TWI582187B - Polymerizable composition, polymer, optical adhesive sheet, image display device and manufacturing method thereof - Google Patents

Description

Polymerizable composition, polymer, optical adhesive sheet, image display device and method of manufacturing same

The present invention relates to a polymerizable composition which is used in, for example, a liquid crystal display device used in a smart phone or a tablet PC, and the like, and a polymer obtained by polymerizing the composition, and the composition is used. A method of manufacturing an image display device, and an image display device manufactured by the method.

Conventionally, as such an image display device, for example, a liquid crystal display device 101 shown in Fig. 6 has been known.

As shown in FIG. 6, the liquid crystal display device 101 has a transparent protective portion 103 composed of, for example, glass or plastic on the liquid crystal display panel 102.

In this case, the surface of the liquid crystal display panel 102 and the polarizing plate (not shown) are provided between the liquid crystal display panel 102 and the protecting portion 103 by being interposed between the protective portion 103 and the spacer 104. A gap 105 is provided between them.

However, due to the gap between the liquid crystal display panel 102 and the protection portion 103 The presence of the gap 105 causes light to scatter, so the contrast or luminance is lowered, and the presence of the voids 105 also hinders the thinning of the panel.

In view of such a problem, it has been proposed to fill a gap between the liquid crystal display panel and the protective portion (see FIG. 1) (for example, Patent Document 1), but the stress of the cured resin at the time of hardening and shrinking is such that The optical glass that sandwiches the liquid crystal of the liquid crystal display panel is deformed, and this causes a display failure such as disorder of alignment of the liquid crystal material.

In order to solve the above problem, for example, Patent Document 2 or Patent Document 3 discloses a curable composition having a low modulus of elasticity and a small volume shrinkage ratio at the time of hardening, which is a polyurethane using urethane acrylate (polyurethane). Acrylate or an ester of a maleic anhydride adduct of a polyisoprene polymer with 2-hydroxyethyl methacrylate.

However, the use of a curable composition of polyurethane acrylate has a large volume shrinkage upon hardening (more than 4.0%); in addition, a maleic anhydride adduct of a polyisoprene polymer is used. The curable composition of the esterified product of 2-hydroxyethyl methacrylate has a small volume shrinkage ratio at the time of curing, but there is a problem that the cured product after hardening has a large color due to heat.

Further, Patent Document 4 discloses an ultraviolet crosslinkable adhesive sheet comprising a monomeric (meth)acrylic copolymer containing a (meth) acrylate having an ultraviolet crosslinkable moiety, In this specification, it is disclosed that vinyl decylamine, N-vinyl decylamine, or (meth) acrylamide compound can be used.

However, these UV crosslinkable adhesive sheets cannot reduce their dielectric properties. number.

In recent years, among mobile phones, smart phones have gradually become mainstream, and machines called tablet PCs have rapidly expanded. In such a machine, a touch panel in which a capacitance mode is mounted is generally used. As an example of the touch panel of the electrostatic capacitance mode, as shown in FIG. 2 or FIG. 3, the polymer between the display portion and the touch panel is filled in the display device in which the Add-On type electrostatic capacitance mode touch panel is mounted ( Layer (a polymer (layer) of 5b described in FIG. 2 and FIG. 3) or a display portion and a touch center filled in a display device equipped with a cover glass-touch center integrated capacitance type touch panel The polymer (layer) between the integral protective portions (the polymer (layer) of 5b described in FIGS. 4 and 5) is desirably a material having a low dielectric constant from the viewpoint of preventing erroneous operation and thinning. .

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-55641

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-282000

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-186958

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2011-184582

In order to solve the above problems, the present invention provides a polymerizable composition which is used for producing a small volume shrinkage during polymerization and dielectric. A polymer having a low constant, good adhesion to glass, little coloring due to heat, and good adhesion to a material used for a light-transmitting protective portion such as glass, and providing the composition A polymer obtained by polymerization of a polymer (including an optical adhesive sheet), an image display device using the polymer, and a method of producing the image display device.

As a result of repeated studies on the above problems, the inventors of the present invention found that the polymerizable composition is a "compound containing (meth)acryl fluorenyl group having a specific structure, and the volume shrinkage during polymerization is small, and The polymer obtained by the polymerization exhibits good adhesion because it has a low dielectric constant and is colored by heat, and exhibits good adhesion to a material for use in a light-transmitting protective portion such as glass, and has completed the present invention.

That is, the present invention (I) relates to a polymerizable composition for forming a polymerizable composition of a polymer layer which is interposed between an image display portion of an image display device and a light transmissive property. The protective portion is characterized in that the polymerizable composition contains the following (component 1) to (component 4), and (component 1): a compound selected from a (meth)acryl fluorenyl group having a polyolefin structural unit. a compound containing a (meth)acryl fluorenyl group having a hydrogenated polyolefin structural unit, a compound containing a (poly)ester structural unit containing a (meth)acryl fluorenyl group, and a (poly)carbonate structural unit ( At least one of a group consisting of a compound of a methyl) acrylonitrile group; (Component 2): a (meth) acrylate compound having a hydrocarbon group having 6 or more carbon atoms; (Component 3): having a guanamine bond a compound having a vinyl group; and (ingredient 4): a photopolymerization initiator.

The polymerizable composition of the present invention (II) is a polymerizable composition according to the invention (I), which further comprises the following (ingredient 5), (ingredient 5): no (meth)acrylic acid in the molecule The base does not have any function of inhibiting radical polymerization, a function of inhibiting radical polymerization, and a photopolymerization initiation function, and is composed of a carbon atom and a hydrogen atom, or a carbon atom, a hydrogen atom, and A compound composed of an oxygen atom at 25 ° C in the form of a liquid or a solid.

The invention (III) is a polymer obtained by polymerizing the polymerizable composition of the invention (I) or the invention (II).

The present invention (IV) relates to a polymerizable composition for producing a polymerizable composition for an optical adhesive sheet which is interposed between an image display portion of an image display device and a light transmissive property. The user who is a polymer layer between the protective portions is characterized in that the polymerizable composition is the polymerizable composition of the invention (I) or the invention (II).

The present invention (V) relates to an optical adhesive sheet having a polymer layer having a thickness of 10 to 1000 μm, which is a polymerizable composition of the present invention (IV), and the polymerizable composition is applied to the polymerizable composition. The photopolymerization initiator is irradiated with light which is sensitized and polymerized.

The invention (VI) relates to a method of manufacturing a video display device, comprising: a base portion having a video display portion, a translucent protective portion, and an image display of a polymer layer interposed between the base portion and the protective portion A method of producing a device, characterized in that the method comprises the step of allowing the polymerizable composition of the invention (II) to be interposed between the base portion and the protective portion And a step of irradiating the polymerizable composition with light sensitizing light to form a polymer layer.

The invention (VII) relates to a method of manufacturing an image display device, which is characterized in that a method of manufacturing a video display device in which a base portion of an image display portion and a light-transmitting protective portion are adhered using an optical adhesive sheet is used. The optical adhesive sheet is the optical adhesive sheet of the invention (V).

The invention (VIII) relates to an image display device manufactured by the method of producing the image display device of the invention (VI) or the invention (VII).

In other words, the present invention relates to the following [1] to [15].

[1] A polymerizable composition for forming a polymerizable layer of a polymer layer, wherein the polymer layer is interposed between an image display portion of a video display device and a translucent protective portion. It is characterized in that the polymerizable composition comprises the following (Component 1) to (Component 4), (Component 1): a compound selected from a (meth)acryl fluorenyl group having a polyolefin structural unit, having a hydrogenated polyolefin a (meth)acrylonitrile group-containing compound having a (poly)ester structural unit, and a (poly)carbonate structural unit containing (meth)acryl oxime At least one of a group consisting of a compound; (Component 2): a (meth) acrylate compound having a hydrocarbon group having 6 or more carbon atoms; (Component 3): a vinyl group-containing compound having a guanamine bond; Ingredient 4): Photopolymerization initiator.

[2] The polymerizable composition according to the above [1], which further comprises (Component 5), (Component 5): There is no (meth)acrylonitrile group in the molecule, and it does not have a function of suppressing radical polymerization, a function of inhibiting radical polymerization, and a photopolymerization initiation function. Any of the functions, consisting of a 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.

[3] The polymerizable composition according to the above [2], wherein the component 5 is selected from the group consisting of a poly(?-olefin) liquid, an ethylene-propylene copolymerization liquid, and a propylene-?-olefin copolymerization liquid. , ethylene-α-olefin copolymerization 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 polyisoprene polyol, hydrogenation At least one of a group consisting of a polymer diol, a hydrogenated petroleum resin, a terpene-based hydrogenated resin, and a hydrogenated rosin ester.

[4] The polymerizable composition according to the above [2] or [3] wherein the component 5 is a compound having one or less carbon-carbon unsaturated bonds in the molecule.

[5] The polymerizable composition according to any one of the above [1] to [4], further comprising the following (component 6), (component 6): a (meth) acrylate having an alcoholic hydroxyl group.

[6] The polymerizable composition according to any one of the above [1], wherein the (meth)acryl fluorenyl group-containing compound having a polyolefin structural unit has a polybutadiene structural unit. And/or a compound containing a (meth) acrylonitrile group of a polyisoprene structural unit.

[7] The polymerizable composition according to any one of the above [1] to [6] wherein the (meth)acryl fluorenyl group-containing compound having a hydrogenated polyolefin structural unit is a hydrogenated polybutadiene. A compound containing a (meth) acrylonitrile group as a structural unit and/or a hydrogenated polyisoprene structural unit.

The polymerizable composition according to any one of the above [1] to [7] wherein the (meth)acryl fluorenyl group-containing compound having a (poly)ester structural unit has a (poly) The (meth)acrylonitrile group-containing compound in the structural unit derived from the ester polyol, and the (poly)ester polyol is produced by using a polyol having 10 or more carbon atoms as a raw material.

The polymerizable composition according to any one of the above [1] to [8] wherein the (meth)acryloyl group-containing compound having a (poly)carbonate structural unit has A compound containing a (meth) acrylonitrile group in a structural unit derived from a carbonate polyol, and the (poly)carbonate polyol is produced by using a polyol having 10 or more carbon atoms as a raw material.

[10] A polymer obtained by polymerizing the polymerizable composition according to any one of the above [1] to [9].

[11] A polymerizable composition for producing a polymerizable composition for an optical adhesive sheet, wherein the optical adhesive sheet is interposed between an image display portion of a video display device and a translucent protective portion. In the case of the polymer layer, the polymerizable composition is a polymerizable composition according to any one of the above [1] to [9].

[12], a light having a polymer layer having a thickness of 10 to 1000 μm The polymer layer is obtained by applying the polymerizable composition of the above [11], irradiating the polymerizable composition with a photopolymerization initiator, and sensitizing the light.

[13] A method of manufacturing an image display device, comprising: a base portion having a video display portion, a translucent protective portion, and a video display device having a polymer layer interposed between the base portion and the protective portion; And a method comprising the steps of: interposing the polymerizable composition according to any one of the above [2] to [9] between the base portion and the protective portion; and the polymerizable composition The step of irradiating the photopolymerization initiator with photosensitive light to form a polymer layer.

[14] A method of manufacturing an image display device, comprising: a method of manufacturing a video display device having a step of bonding a base portion of a video display portion and a translucent protective portion using an optical adhesive sheet, wherein The optical adhesive sheet is the optical adhesive sheet of the above [12].

[15] An image display device manufactured by the method of manufacturing the image display device of the above [13] or [14].

[16] The image display device according to [15] above, wherein the image display unit is a liquid crystal display panel.

According to the polymerizable composition of the present invention, since a polymer having a low dielectric constant can be provided, even if the polymer of 5b (including the optical adhesive sheet) of FIGS. 2 to 5 is made thinner than in the related art, Without capacitor function, the result is more preventive electrical error than the former Work. That is, the image display device such as a liquid crystal panel can be made thin.

Further, when the polymerizable composition of the present invention is applied between the image display portion and the protective portion and the polymerization is suppressed, the stress caused by the volume shrinkage can be minimized, so that the polymerizable composition is used. When the image display device is manufactured by the base portion of the image display portion and the light-transmitting protective portion and polymerized to form a polymer layer, the stress can be applied to the image display portion and protected. The influence of the ministry is kept to a minimum. Therefore, according to the video display device of the present invention, distortion is hardly generated in the video display unit and the protection unit.

Further, the polymerizable composition of the present invention is applied to a cured product which is polymerized between the image display portion and the protective portion and which is polymerized, and the cured product has a large adhesion to the glass used for the protective portion.

Moreover, the refractive index of the polymer and the optical adhesive sheet of the present invention is closer to the refractive index of the constituent panel of the image display unit or the protective panel than the gap between the liquid crystal display panel and the protective portion. The light is reflected by the interface between the protective portion and the polymer, the interface between the polymer and the image display portion, the interface between the protective portion and the optical adhesive sheet, and the interface between the optical adhesive sheet and the image display portion. As a result, the image display device of the present invention can be used as a display having high luminance and high contrast without display failure.

Further, when the image display unit is a liquid crystal display panel, it is possible to reliably prevent display failure such as alignment disorder of the liquid crystal material, and to perform high-quality display.

Further, according to the image display device of the present invention, since the polymer or the optical adhesive sheet is interposed between the image display portion and the protective portion, the impact is strong.

Further, in the case of the polymer and the optical adhesive sheet of the present invention, even if it is subjected to a heat history, it is not easy to be colored, so that high-intensity and high-contrast display can be maintained for a long period of time.

Further, according to the present invention, it is possible to provide a thinner image display device than the prior art in which a gap is provided between the image display portion and the protective portion.

1‧‧‧ display device

2‧‧‧Display Department

3‧‧‧Protection Department (However, in Figure 4 and Figure 5, the touch sensor integrated protection part)

4‧‧‧ spacer

5a, 5b‧‧‧ polymer (layer)

6a, 6b‧‧‧ polarizing plate

7‧‧‧Touch panel

Fig. 1 is a cross-sectional view showing the main part of an embodiment of a display device according to the present invention.

Fig. 2 is a cross-sectional view showing the essential part of an embodiment of a display device according to the present invention.

Fig. 3 is a cross-sectional view showing the main part of an embodiment of a display device according to the present invention.

Fig. 4 is a cross-sectional view showing the main part of an embodiment of a display device according to the present invention.

Fig. 5 is a cross-sectional view showing the main part of an embodiment of a display device according to the present invention.

Fig. 6 is a cross-sectional view showing the main part of a display device related to the prior art.

[Best Practice for Carrying Out the Invention]

The invention is specifically described below.

In addition, the "polymer" described in the present specification is not particularly limited as long as it is a polymer obtained by polymerizing a polymerizable composition, and the "adhesive sheet for optical use" described in the present specification is described. Also included in the meaning of the polymer.

Further, the term "polymer layer interposed between the image display portion and the translucent protective portion" as used in the present specification means all polymer layers between the image display portion and the translucent protective portion. In the meaning, for example, both 5a and 5b of Fig. 2 mean.

In the present specification, the term "(meth)acryl fluorenyl" means acryl fluorenyl and/or methacryl fluorenyl.

In addition, the term "(poly)ester polyol" as used herein means a compound having one or more -COO-bonds (carboxylate bonds) in one molecule and having two or more alcoholic hydroxyl groups. The term "(poly)carbonate polyol" as used in the present specification means having one or more -OCOO-bonds (carbonate linkages) in one molecule and having two or more alcoholic hydroxyl groups. The meaning of the compound.

In addition, in the present specification, when (poly)ester polyol which can be a raw material of "component 1 of the essential raw material component of the polymerizable composition of the present invention (I)" is produced, when (poly)ester plural remains When a polyol of a raw material of an alcohol (i.e., a polyol having no -COO-bond (carboxylate bond)) is defined, the polyol is also included in the (poly)ester polyol. Further, in the present specification, in addition to the raw material polyol contained in the (poly)ester polyol, the polyol of the raw material component of the (poly)ester polyol to be used is newly added to produce the polymerization of the present invention (I). Essential component of sexual composition In the case of the component 1, the polyol to be added is contained in the (poly)ester polyol even if it is a polyol having no -COO-bond (carboxylate bond).

In the present specification, when (poly)carbonate polyol which is a raw material of the component 1 which is an essential raw material component of the polymerizable composition of the present invention (I), (poly)carbonate polyol remains. When the polyol of the raw material (i.e., the polyol having no carbonate bond) is defined, the polyol is also included in the (poly)carbonate polyol. In addition, in the present specification, the present invention (I) is produced by newly adding a polyol of a raw material component of the (poly)carbonate polyol to be used in addition to the raw material polyol contained in the (poly)carbonate polyol. When the component 1 of the essential component of the polymerizable composition is used, the polyol to be added is also included in the (poly)carbonate polyol.

First, the "invention (I)" will be described.

The present invention (I) is a polymerizable composition for forming a polymerizable composition of a polymer layer which is interposed between an image display portion of an image display device and a light-transmitting protective portion. In the meantime, the polymerizable composition contains the following (component 1) to (component 4), (component 1): a compound selected from a (meth)acryl fluorenyl group having a polyolefin structural unit, and having hydrogenation (meth)acryloyl group-containing compound having a (poly)ester structural unit, and (poly)carbonate structural unit containing (poly)carbonate structural unit (meth) At least one of the group consisting of a compound of an acrylonitrile group; (Component 2): a (meth) acrylate compound having a hydrocarbon group having 6 or more carbon atoms; (Component 3): a vinyl group-containing compound having a guanamine bond; and (Component 4): a photopolymerization initiator.

First, the "component 1 of an essential component of the polymerizable composition of the present invention (I)" will be described.

Component 1 of an essential component of the polymerizable composition of the present invention (I) is selected from a compound containing a (meth)acryl fluorenyl group having a polyolefin structural unit, and a (meth) containing hydrogenated polyolefin structural unit. a compound composed of a propylene fluorenyl group, a compound having a (poly)ester structural unit containing a (meth)acryl fluorenyl group, and a compound having a (poly)carbonate structural unit containing a (meth)acryl fluorenyl group At least one.

First, the "compound containing a (meth)acryl fluorenyl group having a polyolefin structural unit will be described.

The compound containing a (meth) acrylonitrile group having a polyolefin structural unit is not particularly limited as long as it is a compound having a polyolefin structural unit and a (meth) acrylonitrile group in one molecule. As the polyolefin structural unit, a compound having a polydiene structural unit is preferred, and it may be selected from, for example, 1,3-butadiene, 1,3-pentadiene, isoprene, 2,3- Dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 2-propyl-1,3-butadiene, 1,3-heptadiene, 6-methyl -1,3-heptadiene, 1,3-hexadiene, 5-methyl-1,3-hexadiene, 2,4-hexadiene, 2,5-dimethyl-2,4- A polydiene structural unit obtained by polymerizing one or more kinds of dienes of a group consisting of hexadiene and 1,3-octadiene.

Among these, a polybutadiene structural unit, a polyisoprene structural unit or a poly(butadiene-isoprene) structural unit is preferred.

The commercially available product of the (meth) acrylonitrile-containing compound having a polyolefin structural unit may, for example, be Kuraprene UC-102 or UC- having a methacryl fluorenyl-containing compound having a polyisoprene structural unit. 203 (manufactured by Kuraray Co., Ltd.), NISSO-PB TE-2000 (manufactured by Nippon Soda Co., Ltd.) having a polymethadienyl structural unit, and a propylene sulfhydryl group-containing compound having a polybutadiene structural unit. NISSO-PB TEA-1000 (made by Nippon Soda Co., Ltd.).

Further, NISSO-PB TE-2000 or NISSO-PB TEA-1000 is a polybutadiene polyol such as NISSO-PB G-1000 or G-2000 (manufactured by Nippon Soda Co., Ltd.), an organic polyisocyanate compound, and the like. A reaction product of an alcoholic hydroxyl (meth) acrylate. In this way, as a raw material for producing a compound containing a (meth)acryl fluorenyl group having a polyolefin structural unit, a polyolefin polyol is suitable, and in addition to the above-mentioned polyolefin polyol, a commercial product is used. Poly bd (manufactured by Idemitsu Kosan Co., Ltd.) which is a liquid polybutadiene having a terminal hydroxyl group, other than the NISSO PB G-1000, G-2000, and G-3000 (manufactured by Nippon Soda Co., Ltd.) of the polybutadiene polyol. Poly Ip (manufactured by Idemitsu Kosan Co., Ltd.) of liquid polyisoprene having a terminal hydroxyl group, KRASOL (manufactured by Cray Valley Co., Ltd.) of liquid polybutadiene diol, and the like.

The method for producing the (meth)acrylonitrile group-containing compound having a polyolefin structural unit is not particularly limited, and for example, it can be produced by the following method.

First, "the use of "polyolefin polyol", "organic polyisocyanate compound", and "(meth)acrylate containing an alcoholic hydroxyl group" as essential raw material components to obtain a polyolefin structural unit (methyl) The case of a compound of an acrylonitrile group will be described.

The polyolefin polyol represented by a polybutadiene polyol or a polyisoprene polyol is a compound having two or more hydroxyl groups in one molecule, preferably having 2 to 4 hydroxyl groups. Further, the hydroxyl value of the polyolefin polyol is preferably from 10 to 120 mgKOH/g, more preferably from 15 to 100 mgKOH/g, particularly preferably from 20 to 80 mgKOH/g. When the hydroxyl value of the polyolefin polyol compound is less than 10 mgKOH/g, the molecular weight and viscosity of the obtained (meth)acrylonitrile-containing polyolefin compound may become too high, and workability may also be deteriorated. The tendency to become difficult. When the hydroxyl value of the polyolefin polyol compound is more than 120 mgKOH/g, the volume shrinkage ratio during polymerization becomes too large, the cohesive force of the polymer becomes too high, and the adhesive property of the polymer cannot be sufficiently exhibited. Can't be called better.

Further, the polybutadiene polyol is a homopolymer of butadiene containing a hydroxyl group. A polyisoprene polyol is a homopolymer of isoprene containing a hydroxyl group.

The organic polyisocyanate compound is not particularly limited as long as it is an organic compound having two or more isocyanate groups in one molecule. Specific examples thereof include 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), and 1,3-bis(isocyanatomethyl) ring. Hexane, 1,4-bis(isocyanatomethyl)cyclohexane, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenyl Methane-4,4'-diisocyanate, 1,3-decyldiisocyanate, 1,4-decyldiisocyanate, lysine triisocyanate, lysine diisocyanate, hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, norbornane diisocyanate, etc., these may be used alone or in combination of two or more. use.

In the component 1 which is an essential component of the polymerizable composition of the invention (I), the viscosity is preferably as low as possible in consideration of the degree of freedom of blending thereafter. As the organic polyisocyanate compound for this purpose, preferred is 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 2,4, 4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate and norbornane diisocyanate, more preferably 1, 3-bis(isocyanatomethyl)cyclohexane, 2,4,4-trimethylhexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate, preferably 2,4,4-trimethylhexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate.

The (meth) acrylate having an alcoholic hydroxyl group is not particularly limited as long as it is a (meth) acrylate having an alcoholic hydroxyl group in one molecule. Specific examples thereof include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, and 2- Hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-(o-phenylphenoxy)propyl acrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylate , 2-hydroxypropyl methacrylate, 3-hydroxypropyl propyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxy-3- Phenoxypropyl methacrylate, 2-hydroxy-3-(o-phenylphenoxy)propyl methacrylate, and the like.

Among these, in consideration of the polymerization rate of the component 1 of the essential component of the invention (I), preferred are 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 . When considering the reactivity with an isocyanate group, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate are preferable, and 4-hydroxybutyl acrylate is preferable.

As a method of reacting a polyolefin polyol, an organic polyisocyanate compound, and an (meth) acrylate containing an alcoholic hydroxyl group, a conventional amine such as dibutyltin dilaurate or dioctyltin dilaurate may be used. The polyolefin polyol, the organic polyisocyanate compound, and the (meth) acrylate containing an alcoholic hydroxyl group are reacted in the presence or absence of a urethanization catalyst to be synthesized in the presence of a catalyst. In the case of the reaction, it is preferred to shorten the reaction time. However, if it is used too much, it may have an adverse effect on the physical property value at the time of actual use as a cured film, so the amount used is relative to a polyolefin polyol, an organic polyisocyanate compound, and an alcoholic hydroxyl group (methyl group). The total amount of the acrylate is 100 parts by mass, preferably 0.001 to 1 part by mass.

