TWI600472B - A container for a discharge device filled with a liquid curable composition, a process for producing a container for a discharge device filled with a liquid curable composition, a discharge device for a liquid curable composition, and a display device - Google Patents

Description

Container for a discharge device filled with a liquid curable composition, method for producing a container for a discharge device filled with a liquid curable composition, discharge device for a liquid curable composition, and display device

The present invention relates to a container for a discharge device filled with a liquid curable composition filled between a protective member and a display module of various display devices, and a method for producing the same. Further, the present invention relates to a discharge device using such a container for a discharge device filled with a liquid curable composition.

Liquid crystal touch panel, organic EL (Electro Luminescence) touch panel, liquid crystal module, plasma display panel (Plasma Display Panel) for electric, electronic or two-wheeled or four-wheeled vehicles In various display devices such as a PDP), a digital and analog tachometer, a gap (air gap) is formed between a protective member (hereinafter sometimes referred to as a cover plate) of a display portion thereof and a display module. Therefore, it is considered that there are problems in impact resistance or visibility.

As a countermeasure against this, for example, the following technologies are used: for the purpose of improving the visibility of a touch panel type smart phone, a tablet type mobile terminal, and a TV (Television), the cover layer/touch on the outermost layer A resin having a refractive index equal to that of the cover sheet is filled between the sensors or between the touch sensor/liquid crystal module. Further, there has been proposed a method in which a reactive liquid curable composition is filled as such a resin in terms of easiness of filling, and ultraviolet rays (UV), electron beams (EB), and the like are used. The active energy ray, heat, moisture, and the like are hardened (Patent Document 1).

Such a reactive liquid curable composition is based on a panel manufacturer The amount used is filled and incorporated into a closed syringe or tube when used in a small amount or a moderate amount, and is filled and incorporated into a large container such as a bottle in a large amount of use. Unlike the case where the former is filled in a closed syringe or tube, when the latter is filled in a large container, a void is always generated in the large container, and the bubble enters the liquid curable composition during transportation. When it is used directly for filling the air gap, bubbles are generated at the time of coating, which causes a manufacturing failure. Therefore, it is necessary to perform defoaming treatment before the bonding step in the panel manufacturer.

In the case of such a defoaming treatment, there is a defoaming method by centrifugation or decompression. However, when a large amount of the liquid curable composition is used at one time, a bottle in which the liquid curable composition is self-incorporated is often used. Transfer to a specific tank for defoaming, or together with the bottle at the time of inclusion, into a specific tank for defoaming.

However, when the liquid curable composition is subjected to reduced pressure defoaming, a part of the liquid component such as a reactive diluent in the preparation is distilled off, causing a decrease in the suitability of the dispensing due to an increase in viscosity, and sticking. At the same time, the problem of performance degradation is followed. Moreover, it is necessary to extend the defoaming time in order to completely remove the microbubbles of the tens of μm grade which are judged to be defective in appearance in the bonding step of the panel manufacturer. In addition, a complicated confirmation step for confirming whether or not the microbubbles have been removed is required. Further, in general, there is almost no case where such a confirmation step is performed only by securing the above-described defoaming time. Therefore, in terms of the actual removal of the microbubbles, countermeasures against reliability are not necessarily taken. Moreover, since the decompression defoaming time in the panel manufacturer takes a long time, there is also a problem that the production efficiency of the panel is lowered.

Further, when the liquid curable composition is filled in the tube or the bottle, the liquid curable composition is in contact with the outside air or light is irradiated onto the composition, and there is a type according to the liquid curable composition. The problem of reduced storage stability after filling is different.

Further, various devices have been proposed and used as the discharge device for the liquid curable composition used in the bonding step of the panel manufacturer. For example, in the case of a small amount of use, it is proposed and widely used to discharge a liquid curable composition while maintaining a sealed state inside the syringe by actuating a plunger disposed in the sealed syringe. . Moreover, in the case of being used in a large amount, a device having the following configuration is proposed and widely used: in the pressurized container in which the liquid curable composition or the bottle is placed, as described above, the pressure is reduced, and the liquid is hardenable. After the composition is subjected to the defoaming treatment, for example, as shown in FIG. 11, a pressurized fluid such as air is injected into the pressurized container 46, and the liquid curable composition in the pressurized container 46 is pressurized by the pressure applied by the pressurized fluid. A is ejected from the ejection nozzle 21 to apply the member 40 (see, for example, Patent Document 2).

However, in the case of the ejection device shown in Fig. 11, which is used especially in a large amount of use, there is a case where the bubble enters because the liquid-hardening composition A in the pressurized container 46 comes into contact with the pressurized fluid. In the liquid curable composition A, bubbles are generated in the liquid curable composition after coating the member 40 such as the cover sheet or the cured product after curing. Further, depending on the type of the liquid curable composition, the properties of the liquid curable composition may be affected by contact with the pressurized fluid. For example, when a moisture curable composition is used as the liquid curable composition, If a person who does not sufficiently remove moisture is used as the pressurized fluid, the hardening starts when the liquid is supplied from the tank to the discharge nozzle, and the viscosity is increased.

Further, although the above problems can be avoided in the case of using a sealed syringe in particular, there is a problem that it is limited to a small amount of use and cannot cope with a large amount of use.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-248347

[Patent Document 2] Japanese Patent Publication No. 2-17264

In view of the above problems, an object of the present invention is to provide a liquid-like hardenability which can be applied to mass production and which is excellent in storage stability and which can prevent the generation of bubbles at the time of coating or hardening without using a defoaming treatment. Further, the container for a discharge device of the composition is provided with a method for producing the container for a discharge device in which the liquid curable composition is filled, and further comprising providing the liquid-curable composition A discharge device for a container for a discharge device.

As a result of intensive studies, the inventors have found that the above problems can be solved by using a container for a discharge device having a specific structure, and the present invention has been completed. That is, the gist of the present invention is as follows.

(1) A container for a discharge device filled with a liquid curable composition, which is filled with a liquid curable composition and can be pressed by an external force Further, the deformer includes a discharge side connection portion connectable to the discharge device and a discharge side seal portion that can open and close the discharge side connection portion at one end side in the longitudinal direction, and includes a connection different from the discharge side. The filling side connecting portion for filling the liquid curable composition in an airtight state, and the filling side sealing portion for sealing the filling side connecting portion to be opened and closed.

(2) The container for a discharge device filled with the liquid curable composition according to the above (1), wherein the container for the discharge device is composed of a sheet-shaped molded body containing a synthetic resin.

(3) The container for a discharge device filled with the liquid curable composition according to the above (2), wherein the sheet-like molded body containing the synthetic resin has a thickness of 0.05 to 0.5 mm.

(4) The container for a discharge device filled with the liquid curable composition according to any one of the above (1), wherein the filling-side connecting portion is formed in a longitudinal direction and a discharge side of the container for a discharge device The connecting portion is the other end side of the opposite side.

(5) The container for a discharge device filled with the liquid curable composition according to any one of the above (1), wherein the liquid curable composition has moisture curability and/or active energy. A line curable composition.

(6) A method of producing a container for a discharge device filled with a liquid curable composition, which is a container for a discharge device filled with a liquid curable composition according to any one of the above (1) to (5) In the method of manufacturing the liquid curable composition which has been subjected to the defoaming treatment in the airtight state via the filling side connecting portion, the filling side is sealed by the filling side sealing portion. Connection.

(7) A discharge device for a liquid-like curable composition, comprising: a container for a pressurizing device; and a container for a discharge device filled with a liquid curable composition according to any one of the above (1) to (5), In a state in which the filling-side sealing portion of the filling-side connecting portion is closed and in a state in which the discharge sealing portion of the discharge-side connecting portion is opened, the pressure-receiving container is disposed; and the discharge valve is ejected through the discharge. The side connecting portion communicates with the inside of the container for the discharge device, and the pressurizing mechanism applies a pressing force from the outside of the container for the discharge device.

(8) The discharge device for a liquid-like curable composition according to the above (7), wherein the discharge device is disposed such that the discharge-side connection portion is located on a lower side in the vertical direction of the discharge device container. Pressurize the container.

(9) The discharge device of the liquid curable composition according to (7) or (8) above, wherein the pressurizing means is a pressurized fluid.

(10) The apparatus for discharging a liquid curable composition according to (9) above, comprising controlling the liquid curable composition to eject from the liquid based on a pressure inside the pressurizing container applied by the pressurizing means A pressure control mechanism for the discharge amount of the container for the device.

(11) The liquid curable composition of any one of the above-mentioned (7) to (10), further comprising a liquid curable composition for controlling the liquid supplied from the container for the discharge device to be ejected from the liquid ejecting composition A discharge control mechanism for the discharge amount of the valve.

(12) A display device using the discharge device of the liquid curable composition according to any one of the above (7) to (11) for protecting members or functionalities Applying a liquid curable composition to the protective member and/or the display module, and bonding the protective member or the functional protective member to the display module via the liquid curable composition to form the liquid The curable composition is obtained by hardening.

According to the present invention, it is possible to easily provide a liquid-curable composition which can be applied to mass production and which is excellent in storage stability and which can prevent generation of bubbles at the time of coating or hardening without using a defoaming treatment at the time of use. The container for the ejection device. Moreover, since the discharge apparatus of the present invention includes the above-described container for a discharge device filled with the liquid curable composition, it is possible to prevent the occurrence of bubbles and to apply a liquid curable composition such as a protective member, and it is easy to obtain. Various display devices excellent in visibility and sharpness of the screen.

1. Container for ejection device

The container for a discharge device used in the present invention can be deformed by a pressing force from the outside while being filled with a liquid curable composition, and can be connected to the discharge device at one end side in the longitudinal direction thereof. a discharge side connection portion, and a discharge side seal portion that can seal the discharge side connection portion to be opened and closed, and includes a filling side that is different from the discharge side connection portion for filling the liquid curable composition in an airtight state The connecting portion and the filling-side sealing portion that can open and close the sealing-side connecting portion.

By providing the discharge side connecting portion and the filling side connecting portion different therefrom, even if the container for the discharge device is filled with the liquid curable composition After the liquid-hardening composition is modified or the like in the vicinity of the filling-side connecting portion for some reason, and a solid component is formed and adhered to the filling-side connecting portion, it may be connected from the discharge side in a state of a non-solid component. Since the liquid curable composition is ejected, the possibility of mixing impurities into the liquid curable composition supplied to the discharge valve can be remarkably reduced. When the filling in the container for the discharge device is completed, the contact with the outside air cannot be completely prevented. Therefore, for example, when the composition having moisture curability described below is used as the liquid curable composition, it is effective. .

The shape and characteristics of the container for the discharge device are not particularly limited as long as they can be deformed by external pressing force in a state in which the liquid curable composition is filled therein, and can be applied to the following discharge device. In the pressure vessel, it is preferable to contain a large amount of the liquid curable composition and to reduce the residual amount of the liquid curable composition in the container after application of the cover sheet or the like, and it is preferable to include softness. In the case of a high sheet-like molded body, it is more preferable to include a sheet-like molded body containing a synthetic resin. Examples of such a synthetic resin include polyethylene (low density, high density), olefin-based resins such as polypropylene, polyvinyl chloride, polyvinylidene chloride, and ethylene-Vinyl alcohol (EVOH). , but not limited to, polyethylene terephthalate, polycarbonate, polystyrene, cedar (polysaccharide), polyamine, polyester, and the like. Further, from the viewpoint of storage stability, it is preferred to use a sheet-like formed body having high gas barrier properties such as oxygen gas or water vapor, and for example, EVOH or cedar which has high gas barrier properties can be used. The resin may be laminated with other synthetic resins to form a sheet. Further, in terms of imparting the same gas barrier properties, it can also be used for the formation of a synthetic resin sheet. The surface of the body is vapor-deposited with aluminum or ruthenium oxide, or used for disposing and laminating aluminum foil between synthetic resins to form a sheet. In the case where the liquid curable composition described below has ultraviolet curability, a sheet-like molded body obtained by using a resin obtained by vapor-depositing aluminum or a sheet made of aluminum foil is used from the viewpoint of light-shielding property. The shaped body can be used.

In addition, the thickness of the sheet-like molded body containing the synthetic resin is not particularly limited as long as it can be deformed by external pressing force while being filled with the liquid curable composition, and is preferably 0.05 to 0.5. Mm. Thereby, a sheet-like molded body containing a synthetic resin having high flexibility can be obtained, and the residual amount of the liquid curable composition in the container after application can be further reduced.

Such a sheet-like formed body can be obtained by extrusion molding into a sheet shape, blow molding, or the like according to a usual method, using the above-mentioned synthetic resin or the like. In addition, the container for a discharge device can be suitably formed into a bag shape by extrusion molding into a sheet-like molded body, or may be formed of a bag-shaped formed body obtained by blow molding.

Moreover, the volume of the container can be arbitrarily selected in consideration of the volume of the container for pressurization of the following discharge device, the amount of use, and the like. In the case of mass production, there is a case where, for example, 0.5 L to 50 L or more of the pressurizing container is used, and the volume which can be applied to the pressurizing container can be appropriately selected. However, in the case of a smaller amount of use, it is also possible to select a volume according to it.

The configuration of the discharge-side connecting portion and the discharge-side sealing portion that can open and close the discharge-side connecting portion is not particularly limited. The structure of the discharge side connecting portion can be connected to the discharge device and can be connected via the discharge side connection portion. The curable composition filled in the container for the discharge device may be supplied to the discharge nozzle of the discharge device. In addition, the discharge side connection portion is provided with a hollow portion that communicates with the inside and outside of the container for the discharge device, and the discharge side seal portion that can be opened and closed to seal the hollow portion of the discharge side connection portion.

The configuration of the discharge-side sealing portion is not particularly limited, and a detachable cover that seals the hollow portion of the discharge-side connecting portion from the outside of the container for the discharge device may be provided, or the hollow portion may be sealed from the inside of the container for the discharge device. The freely opening and closing valve may be provided with a valve that can be freely opened and closed in the hollow portion, or other configurations may be employed. In view of the ease of attachment of the discharge device and the prevention of contact with the outside air, the valve is preferably provided in a state in which the hollow portion is closed without being connected to the discharge device, and is connected to the discharge device. In the state in which the hollow portion is opened, various check valves and the like using an elastic body can be exemplified.

The configuration of the filling-side connecting portion and the filling-side sealing portion that can seal the filling-side connecting portion to be opened and closed is not particularly limited. The structure of the filling-side connecting portion is not particularly limited as long as it is a structure capable of ensuring an airtight state when the liquid curable composition is filled in the container for a discharge device, and the side of the liquid-curable composition is supplied (filled) The connection portion of the device may be configured correspondingly. In addition, the filling-side connecting portion is provided with a hollow portion that communicates with the inside and outside of the container for the discharge device, and the discharge-side sealing portion that can be opened and closed to seal the hollow portion of the discharge-side connecting portion.

