JPWO2014109223A1 - Polymerizable composition, polymer, optical pressure-sensitive adhesive sheet, image display device and method for producing the same - Google Patents

Abstract

In a polymerizable composition for forming a polymer layer interposed between an image display part and a translucent protective part of an image display device, the volume shrinkage during polymerization is small, the dielectric constant is high, glass, etc. There is provided a polymerizable composition for producing a polymer having high adhesion to a material used for the translucent protective part and being less colored by heat. The polymerizable composition of the present invention comprises (Component 1) a (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 10,000, (Component 2) a photopolymerization initiator, and the composition. The polymer obtained by polymerization has a dielectric constant of 5.0 or more measured at 23 ° C., a frequency of 1 MHz, and an applied voltage of 100 mV.

Description

  The present invention relates to a polymerizable composition used in an image display device such as a liquid crystal display device used in, for example, smartphones and tablet PCs, a polymer obtained by polymerizing the composition, and an image display using the composition The present invention relates to a device manufacturing method and an image display device manufactured by the manufacturing method.

Conventionally, for example, a liquid crystal display device 101 shown in FIG. 6 is known as this type of image display device.
As shown in FIG. 6, the liquid crystal display device 101 has a transparent protective part 103 made of, for example, glass or plastic on a liquid crystal display panel 102.
In this case, in order to protect the surface of the liquid crystal display panel 102 and a polarizing plate (not shown), a gap 104 is provided between the liquid crystal display panel 102 and the protective portion 103 by interposing a spacer 104 between the protective portion 103. Is provided.
However, the presence of the gap 105 between the liquid crystal display panel 102 and the protection unit 103 causes light scattering, resulting in a decrease in contrast and brightness, and the presence of the gap 105 hinders thinning of the panel. It has become.

  In view of such problems, it has also been proposed to fill a gap between the liquid crystal display panel and the protective portion (see FIG. 1) (see, for example, Patent Document 1). Due to this stress, the optical glass sandwiching the liquid crystal of the liquid crystal display panel is deformed, which causes display defects such as disordered alignment of the liquid crystal material.

In order to solve the above problems, for example, Patent Document 2 or Patent Document 3 uses a polyurethane acrylate or a polyisoprene polymer maleic anhydride adduct and an esterified product of 2-hydroxyethyl methacrylate with a low elastic modulus. A curable composition having a small volumetric shrinkage during curing is disclosed.
However, the volume shrinkage ratio at the time of curing of the curable composition using polyurethane acrylate is large (greater than 4.0%), and the maleic anhydride adduct of polyisoprene polymer and ester of 2-hydroxyethyl methacrylate Although the curable composition using the chemicals has a small volume shrinkage at the time of curing, it has a problem that coloring of the cured cured product due to heat increases.

Patent Document 4 discloses a photocurable adhesive composition containing a (meth) acrylate oligomer having an ultraviolet crosslinkable moiety and a hindered amine.
However, these photocurable adhesive compositions cannot solve the following problems related to the improvement in capacitance.

  In recent years, smartphones are becoming mainstream in mobile phones, and devices called tablet PCs are rapidly spreading. Such devices are generally equipped with a capacitive touch panel. As an example of the capacitive touch panel, a polymer (layer) (shown in FIG. 2) filled between the display unit and the touch panel in the on-cell capacitive touch panel display device shown in FIG. 5b polymer (layer)) or polymer (layer) filled between the display unit and the protective unit in the In-Cell capacitive touch panel display device (5b described in FIGS. 3 and 4). From the viewpoint of improving sensitivity, a material that contributes to improving the capacitance of the touch panel is desired.

Examples of the high dielectric constant material include (meth) acrylic acid ester monomers having a hydrocarbon group having 1 to 12 carbon atoms and hydroxyl group-containing (meth) acrylic acid ester monomers described in Patent Document 5. , An acrylic polymer compound obtained by copolymerizing a monomer component containing an amide group-containing monomer and a vinyl ester monomer, or 3-ethyl-3-hydroxy described in Patent Document 6 A polymer obtained by polymerizing a composition containing methyl oxetane, an epoxy resin having a hydrogen bonding functional group, and a photocationic polymerization initiator is disclosed. However, these compounds cannot be said to have a sufficient dielectric constant or have insufficient transparency as optical materials.
Moreover, the technique of patent document 5 had the fault that the volatile solvent at the time of manufacture had to be used.

JP 2005-55641 A JP 2008-282000 A JP 2009-186958 A JP 2012-46658 A JP 2012-41456 A JP 2011-105806 A

  In order to solve the above problems, the present invention is excellent in response sensitivity when used in a touch panel, and further has a small volume shrinkage during polymerization, good adhesion to glass, and coloring during heating by heat. And a polymerizable composition for producing a polymer having good adhesion to a material used for a light-transmitting protective part such as glass, and a polymer obtained by polymerizing the composition (for optical use) It is an object of the present invention to provide an image display device using the polymer and a method for producing the image display device.

As a result of repeated studies to solve the above problems, the present inventors have obtained a polymerizable composition containing a specific (meth) acryloyl group-containing compound having a small volume shrinkage during polymerization and obtained by polymerization. Excellent response sensitivity when used for touch panels due to the high dielectric constant of the polymer, reduced coloration due to heat, and good adhesion to materials used for translucent protective parts such as glass As a result, the present invention has been completed.
That is, the present invention (I) is a polymerizable composition for forming a polymer layer interposed between an image display part and a translucent protective part of an image display device, the polymerizable composition But,
(Component 1) contains a (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 10,000, and (Component 2) a photopolymerization initiator, and is obtained by polymerizing the polymerizable composition. The present invention relates to a polymerizable composition characterized in that the polymer has a dielectric constant of 5.0 or more measured under conditions of 23 ° C., frequency 1 MHz, and applied voltage 100 mV.
The present invention (II) is a polymerizable composition for forming a polymer layer interposed between the image display part and the translucent protective part of the image display device, the polymerizable composition comprising:
(Component 1) (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 10,000,
Polymerization obtained by polymerizing the polymerizable composition, comprising (Component 2) a photopolymerization initiator, and (Component 3) a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group. The dielectric constant measured on condition of 23 degreeC of the thing, frequency 1MHz, and applied voltage 100mV is related with polymeric composition characterized by the above-mentioned.
The present invention (III) is a polymerizable composition for forming a polymer layer interposed between the image display part of the image display device and the translucent protective part, the polymerizable composition comprising:
(Component 1) (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 10,000,
(Component 2) Photopolymerization initiator,
(Component 3) a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group, and (Component 4) no alcoholic hydroxyl group or amide group, and a viscosity of 25 ° C. A dielectric constant measured under the conditions of a polymer obtained by polymerizing the polymerizable composition containing a (meth) acryloyl group-containing compound of 500 mPa · s or less at 23 ° C., a frequency of 1 MHz, and an applied voltage of 100 mV. It is related with polymeric composition characterized by being 5.0 or more.
The present invention (IV) is a polymerizable composition for forming a polymer layer interposed between the image display part of the image display device and the translucent protective part, the polymerizable composition comprising:
(Component 1) (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 10,000,
(Component 2) Photopolymerization initiator,
(Component 3) Radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group,
(Component 4) a (meth) acryloyl group-containing compound which does not have any group of an alcoholic hydroxyl group and an amide group and has a viscosity of 500 mPa · s or less at 25 ° C.
(Component 5) Nonionic surfactant having no (meth) acryloyl group, and (Component 6) No (meth) acryloyl group in the molecule, a function for suppressing radical polymerization, a function for inhibiting radical polymerization, light Liquid or solid at 25 ° C., which has neither a polymerization initiation function nor a surface-active function, and is composed of carbon atoms and hydrogen atoms, or is composed of carbon atoms, hydrogen atoms and oxygen atoms And a dielectric constant measured at 23 ° C., a frequency of 1 MHz and an applied voltage of 100 mV of a polymer obtained by polymerizing the polymerizable composition is 5.0 or more. It relates to a polymerizable composition.
The present invention (V) relates to a polymer obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (IV).
The present invention (VI) is a polymerizable composition for producing an optical pressure-sensitive adhesive sheet used as a polymer layer interposed between an image display portion and a translucent protective portion of an image display device. The polymerizable composition is a polymerizable composition of the present invention (I) to the present invention (IV).
The present invention (VII) has a thickness obtained by applying the polymerizable composition of the present invention (VI), irradiating the polymerizable composition with light capable of being photosensitized by the photopolymerization initiator, and polymerizing the polymerizable composition. The present invention relates to an optical pressure-sensitive adhesive sheet having a polymer layer of 10 to 1000 μm.
The present invention (VIII) is a method for producing an image display device comprising a base having an image display portion, a translucent protective portion, and a polymer layer interposed between the base and the protective portion, The method comprises the step of interposing the polymerizable composition of the present invention (IV) between the base part and the protective part, and irradiating the polymerizable composition with light that can be photosensitized by a photopolymerization initiator. The present invention relates to a method for manufacturing an image display device including a step of forming a polymer layer.
This invention (IX) is a manufacturing method of an image display apparatus which has the process of sticking the base which has an image display part, and a translucent protective part using an optical adhesive sheet, Comprising: This optical adhesive sheet is And an optical pressure-sensitive adhesive sheet according to the present invention (VII).
The present invention (X) relates to an image display device manufactured by the manufacturing method of the image display device of the present invention (VIII) or the present invention (IX).

Furthermore, the present invention relates to the following [1] to [15].
[1] A polymerizable composition for forming a polymer layer interposed between an image display portion and a translucent protective portion of an image display device, the polymerizable composition comprising:
(Component 1) contains a (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 10,000, and (Component 2) a photopolymerization initiator, and is obtained by polymerizing the polymerizable composition. A polymerizable composition having a dielectric constant of 5.0 or more measured at 23 ° C., a frequency of 1 MHz, and an applied voltage of 100 mV.
[2] The component 1 has a polyester structural unit including a structural unit derived from a diol having 4 to 9 carbon atoms and a structural unit derived from a dicarboxylic acid having 4 to 10 carbon atoms [1] The polymerizable composition described in 1.
[3] The polymerizable composition as described in [1] or [2], wherein the component 1 has a urethane bond.
[4] (Component 3) The polymerizable composition according to any one of [1] to [3], further comprising a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group.
[5] (Component 4) [1] to [4] further comprising a (meth) acryloyl group-containing compound which does not have any group of an alcoholic hydroxyl group and an amide group and has a viscosity of 500 mPa · s or less at 25 ° C. ] The polymerizable composition in any one of.
[6] The polymerizable composition as described in [5], wherein the component 4 has an ether bond.
[7] (Component 5) Nonionic surfactant having no (meth) acryloyl group, and (Component 6) No (meth) acryloyl group in the molecule, inhibiting radical polymerization, and prohibiting radical polymerization No function, photopolymerization initiating function, or surface activity, and composed of carbon and hydrogen atoms, or composed of carbon, hydrogen, and oxygen atoms at 25 ° C The polymerizable composition according to any one of [1] to [6], further comprising a liquid or solid compound.
[8] The polymerizable composition as described in [7], wherein the component 6 is at least one selected from the group consisting of a polyester polyol, a polycarbonate polyol, and a tackifier.
[9] The component 5 is a nonionic surfactant having no (meth) acryloyl group, wherein the Griffin has an HLB value of 3.0 to 6.0 [7] or [7] 8].
[10] A polymer obtained by polymerizing the polymerizable composition according to any one of [1] to [9].
[11] A polymerizable composition for producing an optical pressure-sensitive adhesive sheet used as a polymer layer interposed between an image display portion and a translucent protective portion of an image display device, wherein the polymerizable composition A polymerizable composition according to any one of [1] to [10], wherein the composition is a polymerizable composition according to any one of [1] to [10].
[12] A film having a thickness of 10 to 1000 μm, obtained by applying the polymerizable composition according to [11], and irradiating the polymerizable composition with light that can be photosensitized by the photopolymerization initiator. An optical pressure-sensitive adhesive sheet having a polymer layer.
[13] A method for manufacturing an image display device, comprising: a base having an image display portion; a translucent protective portion; and a polymer layer interposed between the base portion and the protective portion, the method comprising:
The step of interposing the polymerizable composition according to any one of [7] to [9] between the base portion and the protective portion, and light capable of being photosensitized by a photopolymerization initiator to the polymerizable composition The manufacturing method of the image display apparatus characterized by including the process of irradiating and forming a polymer layer.
[14] A method for manufacturing an image display device, comprising a step of attaching a base portion having an image display portion and a translucent protective portion using an optical pressure-sensitive adhesive sheet, wherein the optical pressure-sensitive adhesive sheet comprises [12] A method for producing an image display device, which is the optical pressure-sensitive adhesive sheet according to the above item.
[15] An image display device manufactured by the method for manufacturing an image display device according to [13] or [14].

  The polymerizable composition of the present invention has a low volume shrinkage during polymerization, the polymer obtained by polymerizing the polymerizable composition has a high dielectric constant, good adhesion to glass, and coloration by heat. Few.

FIG. 1 is a cross-sectional view showing a main part of an embodiment of a display device according to the present invention. FIG. 2 is a cross-sectional view showing a main part of an embodiment of the display device according to the present invention. FIG. 3 is a cross-sectional view showing a main part of an embodiment of the display device according to the present invention. FIG. 4 is a cross-sectional view showing a main part of an embodiment of the display device according to the present invention. FIG. 5 is a cross-sectional view showing a main part of an embodiment of the display device according to the present invention. FIG. 6 is a cross-sectional view showing a main part of a display device according to the prior art.

Hereinafter, the present invention will be specifically described.
In addition, there is no restriction | limiting in particular in a form etc. as long as it is a polymer obtained by superposing | polymerizing polymeric composition as "polymerized substance" as described in this specification, "optical adhesive sheet as described in this specification "Also means included in the polymer.
In addition, the “polymer layer interposed between the image display unit and the translucent protective unit” described in the present specification refers to all polymers between the image display unit and the translucent protective unit. For example, it means that both 5a and 5b in FIG. 5 are included.
Further, the “(meth) acryloyl group” in the present specification means at least one group selected from an acryloyl group and a methacryloyl group.
Furthermore, “polyester polyol” in the present specification means a polymer compound having a —COO— bond (carboxylic acid ester bond) and two or more alcoholic hydroxyl groups in one molecule and having a molecular weight distribution, The “polycarbonate polyol” in the present specification means a polymer compound having —OCOO— bond (carbonate bond) and two or more alcoholic hydroxyl groups in one molecule and having a molecular weight distribution. “Polyether polyol” means a polymer compound having an ether bond and two or more alcoholic hydroxyl groups in one molecule and having a molecular weight distribution.

In addition, in this specification, when manufacturing the polyester polyol which can be a raw material of the component 1 which is an essential raw material component of the polymeric composition of this invention (I), the polyol (namely, -COO) which is a raw material of a polyester polyol. -When a polyol (which does not have a bond (carboxylic ester bond)) remains, this polyol is also defined to be included in the polyester polyol. In addition, in this specification, in addition to the raw material polyol contained in the polyester polyol, a polyol which is a raw material component of the polyester polyol to be used is newly added, and the essential component of the polymerizable composition of the present invention (I) When component 1 is produced, the added polyol shall be included in the polyester polyol even if it is a polyol having no -COO- bond (carboxylic acid ester bond).
Further, in the present specification, when producing a polycarbonate polyol that can be a raw material of Component 1, which is an essential raw material component of the polymerizable composition of the present invention (I), a polyol (that is, a carbonate bond) that is a raw material of the polycarbonate polyol. In the case where a polyol (which does not have any) remains, this polyol is also included in the polycarbonate polyol. In addition, in this specification, in addition to the raw material polyol contained in the polycarbonate polyol, a polyol which is a raw material component of the polycarbonate polyol to be used is newly added, and the essential component of the polymerizable composition of the present invention (I) When component 1 is produced, this added polyol shall be included in the polycarbonate polyol.
Further, in the present specification, when producing a polyether polyol that can be a raw material of Component 1, which is an essential raw material component of the polymerizable composition of the present invention (I), a polyol that is a raw material of the polyether polyol (ie, When a polyol having no ether bond) remains, this polyol is also included in the polyether polyol. In addition, in the present specification, in addition to the raw material polyol contained in the polyether polyol, a polyol which is a raw material component of the polyether polyol to be used is newly added to the polymerizable composition of the present invention (I). When component 1, which is an essential component, is produced, the added polyol shall be included in the polyether polyol.

First, the present invention (I) will be described.
The present invention (I) is a polymerizable composition for forming a polymer layer interposed between an image display part and a translucent protective part of an image display device, the polymerizable composition comprising:
(Component 1) contains a (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 10,000, and (Component 2) a photopolymerization initiator, and is obtained by polymerizing the polymerizable composition. The polymerizable composition has a dielectric constant of 5.0 or more measured at 23 ° C., a frequency of 1 MHz, and an applied voltage of 100 mV.

First, component 1 which is an essential component of the polymerizable composition of the present invention (I) will be described.
Component 1 which is an essential component of the polymerizable composition of the present invention (I) is a (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 10,000.
Component 1 is not particularly limited as long as it has a number average molecular weight in the range of 1,000 to 10,000 and is a polymer compound having a (meth) acryloyl group.
The “polymer compound” described in the present specification means a polymer having a molecular weight distribution.
Further, the “number average molecular weight” described in the present specification is a number average molecular weight measured in terms of polystyrene by gel permeation chromatography (hereinafter referred to as “GPC”).

  The number average molecular weight of the polymer compound of component 1 which is an essential component in the present invention (I) is in the range of 1000 to 10,000. Preferably, it is the range of 1200-8000, More preferably, it is the range of 1500-6000. When the number average molecular weight is less than 1000, the polymer obtained by polymerizing the composition of the present invention (I) is preferably increased in volume shrinkage during polymerization or the polymer becomes too hard. Absent. Further, when the number average molecular weight is 10,000 or more, the viscosity may be too high, which is not preferable.

  Specific examples of the (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 10000 include, for example, polyether (meth) acrylate and polyester (meth) having a number average molecular weight in the range of 1000 to 10,000. ) Acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, urethane (meth) acrylamide, polycarbonate (meth) acrylate, and the like.

