KR20150029535A - Method for manufacturing image display device and image display device manufactured by the manufacturing method - Google Patents

Abstract

The present invention provides a method for manufacturing an image display device and an image display device manufactured by the same. The present invention provides the method for manufacturing the image display device which polymerization composition is disposed between a base part having an image display part and a transparent protection part, between the base part having the image display part and a transparent touch sensor part, or between the transparent touch sensor part and the transparent protection part of a resin material, and polymerizes the polymerization composition by irradiating a light. The present invention hardens the polymerization composition even if the light is irradiated among the transparent protection part of the resin material, a touch sensor having the protection film of the resin material, or the base part having the image display unit. The present invention increases the adhesion of the protection film of the resin material or the transparent protection part of the resin material and the hardened polymerization composition. The present invention includes a composition having acrylyl and a polymerization initiator having an adsorption wavelength in a visible ray area of 380-780 nm, and uses the polymerization composition of which viscosity at 25 °C is 500-50000mPa·s.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing an image display apparatus and an image display apparatus manufactured by the method.

The present invention relates to a method of manufacturing an image display apparatus such as a liquid crystal display apparatus used for a smart phone or a tablet PC, and an image display apparatus manufactured by the method.

Conventionally, as this type of image display apparatus, for example, a liquid crystal display apparatus 101 shown in Fig. 9 is known.

As shown in Fig. 9, the liquid crystal display device 101 has a transparent protective portion 103 made of, for example, glass or plastic on the liquid crystal display panel 102. [

In this case, in order to protect the surface of the liquid crystal display panel 102 and the polarizing plate (not shown), a spacer 104 is interposed between the protective portion 103 and the liquid crystal display panel 102 and the protective portion 103 And an air gap 105 is formed.

However, due to the presence of the air gap 105 between the liquid crystal display panel 102 and the protective portion 103, light scattering occurs, resulting in deterioration of contrast and brightness. In addition, It is becoming an obstacle.

In view of such a problem, there has also been proposed to fill a gap between a liquid crystal display panel and a protective portion with resin (see FIG. 1) (see, for example, Patent Document 1).

In recent years, smart phones have become mainstream in mobile phones, and devices called tablet PCs are rapidly spreading. Such a device is generally equipped with a capacitive touch panel. As an example of a capacitive touch panel, a polymer (layer) (FIG. 2 and FIG. 3) filled between a touch sensor 7 and a protective portion 3 in an outsell-type capacitive touch panel- (A polymeric substance (layer) of 5a described in Fig. 3), a polymeric substance (layer (a polymeric substance (layer) of 5b shown in Figs. 2 and 3) filled between the display portion 2 and the touch sensor 7, (A polymer (layer) of 5b shown in Fig. 4 and Fig. 5) filled in between the display portion 2 of the integrated type capacitive touch panel type display device and the protective portion 3 integrated with a touch center, (The polymer (layer) of 5a shown in Fig. 6) filled between the display portion 2 having the touch center on the surface of the capacitive touch-screen type touch panel and the protective portion 3 and the in- A display unit (2) having a touch center on a touch panel type display device, Polymer (layer) that is filled between the protection unit (3), and the (polymer (layers) in FIG. 7 and 5a shown in Fig. 8).

Methods for producing these polymers (layers) are roughly divided into, for example, as described in Patent Document 2, such as a touch sensor and a protection unit in an outsell-type capacitive touch panel mounted display device, a display unit and a touch sensor, A touch panel type touch panel display device comprising a display unit and a touch center integrated type protective unit, an on-cell type capacitive touch panel type display device, a display unit having a touch center on a surface thereof, A method of manufacturing an image display device having a step of irradiating ultraviolet rays through a polymerizable composition between a display portion having a touch center on a surface of a panel mounted display device and a protective portion and polymerizing the polymerizable composition to form a polymeric layer , A touch sensor in an out-cell type capacitive touch panel mounted display device Between the display panel and the touch sensor, between the display part and the touch sensor, between the display part of the touchscreen-integrated touchscreen-integrated display device and the touchscreen-integrated protection device, and the touch- A step of bonding the display portion having the touch center on the surface of the in-cell type electrostatic capacity type touch panel mounted display device with the protective portion and the protective portion using the optical adhesive sheet as described in Patent Document 3 And a manufacturing method of the image display device.

In the former method, a polymerizable composition is interposed between a base portion having an image display portion and a translucent protection portion, between a base portion having an image display portion and a translucent touch sensor portion, or between a translucent touch sensor portion and a translucent protection portion, And a step of irradiating light to the entire surface of the light-transmitting protective portion and / or the light-transmitting touch sensor portion using an exposing machine to form a polymeric layer by polymerizing the polymerizable composition to obtain an image display device .

In recent years, in order to improve the cost, weight, and impact resistance of the image display apparatus, it has been proposed to use a resin plate such as a laminate of polymethyl methacrylate or polymethyl methacrylate and polycarbonate Is under review. Further, on the surface of the touch sensor, a cyclic polyolefin resin such as cycloolefin polymer or a polyester resin such as polyethylene terephthalate may be used as a protective film, and a polarizing plate on the upper part of the display may be made of a cellulose resin such as triacetyl cellulose or a cycloolefin polymer, Polymethyl methacrylate or the like may be used as a protective film. These resin plates and protective films are often given ultraviolet ray absorbing ability from the viewpoint of ultraviolet ray protection. Therefore, when bonding the base portion having the image display portion and the resin plate, ultraviolet rays are irradiated over the resin plate or over the resin plate after the ultraviolet cut filter. Or a halogen lamp having a wavelength in the infrared region from the visible light or an LED lamp in the visible light region. When the conventional technique is used, the above-mentioned irradiation method does not sufficiently cure, and the adhesion is insufficient, so there is a possibility that a blister (foaming peeling) may occur during use under high temperature and high humidity.

Japanese Patent Application Laid-Open No. 2005-55641 Japanese Patent Application Laid-Open No. 2009-186958 Japanese Patent Application Laid-Open No. 233060/1987

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described problems of the prior art, and it is an object of the present invention to provide an image display device which can be cured by using a resin plate instead of glass, It is another object of the present invention to provide a novel method for manufacturing an image display device having good adhesion to a protective film.

Another object of the present invention is to provide an image display device manufactured by the method of manufacturing the image display device.

As a result of intensive studies to solve the above-described problems, the inventors of the present invention have found that, between the base portion having the image display portion and the translucent protection portion made of resin, between the base portion having the image display portion and the translucent touch sensor portion having the protective film made of resin, A photopolymerizable composition which is adaptable when a polymerizable composition is interposed between at least one selected from the group consisting of a translucent touch sensor part having a protective film and a transparent protective part made of resin and a specific compound as an electrophotopolymerizable composition It is possible to cure even when light is irradiated beyond a base having a touch sensor having a light-transmitting protective portion made of resin or a protective film made of resin or an image display portion by using the resin, and also to provide a resin- It is possible to provide a manufacturing method of a display device and to complete the present invention It came.

That is, the present invention (I)

A manufacturing method of an image display apparatus having a base portion having an image display unit or an image display portion having a base portion having an image display portion and a light transmissive protection portion made of resin, and a translucent touch sensor portion having a translucent protective portion made of resin and a protective film made of resin,

That way,

Between the base having the image display portion and the translucent protection portion made of resin, between the base portion having the image display portion and the translucent touch sensor portion having the resin protective film, and between the translucent touch sensor portion having the protective film made of resin and the translucent protection portion A step of interposing the polymerizable composition in at least one place selected from the group consisting of

And a step of polymerizing the polymerizable composition by irradiating light with at least one light-transmitting portion selected from a light-transmitting touch sensor portion having a resin-made light-transmitting protective portion and a resin-made protective film therebetween,

The polymerizable composition may contain,

(Component 1) a compound having a (meth) acryloyl group, and

(Component 2) A photopolymerization initiator having an absorption wavelength in a visible light region of 380 to 780 nm,

Wherein the polymerizable composition has a viscosity at 25 캜 of 500 to 50000 mPa..

The present invention (II) relates to an image display apparatus which can be manufactured by the image display apparatus manufacturing method of the present invention (I).

More specifically, the present invention relates to the following [1] to [14].

[1] An image display apparatus having a base portion having an image display device or an image display portion having a base having an image display portion and a light-transmissive protection portion made of resin, a translucent protection portion made of resin, and a translucent touch sensor portion having a resin- As a production method,

That way,

Between the base having the image display portion and the translucent protection portion made of resin, between the base portion having the image display portion and the translucent touch sensor portion having the resin protective film, and between the translucent touch sensor portion having the protective film made of resin and the translucent protection portion A step of interposing the polymerizable composition in at least one place selected from the group consisting of

And a step of polymerizing the polymerizable composition by irradiating light over at least one light-transmissive portion selected from a translucent touch sensor portion having a translucent protective portion made of resin and a protective film made of resin,

The polymerizable composition may contain,

(Component 1) a compound having a (meth) acryloyl group, and

(Component 2) A photopolymerization initiator having an absorption wavelength in a visible light region of 380 to 780 nm,

Wherein the polymerizable composition has a viscosity at 25 占 폚 of 500 to 50000 mPa 占 퐏.

[2] The method according to [1]

Wherein the protective film of the translucent protective part or the touch sensor is made of at least one selected from the group consisting of polymethyl methacrylate, polycarbonate, cycloolefin polymer, cellulose and polyester.

[3] The method according to [1] or [2]

The photopolymerization initiator may be at least one selected from the group consisting of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 2,4,6-trimethylbenzoyldiphenylphosphorus Wherein the metal oxide is at least one selected from the group consisting of titanium oxide and titanium oxide.

[4] The method according to any one of [1] to [3]

In the step of polymerizing the polymerizable composition by irradiating light over at least one light-transmissive portion selected from a resin-made light-transmitting protective portion and a resin-made protective film, the amount of light to be irradiated is the ultraviolet light amount Wherein the value of the integrated light amount measured by using the system is 1000 to 10000 mJ / cm < 2 >.

[5] The method according to any one of [1] to [4]

Component 1 comprises a (meth) acryloyl group-containing polymer compound having a number average molecular weight of 1,000 to 40,000 and a (meth) acryloyl group-containing compound having a molecular weight of 500 or less.

[6] The method according to [5]

Wherein the (meth) acryloyl group-containing polymer having a number average molecular weight of 1000 to 40000 is urethane (meth) acrylate.

[7] The method according to [6]

Wherein the urethane (meth) acrylate is a polyester polyol obtained by an ester exchange reaction between a hydrogenated dimer diol and a diester.