The structure of the filling-side sealing portion is not particularly limited, and a detachable lid that seals the hollow portion of the filling-side connecting portion from the outer side of the container for the discharge device may be provided, or the hollow portion may be sealed from the inside of the container for the discharge device. of The valve that is freely opened and closed, or a valve that can be opened and closed freely in the hollow portion, or other configuration may be employed. In view of the ease of attachment of the connection portion of the filling device and the prevention of contact with the outside air, the valve is preferably provided in a state in which the hollow portion is closed without being connected to the filling device, and is filled and filled. In the state in which the hollow portion is opened in a state in which the devices are connected, various check valves and the like using an elastic body can be exemplified. Moreover, from the viewpoint of ensuring the airtightness (sealing property) of the fitting portion between the connection portion of the filling device and the hollow portion of the filling-side connecting portion, a sealing ring containing an elastic body may be disposed on the wall surface constituting the hollow portion.

Moreover, the arrangement of the discharge-side connecting portion may be one end side in the longitudinal direction of the container for a discharge device. In addition, the arrangement of the filling-side connecting portion is not particularly limited, and it is preferable to arrange the self-discharging connecting portion only from the viewpoint of preventing impurities such as solid matter generated in the vicinity of the filling-side connecting portion from being discharged from the discharge-side connecting portion. It is more preferable that the position at a fixed distance is at the other end side on the opposite side to the discharge-side connecting portion in the longitudinal direction of the container for the discharge device.

In addition, the joining of the discharge-side connecting portion and the filling-side connecting portion in the container for the discharge device is not particularly limited as long as the leakage of the curable composition does not occur, and in consideration of the materials and the like, welding and adhesion can be used. And other methods.

Hereinafter, an example of an embodiment of a container for a discharge device filled with a liquid curable composition of the present invention will be described based on the drawings.

1 is a view showing an example of a container for a discharge device in a state in which a liquid curable composition of the present invention is placed in a state in which the container holder 108 is placed in a container for a pressurization of a discharge device. Container for ejection device 101 includes a sheet-like formed body 2 joined to a bag shape, and a filling-side connecting portion 103 and a filling-side sealing portion 105 are disposed at one end in the longitudinal direction (the lower side in FIG. 1), and the other end (the upper side of FIG. 1) The discharge side connecting portion 104 and the discharge side sealing portion 155 are disposed. The inside of the container 101 for a discharge device is in a state in which the liquid curable composition A is filled. 1 is a state in which the discharge side connecting portion 104 is disposed so as to be located on the upper side in the vertical direction of the discharge device container 101, and the liquid supply pipe is inserted into the discharge side connection portion 104 and the discharge side seal portion 155. 119 is connected to the connecting portion 109.

The container holder 108 shown in Fig. 1 has the same configuration as the container holder 8 shown in Figs. 5 and 8 described below. Therefore, the same symbols are given to the common parts. The difference is that in the container holder 108 of FIG. 1, the base portion 116 is not provided with the connecting portion 9 and the liquid supply line 17 provided on the base 16 of the container supporting portion 8. Further, although not shown, a mechanism for fixing the filling-side connecting portion 103 of the container 101 for a discharge device may be provided in the susceptor 116.

A detailed description of the discharge side connecting portion 104 and the discharge side sealing portion 155 shown in Fig. 1 is shown in Fig. 2 . Fig. 2(a) is a perspective view showing the discharge side connecting portion 104 and the discharge side sealing portion 155, and Fig. 2(b) is a cross-sectional view taken along line I-I of Fig. 2(a). Fig. 2 (c) is a perspective view of the discharge side seal portion 155 shown in Figs. 2 (a) and (b). As shown in Fig. 2 (a) and (b), in the present embodiment, the discharge-side connecting portion 104 includes a hollow portion 107 that communicates from one end to the other end, and a discharge-side sealing portion 155 is disposed in the hollow portion 107.

The discharge side seal portion 155 of the present embodiment is a backflow prevention valve called a duckbill valve, and includes a cylindrical valve body 154 as shown in Fig. 2(c), and a projection protruding outward from the valve body 154 at one end portion thereof. 152, from the valve body 154 A pair of inclined lip surfaces 153 extending in a manner to converge toward the other end, and a slit 151 formed in the joint surface of the lip surface 153. Further, before the insertion side sealing portion 155 is inserted into the connection portion 109, the pair of lip surfaces 153 are pressed by the internal pressure of the liquid curable composition A filled in the discharge device container 101, and the slit 151 is closely attached. To prevent leakage of the composition A. The discharge side seal portion 155 of this example is composed of an elastic body from the viewpoint of exerting such a function. The material of the elastomer may be any one that is inert to the composition A, and examples thereof include a polysiloxane resin, various elastomers, and the like.

In the present example, the discharge side seal portion 155 is disposed in the hollow portion 107 of the discharge side connecting portion 104 such that a part thereof is covered by the discharge side connecting portion 104 and the lip surface 153 protrudes outward. Moreover, the inner wall of the hollow portion 107 constituting the discharge-side connecting portion 104 is provided with a concave portion having a structure corresponding to the shape of the protruding portion 152 so as to lock the protruding portion 152 of the discharge-side sealing portion 155. Further, from the viewpoint of ensuring airtightness, it is necessary to perform bonding in a manner to ensure airtightness in a portion where the discharge side connecting portion 104 and the discharge side sealing portion 155 are in contact with each other. The bonding method may employ a conventionally known method such as physical methods such as bonding, welding, and riveting.

Further, in the present embodiment, the inner peripheral surface of the portion (the upper portion of FIG. 2(b)) where the discharge side seal portion 155 is not disposed in the hollow portion 107 of the discharge side connecting portion 104 and the valve body of the discharge side seal portion 155 are provided. The filling side seal portion 155 is disposed with respect to the discharge side connecting portion 104 so that the inner peripheral surface of the inner portion 156 of the 154 portion is aligned. The connecting portion 109 connected to the liquid supply tube 119 is inserted into the hollow portion 107 and the inner hollow portion. In the inside of the 156, the inside of the discharge container 101 is protruded from the slit 151, and the inside and the outside of the discharge container 101 can be communicated. In the ejection container 101 The composition A is discharged from the opening 145 at the front end of the connecting portion 109 to the connecting pipe 119.

In order to allow the discharge-side connecting portion 104 to be easily joined to the sheet-like molded body 2 without gaps, it protrudes outward from the cylindrical body portion 158 in the axial direction with respect to the central axis of the hollow portion 107 (Fig. In the vertical direction of Fig. 2(b), the wing portion 157 which is gradually tapered toward the center axis is provided in two places in the vertical direction (see Fig. 2(a)). In this example, the wing portion 157 has a substantially triangular column shape and a flat surface with respect to the surface, but is not limited thereto, and may be a curved surface.

Further, at one end portion of the discharge side connecting portion 104, a flange portion 144 for hooking the discharge side connecting portion 104 to the hook portion 42 of the container holder 108 as shown in FIG. 1 is provided.

Since the filling-side connecting portion 103 and the filling-side sealing portion 105 have the same configuration as the discharge-side connecting portion 104 and the discharge-side sealing portion 155, respectively, the description of the configurations is omitted.

Although not shown, a cover for closing the opening portion 159 of the hollow portion 107 may be provided in the filling-side connecting portion 103 and the discharge-side connecting portion 104 in order to prevent adhesion or erroneous insertion of foreign matter to the hollow portion 107. In this case, the cover may be removed when the connection portion 109 is connected to the discharge side connection portion 104.

In the present invention, the discharge side seal portion is not limited to those shown in Fig. 2(c), and other forms may be applied. Fig. 3 (a) shows another example of the discharge side seal portion which can be used in the present invention. Fig. 3 (b) is a view showing a state in which the discharge side seal portion 160 shown in Fig. 3 (a) extends in the axial direction. Fig. 3 (c) shows the discharge side seal portion 160 shown in Fig. 3 (a) and the discharge side joint portion shown in Fig. 2 The cross-sectional view corresponding to Fig. 2(b) when the 104 is combined and arranged such that the line connecting the both ends of the slit 161 of Fig. 3(a) is substantially parallel to the slit 151 of Fig. 2 . (d) of FIG. 3 is a view showing a state in which the discharge-side sealing portion 160 shown in FIG. 3(c) is inserted into the connection portion 109 so as to extend in the axial direction. Hereinafter, the aspects specific to the discharge side sealing portion 160 of the present embodiment will be described, and the description of other common aspects will be omitted.

As shown in Fig. 3(c), the discharge side seal portion 160 shown in Fig. 3(a) can be used in combination with the discharge side connection portion 104 shown in Fig. 2. As shown in Fig. 3 (a) and (c), the discharge side seal portion 160 of the present embodiment includes a cylindrical valve body 163 whose one end is sealed and whose other end is open, and a projection which protrudes outward from the valve body 163 at the other end portion thereof. The portion 162 and the slit 161 which is provided on the side wall of the valve body 163 and which is openable and closable in communication with the inside and the outside. In the present example, the slit 161 is formed as a slit perpendicular to the axial direction of the valve body 163 and continuous in the circumferential direction by a specific length. In this example, the number of the slits 161 is two in the opposite wall faces, but the number of the slits 161 is not limited thereto.

Further, as shown in FIGS. 3(b) and 3(d), the connecting portion 109 is inserted into the hollow portion 107 of the discharge-side connecting portion 104 and the inner hollow portion 166 of the discharge-side sealing portion 160, and the valve body is pressed by the tip end portion thereof. One end of the seal of 163 (pushed in the direction of the arrow of Fig. 3(d)), whereby the valve body 163 extends. As a result, the slit 161 forms an opening, and the outside of the discharge side seal portion 160 communicates with the inner hollow portion 166. By maintaining this state, the composition A in the discharge container 101 is discharged from the opening 145 at the front end of the connection portion 109 to the connection pipe 119. Further, the method of maintaining the connection state of the connecting portion 109 is not particularly limited, and a conventionally known method can be employed.

Moreover, the discharge side seal portion 160 of this example can also be used as a filling side seal portion.

Further, in the present invention, as another example of the discharge side connecting portion and the discharge side sealing portion, the one shown in Fig. 4 can be applied. Fig. 4 (a) is a perspective view showing still another example of the discharge side connecting portion of the present invention, and Fig. 4 (b) is a cross-sectional view taken along line II-II of Fig. 4 (a) showing a state in which the discharge side seal portion is closed. Fig. 4(c) is a cross-sectional view taken along line II-II of Fig. 4(a) showing a state in which the discharge side seal portion is opened.

As shown in FIGS. 4(a) to 4(c), the discharge side connecting portion 170 of the present example has a sleeve 171 which is sealed at one end and opened at the other end and in which the hollow portion 175 is formed. The outer sleeve 171 includes a cylindrical main body portion 177 that is sealed at one end, and two openings 172 that communicate with the hollow portion 175 on the outer side of the outer sleeve 171 and that face the side wall of the main body portion 177, and protrude toward the outer side of the main body portion 177. A pair of wing portions 174 and a pair of protrusion portions 173. Similarly to the case of the example of FIG. 2( a ), the wing portion 174 is a structure for facilitating the joint with the sheet-like molded body 2 without a gap, and is not limited to the shape as long as the shape can be achieved. 4 shown. The protrusion 173 is a hook portion 42 for hooking the container holder 108 shown in Fig. 1 . A step is formed between the portion of the hollow portion 175 corresponding to the main body portion 177 and the portion of the corresponding wing portion 174, and the step portion becomes a tapered surface that tapers from a portion of the corresponding body portion 177 to a portion corresponding to the wing portion 174. 176. The peripheral edge portion 183 of the valve body 181 abuts against the tapered surface. Further, in the present example, the position of the tapered surface 176 is provided at the boundary between the hollow portion 175 corresponding to the main body portion 177 and the wing portion 174, but the present invention is not limited thereto and can be appropriately determined.

As shown in FIGS. 4(b) and 4(c), the discharge-side sealing portion 180 of the present embodiment is disposed in a portion of the hollow portion 175 of the discharge-side connecting portion 170 corresponding to the main body portion 177, and includes a valve body 181 and a spring 182. The valve body 181 is substantially cylindrical and A tapered peripheral portion 183 that is in contact with the tapered surface 176 of the discharge-side connecting portion 170 is formed at one end portion. Further, a projection 184 for supporting the spring 182 is formed on the other end side. From the viewpoint of ensuring the adhesion to the tapered surface 176 of the discharge side connecting portion 170, the material of the valve body 181 is preferably an elastic material such as rubber or elastomer. The spring 182 is supported by the projection 184 of the valve body 181 and is supported by a projection 178 disposed on one end side of the seal of the discharge side connecting portion 170.

According to the example shown in FIG. 4, the discharge side connection portion 170 and the discharge side seal portion 180 are provided before the connection portion 109 shown in FIG. 1 is inserted into the hollow portion 175 of the discharge side connection portion 170, as shown in FIG. 4(b). As shown in the figure, the valve body 181 is energized by the spring 182 to abut the peripheral edge portion 183 and adhere to the tapered surface 176, thereby sealing the hollow portion 175 and preventing the composition A in the container for the discharge device from leaking out. On the other hand, as shown in FIG. 4(c), the connecting portion 109 shown in FIG. 1 is inserted into the hollow portion 175, and the front end of the connecting portion 109 abuts against the valve body 181, along the arrow against the urging force of the spring 182. When the direction is pushed in, the hollow portion 175 communicates with the inside of the container for the discharge device via the opening portion 172, and the composition A in the container for the discharge device is discharged from the opening portion 145 of the connection portion 109 to the liquid supply tube 119.

Further, although not shown, in order to prevent adhesion or erroneous insertion of foreign matter to the hollow portion 175, a lid that closes the opening portion 179 of the hollow portion 175 may be provided in the discharge side connecting portion 170. In this case, the cover may be removed when the connection portion 109 is connected to the discharge side connection portion 170.

Moreover, the discharge side seal portion 170 of this example can also be used as the filling side seal portion.

Fig. 5 is a view showing the liquid-hardenable composition of the present invention in a state of being placed on the container holder 8 in the pressurizing container of the discharge device described below. A diagram of another example of a container for a discharge device in a state. The container 1 for a discharge device includes a sheet-like molded body 2 joined to a bag shape, and a filling-side connecting portion 3 is disposed at one end in the longitudinal direction (the upper side in FIG. 5), and is disposed at the other end (the lower side in FIG. 5). There is a discharge side connecting portion 4. The inside of the container 1 for a discharge device is in a state in which the liquid curable composition A is filled. In this example, the filling-side connecting portion, the filling-side sealing portion, the discharge-side connecting portion, and the discharge-side sealing portion are different from those in FIGS. 1 to 4, and the discharge-side connecting portion and the filling-side connecting portion of the discharge device container are changed. In the positional relationship, the discharge side connecting portion 4 is disposed on the container holder 8 so as to be positioned on the lower side (lowest end portion) in the vertical direction in the container 1 for the discharge device. Further, of course, the one shown in FIGS. 2 to 4 can be used as the filling side connecting portion, the filling side sealing portion, the discharge side connecting portion, and the discharge side sealing portion.