The “(meth) acrylate” in the present specification means at least one group selected from acrylate and methacrylate. Furthermore, “(meth) acrylamide” in the present specification means at least one group selected from acrylamide and methacrylamide.
The polyether (meth) acrylate is a (meth) acrylate produced by a dehydration condensation reaction between a polyether polyol and (meth) acrylic acid or a transesterification reaction between a polyether polyol and (meth) acrylic acid ester.
In addition, “(meth) acrylic acid” in the present specification means at least one group selected from acrylic acid and methacrylic acid.
The polyester (meth) acrylate is a (meth) acrylate produced by a dehydration condensation reaction between a polyester polyol and (meth) acrylic acid or a transesterification reaction between the polyester polyol and (meth) acrylic acid ester.
Epoxy (meth) acrylate has a reaction product of an epoxy group-containing compound having an ether bond, an ester bond or a hydrocarbon chain and (meth) acrylic acid, a polyester polycarboxylic acid, an aliphatic hydrocarbon chain, or an aromatic ring. A reaction product of a polycarboxylic acid such as a polycarboxylic acid or a polycarboxylic acid having a heterocyclic ring and an epoxy group-containing (meth) acryloyl group-containing compound such as glycidyl (meth) acrylate or (meth) acryloyloxybutyl glycidyl ether is there.
Urethane (meth) acrylate is a polyaddition reaction using polyol, organic polyisocyanate compound and alcoholic hydroxyl group-containing (meth) acrylate as essential materials, or (meth) acrylate having a polyol and isocyanate group as essential materials. A compound having a urethane bond in the molecule and one or more (meth) acrylate groups by a polyaddition reaction.
Urethane (meth) acrylamide has a urethane bond in the molecule by a polyaddition reaction using polyol, organic polyisocyanate compound and alcoholic hydroxyl group-containing (meth) acrylamide as essential raw materials, and one or more (meta) ) A compound having an acrylate group.
The polycarbonate (meth) acrylate is a (meth) acrylate produced by a condensation reaction between a polycarbonate polyol and (meth) acrylic acid or a transesterification reaction between the polycarbonate polyol and (meth) acrylic acid ester.

In view of the adhesion between the image display portion of the image display device and the translucent protective portion, among these, a (meth) acryloyl group-containing polymer compound having a urethane bond is preferable. Specifically, urethane (meth) acrylate and urethane (meth) acrylamide are preferable in consideration of the adhesion between the image display unit of the image display device and the translucent protective unit.
The “urethane (meth) acrylate” in the present specification is a compound having a urethane bond in the molecule and one or more acrylate groups or methacrylate groups. The “urethane (meth) acrylamide” in the present specification is a compound having a urethane bond in the molecule and having one or more acrylamide groups or methacrylamide groups.

Although there is no restriction | limiting in particular as a manufacturing method of these urethane (meth) acrylate and urethane (meth) acrylamide, For example, it can manufacture with the following method.
First, the case where urethane (meth) acrylate is obtained using polyol, organic polyisocyanate compound and alcoholic hydroxyl group-containing (meth) acrylate as essential raw material components will be described.

The polyol used for the production of this urethane (meth) acrylate has 2 or more alcoholic hydroxyl groups in one molecule, preferably 2 to 3 alcoholic hydroxyl groups, more preferably, It is to have two. The preferred structure of the polyol is polyester polyol, polycarbonate polyol, or polyether polyol, more preferably polyester polyol or polycarbonate polyol, and most preferably polyester polyol.
Moreover, it is preferable that the hydroxyl value of this polyol is 10-120 mgKOH / g, More preferably, it is 15-100 mgKOH / g, Most preferably, it is 20-80 mgKOH / g. When the hydroxyl value of the polyol is less than 10 mgKOH / g, the molecular weight and viscosity of the resulting polyurethane (meth) acrylate are too high, handling properties tend to be poor, and handling tends to be difficult. Further, when the hydroxyl value of the polyol is greater than 120 mgKOH / g, the volume shrinkage during polymerization is too large, the cohesive strength of the polymer is too high, and the adhesive performance of the polymer is not sufficiently exhibited, which is preferable. I can't say that.

The organic polyisocyanate compound is not particularly limited as long as it is an organic compound having two or more isocyanato groups in one molecule. Specifically, for example, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 2 , 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, lysine triisocyanate, lysine diisocyanate, hexamethylene diisocyanate 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexanemethylene diisocyanate, and norbornane diisocyanate. , It may be used in combination of these alone, or two or more.
Component 1 which is an essential component of the polymerizable composition of the present invention (I) preferably has a low viscosity in consideration of the degree of freedom of subsequent blending. Examples of organic polyisocyanate compounds that meet this purpose include 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 2,4,4-trimethylhexamethylene diisocyanate, 2,2 , 4-trimethylhexanemethylene diisocyanate, 1,6-hexamethylene diisocyanate and norbornane diisocyanate are preferred, more preferably 1,3-bis (isocyanatomethyl) cyclohexane, 2,4,4-trimethylhexamethylene diisocyanate and 2, 2,4-trimethylhexanemethylene diisocyanate, most preferred are 2,4,4-trimethylhexamethylene diisocyanate and 2,2,4-trimethylhexanemethylene diisocyanate It is.

The alcoholic hydroxyl group-containing (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having an alcoholic hydroxyl group in one molecule. Specifically, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3 -(O-phenylphenoxy) propyl acrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxy- Examples include 3-phenoxypropyl methacrylate and 2-hydroxy-3- (o-phenylphenoxy) propyl methacrylate. That.
Among these, considering the polymerization rate of component 1 which is an essential component of the present invention (I), preferred are 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxy They are butyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-hydroxy-3- (o-phenylphenoxy) propyl acrylate. In consideration of reactivity with an isocyanate group, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate are preferable, and 4-hydroxybutyl acrylate is most preferable.

  As a method of reacting a polyol, an organic polyisocyanate compound, and an alcoholic hydroxyl group-containing (meth) acrylate, a polyol, an organic polyisocyanate, in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate or dioctyltin dilaurate The compound can be synthesized by reacting the alcoholic hydroxyl group-containing (meth) acrylate, but the reaction in the presence of a catalyst is preferable in terms of shortening the reaction time. However, if too much is used, there is a possibility that the physical property value at the time of actual use as a cured film will be adversely affected, so the amount used is polyol, organic polyisocyanate compound, alcoholic hydroxyl group-containing (meth) acrylate. It is preferable that it is 0.001-1 mass part with respect to 100 mass parts of total amount.

  Although there is no restriction | limiting in particular about the order which performs preparation of a raw material, For example, an organic polyisocyanate compound and a urethanization catalyst as needed are thrown into a reactor, and it stirs, Then, the temperature in a reactor is 40 degreeC ~ At 140 ° C., preferably 50 ° C. to 120 ° C., polyols and, if necessary, polyols are sequentially added, and then the temperature in the reactor is 50 ° C. to 160 ° C., preferably 60 ° C. to 140 ° C. React. Thereafter, the temperature in the reactor is 30 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C., a polymerization inhibitor and a urethanization catalyst are added if necessary, and an alcoholic hydroxyl group-containing (meth) acrylate is added dropwise. To do. During the dropping, the temperature in the reactor is preferably maintained at 30 to 120 ° C, desirably 50 to 100 ° C. After completion of the dropping, the temperature in the reactor is maintained at 30 to 120 ° C., preferably 50 to 100 ° C., to complete the reaction.

  Further, as another method, for example, an organic polyisocyanate compound, and if necessary, a polymerization inhibitor and / or a urethanization catalyst are charged into the reactor, followed by stirring, and then the temperature in the reactor is set to 30 ° C. to 30 ° C. It is added at 120 ° C., preferably 50 ° C. to 110 ° C. by dropwise addition of alcoholic hydroxyl group-containing (meth) acrylate. During the dropping, the temperature in the reactor is preferably maintained at 30 to 120 ° C, desirably 50 to 110 ° C. After completion of the dropwise addition, the temperature in the reactor is maintained at 30 to 120 ° C., preferably 50 to 110 ° C., and reacted. Thereafter, the reaction product is charged into the reactor containing the polyol while stirring so that the temperature in the reactor can be maintained at 30 to 120 ° C, preferably 50 to 100 ° C. The temperature in the reactor is maintained at 30 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C., to complete the reaction.

  When used as component 1 which is an essential component of the present invention (I), when it is necessary to suppress the increase in the viscosity of the oligomer or to reduce the volume shrinkage during polymerization, only a part of the end of the compound is alcohol. It is desirable that the oligomer be sealed with a compound having one hydroxyl group in the molecule containing a functional hydroxyl group-containing (meth) acrylate.

Charge molar ratio of raw materials (that is, (total number of hydroxyl groups of polyol) / (total number of isocyanato groups of organic polyisocyanate compound used) / (one hydroxyl group containing alcoholic hydroxyl group-containing (meth) acrylate) The total number of hydroxyl groups)) when the number of compounds used is adjusted is adjusted according to the molecular weight of the target polyurethane.
However, when the end of the compound is almost completely sealed with a compound having one hydroxyl group in the molecule containing an alcoholic hydroxyl group-containing (meth) acrylate, the total number of hydroxyl groups of the polyol used is used. It is necessary to increase the total number of isocyanato groups in the organic polyisocyanate compound.
In this case, if the ratio of the total number of hydroxyl groups of the polyol used to the total number of isocyanate groups in the organic polyisocyanate compound is close to 1.0, the average molecular weight of the compound produced increases, and from 1.0 As the molecular weight decreases, the average molecular weight decreases.
Although there is no restriction | limiting in particular in the preparation molar ratio of a raw material, It is preferable that the molar ratio of the isocyanate group in the organic polyisocyanate compound with respect to the hydroxyl group of the polyol used is 1.5 or more.
If this ratio is less than 1.5, the viscosity may be too high, which is not preferable.

In addition, when only a part of the terminal of the compound is sealed with a compound having one hydroxyl group containing an alcoholic hydroxyl group-containing (meth) acrylate in the molecule, the polyol to be used and the alcoholic hydroxyl group-containing (meth) acrylate The total number of hydroxyl groups when a compound having one hydroxyl group in the molecule is combined with the total number of isocyanato groups of the organic polyisocyanate compound to be used must be increased.
However, in this case, the total number of hydroxyl groups when the compound having one hydroxyl group in the molecule including the polyol and the alcoholic hydroxyl group-containing (meth) acrylate is combined with the total number of isocyanato groups in the organic polyisocyanate compound. The ratio is preferably 2: 1 or less.
When this ratio is larger than 2: 1, the number of molecules having no (meth) acryloyl group increases, and the shape retention of the polymer after polymerization may be deteriorated, which is not preferable.

  Urethane (meth) acrylamide is an alcoholic hydroxyl group-containing (meth) which is a raw material of the urethane (meth) acrylate produced using a polyol, an organic polyisocyanate compound and an alcoholic hydroxyl group-containing (meth) acrylate as essential raw material components. It can be produced by using alcoholic hydroxyl group-containing (meth) acrylamide instead of acrylate. The production conditions of urethane (meth) acrylamide can be produced under the same conditions as the production conditions of urethane (meth) acrylate.

Next, a case where urethane (meth) acrylate is obtained using (meth) acrylate having a polyol and an isocyanato group as essential raw material components will be described.
The polyol is as described above.
Examples of the (meth) acrylate having an isocyanato group that can be the raw material include 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate.
Examples of 2-isocyanatoethyl acrylate include Karenz AOI (registered trademark) manufactured by Showa Denko KK.
Examples of 2-isocyanatoethyl methacrylate include Kaerens MOI (registered trademark) manufactured by Showa Denko KK.

A urethane (meth) acrylate obtained using a polyol and a (meth) acrylate having one isocyanato group in one molecule as an essential raw material component is generally synthesized by the following method.
Even if the total amount of hydroxyl groups of the polyol is reacted with the (meth) acrylate having an isocyanato group, only a part of the hydroxyl groups of the polyol are reacted with the (meth) acrylate having an isocyanato group to leave some hydroxyl groups. But it doesn't matter.
When all the hydroxyl groups of the polyol are reacted with the (meth) acrylate having an isocyanate group, the ratio of the total number of hydroxyl groups of the polyol to the total number of isocyanate groups of the isocyanate group-containing (meth) acrylate used is 1 or more. There is a need.
When only a part of the hydroxyl group of the polyol is reacted with the (meth) acryloyl group-containing compound having an isocyanato group to leave a part of the hydroxyl group, the isocyanate group-containing (meth) used is determined from the total number of hydroxyl groups of the polyol. It is necessary to charge a small total number of isocyanate groups of acrylate.

  There are no particular restrictions on the production method, but in general, a polyol, a polymerization inhibitor and, if necessary, a urethanization catalyst and an antioxidant are added, put into the reactor, stirring is started, and the temperature in the reactor is increased. The temperature is raised to 40 ° C to 120 ° C, preferably 50 ° C to 100 ° C. Thereafter, (meth) acrylate having an isocyanato group is dropped. During the dropping, the temperature in the reactor is controlled to 40 ° C to 130 ° C, preferably 50 ° C to 110 ° C. After completion of the dropwise addition, the temperature in the reactor is maintained at 40 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C. while continuing stirring to complete the reaction.

In view of increasing the dielectric constant of the polymer obtained by polymerizing component 1, a structural unit derived from a diol having 4 to 9 carbon atoms and a structure derived from a dicarboxylic acid having 4 to 10 carbon atoms It is preferable to use a (meth) acryloyl group-containing polymer compound having a polyester structural unit containing a unit.
As used herein, the “structural unit derived from a diol having 4 to 9 carbon atoms” refers to a structure in which hydrogen in at least one hydroxyl group of two hydroxyl groups of the diol having 4 to 9 carbon atoms is removed. Means. In addition, the “structural unit derived from a dicarboxylic acid having 4 to 10 carbon atoms” in the present specification means OH in two carboxyl groups (—C (═O) OH) of the dicarboxylic acid having 4 to 10 carbon atoms. It means a structure in which a group is removed.
If only a diol having 3 or less carbon atoms is used, it cannot be said that the hydrophilicity of the polymer obtained by polymerizing component 1 becomes too high and the water resistance becomes weak, which is not preferable. In addition, when only a diol having 10 or more carbon atoms is used, the dielectric constant of a polymer obtained by polymerizing Component 1 may decrease, which is not preferable.
Further, if only a dicarboxylic acid having 3 or less carbon atoms is used, the hydrophilicity of the polymer obtained by polymerizing component 1 becomes too high and the water resistance becomes weak, which is not preferable. In addition, when only a dicarboxylic acid having 10 or more carbon atoms is used, the dielectric constant of a polymer obtained by polymerizing component 1 may decrease, which is not preferable.

  Specific examples of the diol having 4 to 9 carbon atoms include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5- Pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1 , 5-pentanediol and the like, and these can be used alone or in combination of two or more. Among these, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol are more preferable. Among them, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and most preferred is 3-methyl-1,5-pentanediol.

  Specific examples of the dicarboxylic acid having 4 to 10 carbon atoms include succinic acid, glutaric acid, methyl succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and phthalic acid. 1,1-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-cyclohexane-1,1-dicarboxylic acid, and the like. It can be used in combination. Among these, glutaric acid, methyl succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,1-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 2-cyclohexane- 1,1-dicarboxylic acid, more preferably glutaric acid, methyl succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid, and most preferably adipic acid.

Next, component 2 which is an essential component of the polymerizable composition of the present invention (I) will be described.
Component 2 which is an essential component of the polymerizable composition of the present invention (I) is a photopolymerization initiator.
The photopolymerization initiator of component 2 is not particularly limited as long as it is a compound that generates radicals that contribute to the initiation of radical polymerization upon irradiation with light such as near infrared rays, visible rays, and ultraviolet rays.

  Specific examples of the photopolymerization initiator of Component 2 include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1,2-hydroxy-2-methyl-1 -Phenylpropan-1-one, α-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- (4-isopropylphenyl) propane- 1-one, 2-hydroxy-2-methyl-1- (4-dodecylphenyl) propan-1-one, and 2-hydroxy-2-methyl-1-[(2-hydroxyethoxy) phenyl] propanone, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methyl Nzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, benzophenone tetracarboxylic acid or its Tetramethyl esters, 4,4'-bis (dialkylamino) benzophenones (eg 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (dicyclohexylamino) benzophenone, 4,4'-bis (diethylamino) ) Benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone), 4-methoxy-4′-dimethylaminobenzophenone, 4,4′-dimethoxybenzophenone, 4-dimethyl Ruaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, fluorenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether) , Benzoinpropyl ether, benzo Isopropyl ether, benzoin isobutyl ether, benzoin phenyl ether, benzyldimethyl ketal), acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, 2,4,6-trimethyl Benzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6-dimethylphenyl) phosphonate, etc. And the like. Examples of bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) phenyl phosphite Oxide, (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1 -Chloro-4-propoxythioxanthone and the like.

  Moreover, a metallocene compound can also be used as a photopolymerization initiator. As the metallocene compound, the transition metal represented by Fe, Ti, V, Cr, Mn, Co, Ni, Mo, Ru, Rh, Lu, Ta, W, Os, Ir, etc. can be used as the metallocene compound, An example is bis (η5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (pyrrol-1-yl) phenyl] titanium.

These photopolymerization initiators can be used alone or in combination of two or more.
Of these, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4, 6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, particularly preferable examples include 1-hydroxycyclohexylphenylketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, most preferably 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide or 1-hydroxycyclohexylphenylketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2 , 4,6-trimethylbenzoylethoxyphenylphosphine oxide.

  1 to 4 may have a function of cutting the ultraviolet region from the viewpoint of protecting the display unit 2 from ultraviolet rays. In that case, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethyl, which is a photopolymerization initiator that can be sensitized even in the visible light region. Benzoylethoxyphenylphosphine oxide is preferably used, and 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are particularly preferable.

  The usage-amount of the component 2 in this invention (I) is 0.05-10.0 mass parts with respect to 100 mass parts of quantity which remove | excluded the component 2 from the whole quantity of the polymeric composition of this invention (I). Is more preferable, 0.1 to 7.0 parts by mass, and particularly preferably 0.2 to 5.0 parts by mass. Insufficient polymerization initiation performance of the polymerization initiator when the amount of Component 2 used is less than 0.05% by mass based on 100 parts by mass of Component 2 from the total amount of the polymerizable composition of the present invention (I). May be undesirable. Moreover, when the usage-amount of the component 2 of this invention becomes more than 10.0 mass% with respect to 100 mass parts of quantity remove | excluding the component 2 from the whole quantity of the polymeric composition of this invention (I), this invention mentioned later is mentioned. When the polymer (V) or the optical pressure-sensitive adhesive sheet of the present invention (VII) described later is placed in a high-temperature environment, it may be easily colored, which is not preferable.