[8] The method according to any one of [5] to [7]

The (meth) acryloyl group-containing compound having a molecular weight of 500 or less,

A (meth) acrylate having a hydrocarbon group having 8 to 18 carbon atoms and (meth) acrylate having an ether bond, and

A (meth) acrylamide-based compound and an alcoholic hydroxyl group-containing (meth) acrylate.

[9] The method according to any one of [1] to [8]

The polymerizable composition may contain,

(Component 3) The method for manufacturing an image display apparatus according to claim 1, further comprising a compound composed of only carbon atoms and hydrogen atoms, or a compound composed only of carbon atoms, hydrogen atoms and oxygen atoms, and having no ethylenic double bond.

[10] The method according to [9]

Component 3,

A compound which is liquid at 25 占 폚 and a compound which is solid at 25 占 폚.

[11] The method according to [10]

Component 3 comprises a compound which is liquid at 25 < 0 > C,

The compound, which is liquid at 25 DEG C,

A liquid polybutene, a liquid polybutadiene, a liquid polybutadiene, a liquid polybutadiene, a liquid polybutadiene, a liquid polybutadiene, a liquid polybutadiene, a liquid polybutadiene, a liquid polybutadiene, And at least one compound selected from the group consisting of liquid hydrogenated polybutadiene, liquid polyisoprene, liquid hydrogenated polyisoprene, liquid polybutadiene polyol, liquid hydrogenated polybutadiene polyol, liquid polyisoprene polyol and liquid hydrogenated polyisoprene polyol Wherein said method comprises the steps of:

[12] The method according to [10]

Component 3 comprises a compound which is liquid at 25 < 0 > C,

The compound, which is liquid at 25 DEG C,

Wherein at least one compound selected from the group consisting of a polyether polyol, a polyester polyol and a polycarbonate polyol is contained.

[13] The method according to [10]

Component 3 comprises a compound which is liquid at 25 < 0 > C,

The compound which is in a liquid state at 25 占 폚 may be a liquid poly (? -Olefin) liquid, an ethylene-propylene copolymer liquid, an ethylene-? -Olefin copolymer liquid, a propylene-? -Olefin copolymer liquid, A liquid hydrogenated polybutene, a liquid hydrogenated polybutene, a liquid hydrogenated polybutadiene, a liquid hydrogenated polyisoprene, a liquid hydrogenated polybutadiene polyol, and a liquid hydrogenated polyisoprene polyol.

[14] The method according to [10]

Component 3 comprises a compound which is solid at 25 < 0 > C,

Wherein the compound which is solid at 25 占 폚 comprises at least one compound selected from the group consisting of a hydrogenated petroleum resin, a terpene-based hydrogenated resin and a hydrogenated rosin ester.

[15] An image display apparatus capable of being manufactured by the method for manufacturing an image display apparatus according to any one of [1] to [14].

(Effects of the Invention)

According to the manufacturing method of an image display apparatus of the present invention, even when a light is irradiated onto a base having a translucent protective portion made of resin, a touch sensor having a resin protective film, or an image display portion, the polymerizable composition can be cured, It is possible to manufacture an image display device having good adhesion between the polymerizable composition and the transparent protective portion of resin or the resin protective film.

1 is a cross-sectional view showing a main portion of an image display apparatus according to a first embodiment of the present invention.
2 is a cross-sectional view showing a main part of a second embodiment of the image display apparatus.
3 is a cross-sectional view showing the main part of the image display apparatus according to the third embodiment.
4 is a cross-sectional view showing the main part of the image display apparatus according to the fourth embodiment.
5 is a cross-sectional view showing the main part of the image display apparatus according to the fifth embodiment.
6 is a cross-sectional view showing the main part of the image display apparatus according to the sixth embodiment.
7 is a cross-sectional view showing the main part of the image display apparatus according to the seventh embodiment.
8 is a cross-sectional view showing the main part of the eighth embodiment of the image display apparatus.
Fig. 9 is a cross-sectional view showing a main part of an image display apparatus according to the related art.
10 is a view schematically showing a manufacturing process of an image display apparatus.
11 is a view schematically showing another embodiment of the manufacturing process of the image display apparatus.

Hereinafter, the present invention will be described in detail.

First, the present invention (I) will be explained.

The present invention (I) is an image display apparatus comprising: a base portion having an image display device or an image display portion having a base portion having an image display portion and a light-transmissive protection portion made of resin; a translucent protection portion made of resin; and a translucent touch sensor portion having a resin- A manufacturing method of a display device,

That way,

Between a base portion having an image display portion of an image display device and a light-transmissive protection portion made of resin, between a base portion having an image display portion of the image display device and a translucent touch sensor portion having a protective film made of resin, And at least one portion selected from the group consisting of resin-made light-transmitting protective portions, and

And a step of polymerizing the polymerizable composition by irradiating light over at least one light-transmissive portion selected from a translucent touch sensor portion having a translucent protective portion made of resin and a protective film made of resin,

The polymerizable composition may contain,

(Component 1) a compound having a (meth) acryloyl group, and

(Component 2) A photopolymerization initiator which absorbs visible light of 380 to 780 nm,

And the viscosity of the polymerizable composition at 25 캜 is 500 to 50000 mPa 占 퐏.

First, between the base portion having the image display portion and the translucent protection portion made of resin, between the base portion having the image display portion and the translucent touch sensor portion having the protective film made of resin, and between the translucent touch sensor portion having resin protective film and the translucent protection The step of interposing the polymerizable composition in at least one place selected from among the parts is described.

The term " between the base portion having the image display portion and the light-transmitting protection portion of the resin " described in this specification means, for example, portion 5b in Figs. 1, 4 and 5 or portion 5a in Figs. Further, the phrase " between the base portion having an image display portion and the light-transmitting touch sensor portion having a protective film made of resin " in this specification means, for example, portion 5b in FIG. 2 or 3, Quot; between the light-transmitting touch sensor unit and the transparent protector made of resin " means, for example, 5a in Fig. 2 or Fig.

Between the base having the image display portion and the translucent protection portion made of resin, between the base portion having the image display portion and the translucent touch sensor portion having the resin protective film, and between the translucent touch sensor portion having the protective film made of resin and the translucent protection portion The method for interposing the polymerizable composition in at least one place selected from the group consisting of

When the polymerizable composition is interposed between the base portion having the image display portion and the translucent protective portion made of resin, the polymerizable composition is applied on the base portion having the image display portion, and then the polymerizable composition applied surface of the base portion having the image display portion, The bonding surface of the translucent protective part made of the resin is contacted through the polymerizable composition or the polymerizable composition is applied on the bonding surface of the translucent protective part made of resin, The bonding surface of the base having the image display portion of the image display portion may be contacted through the polymerizable composition and there is no particular limitation.

Further, the polymerizable composition coating surface of the base portion having the image display portion and the bonding surface of the light-transmitting protective portion made of resin can be made to contact with the bonding surface of the base portion having the image display portion and the polymerizable composition application surface of the light- It is also possible to contact the portion coated with the polymerizable composition as an upper surface or to contact the portion coated with the polymerizable composition as the lower surface, so that there is no particular limitation.

It is necessary to adjust the thickness of the polymerizable composition to a desired thickness by spreading the polymerizable composition between the base portion having the image display portion and the translucent protective portion made of resin after the contact, There is no particular restriction on the reading or spinning by external pressure.

Even when a polymerizable composition is interposed between a base portion having an image display portion and a light-transmitting touch sensor portion, or between a light-transmitting touch sensor portion and a light-transmitting protection portion made of resin, polymerization is performed between a base portion having an image display portion and a light- There is no particular limitation so long as the composition is interposed.

Bonding machines are also commonly used for their bonding. However, it is not essential to use a bonding machine in the present invention, and the present process may be performed without using a bonding machine.

Next, a step of polymerizing the polymerizable composition by irradiating light over at least one light-transmissive portion selected from a translucent protective portion made of resin and a translucent touch sensor portion having a protective film made of resin will be described.

10 is a view schematically showing a manufacturing process of an image display apparatus. The bonding machine 12 is superimposed on the article 11 having the polymerizable composition before polymerization so that the article 11 has a predetermined thickness (step b). 12 is a view of the bonding machine viewed from above and means the upper surface of the bonding portion of the bonding machine. 13 is a light transmitting portion. The article 11 having a predetermined thickness is released from the bonding machine 12 using the bonding machine 12 (step d). The article 11 taken out from the bonding machine 12 is irradiated with the light 14 on the entire surface of the translucent touch sensor part having the translucent protection part made of resin or the protective film made of resin, (Step e). By irradiation of this light, the polymerizable composition is polymerized, and the image display device 1 in which the polymer compound layer is interposed is obtained. In the image display device 1 shown in Fig. 5F, the dot-shaped portion indicates a portion where the polymerizable composition is polymerized.

The lamp used in this process is not particularly limited as far as the component 2 is a lamp capable of emitting photosensitive light. For example, a metal halide lamp, a high pressure mercury lamp, an ultra high pressure UV lamp, a deep UV lamp, a xenon lamp, Lamps and the like can be used. It is also preferable to use a device capable of irradiating the entire surface of the light-transmitting protective portion or the light-transmitting touch sensor portion, or a light-transmitting protective portion such as a conveyor type exposure device or the entire one surface of the light-

The amount of light to be irradiated in the present step is the energy observed using an ultraviolet ray total light amount meter for detecting 405 nm, and is preferably 1000 to 10000 mJ / cm 2, more preferably 1500 to 9000 mJ / cm 2, 2000 to 8000 mJ / cm 2. As an ultraviolet light integrating light amount meter for detecting this 405 nm, for example, IWASAKI ELECTRIC CO., LTD. Manufactured by EYE Ultraviolet ray meter UVPF-A1.

The illuminance of the light used in the present step is preferably 10 to 400 mW / cm 2, more preferably 30 to 300 mW / cm 2, as a value of the illuminance measured using an ultraviolet ray total light amount meter for detecting 405 nm, More preferably 50 to 200 mW / cm < 2 >. If it is less than 10 mW / cm 2, the illuminance becomes insufficient, and depending on the kind of the polymerizable composition, the illuminance necessary for polymerization may be insufficient, which is not preferable. Also, the illuminance of light used in this process is the energy observed using an illuminometer that detects 405 nm, and when it is larger than 400 mW / cm 2, the reaction rate is less than 90% depending on the kind of the polymerizable composition I can not say that this is desirable.

Further, the " value of the illuminance measured using an ultraviolet ray counting photometer for detecting 405 nm " as used herein means the value of the illuminance measured by IWASAKI ELECTRIC CO., LTD. It is the value of the illuminance measured using EYE ultraviolet light measuring system UVPF-A1.

The irradiation of light can be normally carried out once. However, irradiation of light may be divided into two or more times.