The filling-side connecting portion 3 is formed with a hollow portion 7 that communicates the inside and the outside of the container 1 for a discharge device, and a filling-side sealing portion supported by two elastically deformable arms 6 extending from the filling-side connecting portion 3 is disposed. 5. In addition, the filling side seal portion 5 functions as a valve that seals the hollow portion 7 to open and close inside the discharge device container 1 by elastic deformation of the arm portion 6. In Fig. 5, the filling-side sealing portion 5 is in a closed state.

Further, the discharge side sealing portion 5' supported by the elastically deformable two arm portions 6' extending from the discharge side connecting portion 4 is disposed on the discharge side connecting portion 4, and is elastically deformed by the arm portion 6'. The discharge side seal portion 5' functions as a valve that seals the hollow portion 7' to the inside of the discharge device container 1 so as to be openable and closable. In Fig. 5, a connection portion 9 of a container holder 8 that communicates with a discharge device (not shown) is inserted into a hollow portion 7' of the discharge side connecting portion 4, and a discharge side seal portion is inserted. 5' is in an open state.

Further, the connecting portion 9 inserted in the hollow portion 7' of the discharge-side connecting portion 4 presses the discharge-side sealing portion 5' toward the inside of the discharge device container 1 at the tip end portion thereof, and elastically deforms the arm portion 6 to the discharge side. The sealing portion 5' is away from the hollow portion 7', whereby the discharge side sealing portion 5' is opened. When the connecting portion 9 is taken out from the hollow portion 7, the elastically deformed arm portion 6 returns to the original state (shape) before the deformation, and the sealed state in which the discharge-side sealing portion 5' is inserted into the hollow portion 7' is maintained. Therefore, even when the liquid curable composition remains in the container for the discharge device, it can be used as it is. In addition, the sealing state can be maintained by a fitting structure or the like in which the discharge-side sealing portion 5' and the discharge-side connecting portion 4 have a concavo-convex tapered shape (not shown).

The filling-side connecting portion 3, the filling-side sealing portion 5, the discharge-side connecting portion 4, and the discharge-side sealing portion 5' in the present embodiment can be formed by performing injection molding or the like using various resins.

2. Method for producing a container for a discharge device filled with a liquid curable composition

In the present invention, after the container for a discharge device described above is filled in the container for a discharge device by the liquid-solid curable composition which has been subjected to the defoaming treatment in an airtight state, the container for the above-described discharge device is used. The filling side connecting portion is sealed by the filling side seal portion to produce a container for a discharge device filled with the liquid curable composition.

By performing the defoaming treatment on the liquid curable composition in advance, it is possible to eliminate the need for the defoaming treatment at the time of manufacture of a panel or the like, and it is possible to cause a change in the composition of the liquid curable composition due to the defoaming treatment or It is hardened (gelled) and coated on a cover sheet or the like. Also, due to the liquid hardening in an airtight state Since the composition is filled in the container for the discharge device, the liquid curable composition does not come into contact with the outside air, and can be filled in the container for the discharge device in a light-shielded state depending on the conditions. Therefore, according to the method for producing a container for a discharge device filled with a liquid curable composition of the present invention, it is possible to provide a container for a discharge device filled with a liquid curable composition which is excellent in storage stability.

The defoaming treatment is not particularly limited, and examples thereof include decompression and defoaming. In addition, the method of filling the inside of the container for the discharge device in an airtight state is not particularly limited, and examples thereof include a method of connecting the hollow portion of the filling-side connecting portion of the container for the discharge device to the filling device. The fitting portion of the portion is formed into a tapered fitting, or a sealing ring or the like is disposed on the outer peripheral surface of the hollow portion of the hollow portion of the filling-side connecting portion or the connecting portion of the filling device, and the liquid is supplied from the filling device via the filling-side connecting portion. The form-hardening composition is filled in the container for a discharge device, but it is not limited to these.

In addition, when the liquid curable composition is filled in the container for the discharge device, the inside of the container for the discharge device can be further reduced in pressure from the viewpoint of remaining air in the container for the discharge device. status.

Fig. 6 is a view showing an example of a filling device used when the liquid curable composition is filled in a container for a discharge device. As shown in Fig. 6, the filling device B of the present embodiment is configured to have a mixing tank 10 in which a liquid curable composition in a state of being subjected to defoaming treatment in advance, a valve 11 disposed at the bottom thereof, and a regulating discharge device The valve 12 for supplying the liquid to the container 1 and the pipe 13 for connecting the mixing tank 10 and the container for the discharge device 1 via a valve, and measuring the weight (filling amount) of the liquid curable composition filled in the container 1 for the discharge device 14. Further, although not shown, the gauge 14 and the valves 11 and 12 may be configured to be controlled such that the valves 11 and 12 can be opened and closed by a predetermined filling amount.

Fig. 6 shows an example in which the container 1 for a discharge device similar to that shown in Fig. 5 is used. Therefore, the same components are denoted by the same reference numerals, and the description thereof is omitted. In FIG. 6, the discharge-side connecting portion 4 is sealed by the discharge-side sealing portion, and is fitted in the filling-side connecting portion 3 in an airtight state. The connection portion (not shown) of the filling device is in a state in which the filling-side sealing portion is opened away from the hollow portion and the filling-side sealing portion is opened.

Further, although not shown, the pressure reducing pump may be connected to the discharge side connecting portion 4 to set the inside of the discharge device container 1 to a reduced pressure state. Further, as the container for the discharge device, of course, the modification shown in Fig. 1 or the application of the discharge side connection portion shown in Figs. 2 to 4 can be used.

3. Ejection device

The discharge device of the present invention includes: a container for pressurization; and a container for a discharge device filled with the liquid curable composition, wherein the filling-side sealing portion of the filling-side connecting portion is closed and the discharge side is connected The discharge sealing portion is disposed in the pressurizing container, and the discharge valve communicates with the inside of the discharge device container via the discharge side connection portion, and the pressurizing mechanism ejects from the discharge container The device applies a pushing force to the outside of the container.

The container for pressurization is not particularly limited as long as it can be applied from the outside of the container for the discharge device by the pressurizing mechanism, and can be appropriately selected according to the pressurizing mechanism. In the case of imparting mechanical pressurization as a pressurizing mechanism (For example, a machine that applies a pressing force by sandwiching a container for a discharge device between rolls, etc.), the mechanical machine can function as a container for pressurization. In the case where a pressurized fluid is used as the pressurizing means, a pressure-resistant container or the like which can hold the container for the discharge device in an airtight state can be cited. In the present invention, it is preferable to use a sheet-like molded body containing a synthetic resin as a container for a discharge device from the viewpoint of further effectively exhibiting the effect, and further improve the discharge device. From the viewpoint of accuracy and stability of the discharge amount of the container, it is preferable to use a pressurized fluid as the pressurizing means. Therefore, as the container for pressurization, a pressure resistant container is preferably used. Further, the pressurized fluid is not particularly limited, and for example, compressed air, an inert gas or the like can be used.

The arrangement of the container for the discharge device in the container for pressurization is not particularly limited, and can be appropriately determined depending on the configuration of the pressurizing mechanism and the container for the discharge device. When the container for a discharge device includes a sheet-like molded body containing a synthetic resin, it is not necessarily easy to be independent, and when a pressurized fluid is used as a pressurizing mechanism, from the viewpoint of stability of discharge, The need to further stabilize the original posture is higher. Therefore, in the case where the container for the discharge device and the pressurizing mechanism are of such a configuration, it is preferable to use a container holder which can hold the container for the discharge device in a desired posture. In addition, the position of the discharge side connecting portion of the container for the discharge device is not particularly limited, and when the container for the discharge device is placed in the container for pressurization, the discharge side connecting portion can be made vertical in the container for the discharge device. The manner of the upper side of the direction may be set to the lower side of the vertical direction. Here, in order to allow the inside of the discharge device container to communicate with the discharge valve, the connection between the two is arranged in the discharge side connection portion. The tube is provided at one end thereof with a connection portion connectable to the discharge side connection portion, and the connection portion of the pipe is coupled to the discharge side connection portion.

In the case where the discharge side connecting portion is disposed on the upper side in the vertical direction of the container for the discharge device, first, the liquid curable composition on the upper side of the container is discharged to the discharge valve. Therefore, most of the composition placed on the lower side of the container is moved to the upper side, and the container is pressed by the pressing force of the pressurized fluid to adhere the sheet-shaped formed body to the composition, and the composition remains in the container. In order to avoid this, there is a connection portion that uses a cylinder or a tube that communicates from the lower end of the container for the discharge device to the upper end as a pipe, or that is provided at one end (for example, the lower end) of the discharge container from the discharge side connection portion or the discharge side seal portion. The case to the tube or tube at the other end (for example, the upper end). When such a cylinder or tube is provided in the connection portion of the pipe, the discharge side connection portion, or the discharge side seal portion, the problem of remaining is eliminated, but in the case of the former (connection portion of the pipe), the pipe is present. When the connection portion is disposed in the container for the discharge device, the possibility of air being mixed tends to be high, and in the case of the latter (the discharge side connection portion or the discharge side seal portion), the periphery of the tube or the tube is likely to be present. The tendency to fill the corners of the composition, and the possibility of residual air at the time of filling is high.

On the other hand, when the discharge-side connecting portion is disposed on the lower side in the vertical direction of the container for the discharge device, the container for the discharge device is unevenly deformed by the pressing force of the pressurized fluid. In the case where the liquid curable composition is actively moved to the lower side in the vertical direction by its own weight, the sheet-shaped formed body is not adhered to the liquid curable composition via the discharge-side connecting portion. The valve is discharged. Therefore, no need The use of the above-mentioned cylinder as the connecting portion does not prevent the generation of air bubbles due to the incorporation of air caused by it. In this way, since the liquid curable composition in the container for the discharge device can be prevented from being wasted without being generated, the position of the discharge side connecting portion is preferably in the vertical direction in the container for the discharge device. In the side, the container for the discharge device is placed in the pressurized container, and more preferably in the lowermost end portion of the container for the discharge device in the vertical direction.

The configuration of the discharge valve is not particularly limited, and those having a dispensing valve and a coating head can be used.

The dispensing valve is not particularly limited, and various types can be used depending on the application. In the case where the coating amount of the liquid curable composition is controlled with high precision while preventing the generation of bubbles, or when it is necessary to apply the coating at a high speed, it is preferable to use a spool valve, a diaphragm valve, Needle valve, poppet valve, barrel pump, metering pump, plunger pump, piston and spring pump, rotary control pump, etc. Further, in terms of maintainability, durability, and controllability, it is more preferable to use a diaphragm valve, a needle valve, a plunger pump, a piston, and a spring pump.

In addition, the coating head is not particularly limited, and various types can be used depending on the application, and it is preferable that the coating amount of the liquid curable composition can be controlled with high precision while preventing the generation of bubbles. The multi-head method of the dispensing valve, the coating valve, the T mold, and the single-fluid spray gun head are more preferably the multi-head method of the dispensing valve, the coating valve, and the T mold.

Further, as the discharge valve, a known one can be used.

Preferably, the ejection device of the present invention is provided with a pressure control mechanism when a pressurized fluid is used as the pressurizing mechanism, which is based on a pressurizing mechanism The pressure inside the container for pressurization is controlled to control the discharge amount of the liquid curable composition from the container for the discharge device. Thereby, the coating amount of the liquid curable composition discharged from the discharge valve can be accurately controlled.

Moreover, it is preferable that the discharge device of the present invention further includes a discharge control mechanism that controls the discharge amount of the liquid curable composition supplied from the container for the discharge device from the discharge valve. Thereby, the coating amount of the liquid curable composition discharged from the discharge valve can be controlled with high precision.

Further, a known control device can be used as each of the above-described control mechanisms.

Further, when the residual amount of the liquid curable composition in the container for the discharge device is gradually reduced, it is necessary to exchange the container for the discharge device which is newly filled with the liquid curable composition. For the switching of such a container, for example, a method of connecting at least two containers for a discharge device disposed in a container for pressurization and a discharge valve via a switching valve, and switching the switching valve; or not using a switching valve The use of the turntable directly exchanges the containers for the ejection device. In the case where the container for the discharge device is exchanged in this manner, air bubbles generated by the air are mixed in the liquid supply line of the liquid curable composition. In this case, since bubbles are generated after application, it is necessary to remove air bubbles from the liquid supply line. Examples of the method for removing the air bubbles include a method in which a switching valve is provided to the liquid supply line to provide a flow path for deaeration, or a method of providing an automatic defoaming valve. In the case where the flow path for defoaming is provided, there is a method of removing bubbles by the discharge pressure, and a method of removing the bubbles under reduced pressure, and may be appropriately selected.

Further, in the present invention, the liquid curable composition may be a single component or a mixture of a plurality of components such as a two component. Single ingredient in the former In the case of the liquid curable composition, the above-described discharge device can be used. On the other hand, in the latter case, a plurality of containers for a discharge device disposed in a container for pressurization may be prepared, and the liquid may be discharged from each of the discharge device containers so as to have a desired mixing ratio. The curable composition is supplied to the mixing tank, and the liquid mixture is supplied to the discharge valve by a mixer such as a static mixer disposed in the mixing tank.

Next, an example of an embodiment of the discharge device of the present invention will be described based on the drawings.

Fig. 7 is a schematic view showing an example of an embodiment of the discharge device of the present invention. As shown in FIG. 7 , the container 1 for a discharge device filled with the liquid curable composition and the container holder 8 for supporting the container 1 for the discharge device are placed in the container 15 for pressurization, and are kept in an airtight state. Further, the liquid supply pipe 19 is connected to the liquid supply side connecting portion 18 of the lid portion 20 provided in the pressurizing container 15 at one end thereof, and is connected to the base of the container holder 8 at the other end thereof. The hollow liquid supply line 17 (not shown in Fig. 7 and Fig. 5) is connected to the susceptor 16 so as to communicate with each other. Moreover, the connection portion 9 of the container holder 8 is inserted and fitted into the discharge side connecting portion 4 of the container 1 for the discharge device, and the connection portion 9 is communicated with the liquid supply line 17. Further, the liquid supply side connecting portion 18 communicates with the liquid storage portion 22 of the discharge valve 21 via the switching valve 23 and the pipe 27 .

Moreover, the pressurizing side connecting portion 24 provided in the lid portion 20 of the pressurizing container 15 communicates with the supply source 26 via the electromagnetic valve 25 and the pipe 28, and supplies the pressurized fluid from the supply source 26 to the pressurizing container 15 Inside.

Further, the discharge valve 21 includes a dispensing valve 29 and a coating head 30, and in this example, an example in which the slidable air is slidable in an airtight state is used. The space a33 disposed in the inside of the valve 21, the space b34, and the needle 31 and the piston 32 are disposed in the liquid storage portion 22. Further, a pressurized fluid is supplied from the supply source 26 to the space a33 and the space b34 via the electromagnetic valve 25 and the respective pipes 35 and 36 as needed. Further, although the solenoid valve 25 is shown as a whole for the sake of convenience, the pipes 28, 35, and 36 are provided separately.