The polymer obtained by polymerizing the polymerizable composition of the present invention must have a dielectric constant of 5.0 or more measured at 23 ° C., a frequency of 1 MHz, and an applied voltage of 100 mV.
“The dielectric constant of the polymer measured at 23 ° C., a frequency of 1 MHz and an applied voltage of 100 mV” means that a 2.0 mm-thick test piece (polymer) is obtained from Agilent Technologies in a 23 ° C. environment. 4294A Precision Impedance Analyzer 40Hz-110MHz was used as the impedance analyzer manufactured by Agilent Technologies, and 16451B dielectric test fixture manufactured by Agilent Technologies was used as the test fixture. It is the dielectric constant of the polymer under the conditions.
It is known that the capacitance type touch panel is easier to detect touch or proximity as the capacitance generated by the user's fingertip is larger. The capacitance is the area of the electrode formed by the touch sensor and the finger, the dielectric constant of the polymer (layer) filled between the touch sensor and the protective part, the thickness of the panel interposed between the electrodes, etc. Depends on. The higher the dielectric constant of the polymer (layer) is, the easier it is to detect touch or proximity, and the response sensitivity is improved.
In order to prepare a polymerizable composition having a dielectric constant of 5.0 or more at 1 MHz when cured, the total amount of ether bonds, ester bonds and hydroxyl groups per unit mass of the entire polymerizable composition is 5 It is preferably at least 0.0 mmol / g, more preferably at least 5.5 mmol / g, and most preferably at least 6.0 mmol / g. When the total molar amount of ether bonds, ester bonds and hydroxyl groups per unit mass of the entire polymerizable composition is less than 5.0 mmol / g, 1 MHz of a polymer (layer) obtained by polymerizing the polymerizable composition The dielectric constant at 5 tends to be less than 5.0. There is no upper limit to the total of ether bonds, ester bonds, and hydroxyl groups contained in the polymerizable composition. However, if the amount of the ether bond contained in the polymerizable composition is too large, the light transmittance at 370 to 450 nm decreases with time when the polymer (layer) is stored at a high temperature, which is not preferable. . Therefore, the molar amount of ether bonds per unit mass of the entire polymerizable composition is preferably 10 mmol / g or less. In addition, if the total amount of ester bonds and ether bonds per unit mass of the entire polymerizable composition is too large, the polymer (layer) is likely to absorb water, and thus may be whitened when stored under high temperature and high humidity conditions. is there. Since the hydroxyl group contained in the polymerizable composition plays a role of preventing the whitening phenomenon under a high temperature and high humidity condition, the molar amount of the hydroxyl group per unit mass of the entire polymerizable composition is the unit of the entire polymerizable composition. It is preferably 5% to 60%, more preferably 6% to 40%, and most preferably 6% to 30%, based on the total molar amount of ester bond, ether bond and hydroxyl group per mass. There is no upper limit to the ratio of hydroxyl groups to the total molar amount of ester bonds, ether bonds and hydroxyl groups contained in the polymerizable composition, but if the amount of hydroxyl groups contained in the polymerizable composition is too large, the polymer product Since the shape retention of the (layer) under high-temperature and high-humidity conditions may be deteriorated, the ratio of hydroxyl groups per unit mass of the entire polymerizable composition is preferably less than 5 mmol / g.
A more preferable dielectric constant is a dielectric constant measured under the above conditions of 5.5 or more, more preferably 6.0 or more, and particularly preferably 6.1 or more.
When the dielectric constant of the polymer measured under the above conditions is less than 5.0, the sensitivity of the capacitive touch panel may decrease, which is not preferable.
The upper limit of the dielectric constant is not particularly limited. However, when the dielectric constant is increased, the polarity increases, and as a result, the water resistance tends to decrease. In order to prevent the water resistance from being extremely impaired, the dielectric constant is 40 or less. Preferably, it is 20 or less, most preferably 10 or less.

  Moreover, it is preferable that the polymer obtained by polymerizing the polymerizable composition of the present invention has high transparency. Specifically, the polymer is adjusted to a thickness of 200 μm existing between two glasses. The haze is preferably 0.4 or less, and more preferably 0.2 or less.

Next, the present invention (II) will be described.
The present invention (II) is a polymerizable composition for forming a polymer layer interposed between the image display part and the translucent protective part of the image display device, the polymerizable composition comprising:
(Component 1) (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 10,000,
Polymerization obtained by polymerizing the polymerizable composition, comprising (Component 2) a photopolymerization initiator, and (Component 3) a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group. The polymerizable composition is characterized in that the dielectric constant measured under the conditions of 23 ° C., frequency 1 MHz and applied voltage 100 mV is 5.0 or more.

  Component 1 and Component 2 of the present invention (II) are the same as Component 1 and Component 2 of the present invention (I), respectively. However, component 1 in the present invention (II) is obtained by removing component 3 described later from component 1 in the present invention (I).

Next, component 3 which is an essential component of the polymerizable composition of the present invention (II) will be described.
Component 3 which is an essential component of the polymerizable composition of the present invention (II) is a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group.
However, in this specification, the (meth) acryloyl group-containing polymer compound having at least one of an alcoholic hydroxyl group and an amide group and having a number average molecular weight in the range of 1000 to 10,000 is not included in Component 3. Define. That is, in the present specification, a (meth) acryloyl group-containing polymer compound having at least one of an alcoholic hydroxyl group and an amide group and having a number average molecular weight in the range of 1000 to 10,000 is not included in Component 3, and the present invention It is included in Component 1 which is an essential component of the polymerizable composition.
In the present specification, the “radical polymerizable unsaturated group” means a carbon-carbon double bond capable of addition polymerization by a radical generated by a radical polymerization initiator or the like.

Specific examples of the radical polymerizable unsaturated group-containing compound having an amide group as Component 3 include, for example, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-acryloylmorpholine, N-isopropylacrylamide, N- tert-butylacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, N- Methacryloylmorpholine, N-isopropylmethacrylamide, N-tert-butylmethacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylmethacrylamide, Nn-butoxymethylmethacrylate , N-isobutoxymethylmethacrylamide, N-vinyl-pyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide, 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide, etc. be able to. These compounds can be used alone or in combination of two or more.
Among these, preferred are N, N-diethylacrylamide, N-acryloylmorpholine, N-tert-butylacrylamide, N-tert-butylacrylamide, N-ethoxymethylacrylamide, Nn-butoxymethylacrylamide, N -Isobutoxymethyl acrylamide, N-vinyl-pyrrolidone, more preferably N, N-diethylacrylamide, N-acryloylmorpholine, N-ethoxymethylacrylamide, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide And most preferred is N-acryloylmorpholine.

Specific examples of the radical polymerizable unsaturated group-containing compound having an alcoholic hydroxyl group as component 3 include, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate. 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl acrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate , Mention may be made of 2-hydroxy-3-(o-phenylphenoxy) propyl methacrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylamide. These compounds can be used alone or in combination of two or more.
Among these, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate and 2-hydroxybutyl methacrylate are preferable, and 4-hydroxybutyl acrylate is more preferable. 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, and most preferably 2-hydroxypropyl methacrylate.

The amount of component 3 used in the present invention (II) is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, based on the total amount of component 1 and component 3. Preferably, it is 3-10 mass%. When the amount of component 3 used in the present invention (II) is less than 1% by mass based on the total amount of component 1 and component 3, the polymer of the present invention (V) and the present invention (VII) described later This optical pressure-sensitive adhesive sheet may be whitened in a hot and humid environment, which is not preferable. Moreover, when the usage-amount of the component 3 in this invention (II) is more than 30 mass% with respect to the quantity which combined the component 1 and the component 3, at the time of superposition | polymerization of the polymeric composition of this invention (II) There is a possibility that the volume shrinkage rate is increased, which is not preferable.
Moreover, it is preferable that the usage-amount of the component 1 in this invention (II) is 70-99 mass% with respect to the quantity which combined the component 1 and the component 3, More preferably, it is 80-98 mass%. Especially preferably, it is 90-97 mass%. When the amount of component 1 used in the present invention (II) is less than 70% by mass relative to the total amount of component 1 and component 3, the volume shrinkage during polymerization of the polymerizable composition of the present invention (II) The rate may increase, which is not preferable. Moreover, when the usage-amount of the component 1 in this invention (II) is 99 mass% or more with respect to the quantity which combined the component 1 and the component 3, the viscosity of polymeric composition may become high too much. This is not preferable.

  Moreover, the usage-amount of the component 2 in this invention (II) is 0.05-10.0 mass parts with respect to 100 mass parts of quantity which remove | excluded the component 2 from the whole quantity of the polymeric composition of this invention (II). The content is preferably 0.1 to 7.0 parts by mass, and more preferably 0.2 to 5.0 parts by mass. When the amount of component 2 used is less than 0.05 parts by mass with respect to 100 parts by mass of component 2 from the total amount of the polymerizable composition of the present invention (II), the polymerization initiator performance is insufficient. May be undesirable. Moreover, when the usage-amount of the component 2 of this invention becomes more than 10.0 mass parts with respect to 100 mass parts of quantity remove | excluding the component 2 from the whole quantity of the polymeric composition of this invention (II), this invention mentioned later is mentioned. When the polymer (V) or the optical pressure-sensitive adhesive sheet of the present invention (VII) described later is placed in a high-temperature environment, it may be easily colored, which is not preferable.

Next, the present invention (III) will be described.
The present invention (III) is a polymerizable composition for forming a polymer layer interposed between the image display part of the image display device and the translucent protective part, the polymerizable composition comprising:
(Component 1) (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 10,000,
(Component 2) Photopolymerization initiator,
(Component 3) a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group, and (Component 4) no alcoholic hydroxyl group or amide group, and a viscosity of 25 ° C. A dielectric constant measured under the conditions of a polymer obtained by polymerizing the polymerizable composition containing a (meth) acryloyl group-containing compound of 500 mPa · s or less at 23 ° C., a frequency of 1 MHz, and an applied voltage of 100 mV. It is a polymerizable composition characterized by being 5.0 or more.

  Component 1 and Component 2 of the present invention (III) are the same as Component 1 and Component 2 of the present invention (I), respectively, and Component 3 of the present invention (III) is a component of the present invention (II). It is the same as 3. However, the component 1 in the present invention (III) is obtained by removing the aforementioned component 3 and the later-described component 4 from the component 1 in the present invention (I).

Next, component 4 that is an essential component of the polymerizable composition of the present invention (III) will be described.
Component 4 is a (meth) acryloyl group-containing compound which does not have any group of alcoholic hydroxyl group and amide group and has a viscosity of 500 mPa · s or less at 25 ° C.

  Specific examples of component 4 include, for example, cyclohexyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentanyl ethyl acrylate, 4-tert-butylcyclohexyl acrylate. (Meth) acryloyl having a cyclic aliphatic group such as isobornyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanylethyl methacrylate, 4-tert-butylcyclohexyl methacrylate Group-containing compounds, hexyl acrylate, lauryl acrylate, isononyl acrylate, 2-propylheptyl acrylate 4-methyl-2-propylhexyl acrylate, isooctadecyl acrylate, 2-heptylundecyl acrylate, lauryl methacrylate, isononyl methacrylate, 2-propylheptyl methacrylate, 4-methyl-2-propylhexyl methacrylate, isooctadecyl methacrylate, 2 -(Meth) acryloyl group-containing compound having a chain aliphatic group such as heptyl undecyl methacrylate, methoxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, phenoxyethyl (meth) acrylate, 3-methyl-3 -Oxetanylmethyl (meth) acrylate, 1,4-dioxaspiro [4.5] dec-2-ylmethyl (meth) acrylate, (2-methyl-2-ethyl- , 3-Dioxolan-4-yl) methyl (meth) acrylate, etc., (meth) acryloyl group-containing compounds having an ether bond, α-methacryloxy-γ-butyrolactone, cyclic esters such as α-acryloxy-γ-butyrolactone And (meth) acryloyl group-containing compounds having

  Among these, in order to increase the dielectric constant of the polymer of the present invention described later or the optical pressure-sensitive adhesive sheet of the present invention, methoxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, phenoxyethyl (meta ) Acrylate, 3-methyl-3-oxetanylmethyl (meth) acrylate, 1,4-dioxaspiro [4.5] dec-2-ylmethyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolane) (-4-yl) methyl (meth) acrylate and the like (meth) acryloyl group-containing compound having an ether bond, α-methacryloxy-γ-butyrolactone, cyclic esters such as α-acryloxy-γ-butyrolactone (meth) ) An acryloyl group-containing compound is preferred, more preferred Methoxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, phenoxyethyl (meth) acrylate, 3-methyl-3-oxetanylmethyl (meth) acrylate, 1,4-dioxaspiro [4.5] (Meth) acryloyl group-containing compounds having an ether bond in the molecule, such as dec-2-ylmethyl (meth) acrylate and (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate Particularly preferred are diethylene glycol monoethyl ether (meth) acrylate, 3-methyl-3-oxetanylmethyl (meth) acrylate, 1,4-dioxaspiro [4.5] dec-2-ylmethyl (meth) acrylate , (2-methyl-2-ethyl L, 3-dioxolan-4-yl) methyl (meth) acrylate.

  It is preferable that the usage-amount of the component 4 in this invention (III) is 3-40 mass% with respect to the total amount which combined the component 1, the component 3, and the component 4 which are essential components of this invention (III). Preferably, it is 5-35 mass%, Most preferably, it is 7-30 mass%. When the usage-amount of the component 4 in this invention (III) is less than 3 mass% with respect to the total amount which combined the component 1, the component 3, and the component 4 which are essential components of this invention (III), this invention (III ) Is not preferred because the viscosity of the polymerizable composition may become too high. Further, when the amount of component 4 used in the present invention (III) is more than 40% by mass with respect to the total amount of component 1, component 3 and component 4 which are essential components of the present invention (III), Since the volumetric shrinkage during polymerization of the polymerizable composition of the invention (III) may increase, it is not preferable.

  It is preferable that the usage-amount of the component 3 in this invention (III) is 1-27 mass% with respect to the total amount which combined the component 1, the component 3, and the component 4, More preferably, it is 2-18 mass%. Yes, particularly preferably 3 to 10% by mass. When the amount of component 3 used in the present invention (III) is less than 1% by mass based on the total amount of component 1, component 3 and component 4, the polymer of the present invention (V) described later and the present invention The optical pressure-sensitive adhesive sheet (VII) may be whitened in a hot and humid environment, which is not preferable. When the amount of component 3 used in the present invention (III) is more than 27% by mass based on the total amount of component 1, component 3 and component 4, the polymerizable composition of the present invention (III) There is a possibility that the volume shrinkage during polymerization is increased, which is not preferable.

  Moreover, it is preferable that the usage-amount of the component 1 in this invention (III) is 50-96 mass% with respect to the total amount which combined the component 1, the component 3, and the component 4, More preferably, it is 55-93 mass %, Particularly preferably 60 to 90% by mass. When the amount of component 1 used in the present invention (III) is less than 50% by mass based on the total amount of component 1, component 3 and component 4, the polymerization composition of the present invention (III) is polymerized. In some cases, the volumetric shrinkage ratio of the film becomes large, which is not preferable. Moreover, when the usage-amount of the component 1 in this invention (III) is 96 mass% or more with respect to the total amount which combined the component 1, the component 3, and the component 4, the viscosity of polymeric composition becomes high too much. In some cases, it is not preferable.

  Moreover, the usage-amount of the component 2 in this invention (III) is 0.05-10.0 mass parts with respect to 100 mass parts of quantity which remove | excluded the component 2 from the whole quantity of the polymeric composition of this invention (III). The content is preferably 0.1 to 7.0 parts by mass, and more preferably 0.2 to 5.0 parts by mass. When the amount of component 2 used is less than 0.05 parts by mass based on 100 parts by mass of component 2 from the total amount of the polymerizable composition of the present invention (III), the polymerization initiator performance is insufficient. May be undesirable. Moreover, when the usage-amount of the component 2 of this invention becomes more than 10.0 mass parts with respect to 100 mass parts of quantity remove | excluding the component 2 from the whole quantity of the polymeric composition of this invention (II), this invention mentioned later is mentioned. When the polymer (V) or the optical pressure-sensitive adhesive sheet of the present invention (VII) described later is placed in a high-temperature environment, it may be easily colored, which is not preferable.

Next, the present invention (IV) will be described.
The present invention (IV) is a polymerizable composition for forming a polymer layer interposed between the image display part of the image display device and the translucent protective part, the polymerizable composition comprising:
(Component 1) (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 10,000,
(Component 2) Photopolymerization initiator,
(Component 3) Radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group,
(Component 4) a (meth) acryloyl group-containing compound which does not have any group of an alcoholic hydroxyl group and an amide group and has a viscosity of 500 mPa · s or less at 25 ° C.
(Component 5) Nonionic surfactant having no (meth) acryloyl group, and (Component 6) No (meth) acryloyl group in the molecule, a function of suppressing radical polymerization, a function of inhibiting radical polymerization Liquid or solid at 25 ° C., which has neither a polymerization initiation function nor a surface-active function, and is composed of carbon atoms and hydrogen atoms, or is composed of carbon atoms, hydrogen atoms and oxygen atoms And a dielectric constant measured at 23 ° C., a frequency of 1 MHz and an applied voltage of 100 mV of a polymer obtained by polymerizing the polymerizable composition is 5.0 or more. It is a polymerizable composition.

  Component 1 and Component 2 of the present invention (IV) are respectively the same as Component 1 and Component 2 of the present invention (I), and Component 3 of the present invention (IV) is a component of the present invention (II). 3, component 4 of the present invention (IV) is the same as component 4 of the present invention (III). However, Component 1 in the present invention (IV) is obtained by removing the above-mentioned Component 3 and Component 4 from Component 1 in the present invention (I).

Next, component 5 which is an essential component of the polymerizable composition of the present invention (IV) will be described.
Component 5 is a nonionic surfactant that does not have a (meth) acryloyl group. The term “surfactant” in this specification is a generic name for substances having a portion that is familiar with water (hydrophilic group) and a portion that is familiar with oil (lipophilic group / hydrophobic group). And a vesicle, a lamellar structure, etc., and thus a compound having a property capable of uniformly mixing a polar substance and a nonpolar substance.
As a scale representing the degree of hydrophilicity and hydrophobicity (lipophilicity) of nonionic surfactants, Griffin's HLB (Hydrophile-Lipophile Balance) is often used. The HLB of Griffin is a required value with HLB = 0 having no hydrophilic group at all, and HLB = 20 having only a hydrophilic group such as polyethylene glycol. For details, see Shigeo Hayano, This is described in Yukagaku, Vol. 13, No. 4, 220 (1964).

Specific examples of component 5 include glycerin monostearate (HLP of Griffin = 4.3), glycerin monolaurate (HLB of Griffin = 5.4), glycerin monocaprate (HLB of Griffin = 6.8), glycerin Glycerin monofatty acid ester such as monocaprylate (HLP of Griffin = 7.0), propylene glycol monolaurate (HLB of Griffin = 4.2), propylene glycol monopalmitate (HLB of Griffin = 3.8), propylene Propylene glycol monofatty acid esters such as glycol monostearate (Glyphine HLB = 3.7), propylene glycol monooleate (Glyffin HLB = 3.6), propylene glycol monobehenate (Glyphine HLB = 3.4), Sorbita Sorbitan monofatty acid esters such as monolaurate (Glyphine HLB = 8.6), sorbitan monooleate (HLP of Griffin = 4.3), sorbitan monostearate (HLB of Griffin = 4.7), sorbitan tristearate Sorbitan trifatty acid esters such as rate (griffin HLB = 3.0), sorbitan trioleate (griffin HLB = 3.0), sorbitan tribehenate (griffin HLB = 2.5), polyoxyethylene (griffin) Average addition number of ethylene oxide = 20 mol) sorbitan trioleate (HLB of Griffin = 11.0), polyoxyethylene (average addition number of ethylene oxide = 5 mol) glycerin monostearate (HLB of Griffin = 8.7), etc. Of polyoxyethylene And fatty acid esters having a granulation.
These may be used alone or in combination of two or more.

  Among these nonionic surfactants having no (meth) acryloyl group, it is preferable that the HLB value of Griffin is 3.0 to 9.0, more preferably 3. It is 0-7.5, Most preferably, it is 3.0-6.0.