Further, a part of the polymerizable composition may be irradiated (exposed to light) over the bonding machine, and then taken out from the bonding machine to irradiate (expose) the entire surface of the polymerizable composition to light. That is, a liquid crystal display device is provided between a base portion having an image display portion of an image display device and a transparent translucent protection portion made of resin, between a base portion having an image display portion of the image display device and a translucent touch sensor portion having a protective film made of resin, A transparent polymeric composition is interposed between at least one selected from among a touch sensor part and a translucent protective part made of resin, and then, from a transparent touch sensor part having a translucent protection part made of resin and a protective film made of resin, The polymerizable composition is partially polymerized by irradiating light over the selected at least one light-transmissive portion, and then light is applied to the entire surface of at least one light-transmissive portion selected from the light-transmissive touch sensor portion having a resin- The polymerizable composition containing the partially polymerized sites may be polymerized .

An example of a case of manufacturing an image display apparatus by combining this visible light and main exposure will be described with reference to Fig.

First, between the base portion having the image display portion and the translucent protection portion made of resin, between the base portion having the image display portion and the translucent touch sensor portion having the protective film made of resin, and between the translucent touch sensor portion having resin protective film and the translucent protection The polymerizable composition is put in at least one place selected from the group consisting of the parts and the parts, and the article (11) containing the polymerizable composition before polymerization is produced. The bonding device 12 having the light-transmitting portion 13 is superimposed on the article 11 having the polymerizable composition before the polymerization, so that the article 11 has a predetermined thickness (step b). 12 is a view of the bonding machine viewed from above and means the upper surface of the bonding portion of the bonding machine. Subsequently, light is irradiated onto a part of the light-transmitting touch sensor portion having a translucent protective portion made of resin and a protective film made of resin over the bonding machine 12, and the polymerizable composition is partially polymerized (Step c). The article 11 in which a polymerizable composition having a predetermined thickness and a partially polymerized portion is sandwiched using the bonding machine 12 is released from the overlap and is taken out from the bonding machine 12 (step d) . The dot-shaped portion of the article 11 shown in Step d represents a polymerized portion of the polymerizable composition. The article 11 taken out from the bonding machine 12 is then transferred to the article 11 by means of a lamp 14 in a large exposure machine such as a conveyor type so as to have a transparent protective film made of resin and / Light is irradiated to the entire surface of the light-transmitting touch sensor portion (step e). By irradiation of this light, the entire surface of the polymerizable composition is polymerized to obtain the image display device 1 having the polymer layer interposed therebetween.

Further, in the case of manufacturing an image display device by combining the naked light and the main exposure, the light transmittance of the polymerizable composition beyond the at least one light-transmissive portion selected from the translucent touch sensor portion having the translucent protective portion made of resin and the protective film made of resin And a part of the light is irradiated. Here, the term " part " means a time period from the time when the total area of the charged polymerizable composition is filled and the time from the present process to the start of the next step described later, the bonded portion having the bonded portion, the touch sensor portion, If it is an area, it means good. In the step of the galvanizing, it is generally preferable to irradiate light at 3 to 70%, more preferably 4 to 65%, and still more preferably 5 to 60% of the total area of the filled polymerizable composition. If the light is not irradiated to less than 3% of the total area of the filled polymerizable composition, the base portion having the protective portion, the touch sensor portion, and the image display portion bonded at the time from this step to the start of the next step Or the portion of the polymerizable composition not irradiated with light may flow and flow out from the edge of the bonded surface, which is not desirable. In addition, it is possible to irradiate light of 70% or more with respect to the total area of the filled polymerizable composition when the bonding area is small. However, if the bonding area is large, there may be a great restriction on the design of the bonding machine, It is impossible to say that it is practical because the exposure apparatus must be enormous.

As for the lamp used in the process of the galvanizing, the component 2 is not particularly limited as long as it is a lamp capable of emitting photosensitive light. For example, a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure UV lamp, a deep UV lamp, a xenon lamp, , An LED lamp, or the like can be used.

The amount of light used in the step of the blending is preferably 10 to 1,000 mJ / cm2, more preferably 100 to 900 mJ / cm2, as a value of the integrated light quantity measured using an ultraviolet ray total light meter for detecting 405 nm, More preferably 130 to 800 mJ / cm < 2 >. When the amount of light to be irradiated in the step of the galvanizing is less than 10 mJ / cm < 2 > as a value of the integrated light amount measured using an ultraviolet ray total light amount meter for detecting 405 nm, the weighted sum does not advance as necessary, I can not say. When the value of the accumulated light amount measured by using the ultraviolet ray cumulative light amount meter for detecting 405 nm is more than 1000 mJ / cm 2, depending on the composition of the polymerizable composition, the point where the weighted sum is performed and the boundary (A line caused by the difference in refractive index) may be generated in the vicinity of the refractive index difference.

The " value of the accumulated light amount measured using the ultraviolet ray total light amount meter for detecting 405 nm " It is a value of the integrated light amount measured by using the UV-cumulative UV meter UIT-250.

Also, the illuminance of the light used in the step of the naked light is preferably 10 to 400 mW / cm 2, more preferably 30 to 300 mW / cm 2, as a value of the illuminance measured using an ultraviolet ray total light amount meter for detecting 405 nm More preferably 50 to 200 mW / cm < 2 >. If it is less than 10 mW / cm 2, the illuminance becomes insufficient, and depending on the kind of the polymerizable composition, the illuminance necessary for polymerization may be insufficient, which is not preferable. Also, the illuminance of light used in this process is the energy observed using an illuminometer that detects 405 nm, and when it is larger than 400 mW / cm 2, the reaction rate is less than 90% depending on the type of polymerizable composition I can not say that this is desirable.

Further, the " value of the illuminance measured using an ultraviolet ray counting photometer for detecting 405 nm " as used herein means the value of the illuminance measured by IWASAKI ELECTRIC CO., LTD. It is the value of the illuminance measured using EYE ultraviolet light measuring system UVPF-A1.

When the exposure is performed, the main exposure is performed thereafter. This exposure is a step of polymerizing the polymerizable composition by irradiating light to the entire surface of at least one light-transmissive portion selected from a resin-made light-transmitting protective portion and a resin-made protective film portion.

The lamp used in this process is not particularly limited as far as the component 2 is a lamp capable of emitting photosensitive light. For example, a metal halide lamp, a high pressure mercury lamp, an ultra high pressure UV lamp, a deep UV lamp, a xenon lamp, Lamps and the like can be used. It is also preferable to use a device capable of irradiating the entire surface of the light-transmitting protective portion or the light-transmitting touch sensor portion, or a light-transmitting protective portion such as a conveyor type exposure device or the entire one surface of the light-

The amount of light to be irradiated in this exposure process is an energy observed using an ultraviolet ray total light amount meter for detecting 405 nm, preferably 1,000 to 10,000 mJ / cm 2, more preferably 1,500 to 9,000 mJ / cm 2, Lt; 2 > / m < 2 > As an ultraviolet light integrating light amount meter for detecting this 405 nm, for example, IWASAKI ELECTRIC CO., LTD. Manufactured by EYE Ultraviolet ray meter UVPF-A1.

Next, the polymerizable composition used in the method for manufacturing the image display device of the present invention (I) will be described.

The polymerizable composition used in the method for producing an image display device of the present invention (I) has a viscosity at 25 ° C of 500 to 50000 mPa · s, preferably 650 to 47000 mPa · s, more preferably 800 to 45000 mPa · S. When the viscosity of the polymerizable composition at 25 占 폚 is less than 500 mPa 占 퐏, the polymerizable composition is applied to the upper surface of the base portion having the protective portion, the touch sensor portion or the image display portion, The liquid may flow down from the coated surface when the liquid is inverted. Further, when the polymerizable composition is applied to the base portion having the protective portion, the touch sensor portion or the image display portion and the other portion used for bonding is brought into close contact from above, the applied polymerizable composition flows into its own weight of the polymerizable composition , The air bubbles remain in the bonded portion when air is brought into close contact with the other portion used for bonding. When the viscosity of the polymerizable composition at 25 占 폚 is higher than 50000 mPa 占 퐏, the fluidity of the polymerizable composition after covering the parts used for two bonding with the polymerizable composition interposed therebetween is extremely reduced, , It takes a long time to spread the polymerizable composition over the entire surface of the bonding surface, which is not preferable.

The viscosity described in the present specification is a value of viscosity measured under the condition of a rotational speed of 5 rpm using a cone / plate type viscometer (manufactured by Brookfield, model: DV-II + Pro, spindle model: CPE-42).

Next, Component 1, which is a component of the polymerizable composition used in the method of manufacturing the image display device of the present invention (I), will be described.

Component 1 is a compound having a (meth) acryloyl group.

Here, (meth) acryloyl group means acryloyl group and / or methacryloyl group. That is, the component 1 is a compound having one or both of an acryloyl group and a methacryloyl group in the molecule.

However, as described above, the viscosity of the polymerizable composition containing the component 1 at 25 캜 should be 500 to 50000 mPa · s. Therefore, in order to easily satisfy these conditions, the component 1 is preferably used in combination with a (meth) acryloyl group-containing polymer compound having a number average molecular weight of 1000 to 40,000 and a (meth) acryloyl group-containing compound having a molecular weight of 500 or less .

The (meth) acryloyl group-containing polymer having a number average molecular weight of 1000 to 40,000 has a viscosity much higher than 500 mPa · s at 25 ° C. By using these polymer compounds in combination with a (meth) acryloyl group-containing compound having a molecular weight of 500 or less, the viscosity of the polymerizable composition used in the method for producing an image display device of the present invention (I) at 25 ° C can be easily controlled to 500 to 50000 mPa · S can be adjusted.

The number average molecular weight in the present invention is a polystyrene reduced value measured by gel permeation chromatography (GPC).

From the viewpoint of materials, it is preferable to use urethane (meth) acrylate and a (meth) acryloyl group-containing compound having a molecular weight of 500 or less in combination. That is, it is preferable that the (meth) acryloyl group-containing polymer having a number average molecular weight of 1,000 to 40,000 is urethane (meth) acrylate.

Urethane (meth) acrylate is a compound having at least one urethane bond and at least one (meth) acrylate group.

As the urethane (meth) acrylate, polyester polyol urethane (meth) acrylate, polyisoprene urethane (meth) acrylate, polybutadiene urethane (meth) acrylate and hydrogenated polyisoprene urethane desirable.

Urethane (meth) acrylate is a compound obtained by reacting a polyol, a polyisocyanate, a hydroxyl group-containing (meth) acrylate or polyol with an isocyanato group-containing (meth) acrylate. The polyol, polyisocyanate, hydroxyl group-containing (meth) acrylate and isocyanato group-containing (meth) acrylate selected at this time are not particularly limited.