The order in which the raw materials are supplied is not particularly limited. For example, an organic polyisocyanate compound and a urethane catalyst required for the reaction are placed in a reactor, stirred, and then placed in the reactor. The temperature is from 40 ° C to 140 ° C, preferably from 50 ° C to 120 ° C, and the polyolefin polyol, and then the polyol component other than the desired polyolefin polyol, is sequentially added, and then the temperature in the reactor is set. These reactions are carried out at 50 ° C to 160 ° C, preferably 60 ° C to 140 ° C. Thereafter, the temperature in the reactor is added at 30 ° C to 120 ° C, preferably 50 ° C to 100 ° C, and a polymerization inhibitor and a urethane catalyst which are required for the reaction are added, and the alcohol is added by dropping. (meth) acrylate of a hydroxyl group. In the dropping liquid, the temperature in the reactor is maintained at 30 ° C to 120 ° C, preferably 50 ° C to 100 ° C. After the completion of the dropping, the temperature in the reactor is maintained at 30 ° C to 120 ° C, preferably 50 ° C to 100 ° C to completely terminate the reaction.

Further, as another method, for example, an organic polyisocyanate compound, a polymerization inhibitor and/or a urethane catalyst required for the reaction are placed in a reactor, and after stirring, the temperature in the reactor is 30. From °C to 120 ° C, preferably from 50 ° C to 110 ° C, a (meth) acrylate containing an alcoholic hydroxyl group is introduced by dropping. In the dropping liquid, the temperature in the reactor is maintained at 30 ° C to 120 ° C, preferably 50 ° C to 110 ° C. After the completion of the dropping, the temperature in the reactor is maintained at 30 ° C to 120 ° C, preferably 50 ° C to 110 ° C to carry out the reaction. Thereafter, in the reactor in which the polyolefin polyol is placed and the polyol component other than the polyolefin polyol is required, the temperature in the reactor can be maintained at 30 ° C to 120 ° C while stirring. The reaction product is preferably supplied at a temperature of from 50 ° C to 100 ° C. After the introduction, the temperature in the reactor is maintained at 30 ° C to 120 ° C, preferably 50 ° C to 100 ° C, to completely terminate the reaction.

Used as component 1 of an essential component of the present invention (I) When it is necessary to suppress the viscosity increase of the oligomer or reduce the volume shrinkage ratio at the time of polymerization, only a part of the end of the compound is contained in the molecule containing the (meth) acrylate having an alcoholic hydroxyl group. It is preferred that one hydroxy compound is used to seal the oligomer.

The molar ratio of the raw materials to the molar ratio (ie, the total number of hydroxyl groups when the amount of the polyol other than the polyolefin polyol or the polyolefin polyol is combined) / (the isocyanate group of the organic polyisocyanate compound used) The total number) / (the total number of hydroxyl groups in the case where the (meth) acrylate containing an alcoholic hydroxyl group is a total of the number of compounds having one hydroxyl group in the molecule)) is a polyamine group for the purpose The molecular weight of the acid ester is adjusted.

However, when the terminal of the compound is almost completely sealed with a compound having an alcoholic hydroxyl group (meth) acrylate and having one hydroxyl group in the molecule, it is necessary to use an isocyanate of the organic polyisocyanate compound to be used. The total number of acid groups is more than the total number of hydroxyl groups in combination with the polyolefin polyol used and the polyol used in addition to the polyolefin polyol.

In this case, the ratio of the total number of hydroxyl groups when the polyolefin polyol used and the polyol used other than the polyolefin polyol are combined to the total number of isocyanato groups in the organic polyisocyanate compound is When it is close to 1.0, the average molecular weight of the produced compound becomes large, and when it deviates from 1.0, the average molecular weight becomes small.

The molar ratio of the raw material to the molar ratio is not particularly limited, and the number of isocyanato groups in the organic polyisocyanate compound is the same as the hydroxyl group when the polyolefin polyol to be used and the polyol used in addition to the polyolefin polyol are combined. Total Preferably, it is 1.5:1 or more.

If the ratio is less than 1.5:1 and the viscosity is too high, it cannot be called better.

Further, when only a part of the terminal of the compound is sealed with a compound having one hydroxyl group in the molecule containing a (meth) acrylate having an alcoholic hydroxyl group, the polyolefin polyol to be used, The total number of hydroxyl groups in the case where the polyol used in addition to the polyolefin polyol and the (meth) acrylate containing an alcoholic hydroxyl group is a compound having one hydroxyl group in the molecule must be set to be used. The total number of isocyanato groups of the organic polyisocyanate compound is large.

However, in this case, the polyolefin polyol to be used, the polyol used in addition to the polyolefin polyol, and the (meth) acrylate containing an alcoholic hydroxyl group have one hydroxyl group in the molecule. The ratio of the total number of hydroxyl groups in the total combination of the compounds to the total number of isocyanato groups in the organic polyisocyanate compound is preferably 2:1 or less.

When the ratio is larger than 2:1, the number of molecules having no acryl oxime group increases, and the shape retainability of the polymer after polymerization is deteriorated, which is not preferable.

In this way, a polyolefin polyol is used as a raw material component to synthesize urethane (meth) acrylate, and when it is synthesized, a polyolefin structural unit is also produced. In the case of urethane (meth) acrylate, but in the present specification, urethane (meth) acrylate having no polyolefin polyol structural unit is defined as not included in the present invention. (I) Component 1 of the essential ingredients. For example, a polyolefin polyol, 1,3-bis(isocyanatomethyl)cyclohexane, and 2-hydroxyethyl acrylate are used to produce a component having a polyolefin structural unit of component 1 (methyl). In the case of a compound of an acrylonitrile group, a compound of the following formula (1) which does not have a urethane (meth) acrylate of a structural unit of polyolefin is also produced.

However, in the present specification, since the compound of the formula (1) does not have a polyolefin structural unit, it means that it is not contained in the component 1.

Next, "using a polyolefin polyol" and "a compound containing a (meth) acrylonitrile group having one isocyanate group in one molecule" as an essential raw material component to obtain a polyolefin structural unit The case of the compound containing a (meth) propylene group is demonstrated.

The polyolefin polyol is as described above.

Examples of the (meth)acrylonitrile group-containing compound having an isocyanate group which can be used as the above-mentioned raw material include 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate. Wait.

Examples of the 2-isocyanatoethyl acrylate include, for example, Showa Electric Karenz AOI (registered trademark) manufactured by the company.

Examples of the 2-isocyanatoethyl methacrylate include Karenz MOI (registered trademark) manufactured by Showa Denko Co., Ltd., and the like.

Reacting a compound containing a (meth) fluorenyl group having a polyolefin structural unit in a molecule containing a urethane bond and having a terminal having a (meth) acrylonitrile group to obtain an aminocarboxylic acid The ester (meth) acrylate can be generally synthesized by the following method.

Further, the total amount of the hydroxyl group of the polyolefin polyol may be reacted with a compound containing a (meth) acrylonitrile group having an isocyanate group, or only a part of the hydroxyl group of the polyolefin polyol may have an isocyanate. The acid group-containing (meth) acrylonitrile-based compound is reacted, and a part of the hydroxyl group may remain.

When the total number of hydroxyl groups of the polyolefin polyol is reacted with a compound containing a (meth) acrylonitrile group having an isocyanato group, the total number of hydroxyl groups of the polyolefin polyol and the isocyanate group used (A) The ratio of the total number of isocyanato groups of the acrylate must be 1 or more.

When only a part of the hydroxyl group of the polyolefin polyol is reacted with the (meth)acryloyl group-containing compound having an isocyanate group, and a part of the hydroxyl group remains, compared with the hydroxyl group of the polyolefin polyol In total, a smaller total number of isocyanato groups of the (meth) acrylate containing isocyanate groups must be used.

Further, at this time, there may be a polyolefin polyol which does not directly react with a compound having a (meth) acrylonitrile group having an isocyanate group, but the polyolefin polyol is not included in the component 1. . When the polyolefin polyol is a liquid polybutadiene polyol or a liquid polyisoprene polyol, It is included in the component 5.

The manufacturing method is not particularly limited, and generally, a polyolefin polyol, a polymerization inhibitor, and a urethane catalyst or an antioxidant required for the reaction are added to the reactor, stirring is started, and the reactor is started. The temperature inside is raised to 40 ° C to 120 ° C, preferably 50 ° C to 100 ° C. Thereafter, a compound containing a (meth) acrylonitrile group having an isocyanate group is added to the liquid. In the dropping liquid, the temperature in the reactor is controlled to be 40 ° C to 130 ° C, preferably 50 ° C to 110 ° C. After the completion of the dropping, the temperature in the reactor is maintained at 40 ° C to 120 ° C, preferably 50 ° C to 100 ° C, while stirring is continued to complete the reaction.

In addition, as the compound containing a (meth)acryl fluorenyl group having a polyolefin structural unit, the compound containing a (meth) acryl fluorenyl group having a polyolefin structural unit may, for example, be borrowed. A polyolefin (meth) acrylate obtained by a transesterification reaction of a polyolefin polyol with a (meth) acrylate and/or a dehydration condensation reaction of a polyolefin polyol with (meth)acrylic acid. The number of the (meth) acrylonitrile groups in the (meth) acrylate compound may be one or more, and more preferably two to four, in one molecule.

A compound containing a (meth) fluorenyl group having a polyolefin structural unit which does not contain a urethane bond, and a representative synthesis example thereof, a transesterification reaction of a polybutadiene diol with an acrylate, Or a structural formula of a (meth) acrylate compound formed by dehydration condensation reaction of polybutadiene diol with acrylic acid, and transesterification reaction of polyisoprene diol with acrylate, or polyisoprene Dehydration condensation of olefindiol with acrylic acid The structural formula of the (meth) acrylate compound to be produced is represented by the formula (2) and the formula (3), respectively.

(In the formula (2), l, m, and n are integers of 1 or more).

(In the formula (3), q, r, and s are integers of 1 or more).

When the (meth) acrylate compound of the component 1 is produced by transesterification of a polyolefin polyol with a (meth) acrylate, generally, the polyolefin polyol and the lower alkyl (meth) acrylate are In the presence of a transesterification catalyst, the transesterification reaction is carried out by heating, and the corresponding lower alkyl alcohol is produced, and the (meth) acrylate of the component 1 is produced by distillation, for example, according to the Japanese national standard. The production is carried out by the method described in JP-A-2006-45823 or JP-A-2006-45284.

Further, when the (meth) acrylate of the component 1 is produced by a dehydration condensation reaction of a polyolefin polyol and (meth)acrylic acid, the polyolefin polyol and the (meth)acrylic acid are present in the presence of an esterification catalyst. It is produced by heating and performing a dehydration reaction. However, when the reaction is carried out by heating to a high temperature of 150 ° C or higher, there is a risk of causing radical polymerization of the acrylonitrile group in the dehydration condensation reaction. Therefore, the esterification reaction is generally carried out in the presence of a solvent such as cyclohexane or toluene which can be azeotroped with water, and the water formed by the dehydration condensation reaction is removed to the reaction by azeotroping the solvent with water. Outside the device. The catalyst used for the esterification reaction may, for example, be an acid catalyst such as p-toluenesulfonic acid.

As described above, as a method for producing a (meth)acrylonitrile group-containing compound having a polyolefin structural unit which does not contain a urethane bond, there is a transesterification of a polyolefin polyol with a (meth) acrylate. The reaction method and the method for dehydrating and condensing the polyolefin polyol and the (meth)acrylic acid, but the solvent may not be used, or the purification step may be omitted or the purification may be simplified. Method for producing a (meth) acrylonitrile-containing compound having a polyolefin structural unit without a urethane bond by transesterification of a polyolefin polyol with a (meth) acrylate It is appropriate.

Next, the "compound containing a (meth)acryl fluorenyl group having a hydrogenated polyolefin structural unit will be described.

The compound containing a (meth) acrylonitrile group having a hydrogenated polyolefin structural unit is not particularly limited as long as it is a compound having a hydrogenated polyolefin structural unit and a (meth) acrylonitrile group in one molecule. Make The hydrogenated polyolefin structural unit is preferably a compound having a hydrogenated polydiene structural unit, and examples thereof include, for example, hydrogenated 1,3-butadiene, hydrogenated 1,3-pentadiene, and hydrogenated isoprene. Hydrogenation of 2,3-dimethyl-1,3-butadiene, hydrogenation of 2-phenyl-1,3-butadiene, hydrogenation of 2-propyl-1,3-butadiene, hydrogenation of 1,3- Heptadiene, hydrogenated 6-methyl-1,3-heptadiene, hydrogenated 1,3-hexadiene, hydrogenated 5-methyl-1,3-hexadiene, hydrogenated 2,4-hexadiene, One or more types of hydrogenated 2,5-dimethyl-2,4-hexadiene and hydrogenated 1,3-octadiene, and a polydiene structural unit obtained by polymerizing a diene.

Among these, a hydrogenated polybutadiene structural unit, a hydrogenated polyisoprene structural unit, or a hydrogenated poly(butadiene-isoprene) structural unit is preferred.

As a commercial item of the compound containing a (meth) propylene fluorenyl group which has a hydrogenated polyolefin structural unit, the NISSO-PB TEAI-1000 ( Japan's Soda Corporation) and so on.

In addition, NISSO-PB TEAI-1000 is a hydrogenated polybutadiene polyol such as NISSO-PB GI-1000 (made by Nippon Soda Co., Ltd.), an organic polyisocyanate compound, and a (meth) acrylate containing an alcoholic hydroxyl group. The reaction product. Thus, a hydrogenated polyolefin polyol is suitable as a raw material for producing a compound containing a (meth)acryl fluorenyl group having a hydrogenated polyolefin structural unit, and as such a commercially available product, for example, polybutadiene plural NISSO PB GI-1000, GI-2000, GI-3000 (manufactured by Nippon Soda Co., Ltd.), and EPOL (manufactured by Idemitsu Kosan Co., Ltd.), which is a liquid hydrogenated polyisoprene having a terminal hydroxyl group.

In addition, the "hydrogenated polyolefin polyol" described in the present specification is a polyol obtained by hydrogenating and reducing a polyolefin polyol.

The method for producing the (meth)acryl fluorenyl group-containing compound having a hydrogenated polyolefin structural unit is not particularly limited, and for example, it can be produced by the following method.

First, "the use of "hydrogenated polyolefin polyol", "organic polyisocyanate compound", and "(meth)acrylate containing an alcoholic hydroxyl group" as essential raw material components to obtain a hydrogenated polyolefin structural unit ( The case of a compound of a methyl methacrylate group will be described.

The hydrogenated polyolefin polyol represented by hydrogenated polybutadiene polyol or hydrogenated polyisoprene polyol is one having two or more hydroxyl groups in one molecule, preferably having 2 to 4 hydroxyl groups. Further, the hydrogenated polyolefin polyol preferably has a hydroxyl group value of 10 to 120 mgKOH/g, more preferably 15 to 100 mgKOH/g, particularly preferably 20 to 80 mgKOH/g. When the hydroxyl value of the hydrogenated polyolefin polyol compound is less than 10 mgKOH/g, the molecular weight and viscosity of the obtained (meth)acrylic group-containing hydrogenated polyolefin compound become too high, and workability is also deteriorated. The tendency to become difficult. Further, when the hydroxyl value of the hydrogenated polyolefin polyol compound is larger than 120 mgKOH/g, the volume shrinkage ratio during polymerization becomes excessively large, and the cohesive force of the polymer becomes too high, and the adhesive property of the polymer may not be sufficiently exhibited. The situation cannot be called better.

Further, the hydrogenated polybutadiene polyol is a hydrogenated product of a homopolymer of a butadiene containing a hydroxyl group. Hydrogenated polyisoprene The alcohol is a hydride of a homopolymer of isoprene containing a hydroxyl group.

The organic polyisocyanate compound can be used in the production of a compound containing a (meth) acrylonitrile group having a polyolefin structural unit as described above, and the same as those exemplified as the organic polyisocyanate compound.

The (meth) acrylate containing an alcoholic hydroxyl group can be used as a (meth) acrylate containing an alcoholic hydroxyl group in the production of a compound containing a (meth) acrylonitrile group having a polyolefin structural unit as described above. The enumerators are the same.

The method for reacting a hydrogenated polyolefin polyol, an organic polyisocyanate compound, and an (meth) acrylate having an alcoholic hydroxyl group can be exemplified by dibutyltin dilaurate, dioctyltin dilaurate, and the like. Synthesis of a hydrogenated polyolefin polyol, an organic polyisocyanate compound, and an (meth) acrylate containing an alcoholic hydroxyl group in the presence or absence of a urethane catalyst, in the presence of a catalyst When the reaction is carried out, it is preferred to shorten the reaction time. However, if it is used too much, it may have an adverse effect on the physical property value at the time of actual use as a cured film, so the amount used is relative to the hydrogenated polyolefin polyol, the organic polyisocyanate compound, and the alcoholic hydroxyl group (A). The total amount of the acrylate is 100 parts by mass, preferably 0.001 to 1 part by mass.

The order of the input of the raw materials is not particularly limited. For example, the organic polyisocyanate compound and the urethane catalyst required for the reaction are put into the reactor, and after stirring, the temperature in the reactor is set. 40 ° C ~ 140 ° C, preferably 50 ° C ~ 120 ° C, hydrogenated polyolefin polyol, and in addition to the required hydrogenated polyolefin polyols other than polyols The components are added sequentially, and then the reaction is carried out at a temperature in the reactor at 50 ° C to 160 ° C, preferably 60 ° C to 140 ° C. Thereafter, the temperature in the reactor is added at 30 ° C to 120 ° C, preferably 50 ° C to 100 ° C, and a polymerization inhibitor and a urethane catalyst which are required for the reaction are added, and the alcohol is added by dropping. (meth) acrylate of a hydroxyl group. In the dropping liquid, the temperature in the reactor is maintained at 30 ° C to 120 ° C, preferably 50 ° C to 100 ° C. After the completion of the dropping, the temperature in the reactor is maintained at 30 ° C to 120 ° C, preferably 50 ° C to 100 ° C to completely terminate the reaction.

Further, as another method, for example, an organic polyisocyanate compound, a polymerization inhibitor and/or a urethane catalyst required for the reaction are placed in a reactor, and after stirring, the temperature in the reactor is 30. From °C to 120 ° C, preferably from 50 ° C to 110 ° C, a (meth) acrylate containing an alcoholic hydroxyl group is introduced by dropping. In the dropping liquid, the temperature in the reactor is maintained at 30 ° C to 120 ° C, preferably 50 ° C to 110 ° C. After the completion of the dropping, the temperature in the reactor is maintained at 30 ° C to 120 ° C, preferably 50 ° C to 110 ° C to carry out the reaction. Thereafter, in a reactor in which a hydrogenated polyolefin polyol is placed and a polyol component other than the hydrogenated polyolefin polyol is required, the temperature in the reactor can be maintained at 30 ° C to 120 while stirring. The reaction product is introduced at a temperature of ° C, preferably from 50 ° C to 100 ° C. After the introduction, the temperature in the reactor is maintained at 30 ° C to 120 ° C, preferably 50 ° C to 100 ° C, to completely terminate the reaction.

When the component 1 which is an essential component of the invention (I) is used, when it is necessary to suppress the increase in the viscosity of the oligomer or to reduce the volume shrinkage at the time of polymerization, only a part of the end of the compound is contained to contain the alcoholic hydroxyl group. The oligomer of the (meth) acrylate which is a compound having one hydroxyl group in the molecule is preferably used.

The molar ratio of the raw materials to the molar ratio (ie, the total number of hydroxyl groups when the amount of the polyol other than the hydrogenated polyolefin polyol or the hydrogenated polyolefin polyol is combined) / (isocyanic acid of the organic polyisocyanate compound used) The total number of bases) / (the total number of hydroxyl groups in the case where the (meth) acrylate containing an alcoholic hydroxyl group is a total of the number of compounds having one hydroxyl group in the molecule), which is a polyamine for the purpose The molecular weight of the carbamate is adjusted.

However, when the terminal of the compound is almost completely sealed with a compound having an alcoholic hydroxyl group (meth) acrylate and having one hydroxyl group in the molecule, the isocyanate group of the organic polyisocyanate compound used is used. The total number must be set to be more than the total number of hydroxyl groups when the polyol used in addition to the hydrogenated polyolefin polyol and the hydrogenated polyolefin polyol used is combined.

In this case, the ratio of the total number of hydroxyl groups when the hydrogenated polyolefin polyol to be used and the polyol used in addition to the hydrogenated polyolefin polyol are combined with the total number of isocyanato groups in the organic polyisocyanate compound When it is close to 1.0, the average molecular weight of the compound to be produced becomes large, and when it deviates from 1.0, the average molecular weight becomes small.

The molar ratio of the raw material to the molar ratio is not particularly limited, and the number of isocyanato groups in the organic polyisocyanate compound is combined with the hydrogenated polyolefin polyol to be used and the polyol used in addition to the hydrogenated polyolefin polyol. The ratio of the total number of hydroxyl groups is preferably 1.5:1 or more.

If the ratio is less than 1.5:1 and the viscosity is too high, it cannot be called better.

Further, when only a part of the terminal of the compound is sealed with a compound having an alcoholic hydroxyl group (meth) acrylate and having one hydroxyl group in the molecule, the hydrogenated polyolefin polyol to be used, The total number of hydroxyl groups in the case where the polyol used in addition to the hydrogenated polyolefin polyol and the (meth) acrylate containing an alcoholic hydroxyl group are combined in a molecule having one hydroxyl group must be The total number of isocyanato groups of the organic polyisocyanate compound used is large.

However, in this case, the hydrogenated polyolefin polyol to be used, the polyol used in addition to the hydrogenated polyolefin polyol, and the (meth) acrylate containing an alcoholic hydroxyl group have one in the molecule. The ratio of the total number of hydroxyl groups in the total of the hydroxyl group compounds to the total number of isocyanato groups in the organic polyisocyanate compound is preferably 2:1 or less.

When the ratio is larger than 2:1, the number of molecules having no acryl oxime group increases, and the shape retainability of the polymer after polymerization is deteriorated, which is not preferable.

In this way, a hydrogenated polyolefin polyol is used as a raw material component to synthesize a urethane (meth) acrylate, and when the synthesis is carried out, an ureidocarboxylic acid having no hydrogenated polyolefin structural unit is also produced. In the case of an ester (meth) acrylate, in the present specification, a urethane (meth) acrylate having no hydrogenated polyolefin polyol structural unit is defined as being not included in the present invention (I). Ingredients 1 of ingredients. For example, using a hydrogenated polyolefin polyol, 2,2,4-trimethylhexamethylene diiso When a (meth)acryloyl group-containing compound having a hydrogenated polyolefin structural unit of the component 1 is produced by using a cyanate ester and a 2-hydroxyethyl acrylate, an amine group having no polyolefin structural unit is also produced. A compound of the following formula (4) of a formate (meth) acrylate.

However, in the present specification, since the compound of the formula (4) does not have a hydrogenated polyolefin structural unit, it means that it is not contained in the component 1.

Next, "using a hydrogenated polyolefin polyol" and "a compound containing a (meth) acrylonitrile group having one isocyanate group in one molecule" as an essential raw material component to obtain a hydrogenated polyolefin The case of a compound containing a (meth) acrylonitrile group in a structural unit will be described.

The hydrogenated polyolefin polyol is as described above.

Examples of the (meth)acrylonitrile group-containing compound having an isocyanate group which can be used as the above-mentioned raw material include 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate. Wait.

The 2-isocyanatoethyl acrylate is, for example, Karenz AOI (registered trademark) manufactured by Showa Denko Co., Ltd., and the like.

Examples of the 2-isocyanatoethyl methacrylate include Karenz MOI (registered trademark) manufactured by Showa Denko Co., Ltd., and the like.

