315 parts by mass of the monomer mixture forming the crosslinked rubber polymer component (I) shown in Table 1, The emulsion was continuously dropped over 60 minutes to obtain an emulsion of a polymer component having an inner layer coated with an elastic layer.
(3) Next, while maintaining the internal temperature at 80 ° C., 0.14 parts by mass of potassium persulfate was added to the reactor and stirred for 5 minutes. Next, 140 parts by mass of a monomer mixture for forming the hard polymer component (II) shown in Table 1 was continuously dropped into the reactor over 30 minutes. After completion of the dropping, a polymerization reaction was further performed for 60 minutes. By the above operation, an emulsion (AI) containing a multilayer structure polymer (A1) in which an outer layer was coated on an elastic layer having an inner layer was obtained. The emulsion (AI) of the multilayer structure polymer (A1) was frozen and solidified. Subsequently, it was washed with water and dried to obtain a multilayer structure polymer (A1) having a median diameter De in water of 285 nm and a graft ratio of 24% by mass.

(Production Examples 2 to 4 and Production Examples 6 to 8) [Production of Multilayer Polymers (A2 to A4, A6 to A8)]
In Production Example 1, a multilayer structure polymer emulsion (AII to AIV, AVI to AVIII) and a multilayer structure polymer (A2 to A4, A6 to A8) were prepared in the same manner as in Production Example 1 except that the formulation shown in Table 1 was used. Manufactured. The characteristics of each multilayer structure polymer emulsion and multilayer structure polymer are shown in Table 1.

(Production Example 5) [Production of multilayer structure polymer (A5)]
(1) In a reactor equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a monomer inlet tube and a reflux condenser, 1,050 parts by mass of ion-exchanged water, sodium didodecylbenzenesulfonate (Kaosha) (Trade name “Neoperex G25”, solid content 26 mass%) 0.46 parts by mass and sodium carbonate 0.7 parts by mass were charged, and the inside of the reactor was sufficiently replaced with nitrogen gas. Next, the internal temperature was raised to 80 ° C. Next, 0.25 part by mass of potassium persulfate was charged into the reactor and stirred for 5 minutes. Further, in the reactor, a solution obtained by dissolving 6.73 parts by mass of the aqueous sodium dododecylbenzenesulfonate in 70 parts by mass of the polymer component (i) monomer mixture shown in Table 1 was continuously added over 60 minutes. It was dripped in. After completion of dropping, a polymerization reaction was further performed for 30 minutes to obtain an emulsion of polymer component (i) corresponding to the inner layer.
(2) Next, with the internal temperature maintained at 80 ° C., 0.32 parts by mass of potassium persulfate was added to the reactor and stirred for 5 minutes. Next, a solution obtained by dissolving 3.27 parts by mass of the aqueous sodium dododecylbenzenesulfonate in 315 parts by mass of the monomer mixture for forming the crosslinked rubber polymer component (I) shown in Table 1 was added to the reactor for 60 minutes. The polymer component emulsion was obtained by continuously dripping over the inner layer and covering the inner layer with the elastic layer.
(3) Next, while maintaining the internal temperature at 80 ° C., 0.14 parts by mass of potassium persulfate was added to the reactor and stirred for 5 minutes. Next, 315 parts by mass of a monomer mixture forming the hard polymer component (II) shown in Table 1 was continuously dropped into the reactor over 60 minutes. After completion of the dropping, a polymerization reaction was further performed for 60 minutes. By the above operation, an emulsion (AV) containing a multilayer structure polymer (A5) in which an elastic layer having an inner layer was coated with an outer layer was obtained. The emulsion (AV) of the multilayer structure polymer (A5) was frozen and solidified. Subsequently, it was washed with water and dried to obtain a multilayer structure polymer (A5) having a median diameter De in water of 285 nm and a graft ratio of 65% by mass.

In addition, each description of Table 1 is as follows.
* 1: The content (mass%) of the emulsifier in the multilayer structure polymer emulsion.
* 2: Indicates the ratio of the hard polymer component (II) to the multilayer structure polymer.
* 3: Indicates the number average value of the formula weight of the hard polymer component (II).

(Preparation Example 1) [Active energy ray-curable resin adhesive]
Bisphenol A type epoxy resin (trade name “jER-828” manufactured by Japan Epoxy Resin Co., Ltd.) 35% by mass, 3-ethyl-3- (phenoxymethyl) oxetane (trade name “Aron Oxetane OXT-211” manufactured by Toagosei Co., Ltd.) ) 59% by mass, blended with 6% by mass of propylene carbonate solution of triarylsulfonium hexafluorophosphate (trade name “UVI-6992”, active ingredient 50% by mass) manufactured by Dow Chemical Co., Ltd.) as a photocationic polymerization initiator An energy ray curable resin adhesive was prepared. These raw materials were stirred and mixed according to a conventional method.