Specific examples of the polyol as a raw material for the production of urethane (meth) acrylate include hydrogenated dimer diols (in the form of chain), 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, Pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 2-ethyl- Chain aliphatic polyols other than dimer diol such as propanediol, 2,4-diethyl-1,5-pentanediol, 1,10-decanediol, 1,12-dodecanediol, polyolefin polyol and hydrogenated polyolefin polyol, Dimer diol (having an alicyclic structure), 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, tricyclo [5.2.1.0 ^2,6 ] decanedimethanol, 2-methylcyclohexane- 1-dimethanol, trimethylene triol, p-xylylene glycol, bisphenol A ethylene oxide adduct, bisphenol F ethylene oxide adduct, biphenol ethylene oxide Polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol; polyester polyols such as polyhexamethylene adipate, polyhexamethylene succinate, and polycaprolactone; polyester polyols such as < RTI ID = 0.0 & (1,6-hexylene carbonate) diol,?,? - poly (3-methyl-1,5-pentylene carbonate) diol,?,? - poly [ (Poly) carbonate diol such as?,? - methyl- pentamethylene) carbonate] diol and?,? - poly [(1,9-nonylene: A polyester polyol obtained by transesterification of an ester, a structural unit derived from a hydrogenated dimer acid, and a polyester polyol having a structural unit derived from a hydrogenated dimer diol, and commercially available products include Daicel Corporation. The PLACCEL, CD-205, 205PL, 205HL, 210, 210PL, 210HL, 220, 220PL, 220HL, KURARAY CO., LTD. Trade name Kuraray Polyol C-590, C-1065N, C-1015N and C-2015N. These may be used alone or in combination of two or more. In addition, polyols, polyether polyols, (poly) carbonate diols and polyester polyols having an aromatic ring from the viewpoint of adhesiveness to a substrate are preferable. More preferred is a polyester polyol obtained by an ester exchange reaction between a dimer diol and a diester.

Specific examples of polyisocyanates as raw materials for the production of urethane (meth) acrylic acid include 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3- Methyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,3 Xylylene diisocyanate, 1,4-xylylene diisocyanate, lysine triisocyanate, lysine diisocyanate, hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexanemethylene di Isocyanate and norbornane diisocyanate. These may be used alone or in combination of two or more. Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate , 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl acrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylate, 2 Hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxy-3- -Hydroxy-3- (o-phenylphenoxy) propyl methacrylate, and the like. These may be used singly or in a combination of two or more. Examples of the isocyanato group-containing (meth) acrylate include 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate. These may be used singly or in a combination of two or more.

Of the urethane (meth) acrylates, urethane (meth) acrylates containing residues of a polyester polyol obtained by an ester exchange reaction between a hydrogenated dimer diol and a diester are preferred. Herein, the residue of the polyester polyol refers to the residue obtained by removing hydrogen from at least two of the hydroxyl groups from the polyester polyol.

The diester as a raw material of the polyester polyol is not particularly limited, and examples thereof include methyl sebacate.

A hydrogenated dimer diol as a raw material of a polyester polyol is a product obtained by reducing at least one of a dimer acid, a hydrogenated dimer acid and a lower alcohol ester thereof in the presence of a catalyst, converting the carboxylic acid or carboxylate moiety of the dimer acid into an alcohol, Carbon-carbon double bond, the main component is a diol obtained by hydrogenating the double bond.

Dimer acid refers to a fatty acid having 14-22 carbon atoms having 2 to 4 ethylenic double bonds (hereinafter referred to as unsaturated fatty acid A), preferably a fatty acid having 14-22 carbon atoms having two ethylenic double bonds and an ethylenic double (Hereinafter referred to as unsaturated fatty acid B) having 1 to 4 carbon atoms, preferably 14 to 22 carbon atoms, having one or two ethylenic double bonds at the double bond portion Quot; means the obtained dimer acid. Examples of the unsaturated fatty acid A include unsaturated fatty acids such as tetradecadienic acid, hexadecadienic acid, octadecadienic acid (linoleic acid and the like), eicosadienic acid, docosadienic acid, octadecatrienoic acid (linolenic acid and the like), eicosatetraenoic acid (Such as arachidonic acid), and linoleic acid is most preferable. As the unsaturated fatty acid B, in addition to those exemplified above, tetradecenoic acid (e.g., tzu dic acid, phytosteric acid, misteroolic acid, hexadecenoic acid (palmitoleic acid, etc.) as a fatty acid having 14-22 carbon atoms having one ethylenic double bond, Oleic acid or linoleic acid is most preferable. Examples of the oleic acid or linoleic acid include octadecenoic acid (oleic acid, elaidic acid, benzoic acid and the like), eicosanic acid (gadoletic acid and the like) Do.

A hydrogenated dimer is a saturated dicarboxylic acid obtained by hydrogenating a carbon-carbon double bond of the dimer acid.

When a dimer acid having 36 carbon atoms, for example, produced from linoleic acid, linoleic acid or oleic acid is used as the raw material, the structure of the main component of the hydrogenated dimer acid is represented by the following formulas (1) and (2) .

Wherein R ⁴ and R ⁵ are alkyl groups and the total number of carbon atoms, a and b contained in R ⁴ and R ⁵ is 28 (that is, the number of carbon atoms contained in R ⁴ + the number of carbon atoms contained in R ⁵ + a + b = 28 )to be]

Wherein R ⁶ and R ⁷ are alkyl groups and the total number of carbon atoms, c and d contained in R ⁶ and R ⁷ is 32 (ie, the number of carbon atoms contained in R ⁶ + the number of carbon atoms contained in R ⁷ + c + d = 32 )to be]

As commercially available products of hydrogenated dimer acid, for example, PRIPOL (registered trademark) 1009 and the like (manufactured by Croda), EMPOL (registered trademark) 1008 and EMPOL (registered trademark) 1062 (manufactured by BASF) can be mentioned.

The hydrogenated dimer diol is a product obtained by reducing at least one of dimer acid, hydrogenated dimer acid and its lower alcohol ester in the presence of a catalyst to convert the carboxylic acid or carboxylate moiety of the dimer acid into an alcohol, Linking is carried out, the diol having the double bond is hydrogenated as a main component. However, for example, a hydrogenated dimer acid having a structure represented by the formula (4) and the formula (5) as a main component is reduced to prepare a hydrogenated dimer diol In one case, the structure of the main component of the hydrogenated dimer diol is a structure represented by the following formulas (3) and (4).

Wherein R ⁸ and R ⁹ are alkyl groups and the total number of carbon atoms, e and f contained in R ⁸ and R ⁹ is 30 (that is, the number of carbon atoms contained in R ⁸ + the number of carbon atoms contained in R ⁹ + e + f = 30 )to be]

[Wherein, R ¹⁰ and R ¹¹ is alkyl group, and R ¹⁰ and the sum of each number of carbon atoms, g and h contained in R ¹¹ is 34 (i.e., the number of carbon atoms + g + h included in the carbon number + R ¹¹ contained in R ¹⁰ = 34)

Examples of commercial products of hydrogenated dimer diols include PRIPOL (registered trademark) 2033 (produced by Croda) and Sovermol (registered trademark) 908 (manufactured by BASF).

As the urethane (meth) acrylate, a urethane (meth) acrylate containing a structural unit derived from a hydrogenated dimer acid and a residue of a polyester polyol having a structural unit derived from a hydrogenated dimer diol can also be preferably used.

A polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol is produced by reacting an acid component comprising the hydrogenated dimer acid as an essential component and a polyol component containing the hydrogenated dimer diol as an essential component with an esterification catalyst In the presence of a condensation catalyst.

In addition, the polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol is obtained by reacting a lower alkyl ester of an acid containing anhydrone dimer acid as an essential component and a polyol component containing the hydrogenated dimer diol as an essential component Can also be produced by performing an ester exchange reaction in the presence of an ester exchange catalyst.

A (meth) acryloyl group-containing compound having a molecular weight of 500 or less is a compound having a molecular weight of 500 or less and having a (meth) acryloyl group in one molecule.

Examples of the (meth) acryloyl group-containing compound having a molecular weight of 500 or less include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (Meth) acrylate having a cyclic aliphatic group such as dicyclopentanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentyl ethyl (meth) acrylate and 4-tert- butylcyclohexyl (Meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate having a chain aliphatic group such as methyl (meth) acrylate, propyl (meth) acrylate, propylhexyl Acrylate, methoxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, phenoxyethyl (meth) acylate, 3-methyl-3-oxetanylmethyl (Meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (Meth) acryloyl group-containing compound having a cyclic ester such as (meth) acrylate and? - (meth) acryloxy-? -Butyrolactone having an ether bond in the molecule of a (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl (meth) (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N- (meth) acryloylmorpholine , N-isopropyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (Meth) acrylamide, N-isobutoxymethyl (meth) acrylamide and the like.

The lower limit of the molecular weight of the acryloyl group-containing compound is not limited, but the molecular weight of the acryloyl group-containing compound is preferably 86 or more.

The lower limit of the molecular weight of the methacryloyl group-containing compound is not limited, but the molecular weight of the methacryloyl group-containing compound is preferably 100 or more.

Among these (meth) acryloyl group-containing compounds having a molecular weight of 500 or less,

(meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl (Meth) acrylate, isodecyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, hexyl (Meth) acrylate, isopropyl (meth) acrylate, isopropyl (meth) acrylate, ethylhexyl (meth) acrylate, isostearyl (Meth) acrylate and methoxyethyl (meth) acrylate having a hydrocarbon group having from 8 carbon atoms to 18 carbon atoms, such as octadecyl (meth) acrylate and 2-heptylundecyl (meth) acrylate, Ether (meta) (Meth) acrylate, phenoxyethyl (meth) acrylate, 3-methyl-3-oxetanylmethyl (meth) acrylate, 1,4-dioxaspiro [ (Meth) acrylate having an ether bond such as (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate,

(meth) acrylamide, N-isopropyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, Butoxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, Amide, N- (2-hydroxyethyl) (meth) acrylamide and the like, and a (meth) acrylamide compound such as 2-hydroxyethyl (meth) acrylate, 2- (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- (Meth) acrylate having an alcoholic hydroxyl group such as hydroxyethyl (meth) acrylate and hydroxy-3- (o-phenylphenoxy) propyl It is preferable that a combination of the compound.

By using these compounds in combination, it is possible to inhibit the coloring of the polymer in the image display device of the present invention (II) to be described below under high temperature conditions and to suppress the bleaching phenomenon of the polymer in the image display device of the present invention (II) Can be suppressed.