Next, component 6 that is an essential component of the polymerizable composition of the present invention (IV) will be described.
Component 6 has no (meth) acryloyl group in the molecule, does not have any function of suppressing radical polymerization, function of inhibiting radical polymerization, photopolymerization initiating function, or surface-active function, and carbon atom And a hydrogen atom or a compound composed of a carbon atom, a hydrogen atom and an oxygen atom, which is liquid or solid at 25 ° C.
In particular, an image display device is manufactured using a manufacturing method including a step of forming a polymer layer by interposing a polymerizable composition between a base portion having an image display portion and a translucent protective portion and polymerizing the polymerizable composition. In such a case, the polymerizable composition used in this step needs to contain component 6 for the purpose of keeping the volume shrinkage during polymerization low. In addition to suppressing the volume shrinkage during polymerization, it may be used for the purpose of increasing the adhesion of the polymer to an adherend such as glass or acrylic resin.
As the component 6, a compound that is liquid at 25 ° C. or a compound that is solid at 25 ° C. can be used.

  Examples of the compound used as component 6 that is liquid at 25 ° C. include poly (α-olefin) liquid, ethylene-propylene copolymer liquid, propylene-α-olefin copolymer liquid, and ethylene-α-olefin. Copolymer liquid, liquid polybutene, liquid hydrogenated polybutene, liquid polybutadiene, liquid hydrogenated polybutadiene, liquid polyisoprene, liquid hydrogenated polyisoprene, liquid polybutadiene polyol, liquid hydrogenated polybutadiene polyol, liquid polyisoprene polyol, liquid hydrogenated poly Examples include isoprene polyol, polyether polyol, polyester polyol, and polycarbonate polyol.

  The poly (α-olefin) liquid is a liquid produced by polymerization of α-olefin, and the α-olefin is a hydrocarbon compound having one carbon-carbon double bond at the molecular end. 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and the like.

  The ethylene-α-olefin copolymer liquid material is a liquid polymer produced by copolymerizing ethylene and an α-olefin. An α-olefin is a hydrocarbon compound having one carbon-carbon double bond at the molecular end, for example, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, Examples thereof include 1-tetradecene, 1-hexadecene, 1-octadecene and the like.

  The propylene-α-olefin copolymer liquid is a liquid polymer produced by copolymerizing propylene and α-olefin. An α-olefin is a hydrocarbon compound having one carbon-carbon double bond at the molecular end, for example, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, Examples thereof include 1-tetradecene, 1-hexadecene, 1-octadecene and the like.

  Liquid polybutene is a liquid polymer containing isobutene or n-butene as a (co) polymerization component, such as homopolymerization of isobutene, homopolymerization of n-butene, and copolymerization of isobutene and n-butene. It is a compound having a carbon-carbon unsaturated bond. As a commercial product of liquid polybutene, for example, Nisseki Polybutene LV-7, LV-50, LV-100, HV-15, HV-35, HV-50, HV-100, manufactured by JX Nippon Mining & Energy Corporation, HV-300 etc. can be mentioned.

  The liquid hydrogenated polybutene is a liquid material having a side chain obtained by hydrogenating the liquid polybutene. For example, palm reel 4, palm reel 6, palm reel 18, palm reel 24 manufactured by NOF Corporation. And palm reel EX.

  Liquid polybutadiene is a butadiene polymer that is liquid at room temperature. For example, POLYVEST110, POLYVEST130 manufactured by Evonik Degussa, NISSO-PB B-1000, NISSO-PB B-2000, NISSO-PB B- manufactured by Nippon Soda Co., Ltd. 3000 etc. can be mentioned.

  Liquid hydrogenated polybutadiene is a liquid product at room temperature obtained by reductive hydrogenation of a butadiene polymer, and examples thereof include NISSO-PB BI-2000, NISSO-PB B-3000 manufactured by Nippon Soda Co., Ltd. Can do.

  The liquid polyisoprene is a liquid isoprene polymer at room temperature, and examples thereof include Kuraray LIR-30 manufactured by Kuraray Co., Ltd.

  Liquid hydrogenated polyisoprene is a compound that is liquid at room temperature obtained by reductive hydrogenation of an isoprene polymer, and examples thereof include LIR-200 manufactured by Kuraray Co., Ltd.

  The liquid polybutadiene polyol is a polymer that is liquid at room temperature and has two or more hydroxyl groups at the molecular terminals and has a polybutadiene structural unit. For example, NISSO-PB G-1000, NISSO-PB manufactured by Nippon Soda Co., Ltd. Examples thereof include G-2000, NISSO-PB G-3000, and Poly bd manufactured by Idemitsu Kosan Co., Ltd.

  The liquid hydrogenated polybutadiene polyol is a liquid polyol having a structure obtained by reductive hydrogenation of polybutadiene polyol or polybutadiene polycarboxylic acid. And NISSO-PB GI-3000.

  The liquid polyisoprene polyol is a polymer that is liquid at room temperature and has two or more hydroxyl groups at the molecular ends and has a polyisoprene structural unit, and examples thereof include a poly ip manufactured by Idemitsu Kosan.

  The liquid hydrogenated polyisoprene polyol is a liquid polyol having a structure obtained by reductive hydrogenation of polyisoprene polyol or polyisoprene polycarboxylic acid, and examples thereof include Epolle manufactured by Idemitsu Kosan Co., Ltd.

  Examples of the polyether polyol include polypropylene glycol, polytetramethylene glycol, and propylene oxide-tetrahydrofuran copolymer.

  Examples of the polyester polyol include a polycondensate of a polyol and a polycarboxylic acid, a transesterification product of an ester of a polyol and a polycarboxylic acid, a ring-opening polymer of a cyclic ester into a polyol, and the like.

  Examples of the polycarbonate polyol include a polycondensate of polyol and phosgene, or a transesterification product of a polyol with an organic carbonate such as dimethyl carbonate, diethyl carbonate, or ethylene carbonate.

  It is desirable to make the dielectric constant of the polymer of the present invention (V) and the optical pressure-sensitive adhesive sheet of the present invention (VII) described below as high as possible. For that purpose, as the compound used as component 5 and in a liquid state at 25 ° C., preferred are polyether polyol, polyester polyol, and polycarbonate polyol, and more preferred are polyester polyol and polycarbonate polyol.

  Specific examples of the polyol used as a raw material for the polyester polyol include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5- Pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1 , 5-pentanediol, trimethylolethane, trimethylolpropane and the like, and these can be used alone or in combination of two or more. Among these, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol are more preferable. Examples include 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and the most preferable is 3-methyl-1,5-pentanediol.

  Specific examples of the polycarboxylic acid used as a raw material for polyester polyol include succinic acid, glutaric acid, methyl succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid. Phthalic acid, 1,1-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-cyclohexane-1,1-dicarboxylic acid, and the like. More than one type can be used in combination. Among these, glutaric acid, methylsuccinic acid, adipic acid, pimelic acid, suberic acid, 1,1-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 2-cyclohexane-1,1-dicarboxylic acid are preferable. , Terephthalic acid, isophthalic acid, and phthalic acid, more preferably glutaric acid, methylsuccinic acid, adipic acid, pimelic acid, suberic acid, terephthalic acid, isophthalic acid, and phthalic acid. Particularly preferred are glutaric acid, methyl succinic acid, adipic acid and pimelic acid.

  As the ester of polycarboxylic acid used as a raw material for the polyester polyol, the lower alkyl ester of the polycarboxylic acid is generally used.

  Examples of the cyclic ester used as a raw material for the polyester polyol include γ-butyrolactone and ε-lactone.

  Examples of the polyol used as a raw material for the polycarbonate polyol include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,8 -Octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, Examples thereof include trimethylolethane and trimethylolpropane. These can be used alone or in combination of two or more. Among these, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol are more preferable. Examples include 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and the most preferable is 3-methyl-1,5-pentanediol.

In the polymerizable composition of the present invention (IV), a compound that is solid at 25 ° C. can be used as component 6.
The compound that is used as component 6 and is solid at 25 ° C. is preferably a compound having no carbon-carbon unsaturated bond in the molecule.
Such compounds include epoxy resins that are solid at 25 ° C., polyester resins that are solid at 25 ° C., polyol resins that are solid at 25 ° C., hydrogenated petroleum resins that are solid at 25 ° C., terpene hydrogenated resins, hydrogenated Mention may be made of tackifiers such as rosin esters.
Among these, preferred are tackifiers such as hydrogenated petroleum resins, terpene hydrogenated resins, and hydrogenated rosin esters.

  A hydrogenated petroleum resin is a resin obtained by hydrogen reduction of a petroleum resin. Examples of petroleum resins that are raw materials for hydrogenated petroleum resins include aliphatic petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene resins, and the like. Modified products such as hydrogenated products of The synthetic petroleum resin may be C5 or C9.

  A terpene-based hydrogenated resin is a resin obtained by reductive hydrogenation of a terpene-based resin. The terpene resin that is a raw material of the terpene hydrogenated resin includes β-pinene resin, α-pinene resin, β-limonene resin, α-limonene resin, pinene-limonene copolymer resin, pinene-limonene-styrene copolymer resin. Terpene-phenol resin, aromatic modified terpene resin and the like. Many of these terpene resins are resins having no polar group.

The hydrogenated rosin ester is a resin obtained by hydrogenating a rosin ester obtained by esterifying a hydrogenated rosin obtained by hydrogenating a rosin resin or esterifying a rosin. Examples of the rosin resin tackifier include modified rosins such as gum rosin, tall oil rosin, wood rosin, disproportionated rosin, polymerized rosin and maleated rosin.
In this specification, a compound in which some alcoholic hydroxyl groups of polyhydric alcohol are esterified with hydrogenated rosin, and a compound in which all alcoholic hydroxyl groups of polyhydric alcohol are esterified with hydrogenated rosin Both are defined to be included in the hydrogenated rosin ester.

  Among these, hydrogenated rosin esters and terpene-phenol resins are more preferable, hydrogenated rosin esters are more preferable, and triols such as glycerin, trimethylolpropane, and trimethylolethane are particularly preferable. Or hydrogenated rosin ester which is esterification of tetraol such as pentaerythritol and hydrogenated rosin, or triol such as glycerin, trimethylolpropane and trimethylolethane or tetraol and rosin ester such as pentaerythritol (rosin ester) ) Hydrogenated rosin ester obtained by hydrogen reduction.

In addition, in order to balance the polymerizable composition of the present invention (IV) and the viscosity and adhesion of the polymer to the adherend, the compound of Component 6 includes a compound that is liquid at 25 ° C. and 25 ° C. And a solid compound can be used in combination.
More preferably, it is a combination of a polyether polyol, a polyester polyol, and a polycarbonate polyol that are liquid at 25 ° C., and a tackifier that is a solid at 25 ° C., and particularly preferably a polyester polyol and a polycarbonate polyol; A hydrogenated rosin ester is used in combination.
In Component 6, when the compound that is liquid at 25 ° C. and the compound that is solid at 25 ° C. are used in combination, the mass ratio of the compound that is liquid at 25 ° C. and the compound that is solid at 25 ° C. 90:10 to 10:90, more preferably 85:15 to 15:85, and still more preferably 80:20 to 20:80.

The usage-amount of the component 5 in this invention (IV) is 3-40 mass% with respect to the total amount which combined the component 1, the component 3, the component 4, the component 5, and the component 6 which are essential components of this invention (IV). It is preferable that it is, More preferably, it is 4-35 mass%, Most preferably, it is 5-30 mass%. When the amount of component 5 used is less than 3% by mass based on the total amount of component 1, component 3, component 4, component 5 and component 6 as essential components of the present invention (IV), The transparency of the coating film of the polymer obtained by polymerizing the polymerizable composition of IV) may be lost, which is not preferable. In addition, the amount of component 5 used is component 1, which is an essential component of the present invention (IV),
In the case where it exceeds 40% by mass with respect to the total amount of component 3, component 4, component 5 and component 6, the coating of the polymer obtained by polymerizing the polymerizable composition of the present invention (IV) The film strength may be too low, which is not preferable.

  The usage-amount of the component 6 in this invention (IV) is 15-85 mass% with respect to the total amount which combined the component 1, the component 3, the component 4, the component 5, and the component 6 which are essential components of this invention (IV). It is preferable to be, more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass. The usage-amount of the component 6 in this invention (IV) is less than 15 mass% with respect to the total amount which combined the component 1, the component 3, the component 4, the component 5, and the component 6 which are essential components of this invention (IV). And the effect of adding the component 6 (that is, the effect of reducing the volume shrinkage during polymerization) cannot be obtained, which is not preferable. Moreover, the usage-amount of the component 6 in this invention (IV) is 85 mass% with respect to the total amount which combined the component 1, the component 3, the component 4, the component 5, and the component 6 which are essential components of this invention (IV). If the number is increased, the coating strength of the polymer obtained by polymerizing the polymerizable composition of the present invention (IV) may become too low, which is not preferable.

  In addition, the amount of component 1 used in the present invention (IV) is preferably 10 to 40% by mass, more preferably based on the total amount of component 1, component 3, component 4, component 5 and component 6 combined. Is 13-37 mass%, Most preferably, it is 15-35 mass%. When the amount of component 1 used in the present invention (IV) is less than 10% by mass with respect to the total amount of component 1, component 3, component 4, component 5 and component 6, the image display unit of the image display device The adhesion strength of the polymer obtained by polymerizing the polymerizable composition of the present invention (IV) to the above material or the material of the light-transmitting protective part may be lowered, which is not preferable. Moreover, when the usage-amount of the component 1 in this invention (IV) is 40 mass% or more with respect to the total amount which combined the component 1, the component 3, the component 4, the component 5, and the component 6, The viscosity may become too high, which is not preferable.

  It is preferable that the usage-amount of the component 3 in this invention (IV) is 1-15 mass% with respect to the total amount which combined the component 1, the component 3, the component 4, the component 5, and the component 6, More preferably, It is 2-10 mass%, Most preferably, it is 2-8 mass%. When the amount of component 3 used in the present invention (IV) is less than 1% by mass based on the total amount of component 1, component 3, component 4, component 5 and component 6, the later-described present invention (V) The polymer and the optical pressure-sensitive adhesive sheet of the present invention (VII) may be whitened in a hot and humid environment, which is not preferable. In the case where the amount of component 3 used in the present invention (IV) is more than 15% by mass based on the total amount of component 1, component 3, component 4, component 5 and component 6, the present invention (IV) Since the volumetric shrinkage during polymerization of the polymerizable composition may be large, it is not preferable.

  The usage-amount of the component 4 in this invention (IV) is 3-20 mass% with respect to the total amount which combined the component 1, the component 3, the component 4, the component 5, and the component 6 which are essential components of this invention (IV). The content is preferably 4 to 19% by mass, more preferably 5 to 18% by mass. The usage-amount of the component 4 in this invention (IV) is less than 3 mass% with respect to the total amount which combined the component 1, the component 3, the component 4, the component 5, and the component 6 which are essential components of this invention (IV). And the viscosity of the polymerizable composition of the present invention (IV) may become too high, which is not preferable. Moreover, the usage-amount of the component 4 in this invention (IV) is 20 mass% with respect to the total amount which combined the component 1, the component 3, the component 4, the component 5, and the component 6 which are essential components of this invention (IV). When the amount is large, the volumetric shrinkage ratio at the time of polymerization of the polymerizable composition of the present invention (IV) may increase, which is not preferable.

  Moreover, the usage-amount of the component 2 in this invention (IV) is 0.05-10.0 mass parts with respect to 100 mass parts of quantity which remove | excluded the component 2 from the whole quantity of the polymeric composition of this invention (IV). The content is preferably 0.1 to 7.0 parts by mass, and more preferably 0.2 to 5.0 parts by mass. When the amount of component 2 used is less than 0.05 parts by mass with respect to 100 parts by mass of component 2 excluding component 2 from the total amount of the polymerizable composition of the present invention (IV), insufficient polymerization initiation performance of the polymerization initiator May be undesirable. Moreover, when the usage-amount of the component 2 of this invention becomes more than 10.0 mass parts with respect to 100 mass parts of quantity remove | excluding the component 2 from the whole quantity of the polymeric composition of this invention (II), this invention mentioned later is mentioned. When the polymer (V) or the optical pressure-sensitive adhesive sheet of the present invention (VII) described later is placed in a high-temperature environment, it may be easily colored, which is not preferable.

  In addition, when the polymerizable composition of the present invention (IV) is used in a method for producing an image display device of the present invention (VIII) described later, the volume shrinkage ratio at the time of polymerization of the polymerizable composition of the present invention (IV). Is preferably 3.5% or less, more preferably 2.7% or less, and most preferably 2.3% or less. When the volumetric shrinkage during polymerization of the polymerizable composition of the present invention (IV) is greater than 3.5%, the internal stress accumulated in the polymer increases when the polymerizable composition is polymerized. In other words, the interface between the polymer layer 5a or 5b and the display unit 2, the protection unit 3 or the touch panel 7 in contact with the polymer layer 5a or 5b is distorted, which is not preferable.

The viscosity at 25 ° C. of the polymerizable composition of the present invention (I) to the present invention (IV) is not particularly limited, but is preferably 10000 mPa · s or less, more preferably 7000 mPa · s or less, for handling. Especially preferably, it is 5000 mPa · s or less.
The viscosity described in this specification is a cone / plate viscometer (manufactured by Brookfield, model: DV-II + Pro, spindle model: CPE-42) for a composition having a viscosity of 10000 mPa · s or less at 25 ° C. ) Using a temperature of 25.0 ° C. and a rotation speed of 5 rpm.
When the viscosity of the polymerizable composition of the present invention (I) to the present invention (IV) is 10000 mPa · s or less at 25 ° C., the polymerizable composition of the present invention (I) to the present invention (IV) is used in a dispenser. In the case of applying by the conventional drawing method, the spread of the liquid becomes easy after application, and as a result, it becomes easy to spread the composition with a uniform thickness at the required location, and further, the entrainment of bubbles is suppressed. It becomes easy to be done.

  The polymerizable composition of the present invention (I) to the present invention (IV) can be preferably added with a polymerization inhibitor, an inhibitor and an antioxidant.

The polymerization inhibitor and the polymerization inhibitor are not particularly limited as long as they have a polymerization inhibition ability or a function of inhibiting polymerization. For example, phenothiazine, hydroquinone, p-methoxyphenol, p-benzoquinone, Naphthoquinone, phenanthraquinone, tolquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, 2,5-acyloxy-p-benzoquinone, pt-butylcatechol, 2,5- Di-t-butylhydroquinone, p-tert-butylcatechol, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, di-t-butylparacresol hydroquinone monomethyl ether, alpha naphthol, acetamidine acetate , Acetamidine sulfate, Phenylhydra Hydrochloride, hydrazine hydrochloride, trimethylbenzylammonium chloride, laurylpyridinium chloride, cetyltrimethylammonium chloride, phenyltrimethylammonium chloride, trimethylbenzylammonium oxalate, di (trimethylbenzylammonium) oxalate, trimethylbenzylammonium malate, trimethylbenzyl Ammonium tartrate, trimethylbenzylammonium glycolate, phenyl-β-naphthylamine, parabenzylaminophenol, di-β-naphthylparaphenylenediamine, dinitrobenzene, trinitrotoluene, picric acid, cyclohexanone oxime, pyrogallol, tannic acid, resorcin, triethylamine Hydrochloride, dimethylaniline hydrochloride Dibutylamine hydrochloride salt and the like.
These may be used alone or in combination of two or more.
Among these, hydroquinone, p-methoxyphenol, p-benzoquinone, naphthoquinone, phenanthraquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, 2,5-acyloxy-p- Benzoquinone, pt-butylcatechol, 2,5-di-t-butylhydroquinone, p-tert-butylcatechol, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, di-t-butyl -Paracresol hydroquinone monomethyl ether and phenothiazine are preferably used.