Reacting a compound containing a (meth)acryloyl group having a hydrogenated polyolefin structural unit in a molecule containing a urethane bond and having a terminal having a (meth) acrylonitrile group to obtain an amine group A The acid ester (meth) acrylate can be generally synthesized by the following method.

Further, the total amount of the hydroxyl group of the hydrogenated polyolefin polyol may be reacted with a compound containing a (meth) acrylonitrile group having an isocyanate group, or only a part of the hydroxyl group of the hydrogenated polyolefin polyol may be The reaction of the (meth) acrylonitrile-containing compound of the isocyanato group may be carried out, and a part of the hydroxyl group may remain.

When the total amount of the hydroxyl group of the hydrogenated polyolefin polyol is reacted with a compound containing a (meth) fluorenyl group having an isocyanato group, the total number of hydroxyl groups of the hydrogenated polyolefin polyol and the isocyanate group used are used. The ratio of the total number of isocyanato groups of (meth) acrylate must be 1 or more.

When only a part of the hydroxyl group of the hydrogenated polyolefin polyol is reacted with a compound containing a (meth) acrylonitrile group having an isocyanate group, and a part of the hydroxyl group remains, compared with the hydrogenated polyolefin polyol The total number of hydroxyl groups must be reduced by the total number of isocyanato groups of the (meth) acrylate containing isocyanate groups used.

Further, at this time, there may be a hydrogenated polyolefin polyol which does not directly react with a compound containing a (meth) acrylonitrile group having an isocyanate group, but the hydrogenated polyolefin polyol is not included in the component. 1 in. When the hydrogenated polyolefin polyol is a liquid hydrogenated polybutadiene polyol or a liquid hydrogenated polyisoprene polyol, it is contained in the component 5.

There are no special restrictions on the manufacturing method. Generally, the hydrogenated polyolefin is diversified. The alcohol, the polymerization inhibitor, and the urethane catalyst or antioxidant required for the reaction are added to the reactor, the stirring is started, and the temperature in the reactor is raised to 40 ° C to 120 ° C, preferably 50 ° C ~ 100 ° C. Thereafter, a compound containing a (meth) acrylonitrile group having an isocyanate group is added to the liquid. In the dropping liquid, the temperature in the reactor is controlled to be 40 ° C to 130 ° C, preferably 50 ° C to 110 ° C. After the completion of the dropping, the temperature in the reactor is maintained at 40 ° C to 120 ° C, preferably 50 ° C to 100 ° C, while stirring is continued to complete the reaction.

Further, in addition to the compound containing a urethane-containing (meth) acrylonitrile group having a hydrogenated polyolefin structural unit, examples of the compound containing a (meth)acryl fluorenyl group having a hydrogenated polyolefin structural unit include, for example, a hydrogenated polyolefin (meth) acrylate obtained by transesterification of a hydrogenated polyolefin polyol with a (meth) acrylate and/or a dehydration condensation reaction of a hydrogenated polyolefin polyol with (meth)acrylic acid . The number of the (meth) acrylonitrile groups in the (meth) acrylate compound may be one or more, and more preferably two to four, in one molecule.

A compound containing a (meth) fluorenyl group having a polyolefin structural unit which does not contain a urethane bond, and a representative synthesis example thereof, a transesterification reaction of a hydrogenated polybutadiene diol with an acrylate Or a structural formula of a (meth) acrylate compound formed by dehydration condensation reaction of hydrogenated polybutadiene diol with acrylic acid, and transesterification or hydrogenation of hydrogenated polyisoprene diol with acrylate The structural formula of the (meth) acrylate compound produced by the dehydration condensation reaction of polyisoprene diol with acrylic acid is represented by formula (5) and formula (6), respectively.

(In the formula (5), x, y, and z are integers of 1 or more)

(In the formula (6), i, j, and k are integers of 1 or more).

When the (meth) acrylate compound of the component 1 is produced by transesterification of a hydrogenated polyolefin polyol with a (meth) acrylate, the hydrogenated polyolefin polyol and the lower alkyl (meth) acrylate are generally used. The ester is subjected to a transesterification reaction by heating in the presence of a transesterification catalyst, and the corresponding lower alkyl alcohol is produced, and the (meth) acrylate of the component 1 is produced by distillation, for example, according to Japan. The production is carried out by the method described in JP-A-2011-195823 or JP-A-2006-45284.

Also, by hydrogenating polyolefin polyols with (meth) propylene When the (meth) acrylate of the component 1 is produced by the dehydration condensation reaction of an acid, the hydrogenated polyolefin polyol and (meth)acrylic acid are produced by heating and dehydrating in the presence of an esterification catalyst. However, when the reaction is carried out by heating to a high temperature of 150 ° C or higher, there is a risk of causing radical polymerization of the acrylonitrile group in the dehydration condensation reaction. Therefore, the esterification reaction is generally carried out in the presence of a solvent such as cyclohexane or toluene which can be azeotroped with water, and the water formed by the dehydration condensation reaction is removed to the reaction by azeotroping the solvent with water. Outside the device. The catalyst used for the esterification reaction may, for example, be an acid catalyst such as p-toluenesulfonic acid.

As described above, as a method for producing a (meth)acrylonitrile-containing compound having a hydrogenated polyolefin structural unit which does not contain a urethane bond, the hydrogenated polyolefin polyol and the (meth) acrylate are subjected to a method. a method of transesterification, and two types of methods for dehydrating and condensing a hydrogenated polyolefin polyol with (meth)acrylic acid, but without using a solvent, or without purification steps or simplifying purification Industrially, a transesterification reaction of a hydrogenated polyolefin polyol with a (meth) acrylate to produce a (meth) propylene having a hydrogenated polyolefin structural unit containing no urethane bond of component 1. A method of sulfhydryl compound is preferred.

Next, "a compound containing a (meth) acrylonitrile group having a (poly) ester structural unit" and a "compound having a (poly) carbonate structural unit containing a (meth) acryl oxime group will be described.

In general, a raw material of a (meth)acryl fluorenyl group-containing compound having a (poly)ester structural unit is a (poly)ester polyol; The raw material of the (meth) acrylonitrile-containing compound of the (poly)carbonate structural unit is a (poly)carbonate polyol.

Further, in the present specification, when a (poly)ester polyol which can be a raw material of a (meth)acryl fluorenyl group-containing compound having a (poly)ester structural unit is produced, when (poly)ester polyol remains The polyol of the starting material (i.e., the polyol having no carboxylate) means that the polyol is also included in the (poly)ester polyol. Further, in the present specification, in addition to the raw material polyol contained in the (poly)ester polyol, if a polyol having the same structure as the raw material polyol contained in the (poly)ester polyol is newly added, it is produced. When the (meth)acryloyl group-containing compound is contained in the ester structural unit, the added polyol is also included in the (poly)ester polyol.

Further, in the present specification, when a (poly)carbonate polyol which can be a raw material of a (meth) acrylonitrile-containing compound having a (poly)carbonate structural unit is produced, when (poly)carbonic acid remains The polyol of the raw material of the ester polyol (i.e., the polyol having no carbonate bond) means that the polyol is also contained in the (poly)carbonate polyol. Further, in the present specification, in addition to the raw material polyol contained in the (poly)carbonate polyol, a polyol having the same structure as the raw material polyol contained in the (poly)carbonate polyol is newly added to have a polyol having the same structure. When the (poly)carbonate structural unit contains a (meth)acrylonitrile group-containing compound, the added polyol, even if it is a polyol having no carbonate bond, is included in the (poly)carbonate polyol. in.

Can be included as a (poly)ester structural unit (A The (poly)ester polyol which is a raw material of the compound of the acrylonitrile group is not particularly limited as long as it is a compound having one or more -COO-bonds and having two or more alcoholic hydroxyl groups in one molecule. .

The (poly)ester polyol which can be used as a raw material of the (meth) acrylonitrile-containing compound having a (poly)ester structural unit, for example, has a structure derived from a polycarboxylic acid having a chain hydrocarbon chain. a unit of a (poly)ester polyol having a structural unit derived from a polyol having a chain hydrocarbon chain; a structural unit derived from a polycarboxylic acid having a hydrocarbon chain having an alicyclic structure, and having a chain a (poly)ester polyol derived from a structural unit derived from a hydrocarbon chain; having a structural unit derived from a polycarboxylic acid having a chain hydrocarbon chain and derived from a polyol having a hydrocarbon chain having an alicyclic structure a structural unit of (poly)ester polyol; a structural unit derived from a polycarboxylic acid having a hydrocarbon chain having an alicyclic structure, and a structural unit derived from a polyol having a hydrocarbon chain having an alicyclic structure (poly)ester polyol; a structural unit derived from a polycarboxylic acid having a hydrocarbon chain having an aromatic ring structure, and a (poly)ester polyol having a structural unit derived from a polyol having a chain hydrocarbon chain; Having a polycarboxylic acid having a hydrocarbon chain having an aromatic ring structure a structural unit derived from a structural unit derived from a polyol having a hydrocarbon chain having an alicyclic structure; having a structural unit derived from a polycarboxylic acid having a chain hydrocarbon chain, and a (poly)ester polyol having a structural unit derived from a polyol having a hydrocarbon chain structure having an aromatic ring structure; a structural unit derived from a polycarboxylic acid having a hydrocarbon chain having an alicyclic structure, and having an aromatic ring A (poly)ester polyol or the like which is a structural unit derived from a polyol of a hydrocarbon chain.

Among these polyols, a polyol having 8 or more carbon atoms is preferred.

Examples of the polyhydric alcohol having 8 or more carbon atoms include 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 2-methyl-1,1. -cyclohexanedimethanol, tricyclo [5.2.1.0 ^2,6 ]decane dimethanol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decanediol 1,12-dodecanediol, dimer diol, hydrogenated dimer diol, and the like.

Among these polyols having 8 or more carbon atoms, more preferred are polyols having 10 or more carbon atoms, and specific examples thereof include 1,10-nonanediol, 1,12-dodecanediol, and The polymer diol, the hydrogenated dimer diol, and the like are preferably hydrogenated dimer diols among these.

Further, among the polycarboxylic acids, a polycarboxylic acid having 7 or more carbon atoms removed by carbon in a carboxylic acid structure (-COOH) is preferable.

Examples of the polycarboxylic acid include 1,9-sebacic acid, sebacic acid, 1,12-dodecanedioic acid, dimer acid, and hydrogenated dimer acid.

Among the polycarboxylic acids having 7 or more carbon atoms removed by carbon in the carboxylic acid structure (-COOH), sebacic acid, 1,12-dodecanedioic acid, and hydrogenated dimer acid are particularly preferred.

A preferred combination of a polyhydric alcohol and a polycarboxylic acid as a raw material of a (poly)ester polyol, such as a polyol having a carbon number of 8 or more, and a carbon number of 7 carbon atoms removed from a carboxylic acid structure (-COOH) a combination of the above polycarboxylic acids; particularly preferably selected from the group consisting of hydrogenated dimer diols, at least one of azelaic acid, 1,12-dodecanedioic acid, and hydrogenated dimer acid .

The so-called "dimer acid", which will have 2 to 4 B The fatty acid having 14 to 22 carbon atoms (hereinafter referred to as unsaturated fatty acid A) having an ethylenic double bond is preferably a fatty acid having 14 to 22 carbon atoms having two ethylenic double bonds, and having 1 to 4 ethylenic acids. A fatty acid having 14 to 22 carbon atoms (hereinafter referred to as unsaturated fatty acid B) having a double bond is preferably a double bond reaction of a fatty acid having 14 or 22 carbon atoms having one or two ethylenic double bonds. Dimer acid. Examples of the unsaturated fatty acid A include tetradecadienoic acid, hexadecadienic acid, octadecadienoic acid (linolenic acid, etc.), eicosadienoic acid, and docadiene diene. The acid, octadecatrienoic acid (secondary linoleic acid, etc.), eicosatetraenoic acid (arachidonic acid, etc.), etc., are preferably linoleic acid. In addition, as the unsaturated fatty acid B, in addition to the above-mentioned exemplified, a fatty acid having 14 to 22 carbon atoms having one ethylenic double bond may, for example, bedecenoic acid (crude acid, muscara, nutmeg) Acid), hexadecenoic acid (palmitoleic acid, etc.), octadecenoic acid (oleic acid, oleic acid, vaccenic acid, etc.), eicosenoic acid (oleic acid, etc.), The dodecanoic acid (sinapic acid, cetyl acid, glucosinolate, etc.) is preferably oleic acid or linoleic acid.

In the above dimerization reaction, the use ratio (molar ratio) of the unsaturated fatty acid A and the unsaturated fatty acid B is preferably about 1:1.2 to 1.2:1, more preferably 1:1. The dimerization reaction can be carried out by a method described in, for example, Japanese Laid-Open Patent Publication No. Hei 9-136861. That is, for example, a Lewis acid or a Bruce's acid type liquid or solid catalyst may be used for the unsaturated fatty acid A and the unsaturated fatty acid B, preferably a montmorillonite-based activated clay, for A+ B is added in an amount of 1 to 20% by weight, preferably 2 to 8% by weight, by 200 to 270 ° C, Preferably, the dimerization reaction is carried out by heating at 220 to 250 °C. The pressure at the time of the reaction is usually in a state of being slightly pressurized, but it may be at a normal pressure. The reaction time varies depending on the amount of the catalyst and the reaction temperature, but it is usually 5 to 7 hours. After completion of the reaction, the catalyst is filtered, and then the unreacted raw materials and the isomerized fatty acids are distilled off under reduced pressure, and then the dimer acid fraction is distilled off to obtain. The above dimerization reaction is considered to be carried out via the movement (isomerization) of the double bond and the Diels-Alder reaction, but the present invention is not limited thereto.

The obtained dimer acid is usually a mixture of dimer acids having different structures by a bonding site or isomerization of a double bond, and can be used after separation or directly. Further, the obtained dimer acid may contain a small amount of a monomeric acid (for example, 3% by weight or less, particularly preferably 1% by weight or less) or a polymeric acid or the like of a trimeric acid or the like (for example, 3% by weight or less, particularly 1) Weight% or less).

The term "hydrogenated dimer acid" as used in the present specification means a saturated dicarboxylic acid obtained by hydrogenating a carbon-carbon double bond of the above dimer acid.

When the dimer acid is, for example, a dimer acid having a carbon number of 36 produced from linoleic acid and linoleic acid or oleic acid, the structure of the main component of the hydrogenated dimer acid is as shown in the following formula (7) and formula. (8) The configuration shown.

(wherein R ² and R ³ are each an alkyl group, and the total number of carbon atoms, a, and b contained in R ² and R ³ is 28 (that is, the number of carbons contained in R ² + R ^{3 )} The number of carbons contained in +a+b=28)).

(wherein R ⁴ and R ⁵ are each an alkyl group, and the total number of carbons, c, and d contained in R ⁴ and R ⁵ is 32 (that is, the number of carbons contained in R ⁴ + R ^{5 )} The number of carbons contained in +c+d=32)).

The commercially available product of the hydrogenated dimer acid is, for example, PRIPOL (registered trademark) 1009 (manufactured by Croda Co., Ltd.), EMPOL (registered trademark) 1008, and EMPOL (registered trademark) 1062 (manufactured by BASF Corporation).

The "hydrogenated dimer diol" described in the present specification is a dimer acid which is reduced in the presence of a catalyst by at least one of the above dimer acid, the hydrogenated dimer acid, and a lower alcohol ester thereof. a carboxylic acid or a carboxylic acid ester moiety as an alcohol, which hydrogenates the double bond when the starting material has a carbon-carbon double bond The diol is the main component.

For example, a hydrogenated dimer acid having a compound of the formula (7) and the formula (8) as a main component, and a hydrogenated dimer acid to reduce a hydrogenated dimer acid to produce a hydrogenated dimer diol The structure of the main component is a structure shown by the following formula (9) and formula (10).

(wherein R ⁶ and R ⁷ are each an alkyl group, and the total number of carbon atoms, e, and f contained in R ⁶ and R ⁷ is 30 (that is, the carbon number contained in R ⁶ + R ⁷ The number of carbons contained in +e+f=30)).

(wherein R ⁸ and R ⁹ are each an alkyl group, and the total number of carbon atoms, g, and h contained in R ⁸ and R ⁹ is 34 (that is, the carbon number contained in R ⁸ + R ⁹ The number of carbons contained in the +g+h=34)).

As a commercial item of the hydrogenated dimer diol, for example, PRIPOL (registered trademark) 2033 (manufactured by Croda Co., Ltd.) or Sovermol (registered trademark) 908 (manufactured by BASF Corporation).

(Poly) ester polyol which can be a raw material of a (meth) acrylonitrile-containing compound having a (poly)ester structural unit, and is a polyvalent carboxylic acid and a polyol component which is an essential component among the above polyols It can be produced by carrying out a condensation reaction in the presence of an esterification catalyst.

The above esterification reaction is generally carried out at a reaction temperature of about 150 to 250 ° C in order to remove water. The pressure at the time of the reaction is generally carried out under normal pressure or reduced pressure.

Further, it may be a (poly)ester polyol having a raw material of a (meth)acryl fluorenyl group-containing compound in a (poly)ester structural unit, or a lower alkyl ester of the carboxylic acid and a polyhydric alcohol as described above. The polyol component of the essential component is produced by performing a transesterification reaction in the presence of a transesterification catalyst.

The above transesterification reaction is generally carried out at a reaction temperature of about 120 to 230 ° C in order to remove the alcohol. The pressure at the time of the reaction is generally carried out under normal pressure or reduced pressure.

Further, in the present specification, when a (poly)ester polyol which can be a raw material of a (meth)acryl oxime group-containing compound having a (poly)ester structural unit is produced, when (poly)ester polyol remains The polyol of the starting material (i.e., the polyol having no -COO-bond) means that the polyol is also included in the (poly)ester polyol.

That is, when 8% by mass of the raw material polyol remains in the (poly)ester polyol, it means that the polyol is also contained in the (poly)ester polyol.

Further, in the present specification, in addition to the original contained in the (poly)ester polyol When a polyol having the same structure as the raw material polyol contained in the (poly)ester polyol is newly added in addition to the polyol, a compound containing a (poly)ester structural unit containing a (meth)acryl fluorenyl group is produced. The added polyol, even a polyol having no -COO-bond, is included in the (poly)ester polyol.

In other words, the hydrogenated dimer diol is used as the raw material polyol component of the (poly)ester polyol, and in the case of synthesizing (poly)ester polyol, the hydrogenation of the raw material remaining in 8 parts by mass of the synthetic product is 8 parts by mass. When the polymer diol is further added with 5 parts by mass of a hydrogenated dimer diol to produce a (meth) acrylonitrile group-containing compound having a (poly)ester structural unit, it means a residual raw material hydrogenated dimer diol. And the hydrogenated dimer diols added later are all contained in the (poly)ester polyol.

However, the hydroxyl value of the (poly)ester polyol used as a raw material of the polymerizable composition of the invention (I) is in the range of 20 to 100 mgKOH/g, preferably 25 to 80 mgKOH/g, more preferably 30 to 30. 65 mg KOH / g.

As a raw material of the (meth)acryl fluorenyl group-containing compound having the (poly)ester structural unit, when a polyol which can be a raw material of the (poly)ester polyol is used, the mass of the (poly)ester polyol is 100. The portion is preferably 30 parts by mass or less, preferably 25 parts by mass or less.

(Poly)carbonate polyol which can be a raw material of a (meth) acrylonitrile-containing compound having a (poly)carbonate structural unit, as long as it has one or more carbonate bonds in one molecule (-OCOO) -) A compound having two or more alcoholic hydroxyl groups, and is not particularly limited.

The (poly)carbonate polyol which can be used as a raw material of a (meth) acrylonitrile-containing compound having a (poly) carbonate structural unit, for example, can be produced by using a polyol having a chain hydrocarbon chain as a raw material. (poly)carbonate polyol; (poly)carbonate polyol produced using a polyol having a hydrocarbon chain having an alicyclic structure as a raw material; and using a polyol having a hydrocarbon chain having an aromatic ring structure as a raw material (poly)carbonate polyol.

Among the polyols which can be used as a raw material of the (poly)carbonate polyol, a polyol having 8 or more carbon atoms is preferred.

The polyol having a carbon number of 8 or more can be used in the same manner as the above-mentioned polyol having a carbon number of 8 or more which is a raw material of the (poly)ester polyol.

The (poly)carbonate polyol which may be a raw material of a (meth)acryl fluorenyl group-containing compound having a (poly)carbonate structural unit, and the above polyol component, and a dialkyl carbonate or a diaryl carbonate may be used. Or an alkylene carbonate, which is produced by performing a transesterification reaction in the presence of a transesterification catalyst.

The above transesterification reaction is generally carried out at a reaction temperature of about 80 to 230 ° C in order to remove the alcohol. The pressure at the time of the reaction is generally carried out under normal pressure or reduced pressure.

Further, the (poly)carbonate polyol which is a raw material of a (meth)acryl oxime group-containing compound having a (poly)carbonate structural unit can be produced by reacting the above polyol with phosgene.

The above reaction is generally carried out at a reaction temperature of 100 ° C or lower. Should, since hydrochloric acid is produced, it is common to use a base to capture hydrochloric acid.

Further, in the present specification, when a (poly)carbonate polyol which can be a raw material of a (meth)acryl fluorenyl group-containing compound having a (poly)carbonate structural unit is produced, when (poly)carbonic acid remains When a polyol of a raw material of an ester polyol (that is, a polyol having no carbonate bond) is used, the polyol is also included in the (poly)carbonate polyol.

That is, when the (poly)carbonate polyol is a polyol in which 8% by mass of the raw material remains, it means that the residual polyol is contained in the (poly)ester polyol.

In addition, in the present specification, in addition to the raw material polyol contained in the (poly)carbonate polyol, a polyol having the same structure as the raw material polyol contained in the (poly)carbonate polyol is newly added to have a polyol. When a (poly)carbonate structural unit contains a (meth)acrylonitrile group-containing compound, the added polyol, even if it is a polyol having no carbonate bond, is included in the (poly)carbonate polyol. in.

In other words, when the hydrogenated dimer diol is used as the raw material polyol component of the (poly)carbonate polyol, when the (poly)carbonate polyol is synthesized, 8 parts by mass of the raw material remains in 100 parts by mass of the synthetic product. When the hydrogenated dimer diol is further added with 5 parts by mass of a hydrogenated dimer diol to produce a (meth) acrylonitrile group-containing compound having a (poly) carbonate structural unit, it means that the remaining raw material is hydrogenated dimerized. The diol and the hydrogenated dimer diol added later are all contained in the (poly)carbonate polyol.

However, (poly)carbonate used as a raw material of a (meth)acryl fluorenyl group-containing compound having a (poly)carbonate structural unit The hydroxyl value of the polyol is in the range of 20 to 100 mgKOH/g, preferably 25 to 80 mgKOH/g, more preferably 30 to 65 mgKOH/g.

When a polyol which can be a raw material of a (poly)carbonate polyol is used as a raw material of a (meth)acrylonitrile group-containing compound having a (poly)carbonate structural unit, it is relative to a (poly)carbonate polyol. 100 parts by mass is preferably 30 parts by mass or less, preferably 25 parts by mass or less.

As described above, the structural unit derived from the (poly)ester polyol or the structural unit derived from the (poly)carbonate polyol preferably contains a structural unit derived from a polyol having 8 or more carbon atoms, It is preferred to include a structural unit derived from a polyol having a carbon number of 10 or more, and most preferably a structural unit derived from a hydrogenated dimer diol.

That is, it means a compound having a (meth) acrylonitrile group having a (poly)ester structural unit, preferably a (poly)ester polyol having a structural unit derived from a polyol having 8 or more carbon atoms. a compound containing a (meth) acrylonitrile group derived from a structural unit; more preferably: a structural unit having a structural unit derived from a (poly) ester polyol derived from a polyol having a carbon number of 10 or more a compound containing a (meth) acrylonitrile group; most preferably: a (meth)acryl oxime containing a structural unit derived from a (poly)ester polyol having a structural unit derived from a hydrogenated dimer diol Base compound. It means a compound having a (meth) propylene group having a (poly)carbonate structural unit, preferably a (poly)carbonate polyol having a structural unit derived from a polyol having 8 or more carbon atoms. a compound containing a (meth) acrylonitrile group derived from a structural unit More preferably: a compound having a (meth) acrylonitrile group having a structural unit derived from a (poly)carbonate polyol having a structural unit derived from a polyol having 10 or more carbon atoms; A compound having a (meth)acrylinyl group having a structural unit derived from a (poly)carbonate polyol having a structural unit derived from a hydrogenated dimer diol.