Moreover, in this example, the pressure control means 37 is provided, and the discharge amount of the liquid curable composition from the discharge device container 1 is controlled based on the pressure inside the pressurization container 15. In addition, the pressure inside the pressure-receiving container 15 may be connected to the pressure control means 37 by providing a pressure measuring device (not shown) or the like in the pressurizing container 15 in advance. Further, the discharge control means 38 is provided to measure the internal pressure of the space a33 and the space b34 and the internal pressure of the liquid storage 22, and control the operation of the needle 31 and the piston 32 based on the measured value, and control the discharge port 39 from the discharge valve 21. The discharge amount of the liquid curable composition. An internal pressure measuring device (not shown) or the like is provided in the space a33, the space b34, and the stock solution 22, and these may be connected to the discharge amount control unit 38. Further, in the present embodiment, only one supply source of the pressurized fluid is shown, but the supply of the pressurizing container 15 and the discharge control of the discharge valve 21 may be different.

By the discharge device having the above-described configuration as the main configuration, the liquid curable composition in the discharge device container 1 is finally applied onto the member 40 such as a desired protective member from the discharge port 39 of the discharge valve 21. Demand. Further, the discharge valve 21 is connected to an operation device (not shown), and can arbitrarily move a specific range of the XYZ coordinate space to apply a desired amount to a desired position of the member 40. Such an operation device can be suitably utilized by a known person.

The arrangement method of the container 1 for a discharge device in the container 15 for pressurization will be further described based on Figs. As shown in FIG. 5, the container 1 for a discharge device is supported by the container support tool 8, and is disposed in the container 15 for pressurization. As shown in Fig. 8, the container holder 8 includes a susceptor 16, a connecting portion 9 disposed at a substantially central portion thereof, a liquid supply tube 19 connected to the susceptor 16, and a substantially U that connects the both end portions to the susceptor 16. The arcuate portion 41 of the glyph and the hook portion 42 disposed at a substantially central portion of the arcuate portion 41. Further, a liquid supply line 17 is formed inside the susceptor 16, and a connection portion 9 and a liquid supply tube 19 are connected to both end portions thereof. Further, the hook portion 42 is provided with a spring 43 for adjusting the height. Further, as shown in FIG. 5, the flange portion 44 of the filling-side connecting portion 3 is hooked to the hook portion 42 and the fitting portion 9 is inserted into the discharge-side connecting portion 5', whereby the container for the ejection device is fixed to the container 1 The container supports 8 on it. Moreover, in this example, the connection portion 9 has a substantially cylindrical shape, and an opening portion 45 is formed in the vicinity of the front end portion thereof, and the liquid curable composition is discharged from the discharge device container 1 through the opening portion 45. In the present embodiment, the container 8 is supported by the both ends of the discharge device container 1 in the longitudinal direction and the discharge side is provided on the lower side in the vertical (vertical) direction. The liquid curable composition can be actively moved to the discharge side connecting portion by its own weight. Therefore, even in the case of a soft sheet-like formed body, the pressing force by the pressurized fluid can be utilized. Further, the container 1 for the ejection device is prevented from being inadvertently deformed and stable ejection can be performed.

4. Display device

The display device of the present invention includes an impact resistance or visual recognition by forming an air gap between the protective member and the display module and filling the air gap. Various display devices with improved performance. For example, it can be exemplified by liquid crystal type touch panels, organic EL touch panels, liquid crystal modules, plasma display panels (PDPs), digital and analog speed measuring devices used in various electric and electronic devices or two-wheeled and four-wheeled vehicles. It is not limited to these. Further, examples of the electric or electronic device include a touch panel type smart phone, a tablet type mobile terminal, a TV, a digital (video) camera, a printer, a photocopier, and various other measuring devices, but are not limited thereto. In these.

In addition, examples of the protective member include a cover sheet made of transparent glass, synthetic resin, or the like. Examples of the display module include a module such as a liquid crystal, an organic EL, or a PDP.

The display device according to the present invention can be obtained by applying a liquid curable composition to, for example, a protective member and/or a display module using the above-described ejecting device, and bonding the display module via a liquid curable composition. It is obtained by curing the liquid curable composition with the above protective member.

The application of the liquid curable composition may be performed only on the protective member, or may be performed only on the display module, or both the protective member and the display module.

Further, in the present invention, a functional protective member may be used instead of the above protective member. Examples of the functional protective member include a protective member such as a cover sheet and a functional member such as a touch sensor. Further, when the protective member and the functional member are bonded together, the protective member and/or the functional member may be coated with the liquid curable composition, and the protective member and the functional member may be bonded to each other via the liquid curable composition. It is obtained by hardening this liquid hardening composition.

Since the display device of the present invention is obtained by using the above-described discharge device using a container for a discharge device filled with a liquid curable composition, liquid crystals for use in electric or electronic equipment or two-wheeled or four-wheeled vehicles are used. Various display devices such as a touch panel, an organic EL touch panel, a liquid crystal module, a plasma display panel (PDP), and a digital and analog tachometer are excellent in impact resistance and visibility. Moreover, such a display device can be easily obtained by the above-described ejection device.

5. Liquid curable composition

The liquid curable composition filled in the air gap between the cover sheet and the display module of various display devices is preferably a reactive liquid curable composition from the viewpoint of ensuring durability.

The reactive liquid curable composition used in the present invention is not particularly limited as long as it has at least one selected from the group consisting of active energy ray curability, heat curability, and room temperature curability. The active energy ray-curable composition is preferably a UV curable or EB curable composition, and more preferably UV curable from the viewpoint of safety and cost of the irradiation device. The room temperature curable composition is preferably a composition having a moisture curability, in terms of monolithification, in terms of redox hardenability, epoxy curability, moisture curability, and the like.

Further, from the viewpoint of coexisting hardening and hardening of a portion where the active energy ray is not irradiated, a composition having active energy ray hardenability and moisture hardening property is preferable, and UV curability and moisture are more preferable. A curable composition. Examples of such a composition include those in which an active energy ray-curable composition and a moisture-curable composition are mixed, or have active energy in one molecule. A compound which is a compound of a linear curable functional group and a moisture curable functional group.

Examples of such a liquid curable composition having active energy ray curability and moisture curability include a compound (A) having an average of at least one polymerizable carbon-carbon double bond in one molecule, and an average of at least one molecule. A compound (B) having a hydrolyzable alkyl group. Hereinafter, the examples will be described in detail.

<<Compound (A) and Compound (B)>>

The skeleton of the compound (A) (hereinafter sometimes referred to as (A) component) and the compound (B) (hereinafter sometimes referred to as component (B)) may be the same or different, but from the viewpoint of compatibility, it is preferred. It is the skeleton of the same type. Further, the component (A) and the component (B) may be any of a low molecular weight compound, an oligomer, and a polymer, and are preferably oligomeric in terms of balance of flexibility, durability, and hardenability. Or an organic polymer, particularly preferably an organic polymer.

The component (B) is not particularly limited as long as it has high viscosity, and it is preferred to impart thixotropic properties, and it is preferred to add an organic or inorganic thixotropy imparting agent.

The above-mentioned organic polymer means a compound having a structure of a repeating unit of an organic compound and comprising a repeating unit of 100 or more. The above-mentioned oligomer refers to a compound having a structure of a repeating unit of an organic compound and comprising a repeating unit of 2 to 100. The above-mentioned low molecular weight compound means a compound having a structure other than an oligomer or an organic polymer and having substantially no repeating unit structure.

The above organic polymer or oligomer is preferably a polysiloxane, a polyether or a vinyl polymer.

The polyoxyalkylene is preferably an alkyl polyoxyalkylene.

As the above polyether, an oxygen-extended alkyl polymer is preferred, of which It is polyoxyethylene and polyoxypropylene.

The vinyl polymer is preferably mainly selected from the group consisting of polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, and (meth)acrylic monomers and acrylonitrile monomers selected from hydrocarbon polymers. A polymer produced by polymerizing a monomer in a group consisting of an aromatic vinyl monomer, a fluorine-containing vinyl monomer, and a ruthenium-containing vinyl monomer. Here, "mainly" means that 50 mol% or more of the monomer unit constituting the vinyl polymer is the above monomer, preferably 70 mol% or more. Further, the vinyl polymer is preferably a (meth)acrylic polymer produced by polymerizing a polyisobutylene or a (meth)acrylic monomer, and more preferably a (meth)acrylic polymer. The (meth)acrylic polymer is preferably an acrylic polymer, more preferably an acrylate polymer.

The molecular weight distribution of the organic polymer or oligomer of the component (A) and/or the organic polymer or oligomer of the component (B), that is, the weight average measured by Gel Permeation Chromatography (GPC) The ratio (Mw/Mn) of the molecular weight (Mw) to the number average molecular weight (Mn) is not particularly limited, but is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.6 or less, still more preferably 1.5 or less. It is preferably 1.4 or less, and most preferably 1.3 or less. When the molecular weight distribution is 1.8 or more, the viscosity tends to be large and it tends to be difficult to handle. Further, in the GPC measurement according to the present invention, chloroform is used as the mobile phase, and the measurement is carried out using a polystyrene gel column, and the number average molecular weight or the like can be obtained by polystyrene conversion.

Since any of the above oligomers and organic polymers can be collectively described for the main chain, the production method, and the like, the following description will be collectively made.

<polyoxane>

It can be obtained by a method of hydrolyzing a known organochloromethane to produce an organic polyoxyalkylene; Japanese Patent No. 2599517, Japanese Patent Laid-Open No. SHO 56-151731, and Japanese Patent Laid-Open No. 59- A known method such as a method of hydrolyzing alkoxydecane in the presence of a basic catalyst or an acid catalyst described in JP-A-59-68377, JP-A-59-68377. Examples of the terminal functional group of the polymer include an alkoxyalkyl group, a stanol group, and a hydroxyl group.

The number average molecular weight of the polyoxyalkylene to be used in the present invention is not particularly limited, and is 500 to 1,000,000, more preferably 3,000 to 100,000 in the case of measurement by GPC. When the molecular weight is too low, the elongation and the flexibility tend to be insufficient. When the molecular weight is too high, the viscosity tends to increase and the workability such as coating tends to be lowered.

<polyether>

The method for synthesizing the polyether (oxyalkylene-based polymer) is not particularly limited, and for example, it can be obtained by subjecting a monoepoxide to ring-opening polymerization in the presence of a starter and a catalyst.

Specific examples of the initiator include ethylene glycol, propylene glycol, butylene glycol, hexanediol, methyl allyl alcohol, bisphenol A, hydrogenated bisphenol A, neopentyl glycol, and polybutadiene II. Alcohol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polyglycerol, polypropanediol, dipropylene glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and other glycols Or a polyhydric alcohol, various oligomers having a hydroxyl group, and the like.

Specific examples of the monoepoxide include ethylene oxide and propylene oxide. An alkylene oxide such as an alkane, α-butylene oxide, β-butylene oxide, hexylene oxide, epihalohydrin, styrene oxide or oxidized α-methyl styrene; or methyl glycidyl ether; An alkyl glycidyl ether such as ethyl glycidyl ether, isopropyl glycidyl ether or butyl glycidyl ether, allyl glycidyl ether or aryl glycidyl ether.

Examples of the catalyst and the polymerization method include a polymerization method using an alkali catalyst such as KOH; for example, a reaction obtained by reacting an organoaluminum compound with a porphyrin as disclosed in Japanese Laid-Open Patent Publication No. SHO 61-215623 A method for polymerizing a transition metal compound-porphyrin complex catalyst such as a complex compound; for example, a composite metal cyanide disclosed in Japanese Patent Publication No. Sho 46-27250, and Japanese Patent Publication No. SHO 59-15336 The polymerization method of the compound complex catalyst; the polymerization method using a ruthenium catalyst, the polymerization method using a phosphonitrile catalyst, etc., but it is not specifically limited. Among them, in terms of easily obtaining a polymer having a high molecular weight and a small coloration, a polymerization method using a double metal cyanide complex catalyst is preferred.

Further, the main chain skeleton of the oxygen-extended alkyl polymer may be used in the presence of a basic compound such as KOH, NaOH, KOCH ₃ or NaOCH ₃ to utilize a hydroxy-terminated alkylene polymer. The halogenated alkyl group, for example, chain extension of CH ₂ Cl ₂ , CH ₂ Br ₂ or the like is obtained.

Further, in the range in which the properties of the oxygen-extended alkyl polymer are not greatly impaired, other components such as a urethane bond component may be contained in the main chain skeleton of the oxygen-extended alkyl polymer.

The number average molecular weight of the polyether used in the present invention is not particularly limited, and is 500 to 1,000,000 in the case of measurement by GPC, more preferably It is 1,000~100,000. When the molecular weight is too low, the elongation and the flexibility tend to be insufficient. When the molecular weight is too high, the viscosity tends to increase and the workability such as coating tends to be lowered.

<vinyl polymer> (hydrocarbon polymer)

The hydrocarbon-based polymer is a polymer which does not substantially contain a carbon-carbon unsaturated bond other than the aromatic ring, and examples thereof include 1,2-polybutadiene, 1,4-polybutadiene, and polyethylene. , polypropylene, polyisobutylene, hydrogenated polybutadiene, hydrogenated polyisoprene, and the like.

The polymer constituting the main chain skeleton of the hydrocarbon-based polymer which can be used in the present invention can be obtained by the following methods: (1) with, for example, ethylene, propylene, 1,2-butadiene, 1,4-butylene An olefin-based compound having 1 to 6 carbon atoms such as a diene, 1-butene or isobutylene is subjected to homopolymerization or copolymerization as a main component, or (2) is reacted with, for example, butadiene or isoprene. The diene-based compound is subjected to homopolymerization or copolymerization or copolymerization with the above olefin-based compound, followed by hydrogenation or the like.

Among them, polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene are preferred because they are easy to introduce a functional group at the terminal and are easy to control the molecular weight, and the number of terminal functional groups can be increased. Further, since the polyisobutylene is liquid or has fluidity, it is easy to handle, and it is particularly preferable since the main chain does not contain a carbon-carbon unsaturated bond other than the aromatic ring and does not require hydrogenation, and is excellent in weather resistance. All of the monomer units of the polyisobutylene may be formed of isobutylene units, or may be contained in the polyisobutylene in an amount of preferably 50% by weight or less, more preferably 30% by weight or less, and particularly preferably 10% by weight or less. Monomer unit copolymerized with isobutylene.