(Meth) acrylate having a hydrocarbon group of 8 to 18 carbon atoms and (meth) acrylate having an ether bond, and the (meth) acrylamide compound and the alcoholic hydroxyl group-containing (meth) Acrylate is preferably from 40:60 to 90:10, more preferably from 45:55 to 85:15, and particularly preferably from 50:50 to 80:20 by mass ratio. (Meth) acrylate having a hydrocarbon group of 8 to 18 carbon atoms and (meth) acrylate having an ether bond, and a compound selected from the group consisting of the (meth) acrylamide compound and the alcoholic hydroxyl group-containing ) Acrylate is less than 40:60, the water resistance of the polymer may be deteriorated. (Meth) acrylate having a hydrocarbon group of 8 to 18 carbon atoms and (meth) acrylate having an ether bond, and a compound selected from the group consisting of the (meth) acrylamide compound and the alcoholic hydroxyl group-containing (Meth) acrylate is used in an amount greater than 90:10, the whitening phenomenon of the polymer under high temperature and humidity can not be said to be desirable.

The amount of Component 1 to be used in the polymerizable composition used in the method for manufacturing an image display device of the present invention (I) is preferably 25 to 75% by mass, more preferably 25 to 75% by mass with respect to the total amount of Component 1 and Component 3 described later 30 to 70% by mass, particularly preferably 35 to 65% by mass. When the amount of the component 1 used is less than 25% by mass based on the total amount of the component 1 and the component 3 described later, the strength of the polymer film obtained by polymerizing the polymerizable composition may become insufficient. When the amount of the component 1 used is more than 75% by mass based on the total amount of the component 1 and the component 3 described later, the volume shrinkage during polymerization becomes too large, and when the polarizer is twisted, Occurs, and as a result, the adhesion strength between the part bonded to the polymer and the polymer is lowered, which is not desirable.

The ratio of the (meth) acryloyl group-containing polymer compound having a number average molecular weight of 1,000 to 40,000 and the (meth) acryloyl group-containing compound having a molecular weight of 500 or less in component 1 is preferably 45:55 to 85:15 And more preferably in a weight ratio of 50:50 to 80:20. When the ratio of the (meth) acryloyl group-containing polymer compound having a number average molecular weight of 1000 to 40,000 and the (meth) acryloyl group-containing compound having a molecular weight of 500 or less is smaller than 45:55 in mass ratio, the volume shrinkage , Or the coating strength of the polymer may become insufficient, which is not desirable. When the proportion of the (meth) acryloyl group-containing polymer compound having a number average molecular weight of 1,000 to 40,000 and the (meth) acryloyl group-containing compound having a molecular weight of 500 or less is more than 80:20 in mass ratio, It can not be said that it is desirable.

Next, Component 2, which is a component of the polymerizable composition used in the method of manufacturing the image display device of the present invention (I), will be described.

Component 2 is a photopolymerization initiator having an absorption wavelength in a visible light region of 380 to 780 nm.

The photopolymerization initiator having an absorption wavelength in the visible light region of 380 to 780 nm is not particularly limited, and examples thereof include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (absorption wavelength: 200 to 450 nm), bis (eta 5-2,4-cyclopentadien-1-yl) (Absorption wavelength: 200 to 500 nm), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (absorption wavelength: 200 nm), 2,6-difluoro- To 420 nm). Among them, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is preferably used in order to enhance transparency after curing. These compounds may be used alone or in combination of two or more.

In addition, a photopolymerization initiator other than the component 2 may be used in combination with the polymerizable composition used in the method for producing an image display device of the present invention (I). From the viewpoint of curability, the amount of the photopolymerization initiator other than the component 2 is preferably 40 mol% or less based on the total amount of all the photopolymerization initiators.

As the photopolymerization initiator to be used in combination, other acylphosphine oxide-based or -hydroxyalkylphenone-based ones can be mentioned.

Examples of other acylphosphine oxide-based photopolymerization initiators include 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1- Bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- , 6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like.

Examples of the? -hydroxyalkylphenone-based photo polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan- Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2- ) -Benzyl] phenyl} -2-methyl-propan-1-one.

The amount of the photopolymerization initiator used in the polymerizable composition used in the method for producing an image display device of the present invention (I) is preferably 0.1 to 10.0 parts by mass per 100 parts by mass of the total amount of the component 1 and the component 3 described later, Preferably 0.2 to 7.0 parts by mass, and more preferably 0.3 to 5.0 parts by mass. Here, the used amount of the photopolymerization initiator is the total amount of the photopolymerization initiator of the component 2 and the photopolymerization initiator other than the component 2. When the amount of the photopolymerization initiator used is less than 0.1 part by mass based on the total amount of 100 parts by mass of the total of the component 1 and the component 3 described later, the photopolymerization initiator is insufficient and the polymerization may be insufficient. When the amount of the photopolymerization initiator to be used is more than 10.0 parts by mass based on 100 parts by mass of the total amount of the component 1 and the component 3 described later, the molecular weight of the polymer is too small and the strength of the polymer is likely to be insufficient.

In the polymerizable composition used in the method for producing an image display device of the present invention (I), it is preferable to further use and further use the following Component 3.

Component 3 is a compound composed only of a carbon atom and a hydrogen atom, or a compound composed only of a carbon atom, a hydrogen atom and an oxygen atom, and has no ethylenic double bond.

Component 3 is a compound composed of a carbon atom and a hydrogen atom that does not have both a (meth) acryloyl group, a function of inhibiting radical polymerization, a function of prohibiting radical polymerization, and a photopolymerization initiating function, and a (meth) acryloyl group, It can also be said that it is at least one kind of compound selected from the group consisting of a carbon atom, a hydrogen atom and an oxygen atom which does not have a function of inhibiting radical polymerization, a function of prohibiting radical polymerization, and a function of initiating photo polymerization.

Component 3 is used for the purpose of suppressing the volume shrinkage rate during polymerization to a low level. It may also be used for the purpose of increasing the adhesion of the polymer to an adherend such as resin besides suppressing the volume shrinkage during polymerization.

As the component 3, a compound which is liquid at 25 DEG C or a compound which is solid at 25 DEG C can be used.

Examples of the compound which is liquid at 25 占 폚 used as the component 3 include a poly (? -Olefin) liquid, an ethylene-propylene copolymer liquid, an ethylene-? -Olefin copolymer liquid, a propylene- A liquid polyisoprene polyol, a liquid polyisoprene polyol, a liquid polyisoprene polyol, a liquid polyisoprene polyol, a liquid polyisoprene polyol, a liquid polyisoprene polyol, a liquid polyisoprene polyol, a liquid polyisoprene polyol, , Hydrogenated dimer diols, polyether polyols, polyester polyols, polycarbonate polyols and the like.

The poly (? -Olefin) liquid is a liquid product prepared by polymerization of? -Olefin, and? -Olefin is a hydrocarbon compound having one carbon-carbon double bond at the molecular terminal, for example, 1-butene, 1 Pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene.

The ethylene-propylene copolymer liquid material is a liquid phase of a copolymer produced by copolymerizing ethylene and propylene.

The ethylene-? -Olefin copolymer liquid is a liquid polymer produced by copolymerizing ethylene and an? -Olefin. The? -olefin is as described above.

The propylene-? -Olefin copolymer liquid is a liquid polymer produced by copolymerizing propylene and an? -Olefin. The? -olefin is as described above.

Liquid polybutene is a liquid polymer containing isobutene or n-butene, such as a sole polymer of isobutene, a sole polymer of n-butene, a copolymer of isobutene and n-butene, etc., Is a compound having a carbon-carbon unsaturated bond. Examples of commercially available liquid polybutene include Nippon Oil Poly Butene LV-7, LV-50, LV-100, HV-15, HV-35, HV-50, HV-100 and HV -300.

The liquid hydrogenated polybutene is a liquid product having a side chain obtained by hydrogenating the liquid polybutene, and examples thereof include pfilil 4, pfilil 6, pfilil 18, pfilil 24, and pfilil EX manufactured by NOF CORPORATION.

Liquid polybutadiene is a butadiene polymer that is liquid at room temperature. For example, POLYVEST110, POLYVEST 130 or NIPPON SODA CO., LTD. By Evonik Degussa. NISSO-PB B-1000, NISSO-PB B-2000 and NISSO-PB B-3000.

Liquid hydrogenated polybutadiene is a substance which is liquid at room temperature, obtained by reducing hydrogenation of a butadiene polymer. For example, NIPPON SODA CO., LTD. NISSO-PB BI-2000, and NISSO-PB B-3000 manufactured by Tosoh Corporation.

Liquid polyisoprene is an isoprene polymer in a liquid state at room temperature, for example, KURARAY CO., LTD. And Kurapuren LIR-30 manufactured by Mitsubishi Electric Corporation.

Liquid hydrogenated polyisoprene is a substance that is liquid at room temperature obtained by reducing hydrogenation of an isoprene polymer. KURARAY CO., LTD. LIR-200 manufactured by Mitsubishi Electric Corporation.

Liquid polybutadiene polyol is a polymer in liquid state at room temperature having two or more hydroxyl groups at the molecular end and a polybutadiene structural unit, for example, NIPPON SODA CO., LTD. NISSO-PB G-1000, NISSO-PB G-2000, NISSO-PB G-3000, Idemitsu Kosan Co., Ltd. Poly bd produced by the present invention.

The liquid hydrogenated polybutadiene polyol is a liquid polyol having a structure obtained by reducing hydrogenation of polybutadiene polyol or polybutadiene polycarboxylic acid, and NIPPON SODA CO., LTD. NISSO-PB GI-1000, NISSO-PB GI-2000 and NISSO-PB GI-3000.

The liquid polyisoprene polyol is a polymer which is liquid at room temperature and has at least two hydroxyl groups at the molecular end and a polyisoprene structural unit, for example, Idemitsu Kosan Co., Ltd. Poly ip manufactured by Kawasaki Corporation.

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, Idemitsu Kosan Co., Ltd. And EPOL of manufacture.

The hydrogenated dimerdiols are as described above.

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

Examples of the polyester polyol include a polycondensation product of a polyol and a polycarboxylic acid, an ester exchange reaction product of a polyol and a polycarboxylic acid ester, and a ring-opening polymer of a cyclic ester in a polyol.

Examples of the polycarbonate polyol include a polycondensation product of a polyol and a phosgene or an ester exchange reaction product of a polyol with an organic carbonate ester such as dimethyl carbonate, diethyl carbonate, ethylene carbonate and the like.