Among the compounds having a (meth)acryl fluorenyl group derived from a structural unit derived from a (poly)ester polyol and/or a structural unit derived from a (poly)carbonate polyol, a (meth) acrylonitrile-containing compound produced by reacting a (poly)ester polyol and/or a (poly)carbonate polyol with a (meth)acrylic acid or an alkyl (meth) acrylate, A urethane (meth) acrylate synthesized by using a (poly)ester polyol and/or a (poly)carbonate polyol as a raw material component.

In addition, the term "(meth)acrylic acid" as used herein means acrylic acid and/or methacrylic acid. Further, the term "(meth)acrylate" as used herein means acrylate and/or methacrylate.

First, the content ("methyl" produced by the reaction of "(poly)ester polyol and/or (poly)carbonate polyol" with "(meth)acrylic acid or alkyl (meth) acrylate" "Compound of acrylonitrile" will be described.

a (meth)acrylonitrile-containing compound produced by the reaction of a (poly)ester polyol and/or a (poly)carbonate polyol with a (meth)acrylic acid or an alkyl (meth)acrylate, Poly (poly) ester The alcohol and/or (poly)carbonate polyol and (meth)acrylic acid are produced by carrying out a condensation reaction in the presence of an esterification catalyst.

In the above esterification reaction, water is usually removed while the reaction is carried out at a reaction temperature of about 100 to 130 ° C in the presence of a polymerization inhibitor and a catalyst. The pressure at the time of the reaction is generally carried out under normal pressure or reduced pressure.

When the reaction is carried out, the ratio of the total number of hydroxyl groups of the polyol containing the (poly)ester polyol or the (poly)carbonate polyol to the total amount of (meth)acrylic acid is preferably 4:3 to 3: The range of 1 is more preferably in the range of 3:2 to 5:2. When the input ratio is smaller than 4:3, in order to complete the reaction (that is, the (meth)acrylic acid is completely consumed), it takes more time to cause radical polymerization in the reaction. Can't be called better. Further, when the input ratio is larger than 3:1, the ratio of the (meth) acrylate at the end of the polyol containing the (poly)ester polyol or the (poly)carbonate polyol becomes too small. As a result, when the polymerizable composition of the present invention (I) is photopolymerized, the photosensitivity may be deteriorated, and it is not preferable.

Further, a (meth)acrylonitrile-containing compound produced by a reaction of a (poly)ester polyol and/or a (poly)carbonate polyol with a (meth)acrylic acid or an alkyl (meth)acrylate Further, it is also possible to produce a (poly)ester polyol and/or a (poly)carbonate polyol and an alkyl (meth) acrylate by a transesterification reaction in the presence of a transesterification catalyst.

The above transesterification reaction, generally, in the polymerization inhibitor or transesterification In the presence of a medium, the reaction is carried out at a reaction temperature of about 80 to 130 ° C, and the produced alcohol is removed. The pressure at the time of the reaction is generally carried out under normal pressure or reduced pressure.

When the reaction is carried out, the ratio of the total number of hydroxyl groups of the polyol containing the (poly)ester polyol or the (poly)carbonate polyol to the total number of alkyl (meth)acrylates is preferably 4:3. The range of ~3:1 is more preferably in the range of 3:2 to 5:2. When the input ratio is smaller than 4:3, in order to complete the reaction (that is, the alkyl (meth) acrylate is completely consumed), it may take more time, which may be caused in the reaction. Free radical polymerization cannot be said to be preferred. Further, when the input ratio is larger than 3:1, the ratio of the (meth) acrylate at the end of the polyol containing the (poly)ester polyol or the (poly)carbonate polyol becomes too small. As a result, when the polymerizable composition of the present invention (I) is photopolymerized, the photosensitivity may be deteriorated, and it is not preferable.

In these reactions, the (poly)ester polyol or the (poly)carbonate polyol may be used singly or in combination, and the (poly)ester polyol may be used in combination with the (poly)carbonate polyol.

Next, "the synthesis of a urethane (meth) acrylate using a (poly) ester polyol and/or a (poly) carbonate polyol as a raw material component will be described.

The synthesis of a urethane (meth) acrylate by using a (poly)ester polyol and/or a (poly)carbonate polyol as a raw material component is generally synthesized by either of the following two methods.

The first method, which comprises (poly)ester polyol and/or A method of reacting a polyol component of a (poly)carbonate polyol, an organic polyisocyanate compound, and a (meth) acrylate having an alcoholic hydroxyl group.

The second method is a method of reacting a polyol component containing a (poly)ester polyol and/or a (poly)carbonate polyol with a (meth) acrylate containing an isocyanate group.

First, the first method will be described.

The polyol component containing the (poly)ester polyol and/or the (poly)carbonate polyol may be one or more of either (poly)ester polyol or (poly)carbonate polyol. Polyol can be.

As the organic polyisocyanate compound, the same as those exemplified as the organic polyisocyanate compound can be used in the production of the compound containing a (meth) acrylonitrile group having a polyolefin structural unit.

The (meth) acrylate containing an alcoholic hydroxyl group can be used as a (meth) acrylate containing an alcoholic hydroxyl group in the production of a compound containing a (meth) acrylonitrile group having a polyolefin structural unit as described above. The same is listed.

As a method of reacting a polyol component containing a (poly)ester polyol and/or a (poly)carbonate polyol, an organic polyisocyanate compound, and a (meth) acrylate containing an alcoholic hydroxyl group, (Poly)ester polyol and/or (poly)carbonate polyol in the presence or absence of a conventional urethane catalyst such as dibutyltin laurate or dioctyltin dilaurate The polyol component, the organic polyisocyanate compound, and the (meth) acrylate containing an alcoholic hydroxyl group can be reacted In the case of reacting in the presence of a catalyst, it is preferred to shorten the reaction time. However, if it is used too much, it may be adversely affected by the physical property value at the time of actual use as a cured film, and the amount used is relative to the (poly)ester-containing polyol and/or (poly)carbonate polyol. The total amount of the polyol component, the organic polyisocyanate compound, and the hydroxyl group-containing (meth) acrylate is 100 parts by mass, preferably 0.001 to 1 part by mass.

The order in which the raw materials are supplied is not particularly limited, and when the terminal of the compound is almost completely sealed with a compound having an alcoholic hydroxyl group in the molecule containing a (meth) acrylate having an alcoholic hydroxyl group. Usually, the organic polyisocyanate compound and the urethane catalyst required for the reaction are put into the reactor, and after stirring, the temperature in the reactor is 40 to 140 ° C, preferably 50 ° C. ~120 ° C, the (poly) ester polyol and / or (poly) carbonate polyol, and then in accordance with the required (poly) ester polyol or polyol component other than (poly) carbonate polyol Thereafter, the reaction is carried out at a temperature in the reactor at 50 ° C to 160 ° C, preferably 60 ° C to 140 ° C. Thereafter, the temperature in the reactor is added at 30 ° C to 120 ° C, preferably 50 ° C to 100 ° C, and a polymerization inhibitor and a urethane catalyst which are required for the reaction are added, and the alcohol is added by dropping. (meth) acrylate of a hydroxyl group. In the dropping liquid, the temperature in the reactor is maintained at 30 ° C to 120 ° C, preferably 50 ° C to 100 ° C. After the completion of the dropping, the temperature in the reactor is maintained at 30 ° C to 120 ° C, preferably 50 ° C to 100 ° C to completely terminate the reaction.

Further, when only a part of the terminal of the compound has an alcohol containing a (meth) acrylate having an alcoholic hydroxyl group, it has one alcohol in the molecule. When a compound having a hydroxyl group is sealed, usually, an organic polyisocyanate compound, a polymerization inhibitor and/or a urethane catalyst which are required for the reaction are placed in a reactor, stirred, and then placed in the reactor. The temperature is from 30 ° C to 120 ° C, preferably from 50 ° C to 110 ° C, and the (meth) acrylate containing an alcoholic hydroxyl group is introduced by dropping. In the dropping liquid, the temperature in the reactor is maintained at 30 ° C to 120 ° C, preferably 50 ° C to 110 ° C. After the completion of the dropping, the temperature in the reactor is maintained at 30 ° C to 120 ° C, preferably 50 ° C to 110 ° C to carry out the reaction. Thereafter, a reaction is carried out by placing a (poly)ester polyol and/or a (poly)carbonate polyol, and further reacting the desired polyol component other than the (poly)ester polyol or the (poly)carbonate polyol. In the apparatus, while stirring, the temperature in the reactor is maintained at 30 ° C to 120 ° C, preferably 50 ° C to 100 ° C, and the reaction product is introduced, and the temperature in the reactor is maintained. 30 ° C ~ 120 ° C, preferably 50 ° C ~ 100 ° C to complete the reaction.

When the component 1 which is an essential component of the invention (I) is used, when it is necessary to suppress the increase in the viscosity of the oligomer or to reduce the volume shrinkage ratio at the time of polymerization, only a part of the terminal of the compound is contained to contain the alcoholic hydroxyl group. The (meth) acrylate is preferably an oligomer which is sealed with a compound having one alcoholic hydroxyl group in the molecule.

The molar ratio of the raw materials to the molar ratio (ie, (the (poly)ester polyol used, the (poly)carbonate polyol used, and the (poly)ester polyol or (poly)carbonate polyol The total number of hydroxyl groups in the total amount of polyol used) / (the total number of isocyanato groups of the organic polyisocyanate compound used) / (will contain an alcoholic hydroxyl group) The total number of hydroxyl groups in the case where the number of the acrylates in the molecule is a total of the number of the compounds having one alcoholic hydroxyl group) is adjusted depending on the molecular weight of the intended polyurethane.

However, when the terminal of the compound is almost completely sealed with a compound having an alcoholic hydroxyl group (meth) acrylate and having one alcoholic hydroxyl group in the molecule, the isocyanate of the organic polyisocyanate compound used is used. The total number of acid groups must be set to be more than the number of (poly)ester polyols used, the number of (poly)carbonate polyols used, and the (poly)ester polyol or (poly)carbonate polyol. The total number of alcoholic hydroxyl groups in the total number of polyols used.

In this case, the number of (poly)ester polyols used, the number of (poly)carbonate polyols used, and the number of polyols other than the (poly)ester polyol or (poly)carbonate polyol When the ratio of the total number of hydroxyl groups measured in time to the total number of isocyanato groups in the organic polyisocyanate compound is as large as 1.0, the molecular weight becomes large, and when it deviates from 1.0, the molecular weight becomes small.

The molar ratio of the raw material to the molar ratio is not particularly limited, the number of isocyanato groups in the organic polyisocyanate compound, the number of (poly)ester polyols used, the number of (poly)carbonate polyols used, and The ratio of the total number of hydroxyl groups at the time of total use of the polyol other than the ester polyol or the (poly)carbonate polyol is preferably 1.5:1 or more.

If the ratio is less than 1.5:1 and the viscosity is too high, it cannot be called better.

Also, when only one part of the end of the compound is included When the (meth) acrylate having an alcoholic hydroxyl group is sealed with a compound having one alcoholic hydroxyl group in the molecule, the number of (poly)ester polyols used and the number of (poly)carbonate polyols used are The number of the polyol other than the (poly)ester polyol or the (poly)carbonate polyol, and the compound having an alcoholic hydroxyl group in the molecule including the (meth) acrylate containing an alcoholic hydroxyl group. The total number of hydroxyl groups at the time of total number of use must be set to be larger than the total number of isocyanato groups of the organic polyisocyanate compound used.

However, in this case, the number of (poly)ester polyols used, the number of (poly)carbonate polyols used, and the number of polyols other than the polyester polyol or (poly)carbonate polyol, And the total number of hydroxyl groups in the total number of used compounds having one alcoholic hydroxyl group in the molecule containing the (meth) acrylate containing an alcoholic hydroxyl group, and the total number of isocyanato groups in the organic polyisocyanate compound The ratio is preferably 2:1 or less.

When the ratio is larger than 2:1, the number of molecules having no (meth)acryl fluorenyl group increases, and the shape retainability of the polymer after polymerization is deteriorated, which is not preferable.

When a (poly)ester polyol and/or a (poly)carbonate polyol are used as a raw material component, a urethane (meth)acrylate is synthesized, and when it is synthesized, it is also produced without The case of the urethane (meth) acrylate of the structural unit derived from the alcohol, but in the present specification, the urethane (meth) acrylate is defined as not included in the invention (I) One of the essential ingredients. For example, (poly)ester polyol, 1,3-bis(isocyanatomethyl)cyclohexane, and 4-hydroxybutyl acrylate are used to produce the urethane of component 1 (methyl). In the case of acrylate, a compound of the following formula (11) which does not have a urethane (meth) acrylate having a structural unit derived from a polyol is also produced.

However, in the present specification, since the compound of the formula (11) does not have a structural unit derived from the hydrogenated dimer diol, it means that it is not contained in the component 1.

Next, the second method will be described.

The second method is a method of reacting a polyol component containing a (poly)ester polyol and/or a (poly)carbonate polyol with a (meth) acrylate containing an isocyanate group.

As described above, the polyol component containing the (poly)ester polyol and/or the (poly)carbonate polyol may be any one or both of (poly)ester polyol or (poly)carbonate polyol. More than one type of polyol can be used.

The (meth) acrylate containing an isocyanate group is not particularly limited as long as it is a (meth) acrylate having an isocyanate group in one molecule.

Examples of the (meth) acrylate containing an isocyanate group include 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate. Acid esters, etc.

The total number of hydroxyl groups of the polyol component containing the (poly)ester polyol and/or the (poly)carbonate polyol may be reacted with the (meth)acrylate containing an isocyanate group, or the (poly)ester may be included. Only a part of the hydroxyl group of the polyol component of the polyol and/or (poly)carbonate polyol reacts with the (meth) acrylate containing an isocyanate group, and a part of the hydroxyl group may remain.

When the total number of hydroxyl groups of the polyol component containing the (poly)ester polyol and/or (poly)carbonate polyol is reacted with the (meth)acrylate containing an isocyanate group, the (poly)ester polyol is The number of use, the number of (poly)carbonate polyols used, the total number of hydroxyl groups in the total number of polyols other than the (poly)ester polyol or (poly)carbonate polyol, and the use of the different The ratio of the total number of isocyanato groups of the (meth) acrylate of cyanate group must be 1 or more.

Reacting only a part of the hydroxyl group of the polyol component containing the (poly)ester polyol and/or (poly)carbonate polyol with the (meth) acrylate containing isocyanate group, and leaving a part of When the hydroxyl group is used, the number of (poly)ester polyols used, the number of (poly)carbonate polyols used, and the number of polyols other than the (poly)ester polyol or (poly)carbonate polyol The total number of hydroxyl groups at the time of total mixing must be reduced by the total number of isocyanato groups of the (meth) acrylate containing isocyanate groups used.

In order to suppress the volume shrinkage rate at the time of polymerization of the polymerizable composition of the invention (I) to a low level, the number of (poly)ester polyols used, the number of (poly)carbonate polyols used, and the like Ester polyol or The ratio of the total number of hydroxyl groups in the total number of polyols other than the (poly)carbonate polyol to the total number of isocyanato groups of the (meth) acrylate containing isocyanate groups is preferably used. It is in the range of 1.5:1 to 2.5:1, more preferably in the range of 1.7:1 to 2.3:1.

The production method is not particularly limited, and generally, a polyol component containing a (poly)ester polyol and/or a (poly)carbonate polyol, a polymerization inhibitor, and a desired urethane catalyst are required. Or the antioxidant is added, put into the reactor, stirring is started and the temperature in the reactor is raised to 40 ° C to 120 ° C, preferably 50 ° C to 100 ° C. Thereafter, the liquid was added to the (meth) acrylate containing an isocyanate group. In the dropping liquid, the temperature in the reactor is controlled to be 40 ° C to 130 ° C, preferably 50 ° C to 110 ° C. After the completion of the dropping, the temperature in the reactor is maintained at 40 ° C to 120 ° C, preferably 50 ° C to 100 ° C, while stirring is continued to complete the reaction.

The amount of the component 1 used in the invention (I) is preferably from 20 to 80% by mass, more preferably from 20 to 80% by mass based on the total of the components 1, the component 2 and the component 3 which are essential components of the invention (I). 25 to 75 mass%, particularly preferably 30 to 70 mass%.

With respect to the total amount of the components 1, the component 2, and the component 3 which are essential components of the invention (I), when the amount of the component 1 used in the invention (I) is less than 20% by mass, the present invention (the present invention) I) the polymer obtained by polymerizing the polymerizable composition has a reduced coating film strength, or the polymer obtained by polymerizing the polymerizable composition has a high dielectric constant, so it cannot be said to be preferable. . Further, with respect to the components of the essential components of the invention (I) 1. The total amount of the component 2 and the total amount of the component 3, when the amount of the component 1 used in the invention (I) is more than 80% by mass, the viscosity of the polymerizable composition of the invention (I) becomes high. Therefore, it is not appropriate.

Next, the "component 2 of the essential component of the polymerizable composition of the present invention (I)" will be described.

The component 2 which is an essential component of the polymerizable composition of the invention (I) is a (meth) acrylate compound having a hydrocarbon group having 6 or more carbon atoms.

Component 2 preferably does not contain an alcoholic hydroxyl group.

Examples of the (meth) acrylate compound having a hydrocarbon group having 6 or more carbon atoms include cyclohexyl acrylate, isodecyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate, and bicyclo acrylate. Pentyl ester, dicyclopentanyl acrylate, 4-tert-butylcyclohexyl acrylate, isodecyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate a (meth) acrylate compound having a cyclic aliphatic group such as dicyclopentanyl methacrylate, dicyclopentanethyl methacrylate or 4-tert-butylcyclohexyl methacrylate; acrylic acid Hexyl ester, lauryl acrylate, isodecyl acrylate, 2-propylheptyl acrylate, 4-methyl-2-propylhexyl acrylate, isostearyl acrylate, 2-heptyl undecyl acrylate, Lauryl methacrylate, isodecyl methacrylate, 2-propylheptyl methacrylate, 4-methyl-2-propylhexyl methacrylate, isostearyl methacrylate, methacrylic acid A (meth) acrylate compound having a chain aliphatic group such as 2-heptyl undecyl ester or the like.

Among these, in order to suppress the dielectric constant of the polymer of the present invention to be described later or the optical adhesive sheet of the present invention to be low, propylene is preferred. Isodecyl phthalate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentanyl acrylate, 4-tert-butylcyclohexyl acrylate, methyl Isodecyl acrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanethyl methacrylate, methacrylic acid 4- Tert-butylcyclohexyl ester, lauryl acrylate, isodecyl acrylate, 2-propylheptyl acrylate, 4-methyl-2-propylhexyl acrylate, isostearyl acrylate, 2-heptyl acrylate Undecyl ester, lauryl methacrylate, isodecyl methacrylate, 2-propylheptyl methacrylate, 4-methyl-2-propylhexyl methacrylate, isooctadecane methacrylate a (meth) acrylate compound having a hydrocarbon group having a carbon number of 9 or more, such as ester, 2-heptyl undecyl methacrylate or the like; more preferably, isodecyl acrylate or acrylic acid is used in consideration of heat-resistant coloring property. Dicyclopentane ester, dicyclopentanyloxyethyl acrylate, isodecyl methacrylate, dicyclopentane methacrylate , dicyclopentanyl methacrylate, lauryl acrylate, isodecyl acrylate, 2-propylheptyl acrylate, 4-methyl-2-propylhexyl acrylate, isodecyl acrylate, methacrylic acid Lauryl ester, isodecyl methacrylate, 2-propylheptyl methacrylate, 4-methyl-2-propylhexyl methacrylate, isostearyl methacrylate; considering the dilution efficiency of component 4 described later More preferably, it is lauryl acrylate, isodecyl acrylate, 2-propylheptyl acrylate, 4-methyl-2-propylhexyl acrylate, isostearyl acrylate, 2-heptyl isopropyl acrylate Alkyl ester, isodecyl methacrylate, 2-propylheptyl methacrylate, 4-methyl-2-propylhexyl methacrylate, isostearyl methacrylate, 2-glycol methacrylate Octadecane ester; when considering the photopolymerization rate, it is especially good for C Lauryl enoate, isodecyl acrylate, 2-propylheptyl acrylate, 4-methyl-2-propylhexyl acrylate, 2-heptyl undecyl acrylate.

The amount of the component 2 used in the invention (I) is preferably from 15 to 78% by mass, more preferably from 15 to 78% by mass, based on the total of the components 1, the component 2 and the component 3 which are essential components of the invention (I). 20 to 73% by mass, particularly preferably 28 to 70% by mass. The present invention (I) when the amount of the component 2 used in the invention (I) is less than 15% by mass based on the total amount of the components 1, the component 2, and the component 3 which are essential components of the invention (I) The viscosity of the polymerizable composition is too high, so it is not suitable. Further, the present invention is the total amount of the component 2, the component 2, and the component 3 which are essential components of the invention (I), when the amount of the component 2 in the invention (I) is more than 78% by mass. The volume shrinkage ratio at the time of polymerization of the polymerizable composition of (I) may increase or the dielectric constant of the cured product may increase, which is not preferable.

Next, the "component 3 of the essential component of the polymerizable composition of the present invention (I)" will be described.

The component 3 which is an essential component of the polymerizable composition of the invention (I) is a vinyl group-containing compound having a guanamine bond.

Component 3 is used to improve the adhesion between the polymer of the present invention (III) and the optical adhesive sheet of the present invention (V) and a material for use in a light-transmitting protective portion such as glass. The transparency of the polymer of the invention (III) or the optical adhesive sheet of the invention (V) under high temperature and high humidity conditions.

a compound containing a vinyl group having a guanamine bond of component 3, as long as it is The compound having a guanamine bond and a vinyl group in the molecule is not particularly limited.

A vinyl group-containing compound having a guanamine bond has an effect of increasing the adhesion between the glass used for the light-transmitting protective portion.

As a vinyl group-containing compound having a guanamine bond, specifically, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, N-propylene hydrazino, N-isopropyl Acrylamide, N-tert-butyl acrylamide, N-methoxymethyl propylene amide, N-ethoxy methacrylamide, Nn-butoxy methacrylamide, N- Isobutoxymethyl acrylamide, N,N-dimethyl methacrylamide, N,N-diethyl methacrylamide, N-methyl propylene hydrazino, N-isopropyl Methyl acrylamide, N-tert-butyl methacrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl methacrylamide, Nn-butoxymethyl Methyl acrylamide, N-isobutoxymethyl methacrylamide, N-vinyl-pyrrolidone, N-vinyl caprolactam, N-vinylformamide, N-vinyl Ethylamine, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylamide, or the like may be used alone or in combination of two or more.

Among these, as preferred, N, N-diethyl acrylamide, N-propenyl hydrazino, N-tert-butyl acrylamide, N-tert-butyl acrylamide, N - ethoxymethyl acrylamide, Nn-butoxymethyl acrylamide, N-isobutoxymethyl acrylamide, N-vinyl-pyrrolidone, more preferably N-propylene fluorenyl Physin, N-ethoxymethyl acrylamide, Nn-butoxymethyl acrylamide, N-isobutoxymethyl acrylamide.

The amount of the component 3 used in the invention (I) is relative to The total amount of the components 1, the component 2, and the component 3 of the essential component of the invention (I) is preferably 2 to 30% by mass, more preferably 3 to 20% by mass, particularly preferably 4 to 15% by mass. When the amount of the component 3 used in the invention (I) is less than 2% by mass based on the total amount of the component 1, the component 2, and the component 3 which are essential components of the invention (I), the present invention will be described later. The adhesion of the polymer of (III) or the glass of the optical adhesive sheet of the present invention (V) may be insufficient, and it is not preferable. In addition, when the amount of the component 3 used in the invention (I) is more than 30% by mass based on the total amount of the components 1, the component 2, and the component 3 which are essential components of the invention (I), the present invention The volume shrinkage ratio at the time of polymerization of the polymerizable composition of (I) may increase, or the dielectric constant of the cured product may become high, and in a high-temperature environment, it may become easily colored. Can't be called better.