Examples of the monomer component of the hydrocarbon-based polymerization include an olefin having 4 to 12 carbon atoms, a vinyl ether, an aromatic vinyl compound, a vinyl decane, and an allyl decane. For example, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, Ethylene cyclohexene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methyl styrene, dimethyl styrene, monochlorostyrene, dichlorostyrene, β-蒎Alkene, anthracene, vinyl trichlorodecane, vinyl methyl dichlorodecane, vinyl dimethyl chlorodecane, vinyl dimethyl methoxy decane, vinyl trimethyl decane, divinyl dichloro decane, Divinyl dimethoxydecane, divinyl dimethyl decane, 1,3-divinyl-1,1,3,3-tetramethyldioxane, trivinylmethyl decane, tetraethylene Base decane, allyl trichloro decane, allyl methyl dichloro decane, allyl dimethyl chloro decane, allyl dimethyl methoxy decane, allyl trimethyl decane, diene Dichlorodecane, diallyl dimethoxydecane, diallyldimethyl decane, γ-methyl propylene methoxy propyl trimethoxy decane, γ-methyl propylene methoxy propyl group Dimethoxy decane and the like.

In the case of hydrogenated polyisoprene, hydrogenated polybutadiene or other hydrocarbon-based polymer, other monomer units other than the main component monomer unit may be contained in the same manner as in the case of the above polyisobutylene.

The number average molecular weight of the hydrocarbon-based polymer, preferably polyisobutylene, hydrogenated polyisoprene, or hydrogenated polybutadiene is preferably from about 500 to 50,000, and particularly preferably from 1,000 to 10,000 in terms of ease of handling. ~20,000 or so of liquid or fluid.

(Ethylene-based polymer other than hydrocarbon polymer)

The vinyl monomer which is a main chain which can be used for the ethylene-based polymer other than the hydrocarbon-containing polymer in the present invention is not particularly limited, and various types can be used. Specific examples thereof include a (meth)acrylic monomer, an aromatic vinyl monomer, and a fluorine-containing vinyl monomer as described in paragraph [0018] of JP-A-2005-232419. a vinyl monomer, a maleimide monomer, a nitrile group-containing vinyl monomer, a mercapto group-containing vinyl monomer, a vinyl ester, an olefin, a conjugated diene, Vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, and the like. These may be used alone or in combination with a plurality of types. Here, the (meth)acrylic acid means acrylic acid and/or methacrylic acid.

The main chain of the ethylene-based polymer other than the hydrocarbon-removing polymer used in the present invention is preferably mainly selected from a (meth)acrylic monomer, an acrylonitrile monomer, an aromatic vinyl monomer, and the like. At least one of a group consisting of a fluorine-containing vinyl monomer and a ruthenium-containing vinyl monomer is polymerized and produced. Here, "mainly" means that 50 mol% or more of the monomer unit constituting the vinyl polymer (b) is the above monomer, preferably 70 mol% or more.

Among them, the physical properties of the product, etc., are preferably an aromatic vinyl monomer and/or a (meth)acrylic monomer, more preferably an acrylate monomer and/or a methacrylate monomer, and further Good acrylate monomer. Preferred examples of the acrylate monomer include alkyl acrylate monomers, specifically ethyl acrylate, 2-methoxyethyl acrylate, stearyl acrylate, butyl acrylate, 2-ethyl acrylate. Hexyl ester, 2-methoxybutyl acrylate. Yu Ben In the invention, the preferred monomers may be copolymerized with other monomers, and further, block copolymerization may be carried out. In this case, the preferred monomers are preferably contained in an amount of 40% by weight or more by weight.

The number average molecular weight of the ethylene-based polymer other than the hydrocarbon-based polymer in the present invention is not particularly limited, and is preferably in the range of 500 to 1,000,000, more preferably 3,000 to 100,000, in the case of measurement by GPC. Further preferably, it is 5,000 to 80,000, and more preferably 8,000 to 50,000. When the molecular weight is too low, it tends to be difficult to express the original characteristics of the ethylene-based polymer other than the hydrocarbon-based polymer. On the other hand, if it is too high, it tends to be difficult to handle.

The ethylene-based polymer used in the present invention can be obtained by various polymerization methods, and is not particularly limited. From the viewpoints of versatility, controllability, and the like of the monomer, a radical polymerization method and a radical polymerization are preferred. More preferably in control of free radical polymerization. The controlled radical polymerization method can be classified into a "living radical polymerization method" which is one of a "chain transfer agent method" and a living polymerization. Further, it is preferably a living radical polymerization in which the molecular weight and molecular weight distribution of the obtained ethylene-based polymer are easily controlled, and in terms of availability of a raw material and easy introduction of a functional group at a polymer terminal, atom transfer is preferred. Radical Polymerization. The radical polymerization, the controlled radical polymerization, the chain transfer agent method, the living radical polymerization method, and the atom transfer radical polymerization are known polymerization methods. For each of the polymerization methods, for example, Japanese Patent Laid-Open No. 2005-232419 can be referred to. Japanese Patent Laid-Open No. 2006-291073, and the like.

Hereinafter, atom transfer radical polymerization of one of preferred synthesis methods of the vinyl polymer other than the hydrocarbon-removing polymer used in the present invention can be The line is briefly explained.

In the atom transfer radical polymerization, it is preferred to use an organic halide, especially a highly reactive organic halide having a carbon-halogen bond (for example, a carbonyl compound having a halogen at the α position or a halogen at the benzyl position). A compound), or a sulfonium halide compound or the like is used as a starter. Specific examples thereof include the compounds described in paragraphs [0040] to [0064] of JP-A-2005-232419.

In order to obtain an ethylene-based polymer having two or more alkenyl groups which can be subjected to a hydrogenation reaction in one molecule, it is preferred to use an organic halide having two or more starting points or a sulfonium halide compound as a starting agent. Specifically, the following are mentioned.

The vinyl monomer used in the atom transfer radical polymerization is not particularly limited, and all of the above vinyl monomers can be preferably used.

The transition metal complex used as the polymerization catalyst is not particularly limited, and it is preferably a metal which is a central metal of Group 7, Group 8, Group 9, Group 10 or Group 11 of the periodic table. More preferably, the complex is a transition metal complex containing zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel as a central metal, and particularly preferably a copper complex. If the monovalent copper compound used to form the copper complex is specifically exemplified, it is cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, perchloric acid. Copper and so on. In the case of using a copper compound, in order to increase the catalytic activity, 2,2'-bipyridine or a derivative thereof, 1,10-morpholine or a derivative thereof, tetramethylethylenediamine, pentamethyldiamine or the like may be added. A polyamine such as ethyltriamine or hexamethyltris(2-aminoethyl)amine is used as a ligand.

The polymerization can be carried out without a solvent, or can be carried out in various solvents. The type of the solvent is not particularly limited, and examples thereof include the solvents described in paragraph [0067] of JP-A-2005-232419. These may be used alone or in combination of two or more. Further, the polymerization may be carried out in a latex system or a system in which a supercritical fluid CO _{2 is} used as a medium.

The polymerization temperature is not limited and can be carried out in the range of 0 to 200 ° C, preferably in the range of room temperature to 150 ° C.

<<Polymerizable carbon-carbon double bond introduction method (synthesis method of (A) component)>>

The polymerizable carbon-carbon double bond of the component (A) is not particularly limited, and is preferably a (meth)acryl fluorenyl group represented by the formula (1).

-OC(O)C(R ^a )=CH ₂ (1) (wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms).

Further, the polymerizable carbon-carbon double bond of the component (A) is preferably located at the end of the molecular chain.

<Introduction method in polyoxyalkylene>

The introduction method is not particularly limited, and examples thereof include a terminal stanol group-terminated polyoxyalkylene and a hydrolyzable decyl group-containing vinyl compound described in Japanese Patent No. 3193866, using an organic metal or the like as a catalyst. A method of performing a hydrolysis condensation reaction of a (meth) propylene oxime compound containing a hydrolyzable decyl group.

<Import method in polyether>

The method of introducing a polymerizable carbon-carbon double bond into the oxygen-extended alkyl polymer is not particularly limited, and there is a method of: <1> a polyoxyalkylene group having a hydroxyl group terminal and a formula (1) a method for reacting a ruthenium chloride compound, <2> a method for reacting a polyoxyalkylene group having a hydroxyl group with a compound of the formula (1) containing an isocyanato group, and <3> a polyoxyalkylene having a hydroxyl group terminal Alkyl group reacts with a polyfunctional vinyl monomer containing an isocyanato group and a hydroxyl group The method, <4> allows the hydrogenation of a double bond terminal (for example, an allyl terminal) polyoxyalkylene group to react with a polyfunctional hydrazine compound, and further with allyl (meth) acrylate. A method of reacting a hydrogenated compound. The method of <2>, <3> and <4> is more preferably a method of <2> and <3> in terms of reaction stability in terms of ease of reaction.

<Introduction method in ethylene-based polymer>

As a method of introducing a polymerizable carbon-carbon double bond into a vinyl polymer, a known method can be used. For example, the method described in paragraphs [0080] to [0091] of JP-A-2004-203932 is preferred, and the following method is preferred.

(Import method 1)

A method of substituting a terminal halogen group of the ethylene-based polymer of the formula (2) with a compound having a polymerizable carbon-carbon double bond of the formula (3).

-CR ¹ R ² X (2) (wherein R ¹ and R ² are groups bonded to the ethylenically unsaturated group of the vinyl monomer, and X represents chlorine, bromine or iodine)

M ^+- OC(O)C(R)=CH ₂ (3) (wherein R represents hydrogen or an organic group having 1 to 20 carbon atoms, and M ⁺ represents an alkali metal or a quaternary ammonium ion).

The ethylene-based polymer having the terminal structure represented by the general formula (2) can be produced by using the above-mentioned organic halide or sulfonium halide compound as a starting agent and a transition metal complex as a catalyst to ethylene. A method of polymerizing a monomer; or a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent, preferably the former.

The compound represented by the formula (3) is not particularly limited, and specific examples of R include -H, -CH ₃ , -CH ₂ CH ₃ , and -(CH ₂ ) _n CH ₃ (n represents 2) An integer of ~19), -C ₆ H ₅ , -CH ₂ OH, -CN, etc., preferably -H, -CH ₃ . M ⁺ is a counter cation of an oxyanion, and the type of M ⁺ is an alkali metal ion, and specific examples thereof include a lithium ion, a sodium ion, a potassium ion, and a quaternary ammonium ion. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecyl ammonium ion, tetrabutylammonium ion, and dimethylpiperidinium ion. Etc., preferably sodium ion or potassium ion. The amount of the oxyanion to be used in the formula (3) is preferably from 1 to 5 equivalents, more preferably from 1.0 to 1.2 equivalents, per equivalent of the halogen group of the formula (2). The solvent for carrying out the reaction is not particularly limited. However, since it is preferably a polar solvent for the nucleophilic substitution reaction, for example, tetrahydrofuran or two can be used. Alkane, diethyl ether, acetone, dimethyl hydrazine, dimethylformamide, dimethylacetamide, hexamethylphosphonium triamine, acetonitrile, and the like. The temperature at which the reaction is carried out is not limited, and is generally 0 to 150 ° C, and is a terminal group which maintains polymerizability, and is preferably carried out at room temperature to 100 ° C.

(Import method 2)

A method of reacting a vinyl polymer having a hydroxyl group at the terminal with a compound represented by the formula (4).

XC(O)C(R)=CH ₂ (4) (wherein R represents hydrogen or an organic group having 1 to 20 carbon atoms, and X represents chlorine, bromine or a hydroxyl group).

(Import method 3)

A vinyl polymer having a hydroxyl group at the end and a diisocyanate compound The reaction is carried out, and a method of reacting the remaining isocyanate group with a compound represented by the following formula 5 is carried out.

HO-R'-OC(O)C(R)=CH ₂ (5) (wherein R represents hydrogen or an organic group having 1 to 20 carbon atoms, and R' represents a divalent organic group having 2 to 20 carbon atoms ).

Among these methods, the best is (introduction method 1) in terms of easy control.

<<Method for introducing cross-linking decyl group (composition method of component (B))>>

The hydrolyzable alkylene group as used in the present invention is a hydrazine-containing functional group which is crosslinkable by forming a decane bond, and is preferably a group represented by the formula (101).

-[Si(R ¹ ) _2-b (Y) _b O] _m -Si(R ² ) _3-a (Y) _a (101) (wherein R ¹ and R ² may be the same or different and represent a carbon number An alkyl group of 1 to 20, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosalkoxy group represented by (R') ₃ SiO- (wherein R' represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, a plurality of R's may be the same or different), and when two or more R ₁ or R ₂ are respectively present, these may be the same or different; Y represents a hydroxyl group or a hydrolyzable property. Base, when there are two or more Y, these may be the same or different; a represents 0, 1, 2 or 3, b represents 0, 1 or 2, and m represents an integer from 0 to 19, wherein a+ is satisfied Mb≧1).

The hydrolyzable decyl group of the component (B) is preferably located at the end of the molecular chain.

<Introduction method in polyoxyalkylene>

The method of introducing the hydrolyzable decyl group is not particularly limited. For example, when a polydecane compound containing a hydrolyzable decyl group is synthesized by using an acid or a base as a catalyst component, hydrolysis and condensation conditions are adjusted. And A method of reacting a terminally hydrolyzable decyl group; a method of reacting a terminal chloro group-containing polyoxyalkylene with a hydrolyzable decyl group-containing chlorodecane.

<Import method in polyether>

(α) A method of reacting with an anthracene hydrogen compound represented by the formula (102) after introducing an olefin group into an oxygen-terminated alkyl polymer having a functional group such as a hydroxyl group.

HSiX _a R ² _3-a (102) (wherein R ² , X, and a are the same as described above).

Here, as a method of introducing an olefin group, a method of reacting a compound having an unsaturated group and a functional group reactive with a hydroxyl group with a hydroxyl group of an oxygen-extended alkyl polymer is exemplified by a method of bonding an ether bond, an ester bond, a urethane bond, a carbonate bond, or the like; or by adding an olefin group-containing epoxy compound such as allyl glycidyl ether when polymerizing an alkylene oxide A method of introducing a olefin group by polymerization or the like.

(β) A method of reacting an oxygen-extended alkyl group-containing polymer having a functional group reactive with an isocyanate compound with a compound represented by the formula (103).

(R ² -) _3-a SiX _a -R ₃ NCO (103) (wherein R ² , X, and a are the same as defined above, and R ³ is a divalent hydrocarbon group having 1 to 17 carbon atoms).

(γ) After reacting an oxygen-cylene alkyl polymer having a functional group reactive with an isocyanate compound with a polyisocyanate compound such as toluene diisocyanate to introduce an isocyanate group, the isocyanate group is represented by the formula (104) A method in which a W group of a compound is reacted.

(R ² -) _3-a SiX _a -R ³ W (104) (wherein R ² , R ³ , X, a are the same as above, and W is selected from the group consisting of a hydroxyl group, a carboxyl group, a thiol group and an amine group (first or second The active hydrogen-containing group in the grade).

(δ) A method of introducing an olefin group into an oxygen-extended alkyl group-containing polymer having a functional group capable of introducing an olefin group, and reacting the olefin group with a ruthenium compound represented by the formula (104) wherein W is a fluorenyl group.

In the above, the method of introducing the yield and the method of introduction is preferably (α) and (β), and the method of (α) is more preferable in terms of the physical properties of the resin such as viscosity.