Usually, a polymerization inhibitor can be adjusted so that it may become the addition amount of 0.01-5 mass% with respect to the total amount of the polymeric composition of this invention (I)-this invention (IV). However, the amount of the polymerization inhibitor is a value in consideration of the polymerization inhibitor contained in the component 1, component 2, component 3, component 4 and component 6 when the polymerization inhibitor is contained in advance. It is. That is, generally, a polymerization inhibitor is previously contained in component 1, component 2, component 3, component 4 and component 6, but the total amount of this polymerization inhibitor and the newly added polymerization inhibitor is It means that the addition amount is 0.01 to 5% by mass based on the total amount of the polymerizable composition of the present invention (I) to the present invention (IV).
When the polymerization inhibitor is less than 0.01% by mass with respect to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV), the storage stability of the compound is reduced due to insufficient polymerization inhibiting ability. It may be deficient and is not preferred. Moreover, when the amount of the polymerization inhibitor is more than 5% by mass relative to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV), the color becomes darker due to coloring during heat-resistant storage, The polymerization rate at the time of polymerization may decrease, which is not preferable.

Moreover, antioxidant can be added to the polymerizable composition of the present invention (I) to the present invention (IV), and is preferable.
Although it does not specifically limit as antioxidant, For example, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,5-di-tert-butyl-4 7-C9 alkyl ester of hydroxybenzenepropanoic acid, 4,6-bis (octylthiomethyl) -o-cresol, 3,9-bis [2- [3- (3-tert-butyl-4- Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxa Pyro [5,5] -undecane, 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4 '-Thiobis (2-tert-butyl-5-methylphenol), N, N', N "-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3- Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, triethylene glycol bis (3-tert -Butyl-4-hydroxy-5-methylphenyl) propionate, n-octadecyl 3- (4'-hydroxy-3 ', 5'-di-tert) Mention may be made of phenolic antioxidants such as butylphenyl) propionate, among which pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is preferred. , Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, n-octadecyl 3- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate, more preferred is pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate], triethylene glycol Bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, n-octadecyl 3- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate, particularly preferred Is triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, n-octadecyl 3- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate is there.

Usually, antioxidant can be adjusted so that it may become the addition amount of 0.01-5 mass% with respect to the total amount of the polymerizable composition of this invention (I)-this invention (IV). However, the amount of the antioxidant is a value in consideration of the antioxidant contained in the other components such as the component 6 in advance. That is, when the antioxidant may be included in the component 6 or the like in advance, the total amount of this antioxidant and the newly added antioxidant is the present invention (I) to the present invention (IV). ) To 0.01 to 5% by mass relative to the total amount of the polymerizable composition.
When the antioxidant is less than 0.01% by mass relative to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV), the addition effect (that is, the antioxidant effect) may not be exhibited. Yes, it is not preferable. Further, when the amount of the polymerization inhibitor is more than 5% by mass based on the total amount of the polymerizable composition of the present invention (I) to the present invention (IV), the polymer of the present invention (V) described later or the later described From the optical pressure-sensitive adhesive sheet of the present invention (VII), an antioxidant may precipitate or bleed, which is not preferable.

Next, the present invention (V) will be described.
The present invention (V) is a polymer obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (IV).
The polymer of the present invention (V) is a low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, metal halide lamp, electrodeless lamp, LED, etc. It is obtained by polymerizing the polymerizable composition by irradiation through a glass or plastic substrate.

  Moreover, the polymer of this invention (V) is a polymer used as a polymer layer interposed between the image display part of an image display apparatus, and a translucent protection part. This polymer must have a dielectric constant of 5.0 or more under the conditions of 23 ° C., frequency of 1 MHz, and applied voltage of 100 mV.

  Polymer filled between the image display part and the translucent protective part (namely, part 3 shown in FIG. 2) in the on-cell capacitive touch panel display device shown in FIG. Layer) (5b polymer (layer) shown in FIG. 2), the image display unit and the translucent protective unit (that is, the In-Cell type capacitive touch panel display device shown in FIGS. 3 and 4) 3 (described in FIG. 3 and FIG. 4) and the polymer (layer) (5b polymer (layer) described in FIG. 3 and FIG. 4) filled in between (polymerization of the present invention (V)) When the product is used, it is desirable that the dielectric constant of the polymer of the present invention (V) is high. Specifically, a polymer having a dielectric constant of 5.0 or higher is used at 23 ° C., a frequency of 1 MHz, and an applied voltage of 100 mV, and preferably a polymer having 5.5 or higher is used. It is to be.

Moreover, the color coordinate b ^* value described in JIS Z 8729 after storing the polymer adjusted to a thickness of 200 μm existing between the two sheets of glass at 85 ° C. for 500 hours is less than 1.6. It is preferable to become. Moreover, it is preferable that the polymer obtained by polymerizing the polymerizable composition of the present invention has high transparency. Specifically, the polymer is adjusted to a thickness of 200 μm existing between two glasses. The haze is preferably 0.4 or less, and more preferably 0.2 or less.

  Further, “polymerized to a thickness of 200 μm existing between two glasses” described in this specification means two optical glasses having a thickness of 0.7 mm (trade name: Eagle XG manufactured by Corning). ) Between two optical glasses (product name: Eagle XG, manufactured by Corning Co., Ltd.) having a thickness of 0.7 mm. Light through which the photopolymerization initiator can be exposed through the optical glass with a low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, metal halide lamp, electrodeless lamp, LED, etc. as a light source Is a polymer having a thickness of 200 μm, which is obtained by irradiating, and the portion sandwiched between two pieces of glass outside the polymer layer does not contain any spacers, gaskets, or sealants. Than is.

Furthermore, the “color coordinate b ^* value described in JIS Z 8729 after storage at 85 ° C. for 500 hours” described in the present specification is adjusted to a thickness of 200 μm existing between the two glasses. The polymer was held at 85 ° C. for 500 hours, and then measured at 23 ° C. by the method described in JIS Z 8729, using the value of b ^* of the measured color coordinates (psychometric chroma coordinates). is there. However, the reference used when measuring the value of b ^* is one optical glass (manufactured by Corning, trade name: Eagle XG) having a thickness of 0.7 μm. In this invention (V), it is preferable that the value of b ^* measured on the said conditions is 1.6 or less. More preferably, it is 1.2 or less, More preferably, it is 1.0 or less. When the value of b ^* measured under the above conditions is larger than 1.6, the light transmittance at 370 to 450 nm decreases with time, which is not preferable.

  The refractive index of the polymer of the present invention (V) at 25 ° C. is preferably 1.45 to 1.55, and more preferably 1.48 to 1.52. When the refractive index at 25 ° C. is less than 1.45 or larger than 1.55, it is too low compared to the refractive index of the optical glass or the like that is the material of the protective part, so the interface between the display part and the protective part This is not preferable because the difference in refractive index is slightly increased, and the scattering and attenuation of image light from the display unit are slightly increased.

Moreover, it is preferable that the tensile elasticity modulus in 23 degreeC of the polymer of this invention (V) is 1 * 10 < ⁷ > Pa or less, More preferably, it is 1 * 10 < ³ > -1 * 10 < ⁶ > Pa. By setting the tensile modulus at 23 ° C. to 1 × 10 ⁷ Pa or less, the image display part and the protective part are prevented from being distorted due to the influence of stress caused by volume shrinkage during polymerization of the polymerizable composition. be able to.
In addition, the tensile elasticity modulus as described in this specification is a value when a test is performed at a tensile speed of 500 mm / min.

Next, the present invention (VI) and the present invention (VII) will be described.
The present invention (VI) is a polymerizable composition for producing an optical pressure-sensitive adhesive sheet used as a polymer layer interposed between an image display portion and a translucent protective portion of an image display device. The polymerizable composition is a polymerizable composition according to the present invention (I) to the present invention (IV).

Using the polymerizable composition of the present invention (I) to the present invention (IV) as a raw material, the optical pressure-sensitive adhesive sheet of the present invention (VII) can be produced.
The present invention (VII) has a thickness obtained by applying the polymerizable composition of the present invention (VI), irradiating the polymerizable composition with light capable of being photosensitized by the photopolymerization initiator, and polymerizing the polymerizable composition. It is an optical pressure-sensitive adhesive sheet having a polymer layer of 10 to 1000 μm.
The optical pressure-sensitive adhesive sheet of the present invention (VII) is capable of sensitizing a photopolymerization initiator using a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp, an LED or the like as a light source. It is obtained by irradiating light to polymerize the polymerizable composition.

  The optical pressure-sensitive adhesive sheet of the present invention (VII) may be a double-sided pressure-sensitive adhesive sheet in which both surfaces of the sheet are pressure-sensitive adhesive surfaces (pressure-sensitive adhesive layer surface), or only one surface of the sheet is a pressure-sensitive adhesive surface (pressure-sensitive adhesive layer surface). It may be a single-sided pressure-sensitive adhesive sheet. Especially, it is preferable that it is a double-sided adhesive sheet from a viewpoint of bonding two members together. In the present specification, the term “adhesive sheet” includes a tape-shaped material, that is, “adhesive tape”.

  The optical pressure-sensitive adhesive sheet of the present invention (VII) does not have a base material (base material layer), and is a so-called “base-less type pressure-sensitive adhesive sheet” (hereinafter referred to as “base-less optical pressure-sensitive adhesive sheet”). Or an optical pressure-sensitive adhesive sheet having a base material. Examples of the substrate-less optical pressure-sensitive adhesive sheet include, for example, a double-sided pressure-sensitive adhesive sheet composed only of the polymer layer composed of the polymer of the present invention, and a polymer layer composed of the polymer of the present invention and a pressure-sensitive adhesive other than the polymer layer. Examples thereof include a double-sided pressure-sensitive adhesive sheet composed of layers. As a type of pressure-sensitive adhesive sheet having a substrate, it is only necessary to have a polymer layer made of the polymer of the present invention on at least one side of the substrate. Among them, from the viewpoint of reducing the thickness of the optical pressure-sensitive adhesive sheet and improving the optical properties such as transparency, a pressure-sensitive adhesive sheet for baseless optics (pressure-sensitive adhesive sheet for baseless double-sided optics) is preferable, and more preferably polymerization of the present invention. It is a base-less double-sided optical pressure-sensitive adhesive sheet consisting only of a polymer layer made of a product. The “base material (base material layer)” does not include a separator (release liner) that is peeled off when the pressure-sensitive adhesive sheet is used (attached).

  The thickness of the polymer layer of the optical pressure-sensitive adhesive sheet of the present invention (VII) is 10 to 1000 μm, preferably 20 to 700 μm, and more preferably 30 to 500 μm. If the thickness of the polymer layer exceeds 1000 μm, wrinkles may occur during winding during coating, or white turbidity may easily occur due to humidification, which is not preferable. When the thickness of the polymer layer is less than 10 μm, since the polymer layer is thin, the stress cannot be dispersed and peeling may easily occur.

  The optical pressure-sensitive adhesive sheet of the present invention (VII) is used as a polymer layer interposed between an image display part of an image display device and a translucent protective part. For example, the polymerization filled between the image display unit and the translucent protection unit (that is, the part 3 shown in FIG. 2) in the on-cell capacitive touch panel display device shown in FIG. Product (layer) (polymer (b) of 5b described in FIG. 2), image display unit and translucent protective unit in the In-Cell capacitive touch panel display device shown in FIGS. 3 and 4 The polymer (layer) filled in between (ie, the portion 3 shown in FIGS. 3 and 4) (5b polymer (layer) shown in FIGS. 3 and 4) is added to the present invention (VII). When the optical pressure-sensitive adhesive sheet is used, it is desirable that the optical pressure-sensitive adhesive sheet of the present invention (VII) has a high dielectric constant. Specifically, it is preferable to use a polymer having a dielectric constant of 5.0 or more, more preferably 5.5 or more under the conditions of 23 ° C., frequency 1 MHz, and applied voltage 100 mV. It is to use a polymer.

The pressure-sensitive adhesive sheet adjusted to a thickness of 200 μm existing between two sheets of glass has a color coordinate b ^* value of less than 1.6 as described in JIS Z 8729 after being stored at 85 ° C. for 500 hours. Is preferred. More preferably, it is less than 1.2, More preferably, it is less than 1.1, More preferably, it is less than 1.0. If the b ^* value is 1.6 or more, the transmittance of light at 370 to 450 nm decreases with time, which is not preferable.

  The refractive index of the optical pressure-sensitive adhesive sheet of the present invention (VII) at 25 ° C. is preferably 1.45 to 1.55, more preferably 1.48 to 1.52. When the refractive index at 25 ° C. is less than 1.45 or larger than 1.55, the difference in refractive index is too large compared to the refractive index of optical glass, etc., which is the material of the protective part. The difference in refractive index at the interface between the display part and the display part becomes slightly large, and the scattering and attenuation of image light from the display part become slightly large, which is not preferable.

(Method for forming polymer layer of optical pressure-sensitive adhesive sheet)
The method for forming the polymer layer of the optical pressure-sensitive adhesive sheet of the present invention (VII) can be a known or conventional method for forming a polymer layer, and is not particularly limited. When polymerizing such a polymerizable composition having an acryloyl group to form a polymer layer of an optical pressure-sensitive adhesive sheet, for example, the following methods (1) to (3) can be mentioned.
(1) A polymerizable composition having an acryloyl group containing a photopolymerization initiator is coated (coated) with a composition containing additives as necessary on a substrate or a separator (release liner), and a low-pressure mercury lamp , Using a light source such as a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp, and an LED, the photopolymerization initiator irradiates light capable of being polymerized to polymerize the composition. Thus, a polymer layer is formed.
(2) A polymerizable composition having an acryloyl group containing a photopolymerization initiator and a composition (solution) further containing a solvent and, if necessary, an additive are applied (coated) on a substrate or a separator (release liner) And then irradiate the photopolymerization initiator with sensitive light using a light source such as a low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, metal halide lamp, electrodeless lamp, or LED. Then, a polymer layer is formed by polymerizing the composition.
(3) The polymer layer formed in (1) above is further dried.
In addition, a known coating method can be used for coating (coating) in the method for forming the polymer layer, and a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip coater can be used. A roll coater, bar coater, knife coater, spray coater, comma coater, direct coater or the like can be used.

(Base material)
When the optical pressure-sensitive adhesive sheet of the present invention (VII) has a substrate, the substrate is not particularly limited, and examples thereof include various optical films such as a plastic film, an antireflection (AR) film, a polarizing plate, and a retardation plate. It is done. Examples of the material such as the plastic film include, for example, polyester resins such as polyethylene terephthalate (PET), acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate, triacetyl cellulose (TAC), polysulfone, polyarylate, polyimide, Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, ethylene-propylene copolymer, trade name “ARTON (cyclic olefin polymer; manufactured by JSR Corporation)”, trade name “ZEONOR (cyclic olefin polymer; ZEON CORPORATION) A plastic material such as a cyclic olefin polymer. In addition, a plastic material can be used individually or in combination of 2 or more types. In addition, the above-mentioned “substrate” is a portion that is attached to the adherend together with the adhesive layer when the optical adhesive sheet is used (attached) to the adherend (optical member or the like). A separator (release liner) that is peeled off when the adhesive sheet is used (attached) is not included in the “base material”.
Among the above, a transparent substrate is preferable as the substrate. The “transparent substrate” means, for example, a substrate having a total light transmittance (according to JIS K7361) in the visible light wavelength region of 85% or more, more preferably 88% or more. Further, the haze of the base material (according to JIS K7361) is, for example, preferably 1.5% or less, more preferably 1.0% or less. Examples of the transparent substrate include PET films and non-oriented films such as trade names “Arton” and trade names “Zeonoa”.

  The thickness of the said base material is not specifically limited, For example, 12-75 micrometers is preferable. In addition, the said base material may have any form of a single layer and a multilayer. The surface of the substrate may be appropriately subjected to known and conventional surface treatments such as physical treatment such as corona discharge treatment and plasma treatment, and chemical treatment such as undercoating treatment.

  When the optical pressure-sensitive adhesive sheet of the present invention (VII) has a base material, various functional films can be used as the base material. In that case, the pressure-sensitive adhesive sheet of the present invention becomes a pressure-sensitive adhesive functional film having the pressure-sensitive adhesive layer of the present invention on at least one side of the functional film. Although it does not specifically limit as said functional film, For example, optical functionality (polarizability, photorefractive property, light reflectivity, light transmittance, light absorption property, light diffraction property, optical rotation property, visibility, etc.) A film having conductivity, a film having conductivity (such as an ITO film), a film having ultraviolet cutting property, a film having hard coat properties (scratch resistance), and the like. More specifically, a hard coat film (a film on which at least one surface of a plastic film such as a PET film is hard-coated), a polarizing film, a wave plate, a retardation film, an optical compensation film, a brightness enhancement film, a light guide plate , Reflective film, antireflection film, transparent conductive film (such as ITO film), design film, decorative film, surface protective film, prism, color filter and the like. In addition, said "plate" and "film" shall include forms, such as plate shape, film shape, and sheet shape, respectively, for example, "polarizing film" shall also include "polarizing plate" and "polarizing sheet". The “functional film” includes “functional plate” and “functional sheet”.

(Other adhesive layer)
Moreover, when the optical adhesive sheet of this invention (VII) has another adhesive layer, it does not restrict | limit especially as another adhesive layer, For example, a urethane type adhesive, an acrylic adhesive, rubber type | system | group Known and commonly used pressure-sensitive adhesive layers formed from known pressure-sensitive adhesives such as pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, polyamide-based pressure-sensitive adhesives, epoxy-based pressure-sensitive adhesives, vinyl alkyl ether-based pressure-sensitive adhesives, and fluorine-based pressure-sensitive adhesives Is mentioned. The said adhesive can be used individually or in combination of 2 or more types.

  In the optical pressure-sensitive adhesive sheet of the present invention (VII), when the substrate and other pressure-sensitive adhesive layers are not included, the polymerizable composition of the present invention (I) to the present invention (IV) is polymerized. When the obtained polymer layer and other pressure-sensitive adhesive layers are included, the polymer layer obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (IV) and other pressure-sensitive adhesive layers In the case of including a base material and a base material, the base material is combined with a polymer layer obtained by polymerizing the polymerizable composition of the invention (I) to the invention (IV). In the case of including both a layer and another adhesive layer and a substrate, a polymer layer obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (IV), another adhesive layer And the layer which combined the base material is defined as "adhesive layer".