Next, the "component 4 of the essential component of the polymerizable composition of the present invention (I)" will be described.

The component 4 which is an essential component of the polymerizable composition of the invention (I) is a photopolymerization initiator.

The photopolymerization initiator of the component 4 is not particularly limited as long as it can generate a radical which contributes to the radical of the radical polymerization by irradiation with light such as near-infrared rays, visible rays, or ultraviolet rays.

Specific examples of the photopolymerization initiator of the component 4 include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, and 1-hydroxycyclohexyl. Phenyl ketone, 1,2-hydroxy-2-methyl-1-phenylpropan-1-one, α-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1 -ketone, 2-hydroxy-2-methyl-1-(4-isopropylphenyl)propan-1-one, 2- Hydroxy-2-methyl-1-(4-laurylphenyl)propan-1-one, and 2-hydroxy-2-methyl-1-[(2-hydroxyethoxy)phenyl]acetone, two Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4 -Chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide , benzophenone tetracarboxylic acid or its tetramethyl ester, 4,4'-bis(dialkylamino)benzophenone (for example, 4,4'-bis(dimethylamino)benzol Ketone, 4,4'-bis(dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dihydroxyethylamine Base) benzophenone), 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminodiphenyl Ketone, 4-dimethylaminoacetophenone, diphenylethylenedione, anthracene, 2-t-butylhydrazine, 2-methylindole, phenanthrenequinone, anthrone, 2-benzyl -2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl] -1-[4-(4-? Phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone, 2-hydroxy-2-methyl- [4-(1-Methylvinyl)phenyl]propanol oligomers, benzoin, benzoin ethers (eg, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin) Isobutyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloride Acridone, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2,6-dimethoxybenzimidyldiphenylphosphine oxide, 2,6-dichlorobenzamide Diphenylphosphine oxide, 2,4,6-trimethylbenzimidylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzene Methyl methoxy phenyl phosphine oxide, 2,3,5,6-tetramethyl benzhydryl diphenyl phosphine oxide, benzhydryl bis-(2,6-dimethylphenyl)phosphoric acid Ester and the like. Examples of the bis-indenylphosphine oxides include bis-(2,6-dichlorobenzhydryl)phenylphosphine oxide and bis-(2,6-dichlorobenzhydryl)-2,5-di. Methylphenylphosphine oxide, bis-(2,6-dichlorobenzylidene)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzhydryl)-1-naphthyl Phosphine oxide, bis-(2,6-dimethoxybenzylidene)phenylphosphine oxide, bis-(2,6-dimethoxybenzylidene)-2,4,4-trimethyl Pentylphosphine oxide, bis-(2,6-dimethoxybenzylidene)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzylidene Phenylphosphine oxide, (2,5,6-trimethylbenzylidene)-2,4,4-trimethylpentylphosphine oxide, 2-isopropylthioxanthone, 4-isopropyl Thioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

Further, as the photopolymerization initiator, a metallocene compound can also be used. As the metallocene compound, a transition element represented by Fe, Ti, V, Cr, Mn, Co, Ni, Mo, Ru, Rh, Lu, Ta, W, Os, Ir, or the like can be used for the center metal, for example, double (η 5-2,4-cyclopentadien-1-yl)-bis[2,6-difluoro-3-(pyrrol-1-yl)phenyl]titanium.

These photopolymerization initiators may be used alone or in combination of two or more.

Among these, preferred are 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and 2,4,6-trimethylbenzimidazole. Diphenylphosphine oxide, 2,4,6-trimethylbenzhydrylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzimidyldiphenylphosphine oxide; Particularly preferred are 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzhydryldiphenyloxy Phosphine, 2,4,6-trimethylbenzimidylethoxyphenylphosphine oxide; optimally used as 2,4,6-trimethylbenzhydryldiphenylphosphine oxide alone, 2 , 4,6-trimethylbenzimidylethoxyphenylphosphine oxide alone, 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzimidyldiphenylphosphine oxide For the combined use, 2-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethyl benzhydrylethoxy phenyl phosphine oxide, 2,4,6-trimethylbenzhydryldiphenyl Combined with 2,4,6-trimethyl benzhydrylethoxyphenylphosphine oxide, or 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzylidene Three kinds of diphenylphosphine oxide and 2,4,6-trimethyl benzhydrylethoxyphenylphosphine oxide are used in combination.

Further, the protective portion 3 of FIGS. 1 to 5 has a function of providing an ultraviolet ray blocking region from the viewpoint of ultraviolet protection of the display portion 2. In this case, it is preferred to use a photopolymerization initiator which is photosensitive even in the visible light region, such as 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2,3,5,6. -tetramethylbenzimidyldiphenylphosphine oxide, 2,4,6-trimethylbenzhydrylethoxyphenylphosphine oxide; particularly preferably 2,4,6-trimethylbenzhydrazide Ethyl ethoxyphenylphosphine oxide, 2,4,6-trimethyl benzhydryldiphenylphosphine oxide.

The amount of the component 4 used in the invention (I) is preferably 0.05 to 10.0 parts by mass based on 100 parts by mass of the total of the components 1, the component 2 and the component 3 which are essential components of the invention (I). More preferably, it is 0.1 to 7.0 parts by mass, and particularly preferably 0.2 to 5.0 parts by mass. With respect to 100 parts by mass of the total of the components 1, the component 2 and the component 3 which are essential components of the invention (I), when the amount of the component 4 used is less than 0.05 part by mass, the polymerization of the polymerization initiator starts from The initial performance has become insufficient, so it is not appropriate. Again, relative When the total amount of the component 1, the component 2, and the component 3 of the essential component of the invention (I) is 100 parts by mass, when the amount of the component 4 used in the invention (I) is more than 10.0 parts by mass, it will be described later. When the polymer of the present invention (III) or the optical adhesive sheet of the present invention (V) described later is placed in a high-temperature environment, it tends to be easily colored, and it is not preferable.

Next, the "invention (II)" will be described.

The polymerizable composition of the present invention (II) is a polymerizable composition according to the invention (I), which further comprises the following (ingredient 5), (ingredient 5): no (meth)acrylic acid in the molecule The base does not have any function of inhibiting radical polymerization, a function of inhibiting radical polymerization, and a photopolymerization initiation function, and is composed of a carbon atom and a hydrogen atom, or a carbon atom, a hydrogen atom, and A compound composed of an oxygen atom at 25 ° C in the form of a liquid or a solid.

That is, the present invention (II) is a polymerizable composition for forming a polymerizable composition of a polymer layer which is an image display portion and a light transmissive property interposed in an image display device. Between the parts, the polymerizable composition includes the following (component 1) to (component 5), (component 1): a compound selected from a (meth)acryl fluorenyl group having a polyolefin structural unit, a compound containing a (meth)acryl fluorenyl group having a hydrogenated polyolefin structural unit, a compound containing a (poly)ester structural unit containing a (meth)acryl fluorenyl group, and a content having a (poly)carbonate structural unit (A) At least one of a group consisting of a compound of an acrylonitrile group; (Component 2): a (meth) acrylate compound having a hydrocarbon group having 6 or more carbon atoms; (Component 3): a vinyl group having a guanamine bond Chemical (Component 4): photopolymerization initiator; and (Component 5): there is no (meth) acrylonitrile group in the molecule, nor does it have a function of inhibiting radical polymerization, a function of inhibiting radical polymerization, And a compound which is a liquid or solid at 25 ° C, which is composed of a carbon atom and a hydrogen atom, or a carbon atom, a hydrogen atom, and an oxygen atom.

Component 5 preferably has no (meth) acrylonitrile group in the molecule, and does not have any function of inhibiting radical polymerization, a function of inhibiting radical polymerization, and a function of photopolymerization initiation function, and A compound composed of a carbon atom and a hydrogen atom or a liquid or solid at 25 ° C composed of a carbon atom, a hydrogen atom, and an oxygen atom.

Component 1 to Component 4, which are essential components of the present invention (II), are the same as Component 1 to Component 4 of the present invention (I).

The amount of the component 1 used in the invention (II) is preferably from 7 to 70% by mass based on the total amount of the component 1, the component 2, the component 3 and the component 5 which are essential components of the invention (II). More preferably, it is 10 to 60% by mass, and particularly preferably 12 to 50% by mass.

With respect to the total amount of the components 1, the component 2, the component 3, and the component 5 which are essential components of the invention (II), when the amount of the component 1 used in the invention (II) is less than 7 mass%, When the polymer obtained by polymerizing the polymerizable composition of the present invention (II) has a reduced coating film strength, or the polymer obtained by polymerizing the polymerizable composition has a high dielectric constant, it cannot be called. It is better. Further, with respect to the total amount of the components 1, the component 2, the component 3, and the component 5 which are essential components of the invention (II), In the case where the amount of the component 1 used in the invention (II) is more than 70% by mass, the viscosity of the polymerizable composition of the invention (II) is high, which is not preferable.

The amount of the component 2 used in the invention (II) is preferably from 7 to 60% by mass based on the total amount of the component 1, the component 2, the component 3 and the component 5 which are essential components of the invention (II). More preferably, it is 10 to 50% by mass, and particularly preferably 12 to 45% by mass. With respect to the total amount of the components 1, the component 2, the component 3, and the component 5 which are essential components of the invention (II), when the amount of the component 2 in the invention (II) is less than 7 mass%, The viscosity of the polymerizable composition of the invention (II) is too high, which is not preferable. Further, when the amount of the component 2 used in the invention (II) is more than 60% by mass, based on the total amount of the components 1, the component 2, the component 3, and the component 5 which are essential components of the invention (II) In the polymerization of the polymerizable composition of the present invention (II), the volume shrinkage ratio may become large, or the dielectric constant of the cured product may become high, which is not preferable.

The amount of the component 3 used in the invention (II) is preferably 1.0 to 20% by mass based on the total amount of the component 1, the component 2, the component 3 and the component 5 which are essential components of the invention (II). More preferably, it is 1.5 to 13% by mass, and particularly preferably 1.8 to 10% by mass. With respect to the total amount of the components 1, the component 2, the component 3, and the component 5 which are essential components of the invention (II), when the amount of the component 3 used in the invention (II) is less than 1.0% by mass, The adhesiveness of the glass of the invention (III) or the optical adhesive sheet of the invention (V) will be insufficient, and it is not preferable. Further, as the total amount of the components 1, the component 2, the component 3, and the component 5 which are essential components of the invention (II), the component 3 in the invention (II) When the amount of use is more than 20% by mass, the volume shrinkage ratio at the time of polymerization of the polymerizable composition of the invention (II) may increase or the dielectric constant of the cured product may become high, and In a high-temperature environment, there is a case where it becomes easy to be colored, and it cannot be said to be preferable.

The amount of the component 4 used in the invention (II) is preferably 0.05 to 10.0 based on 100 parts by mass of the total of the components 1, the component 2, the component 3 and the component 5 which are essential components of the invention (II). The mass fraction is more preferably 0.1 to 7.0 parts by mass, particularly preferably 0.2 to 5.0 parts by mass. The amount of the component 4 used in the invention (II) is less than 0.05 parts by mass based on 100 parts by mass of the total of the components 1, the component 2, the component 3, and the component 5 which are essential components of the invention (II). In the case where the polymerization initiation property of the polymerization initiator is insufficient, it is not preferable. Further, with respect to 100 parts by mass of the total of the components 1, 2, 3, and 5 which are essential components of the invention (II), the amount of the component 4 used in the invention (II) is 10.0 by mass. When the polymer of the present invention (III) or the optical adhesive sheet of the present invention (V) described later is placed in a high-temperature environment, it may become easily colored, and it is not preferable.

Next, the component 5 of the essential component of the polymerizable composition of the present invention (II) will be described.

The component 5 which is an essential component of the polymerizable composition of the present invention (II) does not have a function of inhibiting radical polymerization, a function of inhibiting radical polymerization, and a function of inhibiting radical polymerization, as long as it does not have a (meth)acrylonitrile group in the molecule. Any of the functions of photopolymerization initiation function, consisting of carbon atoms and hydrogen atoms, or consisting of carbon atoms, hydrogen atoms, and oxygen atoms at 25 ° C for liquid or solid The compound of the present invention is not particularly limited, and is preferably a compound which does not impair the uniformity of the polymerizable composition of the invention (II) which contains the component 1 to the component 5 as essential components at 30 °C.

In the component 5, in particular, a method of manufacturing a method in which a polymerizable composition is interposed between a base having a video display portion and a light-transmitting protective portion and polymerized to form a polymer layer is used. In the case of a display device, it is necessary to contain the component 5 in order to suppress the volume shrinkage rate at the time of polymerization of the polymerizable composition used in this step to a low level. Further, in addition to suppressing the volume shrinkage ratio at the time of polymerization, the component 5 may be used for the purpose of increasing the adhesion of the polymer to the object such as glass or acrylic resin.

As the component 5, a compound which is liquid at 25 ° C or a compound which is solid at 25 ° C can be used.

Examples of the compound which is liquid at 25 ° C used as the component 5 include a poly(α-olefin) liquid material, an ethylene-propylene copolymerization liquid material, a propylene-α-olefin copolymerization liquid material, and ethylene. -α-olefin copolymerization liquid, liquid polybutene, liquid hydrogenated polybutene, liquid polybutadiene, liquid hydrogenated polybutadiene, liquid polyisoprene, liquid hydrogenated poly Isoprene, liquid polybutadiene polyol, liquid hydrogenated polybutadiene polyol, liquid polyisoprene polyol, liquid hydrogenated polyisoprene polyol, hydrogenated dimer II Alcohol, etc.

The poly(α-olefin) liquid material is a liquid material produced by polymerization of an α-olefin, and the so-called α-olefin is a hydrocarbon compound having one carbon-carbon double bond at the molecular terminal, and may be exemplified. Such as 1-butene, 1-pentyl Alkene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and the like.

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

The propylene-α-olefin copolymerization liquid material is a liquid polymer produced by copolymerizing propylene with an α-olefin. The α-olefin is a hydrocarbon compound having one carbon-carbon double bond at the molecular terminal, and examples thereof include 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-decene. 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and the like.

The liquid polybutene is a liquid polymerization in which the (co)polymerization component contains isobutylene or n-butene, such as individual polymerization of isobutylene, polymerization of n-butene alone, copolymerization of isobutylene and n-butene. A compound having a carbon-carbon unsaturated bond bonded to one of the ends. As a commercial item of liquid polybutene, for example, JD Nippon Stone ENERGY, Nippon Polybutylene LV-7, LV-50, LV-100, HV-15, HV-35, HV -50, HV-100, HV-300, etc.

The liquid hydrogenated polybutene is obtained by hydrogenating the liquid polybutene, and is a liquid material having a side chain, and examples thereof include PARLEAM 4, PARLEAM 6, and PARLEAM 18 manufactured by Nippon Oil Co., Ltd. , PARLEAM 24, PARLEAM EX, etc.

So-called liquid polybutadiene, which is liquid at room temperature The butadiene polymer may, for example, be POLYVEST 110 manufactured by Evonik Degussa, POLYVEST 130, or NISSO-PB B-1000, NISSO-PB B-2000, NISSO-PB B-3000 manufactured by Nippon Soda Co., Ltd., or the like.

The liquid hydrogenated polybutadiene which is obtained by reduction hydrogenation of a butadiene polymer and which is liquid at normal temperature, for example, NISSO-PB BI-2000, NISSO-PB B manufactured by Japan Soda Co., Ltd. -3000 and so on.

The liquid polyisoprene is an isoprene polymer which is liquid at normal temperature, and is, for example, Kuraprene LIR-30 manufactured by Kuraray Co., Ltd., and the like.

The liquid hydrogenated polyisoprene is obtained by reducing hydrogenation of an isoprene polymer, and is a liquid polymer at normal temperature, and examples thereof include LIR-200 manufactured by Kuraray Co., Ltd., and the like.

The liquid polybutadiene polyol is a polymer having two or more hydroxyl groups at the molecular terminal and having a polybutadiene structural unit, and is a liquid at room temperature, and examples thereof include NISSO manufactured by Japan Soda Co., Ltd. -PB G-1000, NISSO-PB G-2000, NISSO-PB G-3000, Poly bd by Idemitsu Kosan Co., Ltd., etc.

The liquid hydrogenated polybutadiene polyol is a liquid polyol having a structure obtained by reducing hydrogenation of a polybutadiene polyol or a polybutadiene polycarboxylic acid, and examples thereof include NISSO manufactured by Japan Soda Co., Ltd. -PB GI-1000, NISSO-PB GI-2000, NISSO-PB GI-3000, etc.

So-called liquid polyisoprene polyol, at the end of the molecule For example, a Poly ip manufactured by Idemitsu Kosan Co., Ltd., or the like, which has a polyisoprene structural unit having two or more hydroxyl groups and a polyisoprene structural unit.

The liquid hydrogenated polyisoprene polyol is a liquid polyol having a structure obtained by reducing hydrogenation of a polyisoprene polyol or a polyisoprene polycarboxylic acid, for example, Produced EPOL, etc.

A hydrogenated dimer diol which is a polyol obtained by reducing hydrogenation of a dimer acid. The so-called dimer acid is the same as described above.

The commercially available product of the hydrogenated dimer diol is, for example, PRIPOL (registered trademark) 2033 (manufactured by Croda Corporation) or Sovermol (registered trademark) 908 (manufactured by Cognis Co., Ltd.).

When heat resistance is considered, it is preferably a compound having one or less carbon-carbon unsaturated bonds in the molecule, and more preferably, such as a liquid poly(?-olefin) liquid or ethylene-propylene copolymerization. Liquid, ethylene-α-olefin copolymerization liquid, propylene-α-olefin copolymerization liquid, liquid polybutene, liquid hydrogenated polybutene, liquid hydrogenated polybutadiene, liquid hydrogenation Polyisoprene, liquid hydrogenated polybutadiene polyol, liquid hydrogenated polyisoprene polyol, hydrogenated dimer diol. Further, it is particularly preferred to use a liquid poly(α-olefin) liquid, a copolymerization of ethylene and an α-olefin, a liquid polybutene, a liquid hydrogenated polybutene, and a liquid hydrogenated polybutane. At least one of an olefin and a liquid hydrogenated polyisoprene is at least one selected from the group consisting of a liquid hydrogenated polybutadiene polyol and a liquid hydrogenated polyisoprene polyol.

Further, as the component 5 in the invention (II), a compound which is solid at 25 ° C can also be used.

The compound used as the component 5 at 25 ° C is preferably a compound having no carbon-carbon unsaturated bond in the molecule.

Examples of such a compound include an epoxy resin which is solid at 25 ° C, a polyester resin which is solid at 25 ° C, a polyol resin which is solid at 25 ° C, a hydrogenated petroleum resin, a terpene-based hydrogenated resin, and hydrogenation. Rosin ester and the like.

Among these, a hydrogenated petroleum resin, a terpene-based hydrogenated resin, and a hydrogenated rosin ester are preferable.

The hydrogenated petroleum resin is a resin obtained by reducing and hydrogenating a petroleum resin. Examples of the petroleum-based resin which is a raw material of the hydrogenated petroleum resin include an aliphatic petroleum resin, an aromatic petroleum resin, an aliphatic-aromatic copolymerized petroleum resin, an alicyclic petroleum resin, and a dicyclopentadiene resin. And denatured materials such as these hydrides. The synthetic petroleum resin may be a C5 system or a C9 system.

The terpene-based hydrogenated resin is a resin obtained by reducing hydrogenation of a terpene-based resin. Examples of the terpene-based resin which is a raw material of the terpene-based hydrogenated resin include β-pinene resin, α-pinene resin, β-limonene resin, α-limonene resin, terpene-limonene copolymer resin, and terpene- Limonene-styrene copolymer resin, terpene-phenol resin, aromatic-modified terpene resin, and the like. Most of the terpene-based resins are resins which do not have a polar group.

The hydrogenated rosin ester is a resin obtained by hydrogenating a rosin-based resin, esterifying the obtained hydrogenated rosin, or esterifying the rosin, and then reducing and hydrogenating the obtained rosin ester. Examples of the rosin-based resin adhesion-imparting agent include rubber rosin, tall oil rosin, and wood pine. Denatured rosin, such as fragrant, uneven rosin, polymerized rosin, and male rosin.

Among these, as a terpene-based hydrogenated resin, a resin obtained by reduction hydrogenation of a polydecene, a polylimonene or a terpene-limonene copolymer resin, or a terpene-styrene copolymerization is particularly preferable. A resin obtained by reduction-hydrogenation of a carbon-carbon unsaturated bond other than an aromatic ring of a resin, limonene-styrene copolymer resin or a terpene-limonene-styrene copolymer resin.

Further, in order to obtain a balance between the polymerizable composition of the present invention (II) and the viscosity or the adhesion of the polymer to the object, the compound as the component 5 can be used in combination with the compound at 25 ° C in liquid form. °C is a solid compound, and is preferred.

More preferably, it is used in liquid form at 25 ° C, and is a compound having one or less carbon-carbon unsaturated bonds in the molecule, and is solid at 25 ° C and does not have carbon-carbon in the molecule. A compound that is saturated with a bond.

In the component 5, when used in combination with a compound which is liquid at 25 ° C and a compound which is solid at 25 ° C, a preferred combination ratio is 90:10 to 10:90, more preferably 80:20 to 20 by mass. :80.

The amount of the component 5 used in the invention (II) is preferably 15 to 85% by mass based on the total amount of the component 1, the component 2, the component 3 and the component 5 which are essential components of the invention (II). More preferably, it is 25 to 75 mass%, and particularly preferably 30 to 70 mass%. With respect to the total amount of the components 1, the component 2, the component 3, and the component 5 which are essential components of the invention (II), when the amount of the component 5 used in the invention (II) is less than 15% by mass, The effect of adding the component 5 (that is, the effect of lowering the volume shrinkage ratio at the time of polymerization) cannot be obtained, and therefore it cannot be said to be preferable. Also, with respect to the present invention (II) The total amount of the components 1, the component 2, the component 3, and the component 5 of the essential components, when the amount of the component 5 used in the invention (II) is more than 85 mass%, the invention (II) The coating film strength of the polymer obtained by polymerizing the polymerizable composition is too low, and it is not preferable.

The polymerizable composition of the invention (I) or the polymerizable composition of the invention (II) is used for maintaining the polymer of the invention (III) described later or the optical adhesive sheet of the invention (V) under high temperature and high humidity. The transparency is further preferably contained in the following component 6.

(Component 6): (meth) acrylate having an alcoholic hydroxyl group.

However, component 6 is a compound other than component 2.

The component 6 is not particularly limited as long as it is a (meth) acrylate having an alcoholic hydroxyl group.

Specific examples of the (meth) acrylate having an alcoholic hydroxyl group (i.e., component 6) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, and 2-hydroxy acrylate. Butyl ester, 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, methacrylic acid 2 -Hydroxy-3-phenoxypropyl ester, 2-hydroxy-3-(o-phenylphenoxy)propyl methacrylate, and the like.

When the compatibility of the polymerizable composition of the present invention (I) or the polymerizable composition of the present invention (II) is considered, among The best ones are 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-(o-phenylphenoxy) propyl acrylate, A 2-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate; more preferably 4-hydroxybutyl acrylate, methacrylic acid 2 - Hydroxypropyl ester, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate; most preferably 2-hydroxypropyl methacrylate.

When the polymerizable composition of the invention (I) or the polymerizable composition of the invention (II) is the component 6 used, the total amount of the polymerizable composition of the invention (I) or the invention (II) The total amount of the polymerizable composition is preferably from 0.05 to 10% by mass, more preferably from 0.1 to 6% by mass, still more preferably from 0.2 to 4% by mass, based on the amount of the component 6. With respect to the total amount of the polymerizable composition of the invention (I) or the total amount of the polymerizable composition of the invention (II), when the amount of the component 6 used is less than 0.05% by mass, the heat and humidity resistance property is exhibited. The effect is less, so it is not good. In addition, when the total amount of the polymerizable composition of the invention (I) or the total amount of the polymerizable composition of the invention (II) is used when the amount of the component 6 is more than 10% by mass, In the case where the polymerizable composition of the invention (I) or the polymerizable composition of the invention (II) is turbid, or the polymerizable composition of the invention (I) or the polymerizable composition of the invention (II) is polymerized The dielectric constant of the obtained polymer is too high, so it cannot be said to be preferable.