<Introduction method in ethylene-based polymer> 1) Hydrocarbon polymer

The introduction method is not particularly limited, and in terms of introduction yield and ease of reaction, it is preferred to use a method in which an olefin group is introduced into a hydrocarbon-based polymer in the same manner as in the above (α). A method of reacting an anthracene hydrogen compound represented by the formula (102).

2) Ethylene-based polymers other than hydrocarbons

The method of the introduction is described in the paragraphs [0102] to [0112] of JP-A-2004-210858. Among these methods, in terms of more controllability, it is preferred to produce an alkenyl group by a hydrogenation reaction using a hydroquinone compound having a crosslinkable decyl group. A method of converting an alkenyl group of a polymer into a crosslinkable decyl group.

<<Starting agent (C)>>

In order to rapidly harden or obtain a cured product having sufficient properties, it is preferred to use the initiator (C) in the liquid curable composition used in the present invention. The initiator (C) is not particularly limited, and examples thereof include a photopolymerization initiator. A thermal polymerization initiator, a redox initiator, and the like. Further, the photopolymerization initiator, the thermal polymerization initiator, and the redox initiator may be used singly or as a mixture of two or more. When used as a mixture, various initiators may be used. The amount used is preferably in the following ranges.

The photopolymerization initiator may, for example, be a photoradical initiator, a photoanion initiator, a near-infrared photopolymerization initiator, or the like, preferably a photoradical initiator or a photoanion initiator. It is a photoradical initiator.

Examples of the photoradical initiator include acetophenone, propiophenone, and benzophenone. Alcohol, hydrazine, benzaldehyde, hydrazine, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2,2-diethoxy Acetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diethylphenylbenzene, 3-methoxybenzophenone, 4-methyl Benzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, 3-chloro 3,9-dichloro 3-chloro-8-fluorenyl , benzoin, benzoin methyl ether, benzoin butyl ether, bis(4-dimethylaminophenyl) ketone, benzyl methoxy ketal, 2-chloroox sulphide , 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl- Propane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, benzhydrin, and the like.

Among these, preferred are: α-hydroxyketone compounds (for example, benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxy-cyclohexyl-phenyl-ketone, etc.), phenyl ketone derivatives (for example, acetophenone, Propiophenone, benzophenone, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2,2-diethoxybenzene Ketone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allyl acetophenone, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorodi Benzophenone, 4,4'-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, bis(4-dimethylaminophenyl)one, etc.).

As the photoanion initiator, for example, 1,10-diaminodecane, 4,4'-trimethylene diene may be mentioned. And urethanes and derivatives thereof, cobalt-amine complexes, amine oxyimine groups, ammonium borate, and the like.

As the near-infrared photopolymerization initiator, a near-infrared light absorbing cationic dye or the like can also be used. The near-infrared light absorbing cationic dye is preferably used in the light source of the 650 to 1500 nm, and is disclosed in, for example, Japanese Patent Application Laid-Open No. Hei No. Hei. The near-infrared light absorbing cationic dye-borate anion complex or the like is further preferably a boron-based sensitizer.

These photopolymerization initiators may be used alone or in combination of two or more kinds thereof, or may be used in combination with other compounds.

Specific examples of the combination with other compounds include a combination with an amine such as methyldiethanolamine, dimethylethanolamine or triethanolamine, and a combination of an iodide salt such as diphenyliodonium chloride and methylene blue. Such as pigments and amine combinations.

Further, in the case of using the above photopolymerization initiator, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, benzoquinone or p-tert-butylcatechol may be added as needed.

In the case of using a photopolymerization initiator, the amount thereof to be added is not particularly limited, but in terms of hardenability and storage stability, relative to (B) It is 100 parts by weight, preferably 0.001 to 10 parts by weight.

Further, the thermal polymerization initiator is not particularly limited, and examples thereof include an azo initiator, a peroxide initiator, and a persulfate initiator.

The azo initiator is not limited, and examples thereof include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33), 2, 2 '-Azobis(2-amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis(2,4-dimethylvaleronitrile) (VAZO 52), 2,2'- Azobis(isobutyronitrile) (VAZO 64), 2,2'-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis(1-cyclohexanecarbonitrile) (VAZO 88) (all available from DuPont Chemical), 2,2'-azobis(2-cyclopropylpropionitrile) and 2,2'-azobis(methyl isobutyrate) (V-601) ( Available from Wako Pure Chemical Company).

The suitable peroxide initiator is not limited, and examples thereof include benzamidine peroxide, ethoxylated ruthenium peroxide, laurel peroxide, decyl carboxide, and cetyl peroxydicarbonate. Bis(4-tert-butylcyclohexyl)peroxydicarbonate (Perkadox 16S) (available from Akzo Nobel), di(2-ethylhexyl) peroxydicarbonate, third butyl peroxypivalate Ester (Lupersol 11) (available from Elf Atochem), tributyl-2-ethyl peroxyhexanoate (Trigonox 21-C50) (available from Akzo Nobel), dicumyl peroxide, and the like.

The suitable persulfate initiator is not limited, and examples thereof include potassium persulfate, sodium persulfate, and ammonium persulfate.

As a preferred thermal polymerization initiator, it can be selected from the group consisting of a free azo initiator and a peroxide initiator. Further preferred are 2,2'-azobis(methyl isobutyrate), tert-butyl peroxypivalate, and diperoxide Di(4-tert-butylcyclohexyl) acid, and mixtures thereof.

The thermal polymerization initiator may be used singly or in combination of two or more.

When a thermal polymerization initiator is used, the thermal polymerization initiator is catalytically present in an effective amount, and the amount thereof is not particularly limited, and the component (B) used in the present invention can be set to 100. In the case of parts by weight, it is preferably from about 0.01 to 5 parts by weight, more preferably from about 0.025 to 2 parts by weight.

Further, a redox (redox) initiator which can be used can be used in a wide temperature range. It is especially advantageous that the following initiator types can be used at normal temperatures.

The suitable redox-based initiator is not limited, and examples thereof include a combination of the above-mentioned persulfate initiator and a reducing agent (sodium metabisulfite, sodium hydrogen sulfite, etc.); organic peroxide and tertiary Combination of amines, such as a combination of benzamidine peroxide and dimethylaniline, a combination of cumene hydroperoxide and aniline; a combination of an organic peroxide and a transition metal, such as cumene hydroperoxide and naphthenic A combination of cobalt and the like.

As a preferred redox initiator, it is preferably a combination of an organic peroxide and a tertiary amine, a combination of an organic peroxide and a transition metal, more preferably a combination of cumene hydroperoxide and aniline. A combination of cumene hydroperoxide and cobalt naphthenate. The redox initiator may be used singly or in combination of two or more.

In the case of using a redox-based initiator, the redox-based initiator is catalytically present in an effective amount, and the amount thereof is not particularly limited, and the component (B) which can be used in the present invention can be used. In the case of 100 parts by weight, it is preferably about 0.01 to 5 parts by weight, more preferably about 0.025 to 2 parts by weight. For example, test It is preferable to temporarily fix the liquid curable composition for filling between the flat display module and the transparent cover sheet by using UV-based light. Among the above initiators, it is preferred to use a photopolymerization initiator mainly.

<<hardening catalyst (D)>>

The liquid curable composition used in the present invention is not particularly limited, and a curing catalyst (D) is preferably used. The compound (A) having an average of at least one hydrolyzable alkylene group used in the present invention can be used in the presence or absence of various condensation catalysts (hardening catalysts, sometimes referred to as "hardeners") which are known in the prior art. The siloxane chain is formed to carry out crosslinking and hardening. The properties of the cured product can be widely produced depending on the molecular weight of the polymer, the main chain skeleton, and the rubbery to resinous form.

The liquid curable composition used in the present invention can also be used in various previously known various condensation catalysts used in polymers having a crosslinkable alkylene group.

Examples of such a condensation catalyst include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctoate, dibutyltin dimethyl maleate, and diethyl cis. Dibutyltin phthalate, dibutyltin dibutyl maleate, dibutyltin diisooctyl maleate, dibutyltin di-tridecyl maleate, dibutyltin benzyl maleate , dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethyl maleate, diisooctyl cis a dialkyltin dicarboxylic acid such as dioctyltin phthalate; for example, a dialkylstannolate such as dibutyltin dimethoxide or dibutyltin dibutyltin, such as dibutyl fluorenyl dibutyltin. An intramolecular coordination derivative of a dialkyltin such as dibutyltin diacetate, such as dialkyltin oxide such as dibutyltin oxide or dioctyltin, and, for example, dioctyl phthalate, Reaction of ester compounds such as diisononyl phthalate and methyl maleate a tin compound obtained by reacting a dialkyltin oxide, a carboxylic acid, and an alcohol compound; for example, dicyclobutyl bis-diethoxy phthalate, dioctyltin bis triethoxy phthalate, or the like a tetravalent tin compound such as a reaction product of a base tin with a phthalate compound and an oxygen derivative (a siloxane compound) of the dialkyl tin compound; for example, tin octylate, tin naphthenate, stearic acid a divalent tin compound such as tin or tin versatate, or a reaction product and a mixture thereof with an amine compound such as laurylamine; for example, monobutyltin trioctoate or monobutyltin trioxide Monoalkyltin such as monobutyltin compound or monooctyltin compound; for example, tetrabutyl titanate, tetrapropyl titanate, tetrakis(2-ethylhexyl) titanate, bis(ethylacetamidineacetic acid) Titanates such as titanium isopropoxide; organoaluminum compounds such as aluminum triacetate, aluminum triethylacetate, and aluminum di-isopropoxyacetate; Iron iron, titanium carboxylate, lead carboxylate, vanadium carboxylate, zirconium carboxylate, calcium carboxylate, potassium carboxylate, cerium carboxylate, manganese carboxylate, a metal salt of a carboxylic acid (2-ethylhexanoic acid, neodecanoic acid, terecic acid, oleic acid, naphthenic acid, etc.) such as cerium hydride, nickel carboxylate, cobalt carboxylate, zinc carboxylate or aluminum carboxylate, or a reaction product and a mixture with an amine compound such as laurylamine; zirconium tetraethoxide, zirconium tributoxyacetate, zirconium dibutoxide, zirconium dibutoxide, ethyl acetoacetate a chelate compound such as zirconium acetonide or tetraacetyl acetonate; methylamine, ethylamine, propylamine, isopropylamine, butylamine, pentylamine, hexylamine, octylamine, 2-ethylhexylamine, guanamine An aliphatic first amine such as decylamine, laurylamine, pentadecylamine, hexadecylamine, stearylamine or cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine , dibutylamine, diamylamine, dioctylamine, di(2-ethylhexyl)amine, didecylamine, dilaurylamine, dicetylamine, distearylamine, methylstearylamine An aliphatic second amine such as ethyl stearylamine or butyl stearylamine; an aliphatic third amine such as triamylamine, trihexylamine or trioctylamine; triallylamine or oleyl Aliphatic unsaturated amines such as amines; lauryl benzene An aromatic amine such as an amine, stearyl aniline or triphenylamine; and as other amines, monoethanolamine, diethanolamine, triethanolamine, di-ethyltriamine, tri-ethyltetramine, and oil Amine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, triethylenediamine, anthracene, diphenylguanidine, 2,4,6- Tris(dimethylaminomethyl)phenol, Porphyrin, N-methyl Porphyrin, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo(5,4,0)undecene-7 (1,8-DiazaBicyclo(5,4,0)Undecene-7, DBU Or an amine-based compound, or a salt of the amine-based compound with a carboxylic acid or the like; a reactant and a mixture of an amine-based compound such as a reaction or a mixture of laurylamine and tin octylate with an organotin compound; a low molecular weight polyamine resin obtained from a polyamine and a polybasic acid; an excess of a reaction product of a polyamine and an epoxy compound; γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-Aminopropyltriisopropoxydecane, γ-Aminopropylmethyldimethoxydecane, γ-Aminopropylmethyldiethoxydecane, N-(β-Aminoethyl Aminopropyltrimethoxydecane, N-(β-aminoethyl)aminopropylmethyldimethoxydecane, N-(β-aminoethyl)aminopropyltriethoxy Decane, N-(β-aminoethyl)aminopropylmethyldiethoxydecane, N-(β-aminoethyl)aminopropyltriisopropoxydecane, γ-ureidopropyl Trimethoxy decane, N-phenyl-γ-aminopropyltrimethoxydecane, N-benzyl-γ-aminopropyltrimethyl Oxydecane, N-vinylbenzyl-γ-aminopropyltriethoxydecane, and the like. Further, it can be exemplified that the modified derivatives are an amine-modified decyl polymer, a decylated amine-based polymer, an unsaturated amino decane complex, a phenylamino long-chain alkyl decane, an amine. Further, a decyl alcohol condensation catalyst such as a decane coupling agent having an amine group such as a polyalkylene oxide may be exemplified by other acidic catalysts such as versatic acid or an organic acid phosphate compound, and an alkaline catalyst. A known stanol condensation catalyst or the like.

Examples of the organic acid phosphate compound as the acid catalyst include (CH ₃ O) ₂ -P(=O)(-OH), (CH ₃ O)-P(=O)(-OH) ₂ , (C) ₂ H ₅ O) ₂ -P(=O)(-OH), (C ₂ H ₅ O)-P(=O)(-OH) ₂ , (C ₃ H ₇ O) ₂ -P(=O) (-OH), (C ₃ H ₇ O)-P(=O)(-OH) ₂ , (C ₄ H ₉ O) ₂ -P(=O)(-OH), (C ₄ H ₉ O) -P(=O)(-OH) ₂ , (C ₈ H ₁₇ O) ₂ -P(=O)(-OH), (C ₈ H ₁₇ O)-P(=O)(-OH) ₂ , (C ₁₀ H ₂₁ O) ₂ -P(=O)(-OH), (C ₁₀ H ₂₁ O)-P(=O)(-OH) ₂ , (C ₁₃ H ₂₇ O) ₂ -P(= O) (-OH), (C ₁₃ H ₂₇ O)-P(=O)(-OH) ₂ , (C ₁₆ H ₃₃ O) ₂ -P(=O)(-OH), (C ₁₆ H ₃₃ O)-P(=O)(-OH) ₂ , (HO-C ₆ H ₁₂ O) ₂ -P(=O)(-OH), (HO-C ₆ H ₁₂ O)-P(=O) (-OH) ₂ , (HO-C ₈ H ₁₆ O)-P(=O)(-OH), (HO-C ₈ H ₁₆ O)-P(=O)(-OH) ₂ , [(CH ₂ OH)(CHOH)O] ₂ -P(=O)(-OH), [(CH ₂ OH)(CHOH)O]-P(=O)(-OH) ₂ , [(CH ₂ OH)( CHOH)C ₂ H ₄ O] ₂ -P(=O)(-OH), [(CH ₂ OH)(CHOH)C ₂ H ₄ O]-P(=O)(-OH) _{2 ,} etc. It is not limited to the substances exemplified.