(Separator)
The pressure-sensitive adhesive layer surface (adhesive surface) of the optical pressure-sensitive adhesive sheet of the present invention (VII) may be protected by a separator (release liner) until use. In the case where the optical pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet, each pressure-sensitive adhesive surface may be protected by two separators, respectively, or a single separator whose both surfaces are release surfaces, You may protect in the form wound by the shape. The separator is used as a protective material for the pressure-sensitive adhesive layer, and is peeled off when being applied to an adherend. Moreover, when the adhesive sheet of this invention is a base material-less adhesive sheet, a separator also plays the role of the support body of an adhesive layer. Note that the separator is not necessarily provided. As the separator, a conventional release paper or the like can be used, and is not particularly limited. For example, a substrate having a release treatment layer, a low adhesive substrate made of a fluoropolymer, a low adhesive substrate made of a nonpolar polymer, etc. Can be used. As a base material which has the said peeling process layer, the plastic film, paper, etc. which were surface-treated with peeling processing agents, such as a silicone type, a long-chain alkyl type, a fluorine type, and molybdenum sulfide, are mentioned, for example. Examples of the fluorine-based polymer in the low adhesion substrate made of the above-mentioned fluoropolymer include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chloro Examples include fluoroethylene-vinylidene fluoride copolymer. Moreover, as said nonpolar polymer, olefin resin (for example, polyethylene, a polypropylene, etc.) etc. are mentioned, for example. The separator can be formed by a known or common method. Further, the thickness of the separator is not particularly limited.

In the polymerizable composition of the present invention (I) to (IV), the dielectric constant measured under the conditions of 23 ° C., frequency 1 MHz, applied voltage 100 mV of the polymer obtained by polymerizing the polymerizable composition is 5 0.0 or more. In order to produce a polymerizable composition from which a polymer having a dielectric constant of 5.0 or more measured when polymerized is obtained, the essential components of the present invention (I) to (IV) are added: Preferably, the essential components (I) to (IV) may be mixed uniformly in the presence of a liquid component, more preferably in a liquid state.
When only a compound that is liquid at 25 ° C. is used as component 6, the temperature when mixing each component is preferably in the range of 20 to 100 ° C., more preferably in the range of 30 to 95 ° C. Especially preferably, it is the range of 40-90 degreeC.
When a compound that is solid at 25 ° C. is used as component 6, the compound that is solid at 25 ° C. is component 5 alone, a mixture of component 4 and component 5, component 5 and component 6 at 25 ° C. It is preferable to dissolve in a liquid mixture of compounds or a mixture of component 4, component 5 and component 6 which are liquid at 25 ° C. in advance to obtain a uniform liquid mixture.
The temperature at which the compound that is a solid at 25 ° C. of the component 6 is desirably higher than the softening point of the component 6 that is a solid at 25 ° C. in consideration of the dissolution rate. When component 4 is used for dissolution, it is desirable to dissolve at a temperature of 130 ° C. or lower in order to suppress polymerization during dissolution.
When the polymerizable composition of the present invention (I) to (IV) is produced using the uniform liquid mixture in which the compound that is solid at 25 ° C. is dissolved, this mixed liquid is included. The temperature at the time of mixing each component is preferably in the range of 20 to 100 ° C, more preferably in the range of 30 to 95 ° C, and particularly preferably in the range of 40 to 90 ° C.

Next, the present invention (VIII) will be described.
The present invention (VIII) is a method for producing an image display device comprising a base having an image display portion, a translucent protective portion, and a polymer layer interposed between the base and the protective portion, The method comprises the step of interposing the polymerizable composition of the present invention (IV) between the base part and the protective part, and irradiating the polymerizable composition with light that can be photosensitized by a photopolymerization initiator. The present invention relates to a method for manufacturing an image display device including a step of forming a polymer layer.
Note that “between the base portion having the image display portion and the translucent protective portion” described in the present specification means all the portions between the base portion having the image display portion and the translucent protective portion. For example, it means that any of the locations 5a and 5b in FIG. 5 is included in the expression “between the base portion having the image display portion and the translucent protective portion”.

Hereinafter, preferred embodiments of the image display device will be described more specifically with reference to the drawings. In each figure, the same numerals indicate the same or equivalent components.
For example, FIG. 2, FIG. 3 and FIG. 4 are cross-sectional views showing the main parts of one embodiment of the image display device according to the present invention.
As shown in FIGS. 2, 3, and 4, the display device 1 according to the present embodiment is connected to a drive circuit (not shown) and displays an image display unit 2 that performs a predetermined image display. And a translucent protective portion 3 disposed in close proximity to each other at a distance of.
The “image display device” described in the present specification is not particularly limited as long as it is a device that displays an image, and can be applied to various devices. For example, a liquid crystal display device or an organic EL display device such as a mobile phone or a mobile game device can be used. The image display unit 2 of the present embodiment is a liquid crystal display panel of a liquid crystal display device.
When the image display unit 2 is a liquid crystal display panel, polarizing plates 6a and 6b are provided on the surface thereof as shown in FIG. 2, FIG. 3, or FIG.

As a manufacturing method of the image display device 1 of the present embodiment, for example, first, the spacer 4 and a jetty portion (not shown) are provided on the peripheral edge portion of the image display portion 2, and the region of the present invention (IV) is provided inside these regions. A predetermined amount of the polymerizable composition is dropped.
Then, the protective part 3 is arranged on the spacer 4 of the image display part (liquid crystal display panel) 2, and the polymerization of the present invention (IV) is carried out in the gap between the image display part (liquid crystal display panel) 2 and the protective part 3. The composition is filled without gaps.
Then, the component 2 which is an essential component of the polymerizable composition of the present invention (IV) is irradiated with light capable of being exposed to the polymerizable composition of the present invention (IV) via the protective part 3. The polymerizable composition of the present invention (IV) is polymerized. Thereby, the target image display apparatus 1 is obtained.
According to this image display apparatus 1, since the refractive index of the polymer layer 5 and the protection part 3 is equivalent, a brightness | luminance and contrast can be improved and visibility can be improved.
The process of irradiating the component 2 with photosensitive light is a general ultraviolet irradiation device using a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp or the like as a light source. For example, it can be performed using a belt conveyor type ultraviolet irradiation device. UV irradiation dose is generally from about 1000 mJ / cm ² ~ about 8000 mJ / cm ^2.

  Moreover, since the influence of the stress caused by the volume shrinkage at the time of superposition | polymerization of polymeric composition can be suppressed with respect to the image display part (liquid crystal display panel) 2 and the protection part 3, the liquid crystal display panel 2 and protection Almost no distortion occurs in the section 3, and as a result, no deformation occurs in the image display section (liquid crystal display panel) 2. Therefore, a high-luminance and high-contrast image display with no display defect becomes possible.

  When the polymer of the present invention (V) is used for the polymer layer 5b in FIGS. 2, 3 and 4, the dielectric constant of the polymer in the polymer layer 5b is maintained high. Even if the thickness of the polymer layer is increased to some extent, it is possible to prevent the sensitivity of the touch sensor from being lowered.

Next, the present invention (IX) will be described.
This invention (IX) is a manufacturing method of an image display apparatus which has the process of sticking the base which has an image display part, and a translucent protective part using an optical adhesive sheet, Comprising: This optical adhesive sheet is A method for manufacturing an image display device, which is the optical pressure-sensitive adhesive sheet according to the present invention (VII).
As used herein, “attaching a base portion having an image display portion and a translucent protective portion using an optical adhesive sheet” means that the base portion having an image display portion and a translucent portion are used. Meaning that any part between the protective part and the protective part is included in the expression "the base having the image display part and the translucent protective part are attached using an optical adhesive sheet". For example, even if the adhesive sheet is attached to either 5a or 5b in FIG. 5, "the base having the image display part and the translucent protective part are attached using the optical adhesive sheet" It is included in the expression.

For the purpose of exemplifying the step of attaching the base portion having the image display portion and the translucent protective portion using the optical adhesive sheet, the first base material is a touch sensor integrated protective portion, A manufacturing process in the display device of FIG. 4 in which the base material is a display unit with a polarizing plate will be described as an example.
A step of disposing the optical pressure-sensitive adhesive sheet of the present invention (VII) adjacent to one side of the translucent protective portion which is the first substrate, and a display portion with a polarizing plate which is the second substrate. A step of arranging the surface adjacent to the optical pressure-sensitive adhesive sheet of the present invention (VII), a step of heating and / or pressing the optical pressure-sensitive adhesive sheet of the present invention (VII) to follow a step or a bulge, and If necessary, the optical pressure-sensitive adhesive sheet of the present invention (VII) can be produced by a method including a step of irradiating light capable of being photosensitized by a photopolymerization initiator. These steps can be performed in various orders.

For example, as one specific method, first, one surface of the optical pressure-sensitive adhesive sheet of the present invention (VII) is disposed adjacent to one side of the translucent protective portion which is the first substrate, The surface of the display part with a polarizing plate which is the base material of No. 2 is arranged adjacent to the other surface of the optical pressure-sensitive adhesive sheet of the present invention (VII). That is, the optical pressure-sensitive adhesive sheet of the present invention (VII) is directed so that the surface having a step or bulge faces the translucent protective part (first base material) and the display part with polarizing plate (second base material) ) Sandwich the optical pressure-sensitive adhesive sheet of the present invention (VII).
Next, the optical pressure-sensitive adhesive sheet of the present invention (VII) is heated and / or pressurized to cause the pressure-sensitive adhesive sheet to follow a step or a bump. Thereafter, the present invention (VII) is passed through these substrates from the side of the translucent protective part (first substrate) and / or the display unit with the polarizing plate (second substrate) as necessary. The optical pressure-sensitive adhesive sheet is irradiated with light capable of being photosensitized by the photopolymerization initiator. In this way, the translucent protective part (first base material) and the polarizing plate are attached without forming a gap in the vicinity of the step or the bulge of the translucent protective part (first base material). The display portion (second base material) can be adhered. In this embodiment, the translucent protective part (first base material) and the display part with a polarizing plate (second base material) are placed adjacent to the optical pressure-sensitive adhesive sheet of the present invention (VII), and then In order to heat and / or pressurize the pressure-sensitive adhesive sheet, when there is a step or a bulge on the adherend surface of the display part with the polarizing plate (second base material) (that is, on the polarizing plate attached to the image display module) In the case of applying a pressure-sensitive adhesive sheet), the pressure-sensitive adhesive sheet can be made to follow the steps and bulges of the display portion (second base material) with a polarizing plate to prevent the formation of voids in the vicinity of the shape. it can.

  In the above method, when the photopolymerization initiator irradiates photosensitive light, at least one of the first base material and the second base material passes through them to the optical pressure-sensitive adhesive sheet of the present invention (VII). It is at least partially transparent so that the photoinitiator can irradiate light that can be sensitized. When the step or bulge portion of the first base material does not transmit ultraviolet light, when the ultraviolet light is irradiated from the first base material side, the ultraviolet light is not irradiated directly below the step or bulge portion, but the irradiated portion The polymerization of the pressure-sensitive adhesive sheet proceeds to some extent even in the non-irradiated part due to the movement of radicals generated in the above.

  As another specific method, one surface of the optical pressure-sensitive adhesive sheet of the present invention (VII) is provided on the surface side having a step or a bulge in the translucent protective part (first base material) (that is, in use). Then, the pressure-sensitive adhesive sheet is heated and / or pressurized to cause the pressure-sensitive adhesive sheet to follow a step or a bump. Then, if necessary, after irradiating the open surface of the optical pressure-sensitive adhesive sheet of the present invention (VII) with ultraviolet rays to further polymerize the pressure-sensitive adhesive sheet, the display unit with the polarizing plate (second base material) is formed. It arrange | positions adjacent to the other surface of the said adhesive sheet, and a 2nd base material is affixed on the said adhesive sheet. If the release film is transparent, the pressure-sensitive adhesive sheet can be irradiated with ultraviolet rays through the release film, if necessary. In this example, since the photopolymerization initiator can be irradiated with light capable of being exposed to the entire surface of the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet can be polymerized more uniformly. If the first base material is at least partially transparent so that the photopolymerization initiator necessary for the polymerization of the pressure-sensitive adhesive sheet can irradiate light capable of being sensitized, from the first base material side, if necessary. Irradiation with ultraviolet rays is also possible. In this way, the first base material and the second base material can be bonded together without forming a gap near the step or bulge of the first base material.

  The heating step can be performed using a convection oven, a hot plate, a heat laminator, an autoclave, or the like. In order to promote the flow of the pressure-sensitive adhesive sheet and cause the pressure-sensitive adhesive sheet to follow the step or the protrusion more efficiently, it is preferable to pressurize simultaneously with heating using a heat laminator, an autoclave or the like. Pressurization using an autoclave is particularly advantageous for defoaming the optical pressure-sensitive adhesive sheet. The heating temperature of the optical pressure-sensitive adhesive sheet of the present invention may be any temperature as long as the pressure-sensitive adhesive sheet softens or flows and sufficiently follows a step or a bump, and is generally about 30 ° C. or higher, about 40 ° C. or higher, or about 60 ° C. The temperature may be about 150 ° C. or lower, about 120 ° C. or lower, or about 100 ° C. or lower. When the pressure-sensitive adhesive sheet is pressurized, the applied pressure can be generally about 0.05 MPa or more, or about 0.1 MPa or more, about 2 MPa or less, or about 1 MPa or less.

The process of irradiating light that can be photosensitized by the photopolymerization initiator, which is performed as necessary, uses a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp, etc. It can carry out using the general ultraviolet irradiation device used as, for example, a belt conveyor type ultraviolet irradiation device. UV irradiation dose is generally from about 1000 mJ / cm ² ~ about 8000 mJ / cm ^2.

Finally, the present invention (X) will be described.
The present invention (X) is an image display device manufactured by the manufacturing method of the image display device of the present invention (VIII) or the present invention (IX).
In the image display device of the present invention (X), when the main body of the display device is made of optical glass, the refractive index (n _D ) is generally 1.49 to 1.52. There is also a tempered glass having a refractive index (n _D ) of about 1.55.
The protection part 3 is formed from a plate-like, sheet-like, or film-like translucent member having the same size as the display part 2. As this translucent member, for example, optical glass or plastic (acrylic resin such as polymethyl methacrylate) can be suitably used. An optical layer such as an antireflection film, a light shielding film, or a viewing angle control film may be formed on the front surface or the back surface of the protection unit 3.
When the protection part 3 is formed from an acrylic resin, its refractive index (n _D ) is generally 1.49 to 1.51.
The protection unit 3 is provided on the display unit 2 via a spacer 4 provided on the peripheral edge of the display unit 2. The spacer 4 has a thickness of about 0.05 to 1.5 mm, whereby the distance between the surfaces of the image display unit 2 and the protection unit 3 is maintained at about 1 mm.
In addition, a frame-shaped light shielding portion (not shown) is provided at the peripheral portion of the protection portion 3 in order to improve luminance and contrast.

First, the image display device manufactured by the method for manufacturing the image display device of the present invention (VIII) will be described in detail.
Between the image display part 2 and the protection part 3, polymer layers 5a and 5b are interposed. In the case of the image display device manufactured by the method for manufacturing the image display device of the present invention (VIII), the polymer of the present invention (V) is interposed in the polymer layer 5a and the polymer layer 5b. The transmittance in the visible light region is 90% or more. Here, the thickness of the polymer layer 5a or the polymer layer 5b is preferably 10 to 2000 μm. More preferably, it is 20-1700 micrometers, Most preferably, it is 30-1300 micrometers.
In addition, since the polymer of the present invention (V) is interposed in the polymer layer 5a and the polymer layer 5b, the refractive index (n _D ) at 25 ° C. is the refractive index of the image display unit 2 and the protection unit 3. In order to make it substantially equal, 1.45 to 1.55 are preferable, and more preferably 1.48 to 1.52. Thereby, the brightness | luminance and contrast of the image light from the image display part 2 can be raised, and visibility can be improved.

When an image display device is manufactured by the method for manufacturing an image display device of the present invention (VIII), the polymer of the present invention (V) is interposed in the polymer layer 5a and the polymer layer 5b, so The elastic modulus is 1 × 10 ⁷ Pa or less, preferably 1 × 10 ³ to 1 × 10 ⁶ Pa. Therefore, it is possible to prevent the image display portion and the protection portion from being distorted due to the influence of stress caused by volume shrinkage during polymerization of the polymerizable composition.

  When an image display device is produced by the method for producing an image display device of the present invention (VIII), the polymer composition of the present invention (V) is interposed in the polymer layer 5a and the polymer layer 5b, and therefore the polymerizable composition. The volume shrinkage during polymerization is preferably 3.5% or less, more preferably 2.7% or less, and most preferably 2.3% or less. Thereby, the internal stress accumulated in the polymer layer when the polymerizable composition is polymerized can be reduced, and the interface between the polymer layer 5a and the touch panel 7 or the protective part 3, or the polymer layer 5b and the touch panel. 7. It is possible to prevent the interface with the display unit 2 or the protection unit 3 from being distorted. Therefore, the polymerizable composition is interposed between the touch panel 7 and the protection unit 3, between the touch panel 7 and the display unit 2, or between the display unit 2 and the protection unit 3, and the polymerizable composition is polymerized. In this case, the scattering of light generated at the interface between the polymer layer 5 and the display unit 2, the protection unit 3, and the touch panel 7 can be reduced, and the brightness of the display image can be increased and the visibility can be improved. it can.

  Moreover, when using the polymer of this invention (V) for the polymer layer 5b, since the dielectric constant of these polymers is high, the sensitivity when a person touches can be enlarged.

Next, the image display apparatus manufactured by the image display apparatus manufacturing method of the present invention (IX) will be described in detail.
A polymer layer 5a and a polymer layer 5b or a polymer layer 5b are interposed between the image display unit 2 and the protection unit 3. In the case of an image display device manufactured by the method for manufacturing an image display device of the present invention (IX), the optical pressure-sensitive adhesive sheet of the present invention (VII) is interposed in the polymer layer 5a and the polymer layer 5b. Therefore, the transmittance in the visible light region is 90% or more. Here, the thickness of the polymer layer 5a and the polymer layer 5b is preferably 10 to 1000 μm. More preferably, it is 20-700 micrometers, Most preferably, it is 30-500 micrometers.
In addition, since the optical pressure-sensitive adhesive sheet of the present invention (V) is interposed in the polymer layer 5a and the polymer layer 5b, the refractive index (n _D ) at 25 ° C. is 1.45 to 1.55, preferably 1.48 to 1.52 is preferable because it is almost equal to the refractive index of the image display unit 2 and the protection unit 3. Thereby, the brightness | luminance and contrast of the image light from the image display part 2 can be raised, and visibility can be improved.

  In addition, when an image display device is manufactured by the method for manufacturing an image display device of the present invention (IX), the polymer layer 5a and the polymer layer 5b include the optical pressure-sensitive adhesive sheet of the present invention (VII). The pressure-sensitive adhesive sheet can be made to follow the steps and bulges of the image display unit and the protection unit, and the formation of voids can be prevented even in the vicinity of these shapes.