Further, the polymerizable composition of the invention (II) is used after In the method of producing the image display device of the invention (VI), the volume shrinkage ratio during polymerization of the polymerizable composition of the invention (II) is preferably 3.5% or less, more preferably 2.7% or less, and most preferably 2.3. %the following. When the volume shrinkage ratio at the time of polymerization of the polymerizable composition of the invention (II) is larger than 3.5%, when the polymerizable composition is polymerized, the internal stress accumulated in the polymer becomes excessive, and in the polymer The layer 5a or 5b is distorted at the interface with the image display portion 2, the protection portion 3, or the touch panel 7 that is in contact with the image, and is not preferable.

The polymerizable composition of the invention (I) or the polymerizable composition of the invention (II) has a viscosity at 25 ° C, and is not particularly limited, but is 10,000 mPa in operation. s below is better, to 7000mPa. s is better below, at 5000mPa. s below is particularly good.

Furthermore, the viscosity described in the present specification is about 5000 mPa at 25 ° C. The composition of the viscosity below s is measured by a cone/plate type viscometer (manufactured by Brookfield, Inc., type: DV-II+Pro, rotor type: CPE-42) at a temperature of 25.0 ° C and a number of revolutions of 5 rpm. value.

The viscosity of the polymerizable composition of the invention (I) or the polymerizable composition of the invention (II) at 25 ° C is set to 1000 mPa. When the polymerizable composition of the present invention (I) or the polymerizable composition of the present invention (II) is applied by a scribing method using a dispenser, after coating, The liquid easily spreads, and as a result, it is easy to spread the composition at a uniform thickness as needed, and it is possible to suppress the entrapment of air bubbles.

The polymerizable composition of the invention (I) or the invention (II) As the polymerizable composition, a polymerization inhibitor, a suppressing agent, or an antioxidant may be added and it is preferable.

The polymerization inhibitor or the polymerization inhibiting agent is not particularly limited as long as it has a function of inhibiting polymerization or inhibiting polymerization, and examples thereof include thiophene thiophene. , hydroquinone, p-methoxyphenol, p-benzoquinone, naphthoquinone, phenanthrenequinone, formazan, 2,5-diethyloxy-p-benzoquinone, 2,5-dihexyloxy- P-benzoquinone, 2,5-decyloxy-p-benzoquinone, pt-butylcatechol, 2,5-di-t-butylhydroquinone, p-tert-butylcatechol, single -t-butylhydroquinone, 2,5-di-t-pentylhydroquinone, di-t-butyl ‧ p-cresol hydroquinone monomethyl ether, α-naphthol, acetamidine acetate, B Sulfate, phenyl hydrazine hydrochloride, hydrazine hydrochloride, trimethylbenzylammonium chloride, lauryl pyridine chloride, hexadecyltrimethylammonium chloride, phenyltrimethyl chloride Ammonium, trimethylbenzylammonium oxalate, bis(trimethylbenzylammonium) oxalate, trimethylbenzylammonium maleate, trimethylbenzyltartaric acid ammonium, trimethylbenzyl glycol Ammonium amide, phenyl-β-naphthylamine, p-benzylaminophenol, bis-β-naphthyl p-phenylenediamine, dinitrobenzene, trinitrotoluene, picric acid, cyclohexanone oxime, o-benzene Trisphenol, tannic acid, resorcinol, triethylamine hydrochloride, xylylamine hydrochloride and dibutylamine hydrochloride.

These may be used alone or in combination of two or more.

Among these, hydroquinone, p-methoxyphenol, p-benzoquinone, naphthoquinone, phenanthrenequinone, 2,5-diethyloxy-p-benzoquinone, 2,5-dihexyloxy Base-p-benzoquinone, 2,5-decyloxy-p-benzoquinone, pt-butylcatechol, 2,5-di-t-butylhydroquinone, p-tert-butylcatechol , mono-t-butylhydroquinone, 2,5-di-t-pentylhydroquinone, di-t-butyl ‧ p-cresol hydroquinone monomethyl ether and thiophene For proper use.

In general, the polymerization inhibiting agent can be adjusted so as to be added in an amount of 0.01 to 5% by mass based on the total amount of the polymerizable composition of the invention (I) or the polymerizable composition of the invention (II). However, the amount of the polymerization inhibitor is added to the value of the polymerization inhibitor contained in the component 1, the component 2, the component 3, and the component 6 in advance. That is, generally, the amount of the polymerization inhibiting agent and the total amount of the polymerization inhibitor which is re-added are combined with the amount of the polymerization inhibitor in the component 1, the component 2, the component 3, and the component 6 in advance, in relation to the present invention. The total amount of the polymerizable composition of the invention (I) or the polymerizable composition of the invention (II) is such that it is added in an amount of 0.01 to 5% by mass.

With respect to the total amount of the polymerizable composition of the invention (I) or the polymerizable composition of the invention (II), when the polymerization inhibiting agent is less than 0.01% by mass, the preparation of the mixture is not satisfied due to insufficient polymerization inhibition energy. If stability is insufficient, it cannot be called better. In addition, when the amount of the polymerization inhibiting agent is more than 5% by mass based on the total amount of the polymerizable composition of the invention (I) or the polymerizable composition of the invention (II), the color is formed by heat-resistant storage. It is not preferable to have a color darkening or a decrease in the polymerization speed at the time of polymerization.

The antioxidant is not particularly limited, and examples thereof include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylidene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propane Acid ester], 3,5-di-tert-butyl-4-hydroxyphenylpropanic acid having an alkyl group of 7-9, 4,6-bis(octylthiomethyl)-o- Phenol, 3,9-double [2- [3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxa Spiro[5,5]-undecane, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-butylene bis(6-tert-butyl -3-methylphenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), N,N',N〞-tris(3,5-di-tert-butyl 4--4-hydroxybenzyl)isocyanurate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,1-double (2 -Methyl-4-hydroxy-5-tert-butylphenyl)butane, etc. Among them, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyl) is preferred. Phenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; optimal pentaerythritol tetra[3-(3,5- Di-tert-butyl-4-hydroxyphenyl)propionate].

In general, the antioxidant can be adjusted so as to be added in an amount of 0.01 to 5% by mass based on the total amount of the polymerizable composition of the invention (I) or the polymerizable composition of the invention (II). However, the amount of the antioxidant is added to the value of the antioxidant contained in the other components such as the component 5 in advance. That is, in general, the amount of the antioxidant and the total amount of the re-added antioxidant is combined in advance in the case where the antioxidant is contained in the component 5 or the like, in order to polymerize the polymerizable composition with respect to the present invention (I). Or the total amount of the polymerizable composition of the present invention (II) is such that it is added in an amount of 0.01 to 5% by mass.

With respect to the total amount of the polymerizable composition of the invention (I) or the polymerizable composition of the invention (II), when the antioxidant is less than 0.01% by mass, the addition effect (i.e., oxidation prevention effect) may not be exhibited. ), it cannot be called better. Further, the polymerizable composition of the invention (I) In the total amount of the polymerizable composition of the present invention (II), when the amount of the polymerization inhibiting agent is more than 5% by mass, the polymer of the present invention (III) described later or the optical device of the present invention (V) described later is used. The adhesive sheet precipitates an anti-oxidant exudation, so it cannot be said to be preferable.

Next, the "invention (III)" will be described.

The invention (III) is a polymer obtained by polymerizing the polymerizable composition of the invention (I) or the invention (II).

The polymer of the invention (III) is a low-pressure mercury lamp, 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, an LED or the like as a light source, and the photopolymerization initiator is photosensitive. The light is obtained by irradiating a substrate of glass or plastic to polymerize the polymerizable composition.

Further, the polymer of the invention (III) is used as a polymer which is a polymer layer interposed between the image display portion of the image display device and the light-transmitting protective portion. The polymer had a dielectric constant of 1.2 mm or less and a dielectric constant of 3.0 mm or less at 23 ° C, a frequency of 1 MHz, and an applied voltage of 100 mV, and was present between two sheets of glass, and the thickness was adjusted to 200 μm. After storage at 95 ° C for 500 hours, the chromaticity coordinate b* value described in JIS Z 8729 is preferably less than 1.0.

In addition, the "dielectric constant of the polymer at 23 ° C, a frequency of 1 MHz, and a voltage of 100 mV" is described in the present specification, and a 1.2 mm thick test piece (polymer) is used at 23 ° C. Under the environment, use the impedance analyzer made by Agilent Technologies 4294A precision impedance analyzer 40 Hz-110 MHz, test fixture, using a 16451B dielectric test fixture manufactured by Agilent Technologies, the dielectric constant of the polymer was measured at a frequency of 1 MHz and an applied voltage of 100 mV.

As shown in FIG. 2 or FIG. 3 , a polymer (layer) between the display unit and the touch panel mounted in the display device in which the Add-On type electrostatic capacitance mode touch panel is mounted (described in FIGS. 2 and 3 ) a polymer (layer) of 5b or a polymer between the display portion and the protective portion of the touch center integrated in the display device mounted on the cover glass-touch center integrated capacitive mode touch panel ( Layer (a polymer (layer) of 5b described in FIG. 4 and FIG. 5), when the polymer (layer) described above is a polymer of the invention (III), the polymerization of the invention (III) The dielectric constant of the material is preferably low. Specifically, at 23 ° C, at a frequency of 1 MHz and an applied voltage of 100 mV, it is preferred to use a polymer having a dielectric constant of 1.2 mm or less of a polymer of 1.2 mm or less; more preferably, a polymerization of 2.9 or less is used. Things.

Further, the "polymer having a thickness of 200 μm existing between two sheets of glass" as described in the present specification is used in two optical glasses (manufactured by Corning Co., Ltd., trade name: EAGLE XG) having a thickness of 0.7 mm. a polymer obtained by sandwiching a sheet-like polymer of 200 μm, or a polymerizable composition interposed between two optical glasses (manufactured by Corning Co., Ltd., trade name: EAGLE XG) having a thickness of 0.7 mm, through the optical glass. , with low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, metal halide lamp, electrodeless A lamp, an LED, or the like as a light source, a polymer having a thickness of 200 μm obtained by irradiating light of a photopolymerization initiator, and a portion sandwiched between two sheets of glass on the outer side of the polymer layer does not include a spacer at all. , gaskets or sealants, etc.

Further, the "chromaticity coordinate b* value described in JIS Z 8729 after storage at 95 ° C for 500 hours" as used in the present specification means that it exists between the two sheets of glass and has a thickness. The polymer was adjusted to 200 μm, and after 500 hours in an environment of 95 ° C, the value of the psychometric chroma coordinates b* was measured in a 23 ° C environment by the method described in JIS Z 8729. However, the reference used for measuring the value of b* was an optical glass (manufactured by Corning Co., Ltd., trade name: EAGLE XG) having a thickness of 0.7 μm. In the present invention (IV), the value of b* measured under the above conditions must be less than 1.2. More preferably, less than 1.1 is better, and less than 1.0 is better. When the value of b* measured under the above conditions is 1.2 or more, the transmittance of light of 370 to 450 nm may be lowered over time.

The refractive index of the polymer of the invention (III) at 25 ° C is preferably from 1.45 to 1.55, more preferably from 1.48 to 1.52. When the refractive index at 25 ° C is less than 1.45 or greater than 1.55, the refractive index of the acrylic glass such as optical glass or polymethyl methacrylate which is a material of the protective portion becomes too low, so The difference in refractive index from the interface between the display portion and the protective portion is slightly larger, and scattering and attenuation from the display portion to the image light are slightly larger, which is not preferable.

Further, the polymer of the invention (III) has a tensile modulus at 23 ° C, preferably 1 × 10 ⁷ Pa or less, more preferably 1 × 10 ³ to 1 × 10 ⁶ Pa. By setting the tensile modulus of the polymer at 23 ° C to 1 × 10 ⁷ Pa or less, it is possible to prevent the image display portion and the protective portion from being distorted by the stress caused by the volume shrinkage of the polymerizable composition during polymerization. .

In addition, the tensile elastic modulus described in the present specification is a value when tested at a tensile speed of 500 mm/min.

Next, the "invention (IV)" and the "invention (V)" will be described.

The present invention (IV) is a polymerizable composition for producing a polymerizable composition for an optical adhesive sheet which is an image display portion and a translucent protection interposed in an image display device. The user who is a polymer layer between the parts is characterized in that the polymerizable composition is the polymerizable composition of the invention (I) or the invention (II).

The optical adhesive sheet of the present invention (V) can be produced by using the polymerizable composition of the invention (I) or the polymerizable composition of the invention (II) as a raw material.

The present invention (V) is an optical adhesive sheet having a polymer layer having a thickness of 10 to 1000 μm, and the polymer layer is irradiated with the polymerizable composition of the present invention (IV). The photopolymerization initiator can be obtained by sensitizing light and polymerizing it.

The optical adhesive sheet of the present invention (V) may be a double-sided adhesive sheet on both sides of the sheet to be an adhesive surface (surface of the adhesive layer), or may be one side of the sheet to be an adhesive surface (surface of the adhesive layer). Adhesive sheets. Among them, in terms of bonding two component groups to each other, double-sided adhesion Thin slices are preferred. In addition, in the present specification, when it is called "adhesive sheet", it also includes a tape shape, that is, it also includes "adhesive tape".

The optical adhesive sheet of the present invention (V) may be a so-called "substrate-free" optical adhesive sheet which does not have a base material (base material layer) (hereinafter referred to as "substrate-free optical adhesive sheet". In the case of the case, it may be an optical adhesive sheet having a type of substrate. The non-substrate optical adhesive sheet may, for example, be a double-sided adhesive sheet composed of only a polymer layer composed of the polymer of the present invention, or a polymer layer composed of the polymer of the present invention and A double-sided adhesive sheet composed of an adhesive layer other than the polymer layer. As the adhesive sheet having a substrate type, a polymer layer composed of the polymer of the present invention may be provided on at least one side of the substrate. Among them, from the viewpoint of improving the optical properties such as thinning of the optical adhesive sheet and transparency, it is preferable to use a non-substrate optical adhesive sheet (non-substrate double-sided optical adhesive sheet), and more preferably A substrate-free double-sided optical adhesive sheet comprising only a polymer layer composed of the polymer of the present invention. In addition, the above-mentioned "base material (base material layer)" does not include a separation plate (peeling pad) which is peeled off when the adhesive sheet is used (adhered).

The polymer layer of the optical adhesive sheet of the present invention (V) has a thickness of 10 to 1000 μm, preferably 20 to 700 μm, more preferably 30 to 500 μm. When the thickness of the polymer layer exceeds 1000 μm, wrinkles may occur during winding at the time of coating, or it may become cloudy due to humidification, and it is not preferable. When the thickness of the polymer layer is less than 10 μm, since the polymer layer is thin and the stress cannot be dispersed, peeling is likely to occur.

The optical adhesive sheet of the invention (V) is used as a polymer layer between the image display portion of the image display device and the light-transmitting protective portion. For example, as shown in FIG. 2 or FIG. 3, the polymer (layer) between the display portion and the touch panel in the display device in which the Add-On type electrostatic capacitance mode touch panel is mounted (FIG. 2 and FIG. 3) Aggregation between the display layer of the 5b polymer (layer) or the display unit mounted on the display device with the cover glass-touch center integrated capacitance mode touch panel and the touch center integrated protection portion (layer (a polymer (layer) of 5b described in FIG. 4 and FIG. 5), when the above-mentioned polymer (layer) is an optical adhesive sheet using the invention (V), the present invention ( The dielectric constant of the optical adhesive sheet of V) is preferably low. Specifically, it is preferable to use a 1.2 mm thick optical adhesive sheet having a dielectric constant of 3.0 or less at 23 ° C and a frequency of 1 MHz and an applied voltage of 100 mV; more preferably at 23 ° C. The dielectric constant of the 1.2 mm thick optical adhesive sheet was 2.9 or less under the condition of a frequency of 1 MHz and an applied voltage of 100 mV.

The optical adhesive sheet of the invention (V) is a low-pressure mercury lamp, 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, an LED or the like as a light source, and the photopolymerization initiator can be irradiated. The photosensitive light is obtained by polymerizing a polymerizable composition.

In the invention (V), the optical adhesive sheet having a thickness of 1000 μm which is adjusted between two sheets of glass is stored at 95 ° C for 500 hours, and then the chromaticity coordinates described in JIS Z 8729 are b. * The value is preferably less than 1.2. More preferably, it is less than 1.1, more preferably less than 1.0. When the value of b* measured under the above conditions is 1.2 or more, the transmittance of light of 370 to 450 nm may be lowered over time.

The optical adhesive sheet of the invention (V) has a refractive index at 25 ° C, preferably from 1.45 to 1.55, more preferably from 1.48 to 1.52. When the refractive index at 25 ° C is less than 1.45 or greater than 1.55, the refractive index of the acrylic glass such as optical glass or polymethyl methacrylate which is a material of the protective portion becomes too low, so The difference in refractive index from the interface between the display portion and the protective portion is slightly larger, and scattering and attenuation from the display portion to the image light are slightly larger, which is not preferable.

(Formation method of polymer layer for optical adhesive sheet)

The method for forming the polymer layer of the optical adhesive sheet of the present invention (V) can be carried out by a conventional or conventional method for forming a polymer layer, and is not particularly limited, and the polymerizable composition of the present invention has acrylonitrile. When the polymerizable layer of the base is polymerized to form a polymer layer for an optical adhesive sheet, for example, the following methods (1) to (3) can be mentioned.

(1) a polymerizable composition having an acrylonitrile group containing a photopolymerization initiator, and a composition containing an additive as required, coated (coated) on a substrate or a separation plate (peeling pad), And using a light source of a low-pressure mercury lamp, 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, an LED, etc., irradiating the photopolymerization initiator to sensitize light, by polymerizing the composition A polymer layer is formed.

(2) a polymerizable composition having a propylene fluorenyl group containing a photopolymerization initiator, further comprising a solvent, and a composition containing the additive as needed (solution), coated (coated) on a substrate or separator (peeling pad), dried, and used low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, metal halide lamp, electrodeless A light source such as a lamp or an LED is irradiated with light which is photo-sensitizable by a photopolymerization initiator, and the polymer layer is formed by polymerizing the composition.

(3) The polymer layer formed in the above (1) is further dried.

Further, in the coating (coating) of the above-described method for forming a polymer layer, a conventional coating method may be used, and a conventional coater may be used, and for example, a gravure roll coater or a reverse roll may be used. A coater, a contact roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a riprap coater, a direct coater, and the like.

(substrate)

When the optical adhesive sheet of the present invention (V) 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 phase difference plate. Examples of the material of the plastic film and the like include a polyester resin such as polyethylene terephthalate (PET), an acrylic resin such as polymethyl methacrylate (PMMA), and polycarbonate. Cellulose triacetate (TAC), polyfluorene, polyarylate, polyimine, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, ethylene-propylene copolymer, trade name "ARTON (cyclic olefin system) A plastic material such as a cyclic olefin polymer such as "JSR" (trade name: "ZEONOR (cyclic olefin polymer; manufactured by Japan ZEON)". Furthermore, the plastic materials can be used alone or in combination of two or more. use. In addition, the above-mentioned "substrate" is a portion that adheres to the object together with the adhesive layer when the optical adhesive sheet is used (adhered) to the object (optical member or the like). When the adhesive sheet is used (at the time of pasting), the peeled separation plate (peeling pad) is not included in the "substrate".

Among the above, as the substrate, a transparent substrate is preferred. The above-mentioned "transparent substrate" is preferably a substrate having a total light transmittance (in accordance with JIS K7361) of 85% or more in a visible light wavelength region, more preferably 88% or more. Further, the haze of the substrate (in accordance with JIS K7361) is preferably 1.5% or less, more preferably 1.0% or less. The transparent substrate may, for example, be a PET film or an unaligned film such as "ARTON" or a product name "ZEONOR".

The thickness of the substrate is not particularly limited, but is preferably, for example, 12 to 75 μm. Further, the substrate may be in any form of a single layer or a plurality of layers. Further, the surface of the substrate may be subjected to a conventional surface treatment such as a physical treatment such as a corona discharge treatment or a plasma treatment or a chemical treatment such as a primer treatment.

When the optical adhesive sheet of the invention (V) has a substrate, various functional films can be used as the substrate. In this case, the adhesive sheet of the present invention is an adhesive functional film having the adhesive layer of the present invention on at least one side of the functional film. The functional film is not particularly limited, and examples thereof include optical functionality (polarization property, light refraction property, light reflectivity, light transmittance, light absorbability, light diffraction property, optical rotation property, and Film for visual observation, etc., conductive film (ITO film, etc.), film with ultraviolet barrier, and hard coat layer Sex (scratch resistant) film, etc. More specifically, a hard coat film (a film coated with a hard coat layer on at least one side of a plastic film such as a PET film), a polarizing film, a wave plate, a retardation film, an optical compensation film, and a brightness enhancement are mentioned. Film, light guide plate, reflective film, antireflection film, transparent conductive film (ITO film, etc.), design film, decorative film, surface protection film, enamel, color filter, and the like. In addition, the "plate" and the "film" are each in the form of a plate, a film, or a sheet. For example, the "polarizing film" is a "polarizing plate" or a "polarizing sheet". . In addition, the "functional film" is a "functional board" and a "functional sheet".

(other adhesive layers)

Further, when the optical adhesive sheet of the invention (V) has another adhesive layer, the other adhesive layer is not particularly limited, and examples thereof include an urethane-based adhesive and an acrylic adhesive. a rubber-based adhesive, a polyoxygen-based adhesive, a polyester-based adhesive, a polyamide-based adhesive, an epoxy-based adhesive, a vinyl alkyl ether-based adhesive, a fluorine-based adhesive, or the like. A conventional adhesive layer formed by an adhesive. These adhesives can be used individually or in combination of 2 or more types.

Further, when the optical adhesive sheet of the invention (V) does not contain a substrate and another adhesive layer, the polymerizable composition of the invention (I) or the polymerizable composition of the invention (II) is polymerized. The polymer layer obtained by the method, when another adhesive layer is contained, polymerizes the polymerizable composition of the invention (I) or the polymerizable composition of the invention (II). a layer in which the obtained polymer layer is combined with the other adhesive layer, and when the substrate is contained, the polymerizable composition of the invention (I) or the polymerizable composition of the invention (II) is polymerized. a layer in which the polymer layer is combined with the substrate, and when the other adhesive layer and the substrate are contained together, the polymerizable composition of the invention (I) or the polymerizable composition of the invention (II) is polymerized. The resulting polymer layer, the other adhesive layer and the layer of the substrate are defined as an "adhesive layer".

(separation plate)

The surface (adhesive surface) of the adhesive layer of the optical adhesive sheet of the present invention (V) can be protected by a separation plate (peeling pad) until use. Furthermore, when the optical adhesive sheet of the present invention is a double-sided adhesive sheet, each of the adhesive faces may be protected by two separate separators, or one of the double-sided release sheets may be wound into a separate sheet. Rolled form protection. The separator is used as a protective material for the adhesive layer, and is peeled off when it is adhered to the object. Further, when the adhesive sheet of the present invention is a substrate-free adhesive sheet, the separation sheet also functions as a support for the adhesive layer. Furthermore, the separation plate does not necessarily need to be set. As the separator, a conventional release paper or the like can be used, and it is not particularly limited, and for example, a substrate having a release treatment layer, a low adhesion substrate composed of a fluoropolymer, or a nonpolar polymer can be used. Low adhesion substrate and the like. The base material having the release treatment layer may, for example, be a plastic film or paper surface-treated with a release treatment agent such as polyfluorene-based, long-chain alkyl-based, fluorine-based or molybdenum sulfide. The fluorine-based polymer which is a low-adhesion substrate composed of the above fluoropolymer is exemplified For example, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, and the like. In addition, examples of the nonpolar polymer include an olefin resin (for example, polyethylene, polypropylene, etc.). Further, the separation plate is formed by a conventional or conventional method. Further, the thickness of the separation plate and the like are also not particularly limited.