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

<amine compound>

In order to further increase the activity of the condensation catalyst, it can also be used in the present invention. An amine compound is added to the liquid curable composition.

The amine compound may, for example, be methylamine, ethylamine, propylamine, isopropylamine, butylamine, pentylamine, hexylamine, octylamine, 2-ethylhexylamine, decylamine, decylamine, laurylamine or pentadecane. Aliphatic first amines such as cisamine, hexadecylamine, stearylamine, cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dioctyl Amine, bis(2-ethylhexyl)amine, didecylamine, dilaurylamine, dicetylamine, distearylamine, methylstearylamine, ethylstearylamine, butyl hard An aliphatic second amine such as a fatty amine; an aliphatic third amine such as triamylamine, trihexylamine or trioctylamine; an aliphatic unsaturated amine such as triallylamine or oleylamine; lauryl aniline, An aromatic amine such as stearyl aniline or triphenylamine; and as other amines, monoethanolamine, diethanolamine, triethanolamine, di-ethyltriamine, tri-ethyltetramine, oleylamine, Cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, tri-ethylenediamine, anthracene, diphenylguanidine, 2,4,6-tri Dimethylaminomethyl)phenol, Porphyrin, N-methyl An amine compound such as porphyrin, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo(5,4,0)undecene-7 (DBU), polyamine compound, γ-aminopropyl Trimethoxydecane, γ-aminopropyltriethoxydecane, γ-aminopropyltriisopropoxydecane, γ-aminopropylmethyldimethoxydecane, γ-aminopropyl Methyldiethoxydecane, N-(β-aminoethyl)aminopropyltrimethoxydecane, N-(β-aminoethyl)aminopropylmethyldimethoxydecane, N -(β-Aminoethyl)aminopropyltriethoxydecane, N-(β-aminoethyl)aminopropylmethyldiethoxydecane, N-(β-aminoethyl Aminopropyl triisopropoxydecane, γ-ureidopropyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, N-benzyl-γ-aminopropyl Trimethoxydecane, N-vinylbenzyl-γ-aminopropyltriethoxydecane, and the like. Further, examples thereof include an amine-modified decyl polymer, a decylated amine-based polymer, an unsaturated amino decane complex, a phenylamino long-chain alkyl decane, and an amine. An amine-based decane-based compound having an amine group such as a decane coupling agent having an amine group such as an alkylene oxide, but not limited to the exemplified one. Further, in the aminodecane compound, a methoxy group, an ethoxy group or the like is preferred in terms of the hydrolysis rate. The number of the hydrolyzable groups is preferably two or more, and more preferably three or more. These amine compounds may be used alone or in combination of two or more.

The compounding amount in the case of adding the above-mentioned amine compound is preferably from 0.01 to 50 parts by weight, more preferably from 0.1 to 20 parts by weight, based on 100 parts by weight of the compound (A) having at least one hydrolyzable alkyl group. Share. When the amount of the amine compound is less than 0.01 part by weight, the curing rate may be lowered, and the curing reaction may be difficult to proceed sufficiently. On the other hand, when the compounding amount of the amine compound exceeds 50 parts by weight, the pot life is too short, which is not preferable in terms of workability.

When the amine compound is added, it may be mixed with a curing catalyst in advance, or may be mixed thereafter. When the reaction is carried out by mixing in advance, the catalyst activity becomes higher and the rapid hardenability can be achieved.

In addition, in the liquid curable composition used in the present invention, the above-described amine-containing decane coupling agent may be used as a promoter in the same manner as the amine-based compound in order to further enhance the activity of the condensation catalyst. The amine group-containing decane coupling agent is a compound having a group containing a ruthenium atom to which a hydrolyzable group is bonded (hereinafter referred to as a hydrolyzable decyl group) and an amine group, and examples thereof include the exemplified group. The hydrolyzable group is preferably a methoxy group, an ethoxy group or the like in terms of a hydrolysis rate. The number of the hydrolyzable groups is preferably two or more, and more preferably three or more.

The compounding amount of the amine group-containing decane coupling agent is preferably from 0.05 to 10 times, more preferably from 0.1 to 3 parts by weight, based on the weight ratio of the curing catalyst. When the amount of the amine-containing decane coupling agent is too small or too large, the curing rate is slowed down, and the hardening reaction becomes difficult to sufficiently proceed or the pot life is too short, and workability and the like are also obtained. It is not good. These amine group-containing decane coupling agents may be used alone or in combination of two or more.

By using the above-mentioned amine compound in combination with the above organic acid to increase the catalytic activity, it is more preferable from the viewpoint of reducing the amount of use. In the combination of an organic acid and an amine, there are an acidic phosphate ester and an amine, a combination of a carboxylic acid and an amine, and the like, wherein the organic acid phosphate and the amine are preferred from the viewpoints of higher catalytic activity and rapid hardenability. The combination of an organic carboxylic acid and an amine is further preferably a combination of an organic carboxylic acid and an amine, and more preferably a combination of an aliphatic carboxylic acid and an amine.

Further, an anthracene compound having no amine group or stanol group may be added as a promoter. The antimony compound is not limited, and is preferably phenyltrimethoxydecane, phenylmethyldimethoxydecane, phenyldimethylmethoxydecane, diphenyldimethoxydecane, or diphenyl. Diethoxy decane, triphenyl methoxy decane, and the like.

Diphenyl dimethoxy decane or diphenyl diethoxy decane is preferred because it is inexpensive and readily available.

The amount of the ruthenium compound is at least one hydrolyzable with respect to the average 矽 The alkyl compound (A) is preferably used in an amount of from 0.01 to 20 parts, more preferably from 0.1 to 10 parts, per 100 parts. If the compounding amount of the cerium compound is less than the above range, the effect of accelerating the hardening reaction may be reduced. On the other hand, if the compounding amount of the cerium compound is higher than the range, the hardness or tensile strength of the cured product may be lowered.

Further, the type or amount of the curing catalyst-hardening agent can be controlled for curability, mechanical properties, and the like depending on the purpose or use. Further, the type or amount of the curing catalyst-hardening agent may be changed depending on the reactivity of the alkylene group of the polymer having a crosslinkable alkylene group, and in the case where the reactivity is high, it may be in the range of 0.01 to 1 part. It is sufficiently hardened in a small amount.

The type or addition amount of the hardening catalyst-hardening agent can be, for example, a hydrolyzable alkyl group of the compound (A) having at least one hydrolyzable alkylene group used in the present invention, and a kind of Y in the general formula (101). It is selected in accordance with the number of a, and the curability, mechanical properties, and the like can be controlled depending on the purpose or use. In the case where Y is an alkoxy group, the reactivity of the carbon having a smaller carbon number is higher, and the reactivity of a larger one is higher, so that it can be sufficiently hardened in a small amount.

<<Materials>>

In the liquid curable composition used in the present invention, various formulation agents may be added depending on the desired physical properties.

<Polymerizable monomer and/or oligomer (E)>

The liquid curable composition used in the present invention may contain a monomer and/or an oligomer (E) within a range not detracting from the effects of the present invention. In terms of hardenability, it is preferred that the monomer having a radical polymerizable group and/or oligomerization Or a monomer and/or oligomer having an anionic polymerizable group.

Examples of the radical polymerizable group include a (meth)acrylonyl group such as a (meth)acryl group, a styryl group, an acrylonitrile group, a vinyl ester group, an N-vinyl pyrrolidone group, and an acrylonitrile group. An amine group, a conjugated dienyl group, a vinyl ketone group, a vinyl chloride group or the like. Among them, those having a (meth)acrylinyl group similar to those of the vinyl polymer used in the present invention are preferred.

Examples of the anionic polymerizable group include a (meth)acrylonyl group such as a (meth)acryl group, a styryl group, an acrylonitrile group, an N-vinylpyrrolidone group, an acrylamide group, and a conjugate. Dienyl, vinyl ketone, and the like. Among them, those having a (meth)acrylinyl group similar to those of the vinyl polymer used in the present invention are preferred.

Specific examples of the above-mentioned monomers include those described in paragraphs [0123] to [0131] of JP-A-2006-265488.

As the above oligomer, those described in paragraph [0132] of JP-A-2006-265488 can be cited.

Among the above, a monomer and/or an oligomer having a (meth)acrylinyl group is preferred. Further, the number average molecular weight of the monomer and/or oligomer having a (meth) acrylonitrile group is preferably 5,000 or less. Further, in order to reduce the viscosity for improving the surface hardenability or the workability, the compatibility is good when a monomer is used. Therefore, the molecular weight is preferably 1000 or less.

The amount of the polymerizable monomer and/or the oligomer is based on the improvement of the surface hardenability, the provision of the toughness, and the workability of the viscosity reduction, and the total amount of the component (A) and the component (B). 100 parts by weight (hereinafter also referred to as a part) is preferably from 1 to 200 parts, more preferably from 5 to 100 parts.

<filling material>

The filler is not particularly limited, and examples thereof include a filler described in paragraph [0158] of JP-A-2005-232419. Among these fillers, crystalline cerium oxide, molten cerium oxide, dolomite, carbon black, calcium carbonate, titanium oxide, talc, and the like are preferable. Especially in the case where a high-strength hardened material is to be obtained by using the filler materials, it may be mainly selected from crystalline cerium oxide, molten cerium oxide, anhydrous citric acid, aqueous citric acid, carbon black, surface-treated fine carbonic acid. Filling materials in calcium, calcined clay, clay, and active zinc white. Among them, the specific surface area (using a BET (Brunauer-Emmett-Teller) adsorption method) is preferably 50 m ² /g or more, usually 50 to 400 m ² /g, preferably 100 to 300 m ^{2 .} Ultrafine powdered cerium oxide of around /g. Further, it is preferably a cerium oxide which is subjected to hydrophobic treatment with an organic hydrazine compound such as an organic decane or an organic decane or a diorganopolysiloxane.

Further, in the case where a cured product having a low strength and a large elongation is to be obtained, a filler mainly selected from the group consisting of titanium oxide, calcium carbonate, talc, iron oxide, zinc oxide, white sand balls, and the like may be added. In addition, when the specific surface area of the calcium carbonate is small, the effect of improving the breaking strength and the elongation at break of the cured product may be insufficient. The larger the value of the specific surface area, the larger the effect of improving the breaking strength and the elongation at break of the cured product.

Further, the calcium carbonate is more preferably a surface treatment agent using a surface treatment agent.

In the case of using surface-treated calcium carbonate, it is considered to be improved in the liquid state used in the present invention as compared with the case of using calcium carbonate which has not been surface-treated. The workability of the curable composition further improves the storage stability effect of the liquid curable composition.

As the above-mentioned surface treatment agent, a known surface treatment agent can be used, and for example, a surface treatment agent described in paragraph [0161] of JP-A-2005-232419 can be mentioned. The treatment amount of the surface treatment agent is preferably from 0.1 to 20% by weight, more preferably from 1 to 5% by weight, based on the calcium carbonate. When the amount of the treatment is less than 0.1% by weight, the effect of improving workability may be insufficient. When the amount is more than 20% by weight, the storage stability of the liquid curable composition may be lowered. Although it is not particularly limited, in the case of using calcium carbonate, it is preferable to use colloidal calcium carbonate in the case where the thixotropy of the formulation or the effect of improving the breaking strength and elongation at break of the cured product is particularly desired. On the other hand, those described in paragraph [0163] of Japanese Patent Laid-Open Publication No. 2005-232419, which is incorporated herein by reference.

The filler may be used singly or in combination of two or more kinds depending on the purpose or needs. In the case of using a filler, the amount of addition is preferably 100 parts by weight of the component (A) and the component (B), and more preferably in the range of 5 to 1000 parts by weight, more preferably 20 to 500 parts by weight. It is preferably used in the range of 40 to 300 parts by weight. When the amount is less than 5 parts by weight, the effect of improving the breaking strength, elongation at break, adhesion and weather resistance of the cured product may be insufficient, and if it exceeds 1000 parts by weight, the liquid hardening combination may be present. The situation in which the workability of the object is reduced.

<micro hollow particles>

In order to reduce the weight and reduce the cost without causing a significant decrease in physical properties, it is possible to use a small hollow particle in combination with the reinforcing filler. The fine hollow particles (hereinafter sometimes referred to as "balls") are not particularly limited, and examples thereof include a diameter of 1 mm or less, preferably 500, as described in "The Latest Technology of Functional Filler" (CMC). A hollow body (inorganic ball or organic ball) composed of an inorganic or organic material of μm or less, more preferably 200 μm or less. In particular, it is preferable to use a minute hollow body having a true specific gravity of 1.0 g/cm ³ or less, and it is more preferable to use a minute hollow body of 0.5 g/cm ³ or less.

As the inorganic ball and the organic ball, the ball described in paragraphs [0168] to [0170] of JP-A-2005-232419 can be used. These balls may be used singly or in combination of two or more. Further, in order to improve the dispersibility and workability of the formulation, it is also possible to use a fatty acid, a fatty acid ester, a rosin, a rosin lignin, a decane coupling agent, a titanium coupling agent, an aluminum coupling agent, or a polypropylene glycol for the surface of the ball. Wait for the processor. These balls are used in such a manner that they do not impair the flexibility and elongation in physical properties when the formulation is cured, reduce the weight, and reduce the cost.

The amount of the ball to be added is not particularly limited, and is preferably from 0.1 to 50 parts by weight, more preferably from 0.1 to 30 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). When the amount is less than 0.1 part by weight, the effect of weight reduction is small, and if it is more than 50 parts by weight, there is a case where the tensile strength is lowered in the mechanical properties when the formulation is cured. . Further, when the specific gravity of the ball is 0.1 or more, the amount of addition is preferably from 3 to 50 parts by weight, more preferably from 5 to 30 parts by weight.

<antioxidant>

In the liquid curable composition used in the present invention, various antioxidants may be used as needed. Examples of the antioxidant include a p-phenylenediamine-based antioxidant, an amine-based antioxidant, a hindered phenol-based antioxidant, a phosphorus-based antioxidant as a co-oxidant, and a sulfur-based antioxidant.

<Plasticizer>

In the liquid curable composition used in the present invention, a plasticizer may be formulated as needed.

The plasticizer is not particularly limited. For example, the plasticizer described in paragraph [0173] of JP-A-2005-232419 may be used for the purpose of the adjustment of the physical properties and the adjustment of the properties. Among these, a polyester-based plasticizer or a vinyl-based polymer is preferable in that the effect of lowering the viscosity is remarkable and the volatilization rate at the time of the heat resistance test is low. Further, by adding a polymer plasticizer having a polymer having a number average molecular weight of 500 to 15,000, the viscosity of the liquid curable composition and the cured product obtained by curing the liquid curable composition can be adjusted. It is preferable to maintain the initial physical properties for a long period of time as compared with the case of a low molecular plasticizer which does not contain a plasticizer of a polymer component in the mechanical properties such as tensile strength and elongation. Further, it is not limited, and the polymer plasticizer may have a functional group or a functional group.