The polymerized product obtained by polymerizing the polymerizable composition used in the method for manufacturing the image display device of the present invention (I) has a dielectric constant (refractive index) determined by the site of use (that is, the site used for site 5a or site 5b) Is different. For example, in the case where it is used in the region 5b of FIG. 2 to FIG. 5, the dielectric constant of the polymer is preferably low. When used in the regions 5a of Figs. 2, 3 and 6 to 8, it is preferable that the dielectric constant of the polymer is high.

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

Specific examples of the polycarboxylic acid used as a raw material of the polyester polyol include succinic acid, glutaric acid, methylsuccinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, and 2-cyclohexane-1,1-dicarboxylic acid. They may be used alone or in combination of two or more. Of these, preferred are glutaric acid, methylsuccinic acid, adipic acid, pimelic acid, suberic acid, 1,1-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,1-dicarboxylic acid, terephthalic acid, isophthalic acid and phthalic acid, and more preferably glutaric acid, methylsuccinic acid, adipic acid, pimelic acid, suberic acid, terephthalic acid, isophthalic acid and phthalic acid. Particularly preferred are glutaric acid, methylsuccinic acid, adipic acid, and pimelic acid.

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

A ring-opening polymer of a cyclic ester may be used as the polyester polyol. When a ring-opening polymer of cyclic ester is used,? -Butyrolactone,? -Caprolactone and the like can be mentioned, but a polyester polyol which is a ring-opening polymer of? -Caprolactone is preferable.

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

When the dielectric constant of the polymer is increased, as the compound which is liquid at 25 캜 and used as the component 3 for the purpose, polyether polyol, polyester polyol and polycarbonate polyol are preferable, and polyester polyol, polycarbonate Lt; / RTI >

Preferred as the polyether polyol is polytetramethylene glycol.

When the permittivity of the polymer is lowered, it is preferable to use a poly (alpha-olefin) liquid, an ethylene-propylene copolymer liquid, an ethylene- alpha -olefin copolymer liquid, a propylene- Liquid polybutadiene polyol, liquid polyisoprene polyol, liquid polyisoprene polyol and liquid polyisoprene polyol are preferably used, and the heat-resistant polyisobutylene, liquid polyisoprene, liquid polyisoprene, liquid polyisoprene, liquid polyisoprene, Olefin copolymer liquid, a liquid ethylene-propylene copolymer liquid, an ethylene-alpha-olefin copolymer liquid, a propylene-alpha-olefin copolymer liquid, a liquid polybutene, a liquid hydrogenated poly Butene, liquid hydrogenated polybutadiene, liquid hydrogenated polyisoprene, liquid hydrogenated polybutadiene polyol, and liquid water A spun polyisoprene polyol is preferred.

As the component 3, a compound which is solid at 25 占 폚 may also be used.

As the compound which is used as the component 3 and is solid at 25 占 폚, it is preferable that the compound does not have a carbon-carbon unsaturated bond in the molecule.

Examples of such compounds include epoxy resins which are solid at 25 占 폚, polyester resins which are solid at 25 占 폚, polyol resins which are solid at 25 占 폚, hydrogenated petroleum resins which are solid at 25 占 폚, terpene-based hydrogenated resins and hydrogenated rosin esters .

When used in a polymerizable composition aiming at a high-k polymeric polymer, an especially preferred polymer is a hydrogenated rosin ester.

When used in a polymerizable composition aiming at a polymer having a low dielectric constant, the hydrogenated petroleum resin and the terpene-based hydrogenated resin are particularly preferable.

The hydrogenated petroleum resin is a resin obtained by hydrogen reduction of a petroleum resin. Examples of the petroleum resin as a raw material of the hydrogenated petroleum resin include aliphatic petroleum resin, aromatic petroleum resin, aliphatic-aromatic petroleum resin, alicyclic petroleum resin, dicyclopentadiene resin and modified materials thereof . 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 resin which is a raw material of the terpene-based hydrogenated resin include a? -Pinene resin, an? -Pinene resin, a? -Limonene resin, an? -Limonene resin, a pinene-limonene copolymer resin, a pinene-limonene- And aromatic-modified terpene resins. Most of these terpene resins are resins having no polar group.

Hydrogenated rosin ester A hydrogenated rosin obtained by hydrogenating a rosin-based resin by esterification or rosin esterification to obtain a hydrogen-reduced rosin ester. Examples of the rosin-based resin tackifier include modified rosins such as gum rosin, tolyu rosin, wood rosin, disproportionated rosin, polymerized rosin and maleated rosin.

Also, in the present specification, a compound in which a part of the polyhydric alcohol is esterified with hydrogenated rosin, and a compound in which all alcoholic hydroxyl groups of the polyhydric alcohol are esterified with hydrogenated rosin are also defined as being included in the hydrogenated rosin ester.

In order to balance the viscosity of the polymerizable composition used in the method of manufacturing the image display device of the present invention (I) with the adherence of the polymer to the adherend, the compound of the component 3 is a compound which is liquid at 25 ° C, Can be used in combination.

When a compound which is liquid at 25 占 폚 and a compound which is solid at 25 占 폚 are used in combination at a temperature of 25 占 폚 in Component 3, the mixing ratio is preferably 90:10 to 10:90, and more preferably 80:20 to 20:80 by mass ratio.

The amount of the component 3 used in the polymerizable composition used in the method for manufacturing an image display device of the present invention (I) is preferably 25 to 75% by mass, more preferably 30 to 75% by mass based on the total amount of the component 1 and the component 3, By mass to 70% by mass, and particularly preferably 35% by mass to 65% by mass. When the amount of the component 3 used in the polymerizable composition used in the method for producing an image display device of the present invention (I) is less than 25 mass% with respect to the total amount of the component 1 and the component 3, the effect of adding the component 3 The effect of reducing the volume shrinkage ratio of the film) can not be obtained, which is not preferable. When the amount of component 3 used in the polymerizable composition used in the method (I) of the present invention (I) is more than 75% by mass based on the total amount of component 1 and component 3, the polymeric coating film The strength may be too low, which is not desirable.

The polymerization inhibitor, the antioxidant, the modifier, and the like may optionally be added to the polymerizable composition used in the method for manufacturing the image display device of the present invention (I).

The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone, p-methoxyphenol, p-benzoquinone, naphthoquinone, phenanthraquinone, 2,5-diacetoxy-p-benzoquinone, Butylcatechol, 2,5-di-t-butylhydroquinone, p-tert-butylcatechol, mono-t- Butyl hydroquinone, 2,5-di-t-amyl hydroquinone, di-t-butyl paracresol hydroquinone monomethyl ether and phenothiazine are preferably used.

These may be used singly or in a combination of two or more.

Usually, the polymerization inhibitor may 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 used in the method for producing an image display device of the present invention (I). However, the amount of the polymerization inhibitor is a value obtained by adding the polymerization inhibitor previously contained in the component 1. That is, in general, component 1 contains a polymerization inhibitor in advance, but the amount of the total amount of the polymerization inhibitor and the newly added polymerization inhibitor added to the component (1) Means that the added amount is 0.01 to 5% by mass based on the total amount of the composition.

Examples of the antioxidant include, but are not limited to, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl- Butyl-4-hydroxyphenyl) propionate, and 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane. Among these, preferred are pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5- -Hydroxyphenyl) propionate, most preferably pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate].

Usually, 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 used in the method for producing an image display device of the present invention (I). However, the amount of the polymerization inhibitor is a value obtained by adding an antioxidant previously contained in other components such as Component 3. [ That is, in general, the antioxidant may be contained in advance in the component 3 and the like. However, the total amount of the antioxidant and the total amount of the antioxidant to be added may be different from the amount of the polymerization used in the production method of the image display apparatus of the present invention Means that the added amount is from 0.01 to 5 mass% with respect to the total amount of the composition.

As the modifier, for example, a leveling agent for improving the leveling property can be cited. As the leveling agent, for example, a polyether-modified dimethylpolysiloxane copolymer, a polyester-modified dimethylpolysiloxane copolymer, a polyether-modified methylalkylpolysiloxane copolymer, an aralkyl-modified methylalkylpolysiloxane copolymer, an acrylic ester copolymer and the like can be used. These may be used alone or in combination of two or more. May be added in an amount of 0.01 to 5% by mass based on the total amount of the polymerizable composition used in the method (I) of the present invention. If it is less than 0.01% by mass, the effect of adding the leveling agent may not be exhibited. When the amount is more than 5% by mass, turbidity may occur in the polymerizable composition used in the method for manufacturing the image display device of the present invention (I), which is not preferable.

Finally, the present invention (II) will be described.

The present invention (II) is an image display apparatus which can be manufactured by the method for manufacturing an image display apparatus of the present invention (I).

For example, in the case of Fig. 1, the protective portion 3 is formed of a plate-like, sheet-like or film-like light-transmissive member having the same size as that of the display portion 2. [ As the light transmitting member, for example, a resin such as polymethyl methacrylate, a laminate of polymethyl methacrylate and polycarbonate can be preferably 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 rear surface of the protective portion 3.

When the protective portion 3 is formed of an acrylic resin, its refractive index n _D is generally 1.49 to 1.51.

The protective portion 3 is provided on the display portion 2 through the spacer 4 formed on the periphery of the display portion 2. [ The spacer 4 has a thickness of about 0.05 to 1.5 mm, so that the distance between the surface of the image display portion 2 and the surface of the protective portion 3 is maintained at about 1 mm.

In addition, a frame-shaped shielding portion (not shown) is provided in the periphery of the protective portion 3 in order to improve brightness and contrast.

For example, in the case of Figs. 2 and 3, the polymeric layers 5a and 5b are interposed between the display portion 2 and the protective portion 3. In the case of the image display device manufactured by the manufacturing method of the image display device of the present invention (I), the polymeric layer 5a and the polymeric material layer 5b are used in the manufacturing method of the image display device of the present invention (I) The transmittance of the visible light region becomes 90% or more because a polymer obtained by polymerizing the polymerizable composition is interposed. Here, the thickness of the polymeric layer 5a or the polymeric layer 5b is preferably 10 to 500 mu m. More preferably 10 to 350 占 퐉, and further preferably 10 to 300 占 퐉. The refractive index n _D at 25 ° C is 1.45 to 1.55, preferably 1.48 to 1.52 because the polymer compound is present in the polymer layer 5a or the polymer compound layer 5b. Therefore, the display portion 2 and the protective portion 3). As a result, the brightness and contrast of the image light from the image display section 2 can be increased to improve the visibility.

When the image display device is manufactured by the method of manufacturing the image display device of the present invention (I), since the polymerizers are present in the polymeric layer 5a or the polymeric compound layer 5b, the tensile elastic modulus at 23 ° C is 1 × 10 ⁷ Pa or less, preferably 1 x 10 ³ to 1 x 10 ⁶ Pa. Therefore, it is possible to prevent the display portion and the protective portion from being distorted due to the influence of the stress caused by the volume contraction during the polymerization of the polymerizable composition.