<Example 1>
(Preparation of dispersion (C1))
100 parts by mass of an aqueous dispersion of a carboxy-modified polyester urethane resin (Daiichi Kogyo Seiyaku Co., Ltd., trade name “Superflex 210”, solid content 35%) is diluted with 250 parts by mass of ion-exchanged water. 0.44 parts by mass of emulsion (AI) (solid content 40% by mass) of the obtained multilayer structure polymer (A1) was added and stirred, and the multilayer structure polymer (A1) was added to 100 parts by mass of the carboxy-modified polyester urethane resin. A dispersion (C1) in which a solid content including 0.5 parts by mass was dispersed at a ratio of 10 parts by mass with respect to 100 parts by mass of the dispersion was obtained. This dispersion (C1) contained 19 mass ppm of the emulsifier with respect to the mass of the solid content.

(Production of laminate (D1))
A methacrylic resin composition obtained by referring to Example 1 of International Publication No. 2014/185509 was melted in a single-screw extruder with a Φ65 mm vent equipped with a T die, and the lip opening of the die lip was 1 mm. The film was extruded from a die and drawn with a metal elastic roll and a metal rigid roll under a linear pressure of 30 N / mm to obtain a methacrylic resin film (acrylic film) having a thickness of 160 μm. The dispersion (C1) was applied to one side of the methacrylic resin film using a bar coater so that the thickness after drying and stretching was 1.2 μm, and heated at 130 ° C. Next, this film was subjected to simultaneous biaxial stretching twice at 145 ° C and two times in width at 145 ° C using a tenter type stretching machine, and a thickness having an antiblocking layer on one surface of the methacrylic resin film. A laminate (D1) having a thickness of 40 μm was obtained.

(Production of molded body (F1))
Next, on the anti-blocking layer of the laminate (D1), the active energy ray-curable resin adhesive obtained in Preparation Example 1 was applied at a thickness of 2 μm at 25 ° C., and a 10 μm-thick polarizer (PVA film) The product was prepared by dyeing and stretching with an iodine-based pigment on the coating layer. Moreover, in such a polarizer, the laminate (D1) coated with the active energy ray-curable resin adhesive obtained in Preparation Example 1 is similarly laminated on the surface opposite to the surface on which the laminate is laminated. Combined. Thus obtained laminate (base material / antiblocking layer) / active energy ray curable resin adhesive / polarizer / active energy ray curable resin adhesive / laminate (antiblocking layer / base material). The compact body precursor which has a layer structure in this order was pressed with a roller.
Thereafter, using a metal halide lamp (manufactured by GS YUSASA), the molded body precursor was irradiated with ultraviolet rays so that the integrated light amount became 700 mJ / cm ² . After the ultraviolet irradiation, a molded body (F1) was obtained by allowing to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours. Table 2 shows the evaluation results of the laminate and the molded body.

<Examples 2-5, Comparative Examples 1-3>
In Example 1, dispersions (C2 to C8) were prepared in the same manner as in Example 1 except that the emulsions (AII to AVIII) of the multilayer structure polymers (A2 to A8) obtained in Production Examples 2 to 8 were used. Obtained. These characteristics are shown in Table 2.
Moreover, the laminated body (D2-D8) and the molded object (F2-F8) were produced by the method similar to Example 1 except having used the dispersion liquid (C2-C8) shown in Table 2 in Example 1. FIG. The evaluation results are shown in Table 2.

<Comparative example 4>
(Preparation of dispersion (C9))
100 parts by weight of an aqueous dispersion of carboxy-modified polyester urethane resin (Daiichi Kogyo Seiyaku Co., Ltd., trade name “Superflex 210”, solid content 35%) is diluted with 250 parts by weight of ion-exchanged water. 0.44 parts by mass of a dispersion (manufactured by Nissan Chemical Industries, trade name “Snowtex ZL”, solid content: 40% by mass) was added and stirred, and 0.5% of colloidal silica was added to 100 parts by mass of carboxy-modified polyester urethane resin. A dispersion (C9) in which the solid content including parts by mass was dispersed at a ratio of 10 parts by mass with respect to 100 parts by mass of the dispersion was obtained.

(Production of laminate (D9) and molded body (F9))
In Example 1, a laminate (D9) and a molded body (F9) were produced in the same manner as in Example 1 except that the dispersion (C9) was used instead of the dispersion (C1). The evaluation results are shown in Table 2.