  Moreover, since the optical adhesive sheet of this invention (VII) has a softness | flexibility, even if the protection part 3, the display part 2, and the touchscreen 7 have uneven | corrugated shape, it is uneven | corrugated further on the display surface of an image display unit. Even if a layer having a surface shape (for example, a polarizing plate) is provided, the internal residual stress of the sheet itself is relaxed, and display unevenness in the image display device can be prevented. For example, in the case of the display device of FIG. 4, since the optical pressure-sensitive adhesive sheet has sufficient adhesive force and hydrophilicity, the display surface of the image display unit 2 (for example, a polarizing plate) and the like even under a high temperature and high humidity environment Air bubbles and peeling do not occur at the interface with the optical pressure-sensitive adhesive sheet (that is, the polymer layer 5b) and at the interface between the optical pressure-sensitive adhesive sheet (that is, the polymer layer 5b) and the translucent protective portion 3. No whitening occurs.

  As the optical glass plate used in the image display device of the present invention (X), those used as a glass plate for sandwiching the liquid crystal of the liquid crystal cell or a protective plate for the liquid crystal cell can be preferably used. Moreover, as an acrylic resin board used, what is used as a protective plate of a liquid crystal cell can be used preferably. The average surface roughness of these optical glass plates and acrylic resin plates is usually 1.0 nm or less.

Further, the image display device of the present invention (X) is a polymer obtained by using the polymer of the present invention (V) or the optical pressure-sensitive adhesive sheet of the present invention (VII) between the image display unit 2 and the protection unit 3. Since the layer 5a and the polymer layer 5b are filled, it is strong against impact.
In addition, it can be formed thinner than the conventional example in which a gap is provided between the image display unit 2 and the protection unit 3.

  Further, the image display device of the present invention (X) can take various modes. For example, as illustrated in FIG. 4, the image display device 1 may be manufactured by omitting the spacer 4. In the case of the polymer layer 5b of FIG. 4, for example, the photopolymerizable composition of any one of the present invention (I) to the present invention (IV) is applied onto the polarizing plate 6a on the display unit 2, and the above-mentioned Or, for example, as shown in FIG. 5, a laminate composed of the protective portion 3, the polymer layer 5b, the touch panel 7 and the polymer layer 5a (that is, the optical pressure-sensitive adhesive sheet 5a) is formed. It can be obtained by bonding to the display surface on the image display unit 2 (that is, the surface of the polarizing plate 6a).

  The present invention can be applied not only to the liquid crystal display device described above but also to various panel displays such as an organic EL and a plasma display device.

According to the polymerizable composition of the present invention, a polymer having a high dielectric constant can be provided. Capacitance generated by the user's fingertip during operation of the capacitive touch panel is the area of the electrode formed by the touch sensor and the finger, the thickness of the panel part interposed between the electrodes, and between the fingertip and the touch sensor. It depends on the dielectric constant.
In addition, a panel part is a distance from the surface of the translucent protection part which a fingertip touches to a touch sensor here.

C _f : Capacitance generated between the user's finger and the touch sensor ε ₀ : Dielectric constant of vacuum 8.85 × 10 ⁻¹²
ε _r : dielectric constant of dielectric between electrodes A: effective area of electrodes d: distance between electrodes

  The larger the generated capacitance, the easier it is to detect the touch of the fingertip and the contact location of the fingertip. From equation (1), it can be seen that the material and thickness of the panel are important factors that determine the capacitance. The dielectric constant between the electrodes (between the fingertip and the touch sensor) is determined by the material of the panel portion, and the distance between the electrodes is determined by the thickness. Therefore, since the dielectric constant of the polymer of the present invention filled in 5b of FIGS. 2 to 5 is high, it is easy to detect that the fingertip is touched and where the fingertip contacts.

Furthermore, according to the polymerizable composition of the present invention, it is possible to minimize the stress due to volume shrinkage when it is applied between the image display part and the protective part and polymerized, so that the image display part When an image display device is manufactured using a process of forming a polymer layer by interposing a polymerizable composition between a base portion having a light-transmitting portion and a translucent protective portion, an image display of this stress is performed. The influence on the part and the protection part can be minimized. Therefore, according to the image display device of the present invention, distortion hardly occurs in the image display unit and the protection unit.
Furthermore, since the polymerizable composition of the present invention does not contain a volatile solvent (that is, no solvent), the polymer obtained by polymerizing the polymerizable composition of the present invention is divided into an image display part and a protective part. There is no solvent volatilization step in the manufacturing process when applied between the two, which is advantageous in terms of energy and has a low environmental impact.
Furthermore, the cured product obtained by polymerizing the polymerizable composition of the present invention between the image display part and the protective part has high adhesion to the glass used in the protective part.

In addition, the polymer and the optical adhesive sheet of the present invention have a refractive index that is a configuration panel of the image display unit or a configuration of the protection unit as compared with a gap that is conventionally provided between the liquid crystal display panel and the protection unit. It is close to the refractive index of the panel, and the light at the interface between the protective part and the polymer, the interface between the polymer and the image display part, the interface between the protective part and the optical adhesive sheet, Reflection is suppressed. As a result, according to the image display device of the present invention, high luminance and high contrast display without display defects becomes possible.
Furthermore, when the image display unit is a liquid crystal display panel, display defects such as disorder of alignment of the liquid crystal material can be reliably prevented and high-quality display can be performed.
Furthermore, according to the image display device of the present invention, since the polymer or the optical adhesive sheet is interposed between the image display unit and the protection unit, the image display device is resistant to impact.
Furthermore, since the polymer and the optical adhesive sheet of the present invention are not easily colored even when subjected to a thermal history, it is possible to maintain high brightness and high contrast display for a long time.
In addition, according to the present invention, it is possible to provide a thin image display device as compared with the conventional example in which a gap is provided between the image display unit and the protection unit.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited only to a following example.

<Measurement of viscosity>
For samples having a viscosity of less than 10 Pa · s at a temperature of 25.0 ° C., the viscosity was measured by the following method.
Using 1 mL of sample, viscosity was measured under the conditions of a temperature of 25.0 ° C. and a rotation speed of 5 rpm using a cone / plate viscometer (manufactured by Brookfield, model: DV-II + Pro, spindle model number: CPE-42). The value when it became almost constant was measured.
For a sample having a viscosity of 10 Pa · s or more at a temperature of 25.0 ° C., the viscosity was measured by the following method.
Using a sample of 0.5 mL, a cone / plate viscometer (manufactured by Brookfield, model: DV-II + Pro, spindle model number: CPE-52) under the conditions of a temperature of 25.0 ° C. and a rotation speed of 5 rpm. The value when the viscosity became almost constant was measured.

<Measurement of hydroxyl value>
The measurement was performed according to JIS K 0070.

<Number average molecular weight>
The number average molecular weight is a value in terms of polystyrene measured by GPC under the following conditions.
Device name: HPLC unit HSS-2000 manufactured by JASCO Corporation
Column: Shodex column LF-804
Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI-2031Plus manufactured by JASCO Corporation
Temperature: 40.0 ° C
Sample volume: Sample loop 100 μL
Sample concentration: prepared at around 0.5 wt%

(Execution synthesis example 1-1)
Pripol (registered trademark) 2033 (clad hydrogenated dimer diol, hydroxyl value 202 mg KOH / g) 26.2 parts by mass, 1,4-butanediol (Mitsubishi Chemical Industry) in a 2000 mL reaction vessel equipped with a stirrer and a distillation apparatus 47.2 parts by mass), 65. 3 parts by mass of 3-methyl-1,5-pentanediol (manufactured by Kuraray Co., Ltd.), 721.4 parts by mass of adipic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), Pripol ( (Registered Trademark) 1009 (hydrogenated dimer acid made by Croda) 241.5 parts by mass and stannous chloride (Tokyo Chemical Industry Co., Ltd.) 0.5 parts by mass were charged, and water was distilled off at about 170 ° C. starting from normal pressure. The temperature was gradually raised to 240 ° C., and the condensation reaction was continued. Thereafter, the condensation reaction was further continued while reducing the pressure. After the water stopped distilling, the reaction was further continued for 2 hours, and then the system was returned to normal pressure to complete the reaction. A polyester polyol having a hydroxyl value of 57.0 mgKOH / g (hereinafter referred to as polyester polyol A) was obtained.

(Example synthesis example 2-1)
In a 100 mL reaction vessel equipped with a stirrer, thermometer, dropping funnel and condenser, a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT (registered trademark) ) TMDI, manufactured by Evonik Degussa) 22.94 g, 30 mg of dioctyltin dilaurate and 24 mg of p-methoxyphenol were added to the reaction vessel, and 15.73 g of 4-hydroxybutyl acrylate was added dropwise using a dropping funnel. During the dropping, the temperature in the reaction vessel was adjusted to 70 ° C. or lower. Stirring was continued for 2 hours while maintaining the temperature in the reactor at 70 to 75 ° C. for 2 hours to obtain a reaction product (hereinafter referred to as reaction product α).
In a 300 mL reaction vessel equipped with a stirrer, a thermometer, and a condenser, 150 g of the above-mentioned polyester polyol A was charged and stirring was started. Thereafter, the entire amount of the reaction product α maintained at 60 ° C. was divided into several times and charged into the reaction vessel. Meanwhile, the temperature in the reactor was not allowed to rise above 70 ° C. Thereafter, the temperature in the reactor was maintained at 70 to 75 ° C., and stirring was continued. It was confirmed by IR that absorption of C═O stretching vibration of the isocyanate group was lost, and urethane acrylate having a number average molecular weight of 2460 (hereinafter referred to as “urethane acrylate 1”) was obtained.

(Example synthesis example 2-2)
In a 100 mL reaction vessel equipped with a stirrer, thermometer, dropping funnel and condenser, a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT (registered trademark) ) TMDI, manufactured by Evonik Degussa) 27.83 g, dioctyltin dilaurate 30 mg and p-methoxyphenol 24 mg were charged into a reaction vessel, and 4-hydroxybutyl acrylate 19.08 g was added dropwise using a dropping funnel. During the dropping, the temperature in the reaction vessel was adjusted to 70 ° C. or lower. Stirring was continued for 2 hours while maintaining the temperature in the reactor at 70 to 75 ° C. for 2 hours to obtain a reaction product (hereinafter referred to as reaction product β).
In a 300 mL reaction vessel equipped with a stirrer, a thermometer, and a condenser, 150 g of the above-mentioned polyester polyol A was charged and stirring was started. Thereafter, the entire amount of the reaction product β maintained at 60 ° C. was divided into several times and charged into the reaction vessel. Meanwhile, the temperature in the reactor was not allowed to rise above 70 ° C. Thereafter, the temperature in the reactor was maintained at 70 to 75 ° C., and stirring was continued. It was confirmed by IR that absorption of C═O stretching vibration of the isocyanato group was lost, and urethane acrylate having a number average molecular weight of 2570 (hereinafter referred to as “urethane acrylate 2”) was obtained.

(Example synthesis example 2-3)
In a 300 mL reaction vessel equipped with a stirrer, a thermometer and a condenser, 150 g of the above-mentioned polyester polyol A, 15.73 g of 4-hydroxybutyl acrylate, 30 mg of dioctyltin dilaurate and 24 mg of p-methoxyphenol are put into the reaction vessel and stirred. Started. Thereafter, 22.94 g of a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT (registered trademark) TMDI, manufactured by Evonik Degussa) was added using a dropping funnel. Added dropwise. During the dropping, the temperature in the reaction vessel was adjusted to 70 ° C. or lower. Thereafter, the temperature in the reactor was maintained at 70 to 75 ° C., and stirring was continued. It was confirmed by IR that absorption of C═O stretching vibration of the isocyanato group was lost, and urethane acrylate having a number average molecular weight of 2570 (hereinafter referred to as “urethane acrylate 3”) was obtained.

(Example synthesis example 2-4)
Into a 300 mL reaction vessel equipped with a stirrer, a thermometer and a condenser, the above-mentioned polyester polyol A 150 g, 4-hydroxybutyl acrylate 19.08 g, dioctyltin dilaurate 30 mg and p-methoxyphenol 24 mg are charged and stirred. Started. Thereafter, 27.83 g of a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT (registered trademark) TMDI, manufactured by Evonik Degussa) was added using a dropping funnel. Added dropwise. During the dropping, the temperature in the reaction vessel was adjusted to 70 ° C. or lower. Thereafter, the temperature in the reactor was maintained at 70 to 75 ° C., and stirring was continued. It was confirmed by IR that absorption of C═O stretching vibration of the isocyanate group was lost, and urethane acrylate having a number average molecular weight of 2570 (hereinafter referred to as “urethane acrylate 4”) was obtained.

(Example synthesis 2-5)
In a 100 mL reaction vessel equipped with a stirrer, thermometer, dropping funnel and condenser, a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT (registered trademark) ) TMDI, manufactured by Evonik Degussa) 22.94 g, 30 mg of dioctyltin dilaurate and 24 mg of p-methoxyphenol were added to the reaction vessel, and 15.73 g of 4-hydroxybutyl acrylate was added dropwise using a dropping funnel. During the dropping, the temperature in the reaction vessel was adjusted to 70 ° C. or lower. Stirring was continued for 2 hours while maintaining the temperature in the reactor at 70 to 75 ° C. for 2 hours to obtain a reaction product (hereinafter referred to as reaction product γ).
In a 300 mL reaction vessel equipped with a stirrer, a thermometer and a condenser, a polyester polyol (trade name: Kuraray polyol P-2050, hydroxyl value 57.0 mg KOH / g, Kuraray Co., Ltd., sebacic acid and 3-methyl-1, 75 g of polyester polyol produced using 5-pentanediol as a raw material, polyester polyol (trade name: Kuraray polyol P-2010, hydroxyl value 57.0 mg KOH / g, manufactured by Kuraray Co., Ltd., adipic acid and 3-methyl-1 , 5-pentanediol (polyester polyol produced using a raw material) was added, and stirring was started. Thereafter, the entire amount of the reaction product γ maintained at 60 ° C. was divided into several times and charged into the reaction vessel. Meanwhile, the temperature in the reactor was not allowed to rise above 70 ° C. Thereafter, the temperature in the reactor was maintained at 70 to 75 ° C., and stirring was continued. It was confirmed by IR that the absorption of C═O stretching vibration of the isocyanato group disappeared, and urethane acrylate having a number average molecular weight of 2460 (hereinafter referred to as “urethane acrylate 5”) was obtained.

(Example synthesis example 2-6)
In a 100 mL reaction vessel equipped with a stirrer, thermometer, dropping funnel and condenser, a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT (registered trademark) ) TMDI, manufactured by Evonik Degussa) 27.83 g, dioctyltin dilaurate 30 mg and p-methoxyphenol 24 mg were charged into a reaction vessel, and 4-hydroxybutyl acrylate 19.08 g was added dropwise using a dropping funnel. During the dropping, the temperature in the reaction vessel was adjusted to 70 ° C. or lower. Stirring was continued for 2 hours while maintaining the temperature in the reactor at 70 to 75 ° C. for 2 hours to obtain a reaction product (hereinafter referred to as reaction product ω).
In a 300 mL reaction vessel equipped with a stirrer, a thermometer and a condenser, 75 g of polyester polyol (trade name: Kuraray polyol P-2050, hydroxyl value 57.0 mg KOH / g, manufactured by Kuraray Co., Ltd.), polyester polyol (trade name: Kuraray) Polyol P-2010, hydroxyl value 57.0 mgKOH / g, manufactured by Kuraray Co., Ltd.) 75 g was added, and stirring was started. Thereafter, the entire amount of the reaction product ω maintained at 60 ° C. was divided into several times and charged into the reaction vessel. Meanwhile, the temperature in the reactor was not allowed to rise above 70 ° C. Thereafter, the temperature in the reactor was maintained at 70 to 75 ° C., and stirring was continued. It was confirmed by IR that absorption of the C═O stretching vibration of the isocyanato group was lost, and urethane acrylate having a number average molecular weight of 2570 (hereinafter referred to as “urethane acrylate 6”) was obtained.

(Example formulation 1)
Urethane acrylate 5 99.0 parts by mass, 1-hydroxycyclohexyl phenyl ketone (trade name: IRGACURE (registered trademark) 184, manufactured by BASF) 0.8 parts by mass, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name: 0.2 parts by weight of SpeedCure TPO, manufactured by Lambson) and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX (registered trademark) 1010, manufactured by BASF) 1.0 part by mass was mixed using a rotation / revolution mixer (Sinky Co., Ltd., trade name: Rentaro Awatori ARE-310). This blend was designated as a polymerizable composition A1. The viscosity at 25 ° C. of the polymerizable composition A1 was 29,800 mPa · s.
The molar amount of the ester bond contained per unit mass of the urethane acrylate 5 was 5.46 mmol / g, and the molar amount of the hydroxyl group remaining at the terminal of the urethane acrylate 5 was 0.71 mmol / g per unit mass of the urethane acrylate 5. . The molar amount (mmol / g) of the ester bond per unit mass of the entire polymerizable composition of Example 1 is equal to the molar amount (mmol / g) of the ester bond contained per unit mass of the urethane acrylate 5 described above. (Mass of urethane acrylate 5) / (Mass of polymerizable composition of Example 1) = 99/101.
Similarly, the hydroxyl amount (mmol / g) of the hydroxyl group per unit mass of the entire polymerizable composition of Example Formulation Example 1 is the molar amount of hydroxyl group contained per unit mass of the urethane acrylate 5. The amount (mmol / g) is multiplied by (mass of urethane acrylate 5) / (mass of polymerizable composition of Example 1) = 99/101.
In addition, about the molar amount (mmol / g) of the ester bond per unit mass of the whole polymerizable composition, the number of ester bonds per molecule of the compound containing the ester bond contained in the component of the polymerizable composition, It can be calculated from the molecular weight of the compound and the mass ratio of the compound in the polymerizable composition, and the same applies to the molar amount of the hydroxyl group and the molar amount of the ether bond.
Total molar amount (mmol / g) of ether bond, ester bond and hydroxyl group per unit mass of the entire polymerizable composition, and (mol amount of hydroxyl group per unit mass of the entire polymerizable composition) / (polymerizable composition) The total molar amount of ester bond, ether bond and hydroxyl group per unit mass) was calculated using the numerical values determined above.

(Example formulation examples 2 to 10 and comparative formulation examples 1 to 3)
In the same manner as in Example 1 of blending, blending was performed according to the blending composition shown in Table 1. The formulations prepared in Examples 2 to 10 were designated as polymerizable compositions A2 to A10, respectively, and the formulations prepared in comparative formulation examples 1 to 3 were designated as polymerizable compositions B1 to B3.
In addition, the unit of the number of each component of the implementation formulation example and the comparative formulation example described in Table 1 is “parts by mass”.
The molar amount (mmol / g) of ester bond per unit mass of the entire polymerizable composition of Examples 2-10, the molar amount of hydroxyl group (mmol / g), the molar amount of ether bond (mmol / g), Calculation was performed in the same manner as in Example 1
Also, the total molar amount (mmol / g) of ether bond, ester bond and hydroxyl group per unit mass of the entire polymerizable composition, and (mol amount of hydroxyl group per unit mass of the entire polymerizable composition) / (polymerizable composition) The total molar amount of ester bond, ether bond and hydroxyl group per unit mass of the whole product was also calculated in the same manner as in Example 1 of Formulation.