When the image display device is manufactured by the method of manufacturing the image display device of the present invention (I), since the polymerizate is present in the polymeric layer 5a or the polymeric compound layer 5b, the volume shrinkage ratio 4.0% or less, preferably 3.5% or less, more preferably 2.7% or less. As a result, the internal stress accumulated in the polymeric layer can be reduced when the polymerizable composition is polymerized, and the interface between the polymeric layer 5a and the touch panel 7 or the protective portion 3, the polymeric layer 5b, It is possible to prevent the interface between the touch panel 7, the display unit 2, and the protection unit 3 from being distorted. Therefore, the polymerizable composition is interposed between the touch sensor 7 and the protective portion 3, between the touch sensor 7 and the display portion 2, or between the display portion 2 and the protective portion 3, The scattering of light generated at the interface between the polymeric layer 5a or 5b and the display portion 2, the protective portion 3 and the touch panel 7 can be reduced, and the brightness of the display image can be increased, Can be improved.

When the polymer is used for the polymeric layer (5b), the dielectric constant of the polymeric material is low, so that the thickness of the polymeric layer (5b) can be reduced.

As the resin plate used in the image display apparatus of the present invention (II), a laminate of polymethyl methacrylate, polymethyl methacrylate and polycarbonate can be preferably used. The average surface roughness of these resin plates is usually 1.0 nm or less.

In the image display apparatus according to the present invention (II), since the polymeric layer 5a or 5b made of the polymer is filled between the display portion 2 and the protective portion 3, it is resistant to impact.

It can be formed thin in comparison with the conventional example in which the gap is formed between the display portion 2 and the protective portion 3.

The image display apparatus of the present invention (II) can take various embodiments. The image display device 1 may be manufactured by omitting the spacer 4 as shown in Figs. 3, 5 and 8, for example. In the case of the polymeric layer 5b in Fig. 3, the polymerizable composition is applied on the polarizing plate 6a on the display portion 2, the touch sensor 7 is superimposed on the polymerizable composition, .

5, the polymerizable composition is applied on the polarizing plate 6a on the display portion 2, the touch sensor integrated protective portion 3 is superimposed on the polymerizable composition, Followed by polymerization.

In the case of the polymeric layer 5a of Fig. 8, for example, a polymerizable composition is applied, the protective portion 3 is overlaid on the polymeric composition, and photo-polymerization is performed as described above.

Further, the present invention can be applied not only to the above-described liquid crystal display device but also to various panel displays such as organic EL, plasma display devices and the like.

(Example)

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

≪ Measurement of viscosity &

The viscosity was measured by the following method.

Using 1 ml of the sample, viscosity was measured with a cone / plate type viscometer (manufactured by Brookfield, model: DV-II + Pro, spindle model: CPE-42) The value when it was made was measured.

≪ Measurement of hydroxyl value >

Measured according to JIS K 0070.

<Number average molecular weight>

The number average molecular weight is a polystyrene reduced value measured by GPC under the following conditions.

Device name: JASCO Corporation Production HPLC unit HSS-2000

Column: Shodex (R) column LF-804

Mobile phase: tetrahydrofuran

Flow rate: 1.0 ml / min

Detector: manufactured by JASCO Corporation RI-2031 Plus

Temperature: 40.0 DEG C

Sample amount: Sample loop 100 μl

Sample concentration: About 0.5 mass%

&Lt; Ultraviolet ray cumulative amount >

Is the value of the accumulated light quantity measured by using an ultraviolet light accumulating light meter "UVPF-A1" (manufactured by IWASAKI ELECTRIC CO., LTD.).

<Illumination>

Quot; UVPF-A1 &quot; manufactured by IWASAKI ELECTRIC CO., LTD.

(Synthesis Example 1)

322.2 g of Pripol (registered trademark) 2033 (Croda-produced hydrogenated dimer diol, hydroxyl value: 202 mgKOH / g), and dimethyl sebacate (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a 500 ml reaction vessel equipped with a stirrer and a distillation apparatus. , And 0.18 g of dioctyltin oxide (trade name: DOTO, produced by HOKKO CHEMICAL INDUSTRY CO., LTD.) Were introduced, and ester exchange reaction was carried out under reduced pressure while starting methanol at about 170 ° C. under atmospheric pressure . The total distillation amount of methanol was 24.4 g. To obtain a polyester polyol having a hydroxyl value of 581 mgKOH / g (hereinafter referred to as polyester polyol A).

(Synthesis Example 2)

A 100 mL reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a condenser was charged with a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT ) TMDI, manufactured by Evonik Degussa), 12 mg of dioctyltin dilaurate and 24 mg of p-methoxyphenol were charged in a reaction vessel, and 15.16 g of 4-hydroxybutyl acrylate was added dropwise using a dropping funnel . During the dropping, the temperature in the reaction vessel was set to be 70 DEG C or less. After completion of the dropwise addition, stirring was continued while maintaining the temperature in the reactor at 65 to 70 캜 for 2 hours to obtain a reaction product (hereinafter referred to as a reaction product α).

To a 300 ml reaction vessel equipped with a stirrer, a thermometer and a condenser were added 178.9 g of the above polyester polyol A, 1.1 g of Pripol (registered trademark) 2033 (Croda produced hydrogenated dimer diol, hydroxyl value 202 mgKOH / g) 12 mg of tin dilaurate was added, and stirring was started. Thereafter, 33.7 g of the reaction product? Maintained at a temperature of 60 占 폚 was divided into several portions and charged into the reaction vessel. In the meantime, the temperature in the reactor was prevented from becoming higher than 70 ° C. Thereafter, the temperature in the reactor was maintained at 65 to 70 캜 and stirring was continued. The reaction was terminated by confirming that IR did not absorb C═O stretching vibration of the isocyanato group, and the reaction was terminated to obtain a urethane acrylate having a number average molecular weight of 2300 (hereinafter referred to as "urethane acrylate 1").

(Synthesis Example 3)

180 g of polybutadiene (hydroxyl value: 47.1 mg KOH / g, trade name: NISSO-PB GI-2000, manufactured by NIPPON SODA CO., LTD.) Containing hydrogenated end hydroxyl group was added to a 300 ml separable flask equipped with a condenser, a dropping funnel, 20 mg of dioctyltin dilaurate was placed, and the internal temperature was raised to 50 캜 using an oil bath. Thereafter, 22.86 g of 2-isocyanatoethyl methacrylate (trade name: Karenz M0I (registered trademark), produced by SHOWA DENKO K.K.) was added dropwise over 15 minutes from the dropping funnel. During the dripping, the internal temperature was set not to exceed 70 ° C. After completion of the dropwise addition, stirring was continued by controlling the internal temperature of 70 ± 2 ° C. The absorption of C = 0 stretching vibration of the isocyanate group was not observed in the infrared absorption spectrum. Thus, stirring was stopped and the reaction was terminated to obtain hydrogenated polybutadiene urethane methacrylate 1.

(Synthesis Example 4)

180 g of a polybutadiene polyol (hydroxyl value: 47.1 mg KOH / g, trade name: NISSO-PB G-2000, manufactured by NIPPON SODA CO., LTD.) Was charged in a 300 ml separable flask equipped with a condenser, a dropping funnel, 20 mg of tin dilaurate was placed, and the internal temperature was raised to 50 캜 using an oil bath. Thereafter, 22.86 g of 2-isocyanatoethyl methacrylate (trade name: Karenz M0I (registered trademark), produced by SHOWA DENKO K.K.) was added dropwise over 15 minutes from the dropping funnel. During the dripping, the internal temperature was set not to exceed 70 ° C. After completion of the dropwise addition, stirring was continued by controlling the internal temperature of 70 ± 2 ° C. Absorption of C = O stretching vibration of the isocyanate group was not observed in the infrared absorption spectrum. Therefore, stirring was stopped and the reaction was terminated to obtain polybutadiene urethane methacrylate having a number average molecular weight of 2560 (hereinafter referred to as &quot; urethane methacrylate 1 &quot; .

(Synthesis Example 5)

3200 g of Pripol (registered trademark) 2033 (Croda-produced hydrogenated dimer diol, hydroxyl value of 202 mgKOH / g), Pripol (registered trademark) 1009 (Croda produced hydrogen dimer acid, acid value 194 mg KOH / g), and the mixture was heated to 200 캜 while passing nitrogen through atmospheric pressure, and the condensation reaction was carried out while distilling off water produced by the reaction. When the acid value of the product became 20 or less, 0.08 g of tetraisopropyl titanate was added and the reaction was carried out by gradually increasing the degree of vacuum by means of a vacuum pump to obtain a polyester polyol having a number average molecular weight of 1055 ).

(Synthesis Example 6)

180 g of polyester polyol B and 20 mg of dioctyltin dilaurate were placed in a 300 ml separable flask equipped with a condenser, a dropping funnel, a thermometer and a stirrer, and the internal temperature was raised to 50 캜 by using an oil bath. Thereafter, 24 g of 2-isocyanatoethyl acrylate (trade name: Karenz AOI (registered trademark), produced by SHOWA DENKO K.K.) was added dropwise over 15 minutes from the dropping funnel. During the dripping, the internal temperature was set not to exceed 70 ° C. After completion of the dropwise addition, stirring was continued by controlling the internal temperature of 70 ± 2 ° C. As the absorption of C = O stretching vibration of the isocyanate group was not observed in the infrared absorption spectrum, stirring was stopped and the reaction was terminated to obtain a polyurethane acrylate having a number average molecular weight of 1196 (hereinafter referred to as &quot; urethane acrylate 2 &quot;).

(Formulation Example 1)

10.0 parts by mass of lauryl acrylate (trade name: BLEMMER LA, manufactured by NOF CORPORATION), 25.0 parts by mass of terpene-based hydrogenated resin (trade name: CLEARON (registered trademark) K100, manufactured by YASUHARA CHEMICAL CO., LTD.), The flask was placed in a 200 ml four-neck separable round bottom flask, and the temperature in the 200 ml four-neck separable round bottom flask was raised to 90 캜 using an oil bath with stirring. It was confirmed that the terpene-based hydrogenated resin was completely dissolved in lauryl acrylate, and the temperature was cooled to 50 ° C or lower.