In addition, each notation in Table 2 is as follows.
* 1: The content (part by mass) of the solid content in the dispersion with respect to 100 parts by mass of the dispersion.
* 2: The content (mass ppm) of the emulsifier in the dispersion relative to the mass of the solid content.

It turns out that Examples 1-5 are excellent in blocking prevention property and transparency compared with Comparative Examples 1-4, and are excellent in adhesiveness and suppression of whitening.
Since the content of the methyl methacrylate unit in the hard polymer component (II) constituting the outer layer is less than 75% by mass in Comparative Example 1, the anti-blocking property is inferior.
In Comparative Examples 2 and 3, since the median diameter ratio (Da / De) does not satisfy the formula (1), in Comparative Example 2, the anti-blocking layer was whitened by the active energy ray-curable resin adhesive, and Comparative Example 3 Has poor adhesion.
In Comparative Example 4, colloidal silica was used as an antiblocking agent. Although the anti-blocking property was good, the haze was high and the transparency was inferior, and whitening was not suppressed.
The photograph which observed the cross section of the laminated body (D1) obtained in Example 1 with the reflection electron microscope (The product name "JSM-7600F" by JEOL company) is shown in FIG. FIG. 2 shows that the multilayer structure polymer according to the present invention is unevenly distributed on the surface side of the laminate in the antiblocking layer, and is effective in preventing blocking.

11 Elastic Layer 12 Outer Layer I Crosslinked Rubber Polymer Component (I)
II Rigid polymer component (II)

Claims (17)

A dispersion in which a solid content is dispersed in a dispersion medium,
The solid content includes 100 parts by mass of a water-dispersible resin and 0.1 to 10 parts by mass of a multilayer structure polymer,
The multilayer structure polymer has an elastic body layer and an outer layer covering the elastic body layer,
The elastic body layer is at least one monomer unit selected from the group consisting of units derived from an alkyl acrylate ester having an alkyl group having 1 to 8 carbon atoms and units derived from a conjugated diene monomer ( I-1) containing a crosslinked rubber polymer component (I) having 50% by mass or more,
The outer layer has 75 mass% or more of units derived from methyl methacrylate, and includes a hard polymer component (II) graft-bonded to the crosslinked rubber polymer component (I),
The ratio (Da / De) between the median diameter Da of the multilayer structure polymer in acetone and the median diameter De of the multilayer structure polymer in water measured by a laser diffraction scattering method satisfies the following formula (1). Dispersion.
1.2 <(Da / De) ≦ 2.5 (1)   The dispersion according to claim 1, wherein the median diameter De is 50 to 350 nm.   The dispersion liquid according to claim 1 or 2, wherein a ratio of the hard polymer component (II) in the multilayer structure polymer is 10 to 25% by mass.   The dispersion according to any one of claims 1 to 3, wherein the hard polymer component (II) has 80 to 97% by mass of units derived from methyl methacrylate and 3 to 20% by mass of units derived from an acrylate ester. liquid.   The dispersion liquid according to any one of claims 1 to 4, wherein the crosslinked rubber polymer component (I) further has a unit derived from an aromatic compound.   The dispersion according to any one of claims 1 to 5, wherein the crosslinked rubber polymer component (I) further comprises 1 to 3.5% by mass of a unit derived from a polyfunctional monomer.   The dispersion according to any one of claims 1 to 6, wherein the hard polymer component (II) further has a unit derived from an aromatic compound.   The graft ratio defined by the mass ratio of the hard polymer component (II) grafted to the crosslinked rubber polymer component (I) is 11 to 33% by mass. The dispersion described.   The dispersion liquid in any one of Claims 1-8 whose number average value of the formula weight of the said hard polymer component (II) is 15,000-60,000. The multilayer polymer further has an inner layer inside the elastic layer,
The dispersion according to any one of claims 1 to 9, wherein the inner layer contains a polymer component (i) having 50 mass% or more of units derived from an alkyl methacrylate.   The dispersion liquid in any one of Claims 1-10 containing 1-20 mass parts of said solid content with respect to 100 mass parts of said dispersion liquids.   The dispersion according to any one of claims 1 to 11, which is a dispersion for an anti-blocking layer.   The laminated body which has the antiblocking layer which consists of a dispersion liquid of Claim 12 on the at least single side | surface of the base material which consists of a thermoplastic resin.   The laminate according to claim 13, wherein the thermoplastic resin is a (meth) acrylic resin.   The laminated body of Claim 13 or 14 which has an active energy ray hardening-type resin layer in the single side | surface of the said blocking prevention layer.   The molded object formed by joining this laminated body to a to-be-adhered body through the active energy ray hardening-type resin layer of the laminated body of Claim 15.   The molded body according to claim 16, wherein the adherend is a polarizer and the molded body is a polarizing plate.