The refractive index of the optical adhesive sheet of the invention (V) at 25 ° C is preferably from 1.45 to 1.55, more preferably from 1.48 to 1.52. When the refractive index at 25 ° C is less than 1.45 or greater than 1.55, it is too low in comparison with the refractive index of the acrylic glass such as optical glass or polymethyl methacrylate of the material of the protective portion. The difference in refractive index from the interface between the display portion and the protective portion becomes slightly larger, and scattering and attenuation of image light from the display portion become slightly larger.

Next, the "invention (VI)" will be described.

The invention (VI) is a method of manufacturing a video display device, comprising: a base portion having a video display portion; a translucent protective portion; and an image display device having a polymer layer interposed between the base portion and the protective portion The method of manufacturing the method comprising the steps of: interposing the polymerizable composition of the invention (II) between the base portion and the protective portion; and irradiating the polymerizable composition with photopolymerization The step of sensitizing the light to form a polymer layer.

In addition, the term "between the base portion and the protective portion" as used in the present specification means the meaning of all portions between the base portion having the image display portion and the light-transmitting protective portion, for example, 2 of 5a and Any of 5b is included in the so-called "between the base portion and the protective portion".

Hereinafter, a preferred embodiment of the image display device will be described more specifically with reference to the drawings. In the respective drawings, the same reference numerals denote the same or equivalent constituent elements.

For example, as shown in Fig. 1, Fig. 2, and Fig. 4, there is shown a cross-sectional view of a main portion of an image display device according to an embodiment of the present invention.

As shown in FIG. 1, FIG. 2, and FIG. 4, the display device 1 of the present embodiment includes a video display unit 2 connected to a drive circuit not shown in the drawing, and performs predetermined image display; and transmissive The protection unit 3 is disposed in close proximity to the image display unit 2 at a predetermined distance.

In addition, the "video display device" described in the present specification is not particularly limited as long as it can display an image, and various types can be used. For example, a liquid crystal display device such as a mobile phone or a portable electric amusement instrument, or an organic EL display device can be cited. The video display unit 2 of the present embodiment is a liquid crystal display panel of a liquid crystal display device.

Further, when the image display unit 2 is a liquid crystal display panel, as shown in FIG. 2 or FIG. 4, polarizing plates 6a and 6b are provided on the surface thereof.

As a method of manufacturing the image display device 1 of the present embodiment, for example, first, a spacer 4 and a convex portion not shown in the drawing are provided on a peripheral portion of the image display unit 2, and are dripped in the inner region of the image display unit 2 A polymerizable composition of the present invention (II) in a specified amount.

Then, the protection unit 3 is placed on the spacer 4 of the image display unit (liquid crystal display panel) 2, and the image display unit (liquid crystal display panel) 2 and the security The gap between the protective portions 3 is filled with the polymerizable composition of the present invention (II) without gaps.

After that, the polymerizable component of the present invention (II) is irradiated with light which is sensitive to the component 4 of the essential component of the polymerizable composition of the invention (II), and the polymerizable composition of the invention (II) is formed. Polymerization. Thereby, the intended image display device 1 is obtained.

According to the image display device 1, since the polymer layer 5 and the protective portion 3 have the same refractive index, the luminance or contrast can be improved, and the visibility can be improved.

Furthermore, the step of irradiating the component 4 with light can be used as a light source, such as a low-pressure mercury lamp, 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, or the like, and a general ultraviolet irradiation device can be used. This is carried out using, for example, a conveyor belt type ultraviolet irradiation device. The amount of ultraviolet radiation is generally from about 1000 mJ/cm ² to about 8000 mJ/cm ² .

Further, since the image display unit (liquid crystal display panel) 2 and the protective portion 3 can minimize the influence of the stress caused by the volume contraction during polymerization of the polymerizable composition, the liquid crystal display panel is hardly formed. 2 and the protection unit 3 is distorted. As a result, since the image display unit (liquid crystal display panel) 2 is not deformed, it can be displayed as a high-intensity and high-contrast image without display failure.

Further, in the polymer layer of Fig. 2 or Fig. 4b, when the polymer of the present invention (III) is used, since the dielectric constant of the polymer of the polymer layer of 5b is kept low, even if the polymerization is made The thickness of the object layer is thinned, and the malfunction of the image display device can be prevented, and the image display can be contributed The device is thinned.

Next, the "invention (VII)" will be described.

The invention (VII) is a method of manufacturing an image display device, which is characterized in that the image display device has a step of attaching a base portion of the image display portion and a light-transmitting protective portion using an optical adhesive sheet, and is characterized in that This optical adhesive sheet is the optical adhesive sheet of the invention (V).

In addition, as described in the present specification, "the base portion having the image display portion and the light-transmitting protective portion are adhered using the optical adhesive sheet", regardless of whether it is adhered to the base portion having the image display portion and the light transmittance. Any part between the protective portions is included in the expression "the base portion having the image display portion and the light-transmitting protective portion are adhered using the optical adhesive sheet", for example, whether or not the adhesive sheet is adhered to Any one of 5a or 5b of Fig. 2 is included in the expression "the base portion having the image display portion and the light-transmitting protective portion are adhered using the optical adhesive sheet".

For the purpose of the step of attaching the base portion of the image display portion and the light-transmitting protective portion, the first substrate is a touch sensor integrated protection portion, and the second substrate has a second substrate. The manufacturing steps of the display device of FIG. 5 of the display portion of the polarizing plate will be described as an example.

The step of placing the optical adhesive sheet of the present invention (V) adjacent to the touch sensor mounting surface side of the touch sensor integrated protection portion of the first substrate; The surface of the display portion having the polarizing plate adjacent to the optical adhesive sheet disposed in the (V) of the present invention The step of heating and/or pressurizing the optical adhesive sheet of the present invention (V) to follow the step or the ridge; and further irradiating the optical adhesive sheet of the present invention (V) with a photopolymerization initiator A step of sensitizing light; a method of manufacturing. These steps can be performed in a variety of sequences.

For example, as one specific method, first, the surface of one side of the optical adhesive sheet of the present invention (V) is adjacent to the touch sensor of the touch sensor integrated protection portion of the first substrate. On the mounting surface side, the surface of the display portion having the polarizing plate of the second base material is adjacent to the surface of the other side of the optical adhesive sheet of the present invention (V). In other words, the surface having the step or the bulge is directed to the optical adhesive sheet of the present invention (V), and the touch sensor integrated protection portion (first substrate) and the display portion having the polarizing plate (second substrate) The optical adhesive sheet of the invention (V) is sandwiched.

Next, the optical adhesive sheet of the present invention (V) is heated and/or pressurized to cause the adhesive sheet to follow the step or bulge. After that, the present invention (V) is transmitted through the touch sensor integrated protection portion (first substrate) side and/or the display portion (second substrate) having the polarizing plate as needed. The optical adhesive sheet irradiates the photopolymerizable initiator with sensitized light. In this way, the touch sensor integrated protection portion (first substrate) can be formed without forming a gap in the vicinity of the step or the ridge of the touch sensor integrated protection portion (first substrate). The display portion (second substrate) having a polarizing plate is next. In this embodiment, the touch sensor integrated protection portion (first substrate) and the display portion (second substrate) having the polarizing plate are provided. After the optical adhesive sheet of the invention (V) is adjacent to each other, the adhesive sheet is heated and/or pressurized, so that when the surface of the display portion (second substrate) having the polarizing plate has a step or a bulge (that is, When the adhesive sheet is used on a polarizing plate mounted on the image display module, the adhesive sheet also follows a step or bulge of the display portion (second substrate) having the polarizing plate, thereby preventing the shape from being near the shape A void is formed.

In the above method, when the photopolymerization initiator is irradiated with light, at least one of the first substrate and the second substrate is permeable to the photopolymerization of the optical adhesive sheet of the invention (V). The starting agent is light-sensitive, so that at least part of the substrate is transparent. When the step or the ridge portion of the first substrate is not transparent to ultraviolet rays, when the ultraviolet ray is irradiated from the first substrate side, the ultraviolet ray may not be irradiated directly under the step or the ridge portion, but the portion to be irradiated may be used. The movement of the generated radicals or the like causes a certain degree of polymerization even in the non-irradiated portion of the adhesive sheet.

In another specific method, the surface of one side of the optical adhesive sheet of the present invention (V) is disposed adjacent to the surface side of the touch sensor integrated protection portion (first substrate) having a step or a bulge ( That is, after the touch sensor is mounted on the surface side, the adhesive sheet is heated and/or pressurized to follow the step or bulge. After that, the open surface of the optical adhesive sheet of the present invention (V) is irradiated with ultraviolet rays, and the adhesive sheet is further polymerized, and then the display portion (second substrate) having the polarizing plate is placed adjacent to the adhesive sheet. On the other side, the second substrate is adhered to the adhesive sheet. As long as the release film is transparent, the adhesive sheet may be irradiated with ultraviolet rays through the release film as needed. In this case, because The entire surface of the adhesive sheet can be irradiated with photo-sensitizing light, so that the adhesive sheet can be more uniformly polymerized. The first base material is light-sensitive to light that can be irradiated to the photopolymerization initiator required for the polymerization of the adhesive sheet, and may be irradiated with ultraviolet rays from the first substrate side as long as it is partially transparent. In this manner, the first base material and the second base material can be joined without forming a gap in the vicinity of the step or the bulge of the first base material.

The above heating step can be carried out using a convection oven, a hot plate, a hot press, an autoclave or the like. In order to promote the flow of the adhesive sheet, the adhesive sheet can be more efficiently followed by a step or a bulge to use a hot press, an autoclave or the like, and it is preferable to pressurize while heating. The degassing of the optical adhesive sheet is particularly advantageous by the pressurization of the autoclave. The heating temperature of the optical adhesive sheet of the present invention may be such that the adhesive sheet can be softened or flowed and can sufficiently follow the temperature of the step or the bulge, and is generally about 30 ° C or higher, about 40 ° C or higher, or about 60 ° C or higher. It is below about 150 ° C, below about 120 ° C or may be below about 100 ° C. When the adhesive sheet is pressurized, the pressure to be applied is 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 low-pressure mercury lamp, the medium-pressure mercury lamp, the high-pressure mercury lamp, the ultra-high pressure mercury lamp, the xenon lamp, the metal halide lamp, the electrodeless lamp, etc. may be used as a light source in accordance with the step of irradiating the photopolymerization initiator with the photosensitive light. The ultraviolet irradiation device can be carried out using, for example, a conveyor belt type ultraviolet irradiation device. The amount of ultraviolet radiation is generally from about 1000 mJ/cm ² to about 8000 mJ/cm ² .

Finally, the "present invention (VIII)" will be described.

The invention (VIII) is an image display device manufactured by the method of producing the image display device of the invention (VI) or the invention (VII).

In the image display device of the invention (VIII), when the main body of the display device is formed of optical glass, the refractive index (n _D ) is generally 1.49 to 1.52. Further, there is also a tempered glass having a refractive index (n _D ) of about 1.55.

The protective portion 3 is formed of a light-transmissive member having a plate shape, a sheet shape, or a film shape of the same size as the display portion 2. As the light transmissive member, for example, optical glass or plastic (acrylic resin such as polymethyl methacrylate or the like) 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 protective portion 3.

When the protective portion 3 is formed of an acrylic resin, the 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 a peripheral portion of the display unit 2. The spacer 4 has a thickness of about 0.05 to 1.5 mm, whereby the distance between the image display portion 2 and the surface of the protective portion 3 can be maintained at about 1 mm.

Further, in order to increase the brightness and contrast, a light shielding portion not shown in the frame shape is provided on the peripheral portion of the protection portion 3.

First, an image display device manufactured by the method of manufacturing the image display device of the present invention (VI) will be described in detail.

The polymer layers 5a and 5b are interposed between the image display unit 2 and the protection unit 3 between. In the image display device manufactured by the method for producing an image display device of the invention (VI), since the polymer of the invention (III) is interposed between the polymer layer 5a or the polymer layer 5b, the visible light region is penetrated. The rate is over 90%. Here, the thickness of the polymer layer 5a or the polymer layer 5b is preferably 10 to 2000 μm. More preferably, it is preferably 20 to 1700 μm, and particularly preferably 30 to 1300 μm.

Further, since the polymer of the present invention (III) is a refractive index (n _D ) at 25 ° C in the polymer layer 5 a or the polymer layer 5 b, the refractive index of the image display unit 2 or the protective portion 3 is changed. It is roughly the same, preferably 1.45~1.55, more preferably 1.48~1.52. Thereby, the brightness or contrast of the image light from the image display unit 2 can be improved, and the visibility can be improved.

When the image display device is manufactured by the method for producing an image display device of the invention (VI), since the polymer of the invention (III) is interposed between the polymer layer 5a or the polymer layer 5b, stretching at 23 ° C 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 distortion of the image display portion and the protective portion due to the stress caused by the volume shrinkage of the polymerizable composition at the time of polymerization.

When the image display device is manufactured by the method for producing an image display device of the invention (VI), since the polymer of the invention (III) is interposed between the polymer layer 5a or the polymer layer 5b, the polymerizable composition is polymerized. The volume shrinkage ratio at this time is 4.0% or less, preferably 3.5% or less, more preferably 2.7% or less. Thereby, the internal stress accumulated in the polymer layer during the polymerization of the polymerizable composition can be reduced, and the distortion of the interface between the polymer layer 5a and the touch panel 7 or the protective portion 3 can be prevented, or the polymer layer 5b can be prevented. Distortion occurs at the interface with the touch panel 7, the display portion 2, or the protection portion 3. Therefore, the polymerizable composition is interposed between the touch panel 7 and the protective portion 3, between the touch panel 7 and the display portion 2, or between the display portion 2 and the protective portion 3, and the polymerizable composition is polymerized. In this case, light scattering caused by the interface between the polymer layer 5 and the display unit 2, the protective portion 3, and the touch panel 7 can be reduced, and the brightness of the displayed image can be improved, and the visibility can be improved.

Further, when the polymer of the present invention (III) is used for the polymer layer 5b, since the dielectric constant of the polymers is low, the thickness of the polymer layer 5b can be made thin.

Next, a video display device manufactured by the method of manufacturing the image display device of the present invention (VII) will be described in detail.

The polymer layers 5a and 5b are interposed between the image display unit 2 and the protection unit 3. When the image display device is manufactured by the method of manufacturing the image display device of the invention (VII), since the optical adhesive sheet of the invention (V) is interposed between the polymer layer 5a or the polymer layer 5b, the visible light region is worn. The penetration rate is over 90%. Here, the thickness of the polymer layer 5a or the polymer layer 5b is preferably 10 to 1000 μm. More preferably, it is 20 to 700 μm, and particularly preferably 30 to 500 μm.

Further, since the optical adhesive sheet of the invention (V) is interposed between the polymer layer 5a or the polymer layer 5b, the refractive index (n _D ) at 25 ° C is 1.45 to 1.55, preferably 1.48 to 1.52. Therefore, it is preferable that the refractive index of the image display unit 2 or the protection unit 3 is substantially the same. Thereby, the brightness or contrast of the image light from the image display unit 2 can be improved, and the visibility can be improved.

Further, the system of the image display device of the invention (VII) When the image display device is manufactured by the method of the invention, since the optical adhesive sheet of the invention (V) is interposed between the polymer layer 5a or the polymer layer 5b, the adhesive sheet also follows the step of the image display portion or the protective portion or The bulging prevents the formation of voids near the shapes.

Moreover, since the optical adhesive sheet of the present invention (V) is flexible, even if the protective portion 3, the display portion 2, and the touch panel 7 have an uneven shape, or even the display surface of the image display unit is provided with The layer of the uneven surface shape (for example, a polarizing plate) is also moderated by the internal residual stress of the sheet itself, and the display unevenness of the image display device can be prevented. For example, in the display device of Fig. 4, since the optical adhesive sheet has sufficient adhesiveness and hydrophilicity, the display surface (for example, a polarizing plate) of the image display unit 2 is formed even in a high-temperature and high-humidity environment. The interface between the optical adhesive sheet (ie, the polymer layer 5b) and the interface between the optical adhesive sheet (ie, the polymer layer 5b) and the touch sensor integrated protection portion 3 do not cause bubbles or peeling. In addition, there will be no whitening.

As the optical glass plate used in the image display device of the invention (VIII), a glass plate for holding a liquid crystal of a liquid crystal cell or a user of a protective plate for a liquid crystal cell can be preferably used. Further, as the acrylic resin plate to be used, a user who is a protective sheet for a liquid crystal cell can be preferably used. The average surface roughness of the optical glass sheets or acrylic sheets is usually 1.0 nm or less.

Further, in the image display device of the invention (VIII), the polymer of the invention (III) is filled between the image display unit 2 and the protective portion 3, Or the polymer layer 5 used for the optical adhesive sheet of the invention (V) is strong against impact.

Further, compared with the prior art in which the gap between the image display unit 2 and the protective portion 3 is provided, a thin shape can be formed.

Further, the image display device of the invention (VIII) can take various aspects. For example, as shown in FIG. 3 or FIG. 5, the spacer 4 may be omitted to manufacture the image display device 1. In the case of the polymer layer 5b of Fig. 3, for example, the photopolymerizable composition of the invention (I) or the invention (II) is applied onto the polarizing plate 6a on the display unit 2, and the touch panel 7 is further applied. The photopolymerization is carried out in the same manner as described above; or, for example, the protective portion 3, the polymer layer 5a, the touch panel 7, and the polymer layer 5b (that is, the optical adhesive sheet 5b) are formed. The laminate is obtained by being bonded to the display surface of the image display unit 2 (that is, the surface of the polarizing plate 6a).

Further, in the case of the polymer layer 5b of Fig. 5, for example, the photopolymerizable composition of the invention (I) or the invention (II) is applied onto the polarizing plate 6a on the display unit 2, and then the touch is applied. The sensor-integrated protection portion 3 is superposed thereon and photopolymerized in the same manner as described above; or, for example, the touch sensor integrated protection portion 3 and the polymer layer 5b (that is, the optical adhesive sheet) The laminated body composed of 5b) is obtained by being bonded to the display surface of the image display unit 2 (that is, the surface of the polarizing plate 6a).

Moreover, the present invention can be applied not only to the liquid crystal display device as described above, but also to various flat displays such as an organic EL or a plasma display device.

[Examples]

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the following examples.

<Measurement of viscosity>

The viscosity was measured by the following method.

Using a 1 mL sample, a cone/plate type viscometer (manufactured by Brookfield, Inc., type: DV-II+Pro, rotor type: CPE-42) was used, and the viscosity was determined to be substantially constant at a temperature of 25.0 ° C and a number of revolutions of 5 rpm. value.

<Measurement of hydroxyl number>

The measurement was carried out in accordance with JIS K 0070.

Implementation Synthesis Example 1

In a 500 mL reaction vessel equipped with a stirring device and a distillation apparatus, Pripol (registered trademark) 2033 (hydrogenated dimer diol manufactured by Croda Co., Ltd., hydroxyl group: 202 mgKOH/g), 322.2 g, and dimethyl sebacate (Tokyo Chemicals Co., Ltd.) were charged. Industrial Co., Ltd., 87.5 g, dioctyltin oxide (trade name: DOTO, manufactured by Kitagawa Chemical Co., Ltd.), 0.18 g, gradually evaporates at a temperature of about 170 ° C under normal pressure, and gradually decompresses the ester. Exchange reactions. The total amount of methanol distilled was 24.4 g. A (poly)ester polyol (hereinafter referred to as (poly)ester polyol A) having a hydroxyl value of 58.1 mgKOH/g was obtained.

2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene in a 100 mL reaction vessel equipped with a stirring device, a thermometer, a dropping funnel and a condenser A mixture of diisocyanate (trade name: VESTANAT (registered trademark) TMDI, manufactured by Evonik Degussa Co., Ltd.) 21.89 g, dioctyltin dilaurate 12 mg, and p-methoxyphenol 24 mg were placed in a reaction vessel, and dripped The funnel was dropped into 15.16 g of 4-hydroxybutyl acrylate. In the dropping liquid, the temperature in the reaction vessel was made 70 ° C or lower. After the completion of the dropping, the temperature in the reactor was maintained at 65 to 70 ° C for 2 hours, and stirring was continued to obtain a reaction product (hereinafter referred to as reaction product α).

In a 300 mL reaction vessel equipped with a stirring device, a thermometer, and a condenser, 178.9 g of the above (poly)ester polyol A and Pripol (registered trademark) 2033 (hydrogenated dimer diol manufactured by Croda Co., Ltd., hydroxyl group 202 mgKOH) were charged. /g) 1.1 g, and 12 mg of dioctyltin dilaurate, stirring was started. Thereafter, 33.7 g of the reaction product α having a temperature maintained at 60 ° C was placed in the reaction vessel in portions. In the meantime, the temperature in the reactor was made not higher than 70 °C. Thereafter, the temperature in the reactor was maintained at 65 to 70 ° C and stirring was continued. With IR, it was confirmed that the absorption of the C=O stretching vibration of the isocyanate group disappeared, and the reaction was completed. As a result of analysis by liquid chromatography, it was confirmed that a reaction product of 4-hydroxybutyl acrylate: VESTANAT (registered trademark) TMDI = 2:1 (mole ratio) was present in the product (that is, the following formula ( 12) The mixture with the following formula (13)) was 2% by mass. The reaction product of this 4-hydroxybutyl acrylate: VESTANAT (registered trademark) TMDI = 2:1 (mole ratio) was set as "amino acrylate C" Oleate monomer α". Further, the urethane acrylate monomer 1 is removed from the reaction product by the urethane acrylate monomer 1.

Implementation Synthesis Example 2

Hydrogenated polybutadiene polyol (manufactured by Nippon Soda Co., Ltd., trade name: NISSO-PB GI-2000, hydroxyl value 47.3 mgKOH/g) 540.0 g, acrylic acid n was placed in a 1-liter four-necked flask equipped with a stirrer and a distillation apparatus. 162.0 g of butyl ester, 0.81 g of dioctyltin dilaurate, and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate of pentaerythritol (manufactured by BASF Corporation) Name: IRGANOX 1010) 3.51g, heated to 130 ° C under air flow, and the resulting mixture of n-butanol and n-butyl acrylate is slowly distilled off to the reaction system after about 10 hours while refluxing. . After n-butanol and n-butyl acrylate were not formed, the pressure in the reaction system was reduced to 10 kPa using a vacuum pump, and n-butanol and n-butyl acrylate were again distilled off to Out of line. After maintaining at 50 Pa for about 1.5 hours, the reactor was cooled to obtain a hydrogenated polybutadiene 1 containing an acrylonitrile group.

Implementation Synthesis Example 3

Hydrogenated polybutadiene polyol (manufactured by Nippon Soda Co., Ltd., trade name: NISSO-PB GI-3000, hydroxyl value 29.5 mgKOH/g) 540.0 g, acrylic acid n was placed in a 1-liter four-necked flask equipped with a stirrer and a distillation apparatus. - butyl ester 101 g, dioctyltin dilaurate 0.81 g, and pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name, manufactured by BASF Corporation) : IRGANOX 1010) 3.51 g, heated to 130 ° C under an air flow, and the resulting mixture of n-butanol and n-butyl acrylate was slowly distilled off to the outside of the reaction system while refluxing for about 10 hours. After n-butanol and n-butyl acrylate were not formed, the pressure in the reaction system was reduced to 10 kPa using a vacuum pump, and n-butanol and n-butyl acrylate were again distilled off to the outside of the system. After maintaining at 50 Pa for about 1.5 hours, the reactor was cooled to obtain a hydrogenated polybutadiene 2 containing an acrylonitrile group.