Thereafter, 25.0 parts by mass of the urethane acrylate 1, 25.0 parts by mass of liquid hydrogenated polybutadiene polyol (trade name: NISSO-PB GI-1000, manufactured by NIPPON SODA CO., LTD.), 14.0 parts by mass of liquid polybutene HV- 1.0 part by mass of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX (registered trademark) , 4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure (registered trademark) 819, manufactured by BASF) were placed in the 200 ml four-neck round bottom flask, And the stirring was continued until the solution became homogeneous to obtain a pale yellow uniform solution having a viscosity of 3300 mPa · s at 25 ° C. The resulting blend was referred to as Polymerizable Composition A1.

(Formulation Examples 2 to 4 and Comparative Formulation Example 1)

Were compounded according to the composition shown in Table 1 by the same method as in Formulation Example 1. The formulations prepared in Formulation Examples 2 to 4 were respectively referred to as Polymerizable Composition A2 to Polymerizable Composition A4, and the formulations prepared in Comparative Formulation Example 1 were referred to as Polymerizable Composition B1.

Also, the numbers in Table 1 refer to "parts by mass" unless otherwise specified.

* 1 Dicyclopentenyloxyethyl methacrylate (trade name: FA-512M, manufactured by Hitachi Chemical Co., Ltd., molecular weight 262.35)

* 2 Lauryl acrylate (trade name: BLEMMER LA, manufactured by NOF CORPORATION, molecular weight: 240.38)

* 3 N-acryloylmorpholine (trade name: ACMO, manufactured by KOHJIN Film & Chemical Co., Ltd., molecular weight: 141.17)

* 4 N, N-diethylacrylamide (trade name: DEAA, produced by KOHJIN Film & Chemical Co., Ltd., molecular weight: 127.19)

* 5 2-Hydroxypropyl methacrylate (manufactured by NIPPON SHOKUBAI CO., LTD., Molecular weight: 144.17)

* 6 2-hydroxybutyl methacrylate (trade name: Light ester HOB (N), manufactured by KYOEISHA CHEMICAL Co., Ltd., molecular weight: 158.20)

* 7 Terpene-based hydrogenated resin CLEARON (registered trademark) P85 (manufactured by YASUHARA CHEMICAL Co., Ltd.)

* 8 Terpene-based hydrogenated resin CLEARON (registered trademark) K100 (manufactured by YASUHARA CHEMICAL Co., Ltd.)

* 9 Liquid hydrogenated polybutadiene polyol NISSO-PB GI-1000 (manufactured by NIPPON SODA CO., LTD.)

* 10 Liquid hydrogenated dimer diol (trade name: Pripol 2033, manufactured by Croda)

※ 11 Liquid polybutene HV-15 (manufactured by JX Nippon Oil & Energy Corporation)

※ 12 liquid polybutadiene POLYVEST 110 (made by Evonik Degussa)

* 13 IRGANOX (registered trademark) 1010 (compound name: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

* 14 Photopolymerization initiator IRGACURE 184 (Compound name: 1-hydroxycyclohexyl phenyl ketone, produced by BASF, absorption wavelength: 200 to 380 nm)

* 15 Photopolymerization initiator IRGACURE 819 (compound name: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, manufactured by BASF, absorption wavelength 200 to 450 nm)

&Lt; Preparation of polymer film &

An acrylic resin plate (MR-200, manufactured by Mitsubishi Rayon Co., Ltd.) having a thickness of 0.8 mm was cut out into a size of 50 mm x 50 mm, and the polymerizable composition A1 to the polymerizable composition A4 and the polymerizable composition B1 (Manufactured by GS Yuasa Lighting, trade name: GSN2-40) using an ultraviolet absorber filter SC40 (manufactured by FUJIFILM CORPORATION), and the irradiation intensity was 190 mW / Cm &lt; 2 &gt; (value of 405 nm) and an irradiation dose of 5000 mJ / cm &lt; 2 &gt; (value of 405 nm) to obtain a polymer film for evaluation test with a thickness of about 0.2 mm sandwiched on a resin plate.

The polymeric films A1 to A4, and the polymeric films B1 to A4 are respectively referred to as polymeric films A1 to A4 and polymeric films B1, respectively.

&Lt; Measurement of hardening rate &

(Monomer, oligomer) from each of the polymerizable composition A1 to the polymerizable composition A4 before the irradiation, the polymerizable composition B1 and the polymerized film A1 to polymerized film A4, and the polymerized film B1 after polymerization were mixed in an amount of 0.2 wt% , And the peak intensity I ₀ of the curing component in the polymerizable composition and the peak intensity I _I of the polymer component in the polymer film were determined by liquid chromatography, And the curing rate was calculated.

Curing rate (%) = (I ₀ -I _I ) / I _O × 100

The results are shown in Table 2.

<Measurement of Adhesion>

The polymeric film A1, the polymerizable composition A4, and the polymeric film B1 having a film thickness of about 0.2 mm prepared in the above manner were fixed to a tensile tester (EZ Test / CE manufactured by Shimadzu Corporation), and a tensile rate of 10 mm / min And the adhesion was determined. The results are shown in Table 2.

<Test for blister (foaming peeling)>

The polymeric film A1, the polymerizable composition A4, and the polymeric film B1 having a film thickness of about 0.2 mm prepared in the above manner were placed in a high-temperature thermostat (THC-64 manufactured by IMV Corporation) at 65 ° C and 93% for 3 days, Peeling, and floating.

○: No foaming, peeling, or floating

X: Foaming, peeling, and floating

The results are shown in Table 3.

The present invention can be suitably used for manufacturing an image display device.

1 display unit 2 display unit
3 Protective part 4 Spacer
5a, 5b Polymerization or polymeric layer 6a, 6b Polarizer
7 Touch sensor

Claims (15)

A manufacturing method of an image display apparatus having a base portion having an image display device or an image display portion having a base having an image display portion and a light-transmitting protection portion made of resin, a translucent protection portion made of resin, and a translucent touch sensor portion having a resin- ,
That way,
Between the base portion having the image display portion and the translucent protection portion made of resin, between the base portion having the image display portion and the translucent touch sensor portion having the protective film made of resin, and between the translucent touch sensor portion having the protective film made of resin and the translucent protection portion made of resin A step of interposing the polymerizable composition in at least one selected from the group consisting of
And a step of polymerizing the polymerizable composition by irradiating light over at least one light-transmissive portion selected from a translucent touch sensor portion having a translucent protective portion made of resin and a protective film made of resin,
The polymerizable composition may contain,
(Component 1) a compound having a (meth) acryloyl group, and
(Component 2) A photopolymerization initiator having an absorption wavelength in a visible light region of 380 to 780 nm,
Wherein the polymerizable composition has a viscosity at 25 占 폚 of 500 to 50000 mPa 占 퐏. The method according to claim 1,
Wherein the protective film of the translucent protective part or the touch sensor is made of at least one selected from the group consisting of polymethyl methacrylate, polycarbonate, cycloolefin polymer, cellulose and polyester. 3. The method according to claim 1 or 2,
The photopolymerization initiator may be at least one selected from the group consisting of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 2,4,6-trimethylbenzoyldiphenylphosphorus Wherein the metal oxide is at least one selected from the group consisting of titanium oxide and titanium oxide. 3. The method according to claim 1 or 2,
In the step of polymerizing the polymerizable composition by irradiating light over at least one light-transmissive portion selected from a resin-made light-transmitting protective portion and a resin-made protective film, the amount of light to be irradiated is the ultraviolet light amount Wherein the value of the integrated light amount measured by using the system is 1000 to 10000 mJ / cm &lt; 2 &gt;. 3. The method according to claim 1 or 2,
Component 1 comprises a (meth) acryloyl group-containing polymer compound having a number average molecular weight of 1,000 to 40,000 and a (meth) acryloyl group-containing compound having a molecular weight of 500 or less. 6. The method of claim 5,
Wherein the (meth) acryloyl group-containing polymer having a number average molecular weight of 1000 to 40000 is urethane (meth) acrylate. The method according to claim 6,
Wherein the urethane (meth) acrylate comprises a residue of a polyester polyol obtained by an ester exchange reaction between a hydrogenated dimer diol and a diester. 6. The method of claim 5,
The (meth) acryloyl group-containing compound having a molecular weight of 500 or less,
A (meth) acrylate having a hydrocarbon group having 8 to 18 carbon atoms and (meth) acrylate having an ether bond, and
A (meth) acrylamide-based compound and an alcoholic hydroxyl group-containing (meth) acrylate. 3. The method according to claim 1 or 2,
The polymerizable composition may contain,
(Component 3) The method for manufacturing an image display apparatus according to claim 1, further comprising a compound composed of only carbon atoms and hydrogen atoms, or a compound composed only of carbon atoms, hydrogen atoms and oxygen atoms, and having no ethylenic double bond. 10. The method of claim 9,
Component 3,
A compound which is liquid at 25 占 폚 and a compound which is solid at 25 占 폚. 11. The method of claim 10,
Component 3 comprises a compound which is liquid at 25 &lt; 0 &gt; C,
The compound, which is liquid at 25 DEG C,
A liquid polybutene, a liquid polybutadiene, a liquid polybutadiene, a liquid polybutadiene, a liquid polybutadiene, a liquid polybutadiene, a liquid polybutadiene, a liquid polybutadiene, a liquid polybutadiene, And at least one compound selected from the group consisting of liquid hydrogenated polybutadiene, liquid polyisoprene, liquid hydrogenated polyisoprene, liquid polybutadiene polyol, liquid hydrogenated polybutadiene polyol, liquid polyisoprene polyol and liquid hydrogenated polyisoprene polyol Wherein said method comprises the steps of: 11. The method of claim 10,
Component 3 comprises a compound which is liquid at 25 &lt; 0 &gt; C,
The compound, which is liquid at 25 DEG C,
Wherein at least one compound selected from the group consisting of a polyether polyol, a polyester polyol and a polycarbonate polyol is contained. 11. The method of claim 10,
Component 3 comprises a compound which is liquid at 25 &lt; 0 &gt; C,
The compound which is in a liquid state at 25 占 폚 may be a liquid poly (? -Olefin) liquid, an ethylene-propylene copolymer liquid, an ethylene-? -Olefin copolymer liquid, a propylene-? -Olefin copolymer liquid, A liquid hydrogenated polybutene, a liquid hydrogenated polybutene, a liquid hydrogenated polybutadiene, a liquid hydrogenated polyisoprene, a liquid hydrogenated polybutadiene polyol, and a liquid hydrogenated polyisoprene polyol. 11. The method of claim 10,
Component 3 comprises a compound which is solid at 25 &lt; 0 &gt; C,
Wherein the compound which is solid at 25 占 폚 comprises at least one compound selected from the group consisting of a hydrogenated petroleum resin, a terpene-based hydrogenated resin and a hydrogenated rosin ester. An image display apparatus capable of being manufactured by the method for manufacturing an image display apparatus according to any one of claims 1 to 3.

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