* 1 Claprene (registered trademark) UC-203 (maleic anhydride adduct of polyisoprene polymer and esterified product of 2-hydroxyethyl methacrylate, manufactured by Kuraray Co., Ltd., number average molecular weight: 35,000)
* 2 N, N-diethylacrylamide (trade name: DEAA, manufactured by Kojin Film & Chemicals Co., Ltd.)
* 3 N-acryloylmorpholine (trade name: ACMO, manufactured by Kojin Film & Chemicals Co., Ltd.)
* 4 2-hydroxypropyl methacrylate (trade name: HPMA, manufactured by Nippon Shokubai Co., Ltd.)
* 5 4-hydroxybutyl acrylate (trade name: 4HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
* 6 2-hydroxybutyl methacrylate (trade name: Light Ester HOB (N), manufactured by Kyoeisha Chemical Co., Ltd.)
* 7 Diethylene glycol monoethyl ether acrylate (trade name: Biscoat # 190, manufactured by Osaka Organic Chemical Industry Co., Ltd., viscosity (25 ° C.): 3 mPa · s)
* 8 Phenoxyethyl acrylate (trade name: Biscoat # 192, manufactured by Osaka Organic Chemical Industry Co., Ltd., viscosity (25 ° C.): 9 mPa · s)
* 9 Dicyclopentenyloxyethyl methacrylate (trade name: FA-512M, manufactured by Hitachi Chemical Co., Ltd., viscosity (25 ° C.): 18 mPa · s)
* 10 Lauryl acrylate (Brandmer LA, manufactured by NOF CORPORATION, viscosity (25 ° C.): 4 mPa · s)
* 11 Glycerol monolaurate (trade name: Poem M-300, manufactured by Riken Vitamin Co., Ltd.)
* 12 Propylene glycol monolaurate (trade name: Riquemal PL-100, manufactured by Kyoeisha Chemical Co., Ltd.)
* 13 Hydrogenated rosin ester resin (trade name: Pine Crystal KE-100, manufactured by Yasuhara Chemical Co., Ltd.)
* 14 Hydrogenated rosin ester resin (trade name: Pine Crystal KE-311, manufactured by Yasuhara Chemical Co., Ltd.)
* 15 Terpene-phenol resin (trade name: YS Polystar TH130, manufactured by Yasuhara Chemical Co., Ltd.)
* 16 Terpene-based hydrogenated resin (trade name: CLEARON (registered trademark) P85, manufactured by Yasuhara Chemical Co., Ltd.)
* 17 Polyester polyol (trade name: Kuraray polyol P-2050, manufactured by Kuraray Co., Ltd.)
* 18 Polyester polyol (trade name: Kuraray polyol P-2011, manufactured by Kuraray Co., Ltd.)
* 19 Liquid polybutadiene (trade name: POLYVEST (registered trademark) 110, manufactured by Evonik Degussa)
* 20 IRGANOX (registered trademark) 1010 (compound name: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF)
* 21 Photopolymerization initiator SpeedCure TPO (compound name: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by Lambson)
* 22 Photopolymerization initiator IRGACURE (registered trademark) 184 (compound name: 1-hydroxycyclohexyl phenyl ketone, manufactured by BASF)

<Manufacture of optical adhesive sheet>
Polymeric composition A1 to polymerizable composition A10 and polymerizable composition B1 to B3 shown in Table 1 were each coated with silicone so as to have a film thickness of 200 μm using an applicator (hereinafter referred to as PET). After coating on a film (100 mm × 100 mm × 50 μm) and covering the upper surface with a PET film coated with 25 μm thick silicone, a conveyor type ultraviolet irradiation device using a metal halide lamp (GS Yuasa Lighting Co., Ltd.) Manufactured and trade name: GSN2-40), and ultraviolet rays were irradiated through a silicone-coated PET film under the conditions of irradiation intensity of 190 mW / cm ² (value of 365 nm) and irradiation amount of 4000 mJ / cm ² (value of 365 nm). Irradiated to polymerize, the film thickness sandwiched between release PET films is about To obtain an optical pressure-sensitive adhesive sheet for 00Myuemu. The said adhesive sheet for optics manufactured using polymeric composition A1-polymerizable composition A10 and polymeric composition B1-B3 was made into adhesive sheet A1-adhesive sheet A10 and adhesive sheet B1-B3, respectively.

<Method for preparing test piece using the pressure-sensitive adhesive sheet and evaluation of initial optical properties>
In the pressure-sensitive adhesive sheet A1 to pressure-sensitive adhesive sheet A10 and pressure-sensitive adhesive sheets B1 to B3, two glass plates (50 mm × 50 mm × 0.7 mm, glass type, product name: EAGLE XG ( A test piece was prepared by pasting the adhesive sheet so as to be sandwiched from both sides with a registered trademark and CORNING.
Test pieces prepared using the pressure-sensitive adhesive sheets A1 to A10 and the pressure-sensitive adhesive sheets B1 to B3 were designated as test pieces AS1 to AS10 and test pieces BS1 to BS3, respectively. The total light transmittance, b ^* , and haze of these test pieces were measured by the method described later. The results are shown in Table 3.

<Test specimen preparation method and initial optical property evaluation>
The polymerizable composition A3 to the polymerizable composition A10 and the polymerizable compositions B1 to B3 are each made of a glass plate (50 mm × 50 mm × 0.7 mm, glass) so that the film thickness becomes 200 μm using a bar coater. Type Product name: EAGLE XG (registered trademark, manufactured by CORNING), sandwiched between glass plates of the same type and shape, conveyor type ultraviolet irradiation device using metal halide lamp (manufactured by GS Yuasa Lighting Co., Ltd., product name: GSN2) -40), polymerized by irradiating with ultraviolet rays through the glass plate under the conditions of irradiation intensity of 190 mW / cm ² (value of 365 nm) and irradiation amount of 4000 mJ / cm ² (value of 365 nm), and sandwiched between the glass plates A polymer film for an evaluation test having a thickness of about 200 μm was obtained. A polymer film for evaluation test having a thickness of about 200 μm sandwiched between the glass plates, produced using the polymerizable compositions A3 to A10 and the polymerizable compositions B1 to B3, was respectively tested with specimens AL3 to test. Piece AL10 and test pieces BL1 to BL3 were used. The total light transmittance, b ^* , and haze of these test pieces were measured by the method described later. The results are shown in Table 3.

<Measurement of total light transmittance>
Using one glass plate (50 mm × 50 mm × 0.7 mm, glass type, trade name: EAGLE XG (registered trademark), CORNING) as a reference, the test piece AS1 to test piece AS10, the test piece AL3 to test piece The total light transmittances of AL10, test pieces BS1 to BS3, and test pieces BL1 to BL3 were measured according to JIS K 7361-1. The results are shown in Table 3.

<Measurement of b ^* >
Using one glass plate (50 mm × 50 mm × 0.7 mm, type of glass, trade name: EAGLE XG (registered trademark), CORNING) as a reference, the test piece AS1 to test piece AS10, the test piece AL3 to test piece B ^* of AL10, test pieces BS1 to BS3 and test pieces BL1 to BL3 were measured according to JIS Z 8729. The results are shown in Table 3.

<Measurement of haze>
Using one glass plate (50 mm × 50 mm × 0.7 mm, glass type, trade name: EAGLE XG (registered trademark), CORNING) as a reference, the test piece AS1 to test piece AS10, the test piece AL3 to test piece The hazes of AL10, test pieces BS1 to BS3, and test pieces BL1 to BL3 were measured according to JIS K7136. The results are shown in Table 3.

<Measurement of dielectric constant>
Using two PET-coated PET films, a polymerizable composition A1 to a polymerizable composition A10 and a polymerizable composition B1 to B3 are sandwiched between them so that the film thickness is about 2 mm. Using a conveyor type ultraviolet irradiation device using a lamp (manufactured by GS Yuasa Lighting Co., Ltd., trade name: GSN2-40), an irradiation intensity of 190 mW / cm ² (value of 365 nm) through a PET film coated with silicone, Polymerization was performed by irradiating ultraviolet rays under the condition of an irradiation amount of 4000 mJ / cm ² (value of 365 nm) to obtain a polymer film for evaluation test having a film thickness of about 2 mm sandwiched between PET films coated with silicone. The polymer film was peeled off from the PET film coated with silicone, and measured using an impedance analyzer (trade name: 4294A Precision Impedance Analyzer 40 Hz-110 MHz, manufactured by Agilent Technologies, Inc.). The results are shown in Table 2.
In addition, the polymer film of thickness 2mm which peeled the PET film coated with silicone obtained by superposing | polymerizing polymeric composition A1-polymerizable composition A10 and polymeric composition B1-B3, respectively, The polymer film A1 to the polymer film A10 and the polymer films B1 to B3 are used.

<Measurement of volumetric shrinkage during polymerization>
The polymerizable compositions A1 to A10 and the polymerizable compositions B1 to B3 before polymerization and the density of the polymer obtained by polymerizing them were measured using an automatic hydrometer (model: DMA-220H, manufactured by Shinko Denshi Co., Ltd.) The measurement was performed under a temperature condition of 23 ° C., and the volume shrinkage during polymerization was determined from the following formula.
Volume shrinkage during polymerization (%) = [(density of polymer-density of polymerizable composition) / (density of polymer)] × 100
The results are shown in Table 2.

<Measurement of refractive index>
Using the polymer film A1 to the polymer film A10 and the polymer films B1 to B3, measurement was performed according to JIS K 7105. The results are shown in Table 2.

<Measurement of tensile modulus>
The polymer film A1 to the polymer film A10 and the polymer films B1 to B3 were fixed to a tensile tester (manufactured by Shimadzu Corporation, EZ Test / CE), and tested at 23 ° C. with a pulling speed of 500 mm / min. The tensile modulus was obtained. The results are shown in Table 2.

<Adhesion to glass>
On the outer glass surfaces (both sides) of the test piece AS1 to test piece AS10, the test piece AL3 to the test piece AL10, the test piece BS1 to BS3, and the test piece BL2, respectively, a tensile tester (manufactured by Shimadzu Corporation, EZ Test). / CE) A plastic jig was affixed using a double-sided tape so that it could be sandwiched between chuck parts. Then, two glasses with a polymer film with a plastic jig attached are attached to a tensile tester (manufactured by Shimadzu Corporation, EZ Test / CE), and the glass on both sides is peeled off at a speed of 500 mm / min. The film was pulled in the peeling direction to evaluate the adhesion to glass (unit: N / cmφ). The results are shown in Table 4. “N / cmφ” means a force per unit area of a circle having a diameter of 1 cm (unit: N).

<Measurement of total light transmittance, b ^* value and haze when stored under high temperature conditions>
The test piece AS1 to test piece AS10, test piece AL3 to test piece AL10, test piece BS1 to BS3 and test piece BL1 to BL3 are put in a thermostat of 70 ° C. and 85 ° C., respectively, and the test piece after 500 hours has passed. The total light transmittance, b ^* value and haze were measured by the above method. The results are shown in Table 3.

<Measurement of total light transmittance, b ^* value and haze when stored under high temperature and high humidity>
The test piece AS1 to test piece AS10, test piece AL3 to test piece AL10, test piece BS1 to BS3, and test piece BL1 to BL3 are put in a constant temperature and humidity machine with a temperature of 60 ° C. and a humidity of 90% RH, respectively, and 500 hours have passed. Using the later test piece, the total light transmittance, b ^* value and haze were measured by the method described above. The results are shown in Table 3.

<Response evaluation of touch panel display>
Polymeric tempered glass (70 mm × 70 mm × 0.7 mm, type of glass, product name: Corning Gorilla) was prepared using an applicator for each of the polymerizable composition A10 and the polymerizable composition B1 shown in Table 1. Glass (registered trademark), manufactured by CORNING), and the upper surface was covered with a 25 μm thick silicone-coated PET film (release film), and then a conveyor type ultraviolet irradiation device using a metal halide lamp (GS Corporation) Using Yuasa Lighting Co., Ltd., trade name: GSN2-40), through a PET film coated with silicone, under the conditions of irradiation intensity of 190 mW / cm ² (value of 365 nm) and irradiation dose of 4000 mJ / cm ² (value of 365 nm). Polymerization was performed by irradiation with ultraviolet rays. The release film is removed from the laminate thus prepared so that bubbles do not enter the polymer (layer) surface at the interface, and the protective part of the capacitive touch panel display device (the above chemically strengthened glass) ) And laminates created by attaching them to AL10-2 and BL1-2, respectively.
Further, the above-mentioned pressure-sensitive adhesive sheet A10 and pressure-sensitive adhesive sheet B1 were used as a release film and a chemically tempered glass (70 mm × 70 mm × 0.7 mm, glass type, trade name: Corning Gorilla Glass (registered trademark), manufactured by CORNING). The film was affixed so as to be sandwiched from both sides so that air bubbles would not enter each interface with a PET film coated with silicone. Then, the release film is removed from the laminate, and the polymer (layer) surface is attached to the protective part of the capacitive touch panel display device (the above-mentioned chemically tempered glass) so that air bubbles do not enter the interface. Let the laminated body created by attaching it be AS10-2 and BS1-2, respectively.
Chemical drawing of AL10-2, BL1-2, AS10-2, BS1-2 using a drawing function that has the function of appearing as a line when scrolled on the protective part with a finger. The response from above was compared. At this time, when the line was interrupted in the middle, x was indicated, and when the line could be drawn smoothly without interruption until the end, it was indicated as ◯. The results are shown in Table 5.

From the results of Table 2, Table 3 and Table 4, the polymer obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (III) has good adhesion to glass and high temperature conditions. It was found that even when stored for a long period of time under high temperature and high humidity conditions, the appearance change such as coloring hardly occurs, and good light transmittance can be maintained.
In addition, the polymerizable composition of the present invention (IV) has a low volume shrinkage during polymerization, and the polymer obtained by polymerizing the polymerizable composition of the present invention (IV) has an adhesive property to glass. It was found that, even when stored under high temperature conditions or high temperature and humidity conditions for a long period of time, appearance changes such as coloring hardly occur and good light transmittance can be maintained.

  From Table 5, it was confirmed that the laminate using a polymer film having a dielectric constant of 5.0 or more was excellent in response sensitivity as a touch panel.

As described above, the polymer film obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (III) has good adhesion to glass and is subjected to high temperature conditions or high temperature and high humidity conditions. Even when stored for a long time, appearance changes such as coloring hardly occur, and good light transmittance can be maintained. Further, the polymerizable composition of the present invention (IV) has a low volume shrinkage during polymerization, and the polymer film obtained by polymerizing the polymerizable composition of the present invention (IV) is adhered to glass. Even when it is stored for a long time under high temperature conditions or high temperature and high humidity conditions, appearance changes such as coloring hardly occur, and good light transmittance can be maintained. Therefore, when the polymer film is used as a transparent optical resin layer interposed between the image display portion and the translucent protective portion of the image display device, a good optical adhesive layer can be provided. .
Therefore, it is useful to use the polymer in an image display device.

DESCRIPTION OF SYMBOLS 1 Display apparatus 2 Display part 3 Protection part 4 Spacer 5a, 5b Polymer (layer)
6a, 6b Polarizing plate 7 Touch sensor

Claims (15)

A polymerizable composition for forming a polymer layer interposed between an image display portion and a translucent protective portion of an image display device, the polymerizable composition comprising:
(Component 1) contains a (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 10,000, and (Component 2) a photopolymerization initiator, and is obtained by polymerizing the polymerizable composition. A polymerizable composition having a dielectric constant of 5.0 or more measured at 23 ° C., a frequency of 1 MHz, and an applied voltage of 100 mV.   The component 1 is a (meth) acryloyl group-containing polymer compound having a polyester structural unit including a structural unit derived from a diol having 4 to 9 carbon atoms and a structural unit derived from a dicarboxylic acid having 4 to 10 carbon atoms. The polymerizable composition according to claim 1.   The polymerizable composition according to claim 1, wherein the component 1 is a (meth) acryloyl group-containing polymer compound having a urethane bond. (Component 3) The polymerizable composition according to any one of claims 1 to 3, further comprising a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group. (Component 4) The compound according to any one of claims 1 to 4, further comprising a (meth) acryloyl group-containing compound which does not have any group of an alcoholic hydroxyl group and an amide group and has a viscosity of 500 mPa · s or less at 25 ° C. The polymerizable composition according to item.   The polymerizable composition according to claim 5, wherein the component 4 has an ether bond. (Component 5) Nonionic surfactant having no (meth) acryloyl group, and (Component 6) No (meth) acryloyl group in the molecule, a function to suppress radical polymerization, a function to inhibit radical polymerization, light Liquid or solid at 25 ° C., which has neither a polymerization initiation function nor a surface-active function, and is composed of carbon atoms and hydrogen atoms, or is composed of carbon atoms, hydrogen atoms and oxygen atoms The polymerizable composition according to any one of claims 1 to 6, further comprising a compound having a shape.   The polymerizable composition according to claim 7, wherein the component 6 is at least one selected from the group consisting of a polyester polyol, a polycarbonate polyol, and a tackifier.   The said component 5 is a nonionic surfactant which does not have a (meth) acryloyl group whose HLB value of Griffin is 3.0-6.0, The Claim 7 or 8 characterized by the above-mentioned. Polymerizable composition.   The polymer obtained by superposing | polymerizing the polymeric composition of any one of Claims 1-9.   A polymerizable composition for producing an optical pressure-sensitive adhesive sheet used as a polymer layer interposed between an image display portion and a translucent protective portion of an image display device, wherein the polymerizable composition is A polymerizable composition, which is the polymerizable composition according to claim 1.   A polymer layer having a thickness of 10 to 1000 μm obtained by applying the polymerizable composition according to claim 11 and irradiating the polymerizable composition with light capable of being photosensitized by a photopolymerization initiator to polymerize the polymerizable composition. An optical pressure-sensitive adhesive sheet comprising: A method for manufacturing an image display device, comprising: a base having an image display portion; a translucent protective portion; and a polymer layer interposed between the base portion and the protective portion, the method comprising:
A step of interposing the polymerizable composition according to any one of claims 1 to 9 between the base portion and the protective portion, and light capable of being photosensitized by a photopolymerization initiator to the polymerizable composition. The manufacturing method of the image display apparatus characterized by including the process of irradiating and forming a polymer layer.   It is a manufacturing method of the image display apparatus which has the process of affixing the base which has an image display part, and a translucent protection part using an optical adhesive sheet, Comprising: This optical adhesive sheet is a method of Claim 12. A method for manufacturing an image display device, which is an optical pressure-sensitive adhesive sheet.   The image display apparatus manufactured by the manufacturing method of the image display apparatus of Claim 13 or 14.

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