Implementation Synthesis Example 4

Into a one-liter four-necked flask equipped with a stirrer and a distillation apparatus, hydrogenated polyisoprene polyol (trade name: EPOL, hydroxyl value: 49.9) 540.0 g and n-butyl acrylate 162.0 g were charged. 0.81 g of dioctyltin dilaurate and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (manufactured by BASF Corporation, trade name: IRGANOX 1010) 3.51 g, heated to 130 ° C under air flow, The mixed liquid of the produced n-butanol and n-butyl acrylate was slowly distilled off to the outside of the reaction system in about 10 hours while refluxing. After n-butanol and n-butyl acrylate were not formed, the pressure in the reaction system was reduced to 10 kPa using a vacuum pump, and n-butanol and n-butyl acrylate were again distilled off to the outside of the system. After maintaining at 50 Pa for about 1.5 hours, the reactor was cooled to obtain a hydrogenated polyisoprene 1 containing an acrylonitrile group.

Implementation Synthesis Example 5

In a 300 mL liquid separation bottle equipped with a condenser, a dropping funnel, a thermometer, and a stirrer, a polybutadiene containing a hydrogenated terminal hydroxyl group was introduced (hydroxyl price: 47.1 mgKOH/g, trade name: NISSO-PB GI-2000, Japan Soda 180 g of company and 20 mg of dioctyltin dilaurate were used to raise the internal temperature to 50 ° C using an oil bath. Thereafter, 22.86 g of 2-isocyanatoethyl methacrylate (trade name: Karenz MOI, manufactured by Showa Denko Co., Ltd.) was placed, and the dropping was carried out by a dropping funnel for 15 minutes. Between the droppings, the internal temperature should not exceed 70 °C. After the completion of the dropping, the internal temperature was managed at 70 ± 2 ° C and stirring was continued. In the infrared absorption spectrum, since the absorption of the C=O stretching vibration of the isocyanate group was not observed, the stirring was stopped and the reaction was terminated to obtain a hydrogenated polybutadienyl urethane methacrylate 1.

Implementation Synthesis Example 6

In a 1000 mL four-neck round bottom flask equipped with a stirrer, a thermometer, and a rectification column, PRIPOL2033 (98.2% by mass of dimer diol, 0.6% by mass of monohydric alcohol, 1.2% by mass of trimer triol, and hydroxyl group: 200.0 g (202 mg KOH/g), 166.3 g (1.408 mol) of diethyl carbonate (manufactured by Wako Pure Chemical Industries, Ltd.), and 1.617 g (5.04 mmol) of tetra-n-butyl titanate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) were kept. After nitrogen gas flow for 30 minutes, nitrogen supply was stopped, and the oil bath was set to 150 ° C and heated. While the reaction was proceeding, a small amount of ethanol containing diethyl ether was distilled off from the rectification column and taken up in a 300 mL eggplant type flask. The decrease in the distillation rate of ethanol was observed, and the set temperature of the oil bath was slowly increased, and finally the temperature was raised to 200 °C. Thereafter, as the reaction progressed, the inside of a 1000 mL four-neck round bottom flask was slowly decompressed, and finally, the pressure was reduced to 5,333 Pa, and the reaction was carried out for a total of 8 hours. Thereafter, the mass of diethyl carbonate in the obtained ethanol (which contains a small amount of diethyl carbonate) was analyzed by gas chromatography. Thereafter, the distilled carbon dioxide was re-added, and the temperature of the oil bath was set to 190 ° C to carry out the reaction again, and the reaction was continued for 2 hours under normal pressure. In the meantime, the temperature of the oil bath was slowly raised to 200 °C. Thereafter, the inside of a 1000 mL four-neck round bottom flask was slowly reduced again, and finally, the pressure was reduced to 5,333 Pa, and a total of 12 hours of reaction was started from the reaction. After completion of the reaction, a pale yellow viscous liquid (hereinafter referred to as (poly)carbonate polyol A) was obtained in a 1000 mL four-neck round bottom flask. The hydroxyl value of the (poly)carbonate polyol A was 58.9 mgKOH/g.

2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene in a 100 mL reaction vessel equipped with a stirring device, a thermometer, a dropping funnel and a condenser Mixture of diisocyanate (trade name: VESTANAT (registered trademark) TMDI, Evonik Degussa 21.89 g, 12 mg of dioctyltin dilaurate, and 24 mg of p-methoxyphenol were placed in a reaction vessel, and 15.16 g of 4-hydroxybutyl acrylate was added dropwise with a dropping funnel. In the dropping liquid, the temperature in the reaction vessel was made 70 ° C or lower. After the completion of the dropping, the temperature in the reactor was maintained at 65 to 70 ° C for 2 hours, and stirring was continued to obtain a reaction product (hereinafter referred to as reaction product β).

In a 300 mL reaction vessel equipped with a stirring device, a thermometer, and a condenser, the above-mentioned (poly)carbonate polyol A 178.9 g and Pripol (registered trademark) 2033 (hydrogenated dimer diol manufactured by Croda Co., Ltd.) were charged. 202 mg of KOH/g) and 12 mg of dioctyltin dilaurate were started to stir. Thereafter, 33.7 g of the reaction product β having a temperature maintained at 60 ° C was placed in the reaction vessel in portions. In the meantime, the temperature in the reactor was made not higher than 70 °C. Thereafter, the temperature in the reactor was maintained at 65 to 70 ° C and stirring was continued. With IR, it was confirmed that the absorption of the C=O stretching vibration of the isocyanate group disappeared, and the reaction was completed. As a result of analysis by liquid chromatography, it was confirmed that 4-hydroxybutyl acrylate: VESTANAT (registered trademark) TMDI = 2:1 (mole ratio) reaction product was present in the product (that is, formula (12) The mixture with the formula (13) was 2% by mass. The reaction product of the 4-hydroxybutyl acrylate: VESTANAT (registered trademark) TMDI = 2:1 (mole ratio) was referred to as "urethane acrylate monomer α". Further, the urethane acrylate monomer 2 is removed from the reaction product by the urethane acrylate monomer 2.

(Implementing blending example 1)

55.0 parts by mass of the above-mentioned hydrogenated polyisoprene containing acrylonitrile group, isodecyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: ISTA), 40.0 parts by mass, N-vinyl-2-pyrrolidine 5.0 parts by mass of ketone, 0.8 parts by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Corporation, trade name: Irgacure 184), and 2,4,6-trimethylbenzhydryldiphenylphosphine oxide (Lambson Corporation) The product name: SpeedCure TPO) is 0.4 parts by mass, and is mixed using a self-rotating ‧ revolution mixer (manufactured by Thinky, trade name: defoaming chain Taro ARE-310). This mixture was made into the polymerizable composition A1. The viscosity of the polymerizable composition A1 at 25 ° C was 4,400 mPa·s.

(Implementing blending example 2 to implementing blending example 10 and comparing blending example 1 to comparing blending example 2)

The blending compositions shown in Table 1 were blended in the same manner as in the blending example 1. The blends prepared in the blending examples 2 to 10 were each a polymerizable composition A2 to a polymerizable composition A10, and the blends prepared by the comparative blending example 1 and the comparative blending example 2 were each polymerized. The composition B1 and the polymerizable composition B2.

*1 urethane acrylate violet UV-3000B (polyester urethane acrylate, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)

*2 Kuraprene UC-203 (an ester of maleic anhydride adduct of polyisoprene polymer and 2-hydroxyethyl methacrylate, manufactured by Kuraray)

*3 Isodecyl acrylate (product name: IBXA, Osaka Organic Chemical Industry Co., Ltd.)

*4 Dicyclopentenyloxyethyl methacrylate (trade name: FA-512M, manufactured by Hitachi Chemical Co., Ltd.)

*5 Lauryl acrylate (trade name: BLEMMER LA, Nippon Oil Co., Ltd.)

*6 Isooctyl acrylate (product name: ISTA, Osaka Organic Chemical Industry Co., Ltd.)

*7 N,N-Dimethyl acrylamide (trade name: DEAA, (share) Xingren system)

*8 N-Propyl Mercaptomorpholine (trade name: ACMO, (share) Xingren system)

※9 N-vinyl-2-pyrrolidone (made by Japan Catalyst)

*10 2-Hydroxypropyl methacrylate (trade name: HPMA, manufactured by Mitsubishi Rayon Co., Ltd.)

*11 4-Hydroxybutyl acrylate (trade name: 4HBA, Osaka Organic Chemical Industry Co., Ltd.)

※12 2-Hydroxybutyl methacrylate (trade name: Lightester HOB(N), Co., Ltd. Chemical Co., Ltd.)

*13 Terpene-based hydrogenated resin CLEARON (registered trademark) P85 (Akabara Chemical Co., Ltd.)

*14 Terpene hydrogenated resin CLEARON (registered trademark) K100 (Ahara Chemical Co., Ltd.)

*15 Terpene-based hydrogenated resin CLEARON (registered trademark) M105 (Akabara Chemical Co., Ltd.)

*16 Hydrogenated polybutadiene polyol NISSO-PB GI-1000 (made by Japan Soda Co., Ltd.)

*17 Hydrogenated polybutadiene NISSO-PB BI-2000 (made by Japan Soda Co., Ltd.)

*18 Poly (α-olefin) liquid Spectrasyn40 (made by Exxon Mobil Co., Ltd.)

*19 Liquid polybutene HV-15 (JX Nissan Nikko ENERGY Co., Ltd.)

*20 Liquid polybutene HV-35 (JX Nissan Nikko ENERGY Co., Ltd.)

*21 Liquid polybutadiene POLYVEST 110 (manufactured by Evonik Degussa)

*22 IRGANOX 1010 (Compound name: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF)

*23 Photopolymerization initiator SpeedCure TPO (Compound name: 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, manufactured by Lambson)

*24 Photopolymerization initiator IRGACURE 184 (Compound name: 1-hydroxycyclohexyl phenyl ketone, manufactured by BASF)

<Manufacture of optical adhesive sheets>

Each of the polymerizable composition A1 to the polymerizable composition A10, the polymerizable composition B1, and the polymerizable composition B2 shown in Table 1 was applied to a polysiloxane by using an applicator to have a film thickness of 200 μm. A coated polyethylene terephthalate (hereinafter referred to as PET) film (100 mm × 100 mm × 50 μm) was coated with a PET film having a coating thickness of 25 μm, and then conveyed using a metal halide lamp. A belt type ultraviolet irradiation device (manufactured by GS YUASA LIGHTING, trade name: GSN2-40), a PET film coated with a polyoxynitride coating, with an irradiation intensity of 190 mW/cm ² (value of 365 nm) and an irradiation amount of 2800 mJ/ Under the conditions of cm ² (value of 365 nm), the polymerizable composition was polymerized by irradiation with ultraviolet rays, and an optical adhesive sheet having a film thickness of about 200 μm sandwiched between the release PET films was obtained. The optical adhesive sheet produced by using the polymerizable composition A1 to the polymerizable composition A10, the polymerizable composition B1, and the polymerizable composition B2 is used as the adhesive sheet A1 to the adhesive sheet A10, the adhesive sheet B1, and the adhesive sheet, respectively. Sheet B2.

<Method for Producing Test Piece Using the Adhesive Sheet, and Evaluation of Initial Optical Characteristics>

The adhesive sheet A1 to the adhesive sheet A10, the adhesive sheet B1, and the adhesive sheet B2 are respectively made of two glass sheets (50 mm × 50 mm × 0.7 mm, glass type) so that bubbles do not enter the interface: EAGLE XG (registered trademark), manufactured by CORNING) A double-bread sheet of the adhesive sheet was adhered to two sheets of glass sheets to form a test piece.

The test pieces prepared by using the adhesive sheet A1 to the adhesive sheet A10, the adhesive sheet B1, and the adhesive sheet B2 were set as test pieces AS1 to AS10, test pieces BS1, and test pieces BS2, respectively. The total light transmittance and b* of the test pieces were measured by the method described later. The results are shown in Table 3.

<Method for producing test piece and evaluation of initial optical characteristics>

Each of the polymerizable composition A3 to the polymerizable composition A10, the polymerizable composition B1, and the polymerizable composition B2 was applied to a glass plate (50 mm × by using a bar coater to have a film thickness of 200 μm). 50mm × 0.7mm, the type of glass: EAGLE XG (registered trademark), manufactured by CORNING), and the same type of glass plate is used to transport the belt type ultraviolet irradiation device using metal halide lamps ((GS) GS YUASA LIGHTING, trade name: GSN2-40), irradiated with ultraviolet rays through a glass plate under the conditions of an irradiation intensity of 190 mW/cm ² (a value of 365 nm) and an irradiation amount of 2800 mJ/cm ² (a value of 365 nm) to form a polymerizable composition. Polymerization was carried out to obtain a polymer film for evaluation test having a film thickness of about 200 μm sandwiched between glass plates. The polymer film for evaluation test which is formed by using the polymerizable compositions A3 to A10, the polymerizable composition B1, and the polymerizable composition B2 and having a thickness of about 200 μm between the glass plates is used as a test piece AL3. ~ Test piece AL10, test piece BL1 and test piece BL2. The total light transmittance and b* of the test pieces were measured by the method described later. The results are shown in Table 3.

<Measurement of total light transmittance>

A test piece AS1 to test piece AS10, test piece AL3 to test piece AL10, and test piece were used as a reference material using a single glass plate (product name of 50 mm × 50 mm × 0.7 mm glass: EAGLE XG (registered trademark) CORNING). The total light transmittance of the sheet BS1, the test piece BS2, the test piece BL1, and the test piece BL2 was measured in accordance with JIS K 7361-1. The results are shown in Table 3.

<b ^* determination>

A test piece AS1 to test piece AS10, test piece AL3 to test piece AL10, and test piece were used as a reference material using a single glass plate (product name of 50 mm × 50 mm × 0.7 mm glass: EAGLE XG (registered trademark) CORNING). The b* of the sheet BS1, the test piece BS2, the test piece BL1, and the test piece BL2 is measured in accordance with JIS Z 8729. The results are shown in Table 3.

<Measurement of haze>

One piece of glass plate (product name: EAGLE XG (registered trademark) CORNING, 50 mm × 50 mm × 0.7 mm glass) was used as a reference, and the test piece AS1 to test piece AS10, test piece AL3 to test piece AL10, test The haze of the sheet BS1, the test piece BS2, the test piece BL1, and the test piece BL2 was measured in accordance with JIS K 7136. The results are shown in Table 3.

<Measurement of Dielectric Constant>

Two sheets of a PET film having a polyoxynitride coating layer were used, and the polymerizable composition A1 to the polymerizable composition A10, the polymerizable composition B1, and the polymerizable composition B2 were used to have a thickness of 1.2 mm. The package is made of a PET film of a polyfluorene-coated epoxy film by a conveyor belt type ultraviolet irradiation device (manufactured by GS YUASA LIGHTING, trade name: GSN2-40) using a metal halide lamp, and has an irradiation intensity of 190 mW/cm ^{2 .} (A value of 365 nm) and an irradiation amount of 2,800 mJ/cm ² (a value of 365 nm), an ultraviolet ray was irradiated, and the polymerizable composition was polymerized to obtain an evaluation test of a film thickness of about 2 mm sandwiched between PET films of a polyfluorene oxide coating. A polymer film is used. The polymer film was peeled off from the PET film of the polyoxynitride coating, and the dielectric constant of the polymer film was measured using an impedance analyzer (manufactured by Agilent Technologies, trade name: 4294A precision impedance analyzer 40 Hz - 110 MHz). The results are shown in Table 2.

Further, a polymer obtained by polymerizing the polymerizable composition A1 to the polymerizable composition A10, the polymerizable composition B1, and the polymerizable composition B2, and having a thickness of 2 mm after peeling off the PET film of the polyfluorene oxide coating layer The film was designated as a polymer film A1 to a polymer film A10, a polymer film B1, and a polymer film B2, respectively.

<Measurement of volume shrinkage rate during polymerization>

The polymerizable compositions A1 to A10, the polymerizable composition B1, and the polymerizable composition B2 before polymerization, and the density of the polymer after the polymerization were subjected to an automatic hydrometer (type: DMA-220H, new photoelectron ( ))), measured at a temperature of 23 ° C, from the following formula to determine the polymerization Volume shrinkage.

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>

The polymer film A1 to polymer film A10, the polymer film B1, and the polymer film B2 were measured in accordance with JIS K 7105. The results are shown in Table 2.

<Measurement of Tensile Elastic Modulus>

The polymer film A1 to the polymer film A10, the polymer film B1, and the polymer film B2 were each fixed to a tensile tester (EZ Test/CE, manufactured by Shimadzu Corporation), and stretched at 23 ° C. The test was carried out at a speed of 500 mm/min to obtain a tensile modulus of elasticity. The results are shown in Table 2.

<Adhesion to glass>

The glass surface (double-sided) on the outer side of the test piece AS1~ test piece AS10, test piece AL3~ test piece AL10, test piece BS1, test piece BS2, test piece BL1 and test piece BL2, respectively, can be subjected to a tensile test Using a double-sided tape to attach the plastic jig to the clip of the machine (made by Shimadzu Corporation, EZ Test/CE). After that, two sheets of glass with a polymer film adhered to a plastic jig were attached to a tensile tester (EZ Test/CE, manufactured by Shimadzu Corporation), and the double-sided glass was peeled off at a speed of 500 mm/min. The direction is stretched to evaluate the adhesion to the glass. The results are shown in Table 4.

<Measurement of total light transmittance, b* value, and haze when stored under high temperature conditions>

The test pieces AS1 to AS10, the test piece AL3 to the test piece AL10, the test piece BS1, the test piece BS2, the test piece BL1, and the test piece BL2 are placed in a thermostat at 70 ° C and 85 ° C, respectively. After the hour, the total light transmittance, the b* value, and the haze were measured by the methods described above. The results are shown in Table 3.

<Measurement of total light transmittance, b* value, and haze when stored under high temperature and high humidity conditions>

The test piece AS1~ test piece AS10, the test piece AL3~ test piece AL10, the test piece BS1, the test piece BS2, the test piece BL1 and the test piece BL2 are respectively placed in a constant temperature and humidity machine having a temperature of 60 ° C and a humidity of 90% RH. In the test piece after 500 hours, the total light transmittance, the b* value, and the haze were measured by the methods described above. The results are shown in Table 3.

7 It can be seen from the results of Table 2, Table 3, and Table 4 that the polymer obtained by polymerizing the polymerizable composition of the present invention (I) has high adhesion to glass even under high temperature conditions. When it is stored for a long period of time, it is also less likely to cause a change in the appearance of coloring or the like, and good light transmittance can be maintained.

Further, the polymerizable composition of the invention (II) has a low volume shrinkage ratio during polymerization, and the polymer obtained by polymerizing the polymerizable composition of the invention (II) is stored for a long period of time even under high temperature conditions. At the same time, it is also less likely to cause a change in the appearance of coloring or the like, and good light transmittance can be maintained.

[Industry Utilization]

As described above, the polymer film obtained by polymerizing the polymerizable composition of the invention (I) has high adhesion to glass, and it is less likely to cause coloring or the like even when stored under a high temperature for a long period of time. A change in appearance maintains good light penetration. Moreover, the volume shrinkage rate at the time of polymerization of the polymerizable composition of the invention (II) is low, and the polymer film obtained by polymerizing the polymerizable composition of the invention (II) is long under a high temperature condition. When it is preserved, it is also less likely to cause a change in the appearance of coloring or the like, 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 of the image display device and the light-transmitting protective portion, a good optical adhesive layer can be provided.

That is, the polymer is suitable for use in an image display device.

Claims (13)

A polymerizable composition for forming a polymerizable layer of a polymer layer, wherein the polymer layer is interposed between an image display portion of a video display device and a translucent protective portion, and is characterized in that The polymerizable composition contains the following (component 1) to (component 4) and further (component 5), and (component 1) is selected from the group consisting of a compound containing a (meth)acryl fluorenyl group having a polyolefin structural unit, and having (meth)acryloyl group-containing compound having a (poly)ester structural unit, and (poly)carbonate structural unit containing (poly)carbonate structural unit (methyl) At least one of a group consisting of a compound of an acrylonitrile group; (Component 2): a (meth) acrylate compound having a hydrocarbon group having 6 or more carbon atoms; (Component 3): a compound containing a vinyl group having a guanamine bond (Component 4): photopolymerization initiator; (Component 5): no (meth) acrylonitrile group in the molecule, no function of inhibiting radical polymerization, function of inhibiting radical polymerization, and photopolymerization Any of the functions of the sexual initiation function, and is composed of carbon atoms and hydrogen atoms. Or a compound consisting of a carbon atom, a hydrogen atom, and an oxygen atom at 25 ° C in a liquid or solid form, and the compound which is liquid at 25 ° C is selected from the group consisting of poly(α-olefin) liquid and ethylene. - propylene copolymerization liquid, propylene-α-olefin copolymerization liquid, ethylene-α-olefin copolymerization liquid, liquid polybutene, liquid hydrogen Polybutene, liquid polybutadiene, liquid hydrogenated polybutadiene, liquid polyisoprene, liquid hydrogenated polyisoprene, liquid polybutadiene polyol, liquid hydrogenated poly At least one of a group consisting of a butadiene polyol, a liquid polyisoprene polyol, a liquid hydrogenated polyisoprene polyol, and a hydrogenated dimer diol, which is solid at 25 ° C The compound is selected from the group consisting of an epoxy resin which is solid at 25 ° C, a polyester resin which is solid at 25 ° C, a polyol resin which is solid at 25 ° C, a hydrogenated petroleum resin, a terpene-based hydrogenated resin, and a hydrogenated rosin ester. At least one of the groups is a combination of a compound which is liquid at 25 ° C and a compound which is solid at 25 ° C in a mass ratio of 90:10 to 10:90. The polymerizable composition of claim 1, which further comprises the following (ingredient 6), (ingredient 6): a (meth) acrylate having an alcoholic hydroxyl group. The polymerizable composition according to claim 1 or 2, wherein the (meth)acryl fluorenyl group-containing compound having a polyolefin structural unit has a polybutadiene structural unit and/or a polyisoprene structural unit. A compound containing a (meth) acrylonitrile group. The polymerizable composition of claim 1 or 2, wherein the (meth) acrylonitrile-containing compound having a hydrogenated polyolefin structural unit has a hydrogenated polybutadiene structural unit and/or a hydrogenated polyisoprene. A compound containing a (meth) acrylonitrile group in a structural unit. The polymerizable composition of claim 1 or 2, wherein the compound having a (poly)ester structural unit containing a (meth)acrylinyl group is A (meth)acrylonitrile group-containing compound having a structural unit derived from a (poly)ester polyol, wherein the (poly)ester polyol is produced using a polyol having 10 or more carbon atoms as a raw material. The polymerizable composition of claim 1 or 2, wherein the (meth)acryl fluorenyl group-containing compound having a (poly)carbonate structural unit has a structural unit derived from a (poly)carbonate polyol. The (meth)acrylonitrile group-containing compound is produced by using a polyhydric alcohol having 10 or more carbon atoms as a raw material. A polymer obtained by polymerizing the polymerizable composition according to any one of claims 1 to 6. A polymerizable composition for producing a polymerizable composition for an optical adhesive sheet, which is an polymerization between an image display portion and a light-transmitting protective portion which are interposed between an image display device The layered user is characterized in that the polymerizable composition is a polymerizable composition according to any one of claims 1 to 6. An optical adhesive sheet having a polymer layer having a thickness of 10 to 1000 μm, which is coated with a polymerizable composition as claimed in claim 8, and which is sensitized by irradiating the polymerizable composition with a photopolymerization initiator The light and the polymerization of it. A method of manufacturing an image display device, comprising: a base portion having a video display portion, a translucent protective portion, and a method of manufacturing an image display device interposed between the base portion and the protective portion; The method comprises the steps of: interposing the polymerizable composition according to any one of claims 1 to 6 in the foregoing a step between the base and the protective portion; and a step of irradiating the polymerizable composition with light sensitizable to the photopolymerization initiator to form a polymer layer. A method of manufacturing an image display device, comprising: a method of manufacturing an image display device having a step of bonding a base portion of a video display portion and a translucent protective portion using an optical adhesive sheet, wherein the optical adhesive sheet is used It is an optical adhesive sheet as claimed in claim 9. An image display device manufactured by the method of manufacturing an image display device according to claim 10 or 11. The image display device of claim 12, wherein the image display portion is a liquid crystal display panel.