The number average molecular weight of the above polymer plasticizer is described as 500 to 15,000, preferably 800 to 10,000, more preferably 1,000 to 8,000. If the molecular weight is too low, there is a case where the plasticizer flows out over time in the case of being heated or in contact with the liquid, and the initial physical properties cannot be maintained over a long period of time. Moreover, when the molecular weight is too high, the viscosity tends to increase and the workability tends to decrease.

Among these polymer plasticizers, those which are compatible with the vinyl polymer are preferred. Among them, a vinyl polymer is preferred in terms of compatibility, weather resistance, and heat aging resistance. The vinyl polymer is preferably a (meth)acrylic polymer, and more preferably an acrylic polymer. The method for synthesizing the acrylic polymer may be, for example, a solvent obtained by solution polymerization or a solventless acrylic polymer. Since the latter acrylic plasticizer can use a high-temperature continuous polymerization method without using a solvent or a chain transfer agent (USP 4414370, Japanese Patent Laid-Open No. 59-6207, Japanese Patent Publication No. Hei 5-58005, Japanese Patent Laid-Open It is more preferably produced by the publication No. 1-313522 and USP 5010166). The example is not particularly limited, and examples thereof include the East Asian synthetic product UP series (see Industrial Materials, October 1999). Of course, as another synthesis method, a living radical polymerization method can also be cited. According to this method, since the molecular weight distribution of the polymer is narrow and the viscosity can be made low, it is preferable, and the atom transfer radical polymerization method is more preferable, but it is not limited thereto.

The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow, and preferably is less than 1.8. More preferably, it is 1.7 or less, more preferably 1.6 or less, further preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less.

The plasticizer containing the above-mentioned polymer plasticizer may be used singly or in combination of two or more kinds, but it is not necessarily essential. Further, a polymer plasticizer can be used as needed, and further, a low molecular plasticizer can be used in combination within a range that does not adversely affect physical properties.

Furthermore, the plasticizers can be formulated at the time of polymer manufacture.

The amount used in the case of using a plasticizer is not limited, as opposed to The total of the component (A) and the component (B) is 100 parts by weight, preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight. If it is less than 1 part by weight, the effect as a plasticizer tends to be difficult to be exhibited, and if it exceeds 100 parts by weight, the mechanical strength of the cured product tends to be insufficient.

<Reactive diluent>

In addition to the above plasticizer, the following reactive diluent may be used in the liquid curable composition used in the present invention. As a reactive diluent, when a low boiling point compound which can be volatilized in hardening and aging is used, a shape change occurs before or after hardening or an adverse effect on the environment due to a volatile matter, and therefore, a boiling point at a normal temperature is particularly preferable. It is an organic compound of 100 ° C or more.

Specific examples of the reactive diluent include 1-octene, 4-ethylenecyclohexene, allyl acetate, 1,1-diethyloxy-2-propene, and 1-undecenoic acid. Ester, 8-ethyloxy-1,6-octadiene, etc., but is not limited thereto.

The amount of the reactive diluent to be added is preferably from 0.1 to 100 parts by weight, more preferably from 0.5 to 70 parts by weight, still more preferably from 1 to 50 parts by weight, per 100 parts by weight of the total of the components (A) and (B). .

<light stabilizer>

In the liquid curable composition used in the present invention, a light stabilizer may be added as needed. Various types of light stabilizers are known, and examples thereof include those described in "Antioxidant Manual" issued by DaeCheng Corporation, "Degradation and Stabilization of Polymer Materials" (235-242) issued by CMC Chemicals, and the like. , but not limited to these.

Although it is not particularly limited, among the light stabilizers, preferred are ultraviolet absorbers, and specific examples thereof include Tinvin P, Tinvin 234, Tinvin 320, Tinvin 326, Tinvin 327, Tinvin 329, and Tinvin 213 (all of which are Japanese Ciba). - a benzotriazole compound such as that manufactured by Geigy Co., Ltd. or a third such as Tinvin 1577 or the like A benzoate-based compound such as a benzophenone-based compound such as CHIMASSORB 81 or a Tinvin 120 (manufactured by Ciba-Geigy Co., Ltd., Japan).

Further, it is also preferably a hindered amine-based compound. Specific examples of such a compound include those described in JP-A-2006-274084, but are not limited thereto. Further, there is a case where the combination of the ultraviolet absorber and the hindered amine compound can further exert an effect, and therefore, it is not particularly limited and may be used in combination, and is preferably used in combination.

The light stabilizer may be used in combination with the above-mentioned antioxidant, and it is particularly preferable that the effect is further exerted by the combination, especially in the case where the weather resistance is improved. It is also possible to use Tinvin C353 or Tinvin B75 (all of which are manufactured by Ciba-Geigy Co., Ltd., Japan) in which a light stabilizer and an antioxidant are mixed in advance.

The amount of the light stabilizer to be used is preferably in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the total of the component (A) and the component (B). If it is less than 0.1 part by weight, the effect of improving weather resistance is small, and if it exceeds 10 parts by weight, there is no significant difference in effect and it is economically disadvantageous.

<Adhesion imparting agent>

In order to further improve the adhesion of the substrate, an adhesion imparting agent can be added to the liquid curable composition used in the present invention. As an adhesion imparting agent, A compound containing a crosslinkable decyl group and a vinyl monomer having a polar group are preferable, and a decane coupling agent or an acid group-containing vinyl monomer is further preferable. For the purpose of exemplifying the above, the adhesion imparting agent described in paragraph [0184] of JP-A-2005-232419 may be mentioned.

As the decane coupling agent, an epoxy group, an isocyanate group, an isocyanurate group, a urethane group, an amine group, a fluorenyl group, a carboxyl group, a halogen group, a (meth)acryl group, etc. may be contained in the molecule. A decane coupling agent having an organic group other than a carbon atom and a hydrogen atom and a crosslinkable decyl group.

Specifically, the one described in paragraph [0185] of JP-A-2005-232419 contains an organic group having an atom other than a carbon atom and a hydrogen atom, and a crosslinkable decyl group. Decane coupling agent. Among these, in terms of hardenability and adhesion, an alkoxysilane having an epoxy group or a (meth)acryl group in the molecule is more preferable.

Examples of the vinyl monomer having a polar group include (meth)acrylic acid, acryloxyketo acid, citraconic acid, fumaric acid, itaconic acid, crotonic acid, and the like as a carboxyl group-containing monomer. Maleic acid or its esters, maleic anhydride and its derivatives, and the like. Examples of the ester of the carboxyl group-containing monomer include 2-(succinic acid) (meth) propylene methoxyethyl ester and hexahydrophthalic acid 2-(meth) propylene methoxyethyl ester. Further, examples of the sulfonic acid group-containing monomer include vinylsulfonic acid, (meth)acrylsulfonic acid, allylsulfonic acid, styrenesulfonic acid, vinylbenzenesulfonic acid, and 2-acrylamide- 2-methylpropanesulfonic acid or a salt thereof. Further, examples of the phosphoric acid group-containing monomer include 2-(phosphoric acid (meth) propylene methoxyethyl ester), 2-(methyl) propylene methoxy propyl phosphate, and 2-(methyl) propylene phosphate.醯oxy-3-chloropropyl ester, 2-(methyl) propylene methoxyethyl phenyl phosphate Wait. Among them, a phosphate group-containing monomer is preferred. Further, the monomer may have two or more polymerizable groups.

Specific examples of the adhesion imparting agent other than the decane coupling agent and the polar group-containing vinyl monomer are not particularly limited, and examples thereof include an epoxy resin, a phenol resin, a modified phenol resin, and a cyclopentadiene- Phenolic resin, xylene resin, chlorinated resin, petroleum resin, terpene resin, indophenol resin, sulfurized rosin resin, alkyl titanate, aromatic polyisocyanate, and the like.

The above-mentioned adhesion imparting agent is preferably added in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (B). When it is less than 0.01 part by weight, the effect of improving the adhesion tends to be small, and if it exceeds 20 parts by weight, the physical properties of the cured product tend to be lowered. It is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight.

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

<solvent>

In the liquid curable composition used in the present invention, a solvent may be formulated as needed. Examples of the solvent to be blended include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve acetate; acetone and methyl ethyl ketone; A ketone solvent such as methyl isobutyl ketone or diisobutyl ketone. These solvents can also be used in the manufacture of polymers.

<Other additives>

In order to adjust various physical properties of the liquid curable composition or the cured product thereof, the liquid curable composition used in the present invention may be added as needed. Kind of additives. Examples of such an additive include a flame retardant, an anti-aging agent, a radical inhibitor, a metal deactivator, an anti-odor oxidizing agent, a phosphorus-based peroxide decomposing agent, a slip agent, a pigment, and a foaming agent. Wait. These various additives may be used alone or in combination of two or more. Specific examples of such an additive are described in, for example, Japanese Patent Publication No. Hei 4-69659, Japanese Patent Publication No. Hei 7-108928, Japanese Patent Laid-Open No. Hei 63-254149, and Japanese Patent Laid-Open No. 64-22904 The specifications of the bulletin are medium.

The liquid curable composition used in the present invention can be prepared as a single component in which all the formulated components are previously prepared and sealed, or can be prepared to remove only the starting agent A before molding, and will start The first component is mixed with a filler B, a plasticizer, a solvent, and the like, and the two components are mixed.

<<hardening method>>

In the hardening method, two kinds of hardening methods are sequentially described, but each hardening method for obtaining hardening of the gel and complete hardening thereof is carried out by the following method as a hardening of the liquid curable composition. The method is not particularly limited.

When a thermal polymerization initiator is used as the component (C), the curing temperature thereof depends on the type of the thermal polymerization initiator, the component (A), the component (B), and other compounds to be added. Different, but usually it is preferably from 50 ° C to 250 ° C, more preferably from 70 ° C to 250 ° C.

In the case where a photopolymerization initiator is used as the component (C), it can be hardened by irradiating light or an electron beam with an active energy ray source. The active energy ray source is not particularly limited, and examples thereof include a high pressure mercury lamp, a low pressure mercury lamp, an electron beam irradiation device, and a halogen depending on the nature of the photopolymerization initiator to be used. Lamps, light-emitting diodes, semiconductor lasers, metal halide lamps, etc. When a photopolymerization initiator is used as the component (C), the curing temperature is preferably from 0 ° C to 150 ° C, more preferably from 5 ° C to 120 ° C.

When a redox initiator is used as the component (C), the curing temperature is preferably from -50 ° C to 250 ° C, more preferably from 0 ° C to 180 ° C.

The liquid curable composition used in the present invention can be hardened by moisture hardening. The relative humidity at the time of moisture hardening is preferably from 5 to 95%, more preferably from 10 to 80%.

Further, the liquid curable composition used in the present invention can be cured by photohardening, heat curing, or room temperature hardening depending on the kind of the initiator (C), while performing moisture curing. When two or more kinds of mixtures are used as the component (C), the curing conditions are appropriately combined depending on the kind of the initiator. The liquid curable composition used in the present invention can be cured by photohardening and heat hardening, or a combination of photohardening and room temperature hardening by using two or more kinds of initiators in combination, so that light can be used by light. It hardens quickly and does not harden for parts that are not illuminated.

[Examples]

The present invention will be described in more detail below by way of specific examples, but the invention is not limited to the following examples.

Further, in the following examples, "number average molecular weight" and "molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)" were calculated by a standard polystyrene conversion algorithm using gel permeation chromatography (GPC). . Among them, those who used a polystyrene crosslinked gel (shodex GPC K-804 and K-802.5; manufactured by Showa Denko Co., Ltd.) as a GPC column and used chlorine Imitation as a GPC solvent.

¹ H-NMR (Nuclear Magnetic Resonance) was measured using ASX-400 (400 MHz) manufactured by Bruker, using chloroform as a solvent, and measuring at 23 °C.

In the following examples, the "average terminal crosslinkable decyl group or (meth) acryl fluorenyl group" is "the number of crosslinkable decyl groups and the number of (meth) acrylonitrile groups introduced per molecule with respect to the polymer", This was calculated by ¹ H-NMR analysis and the number average molecular weight determined by GPC.

In addition, "parts" and "%" in the following examples and comparative examples indicate "parts by weight" and "% by weight", respectively.

<Manufacture of (meth)acrylic polymer having (meth)acryloxyl group at the terminal> (Manufacturing Examples 1, 2)

The amount of each raw material used is shown in Table 1.

(1) Polymerization step

The acrylate (premixed acrylate) is deoxygenated. The inside of the stainless steel reaction vessel with a stirrer was deoxidized, and cuprous bromide and one part of all acrylates (described as initial addition monomers in Table 1) were added and heated and stirred. Adding and mixing acetonitrile (referred to as acetonitrile for polymerization in Table 1), diethyldiethyl 2,5-dibromohexanide (DBAE) or ethyl 2-bromobutyrate as a starter The polymerization reaction was started by adding pentamethyldiethylideneamine (hereinafter abbreviated as triamine) at a stage where the temperature of the mixture was adjusted to about 80 °C. The residual acrylate (described as an additional monomer in Table 1) was added successively, and the polymerization reaction was continued. Polymerization In the middle, triamine is added as appropriate to adjust the polymerization rate. In Table 1, the total amount of the triamine used in the polymerization is represented by a triamine for polymerization. When the polymerization proceeds, the internal temperature rises due to the heat of polymerization. Therefore, the polymerization is carried out while adjusting the internal temperature to about 80 ° C to about 90 ° C.

(2) Oxygen treatment step

When the monomer conversion rate (polymerization rate) is about 95% or more, an oxygen-nitrogen mixed gas is introduced into the gas phase portion of the reaction vessel. While maintaining the internal temperature at about 80 ° C to about 90 ° C, the reaction solution was heated and stirred for several hours to bring the polymerization catalyst in the reaction liquid into contact with oxygen. The acetonitrile and the unreacted monomer were removed by depressurization under reduced pressure to obtain a concentrate containing the polymer. The concentrate is clearly colored.

(3) First crude purification

Butyl acetate was used as a dilution solvent for the polymer. The concentrate of "(2) Oxygen treatment step" is diluted with butyl acetate of 100 to 150 kg per 100 kg of the polymer, and a filter aid (Radiolite R900, manufactured by Showa Chemical Industry Co., Ltd.) and/or adsorption is added. Agent (Kyoword 700SEN, Kyoword 500SH). After introducing an oxygen-nitrogen mixed gas into the gas phase portion of the reaction vessel, the mixture was heated and stirred at about 80 ° C for several hours. Filter to remove insoluble catalyst components. The filtrate was colored due to the polymerization catalyst residue and was slightly cloudy.

(4) Second crude purification

The filtrate was added to a stainless steel reaction vessel equipped with a stirrer, and an adsorbent (Kyoword 700SEN, Kyoword 500SH) was added. After introducing an oxygen-nitrogen mixed gas into the gas phase portion and heating and stirring at about 100 ° C for several hours, insoluble components such as an adsorbent are removed by filtration. The filtrate is almost colorless and transparent The clear liquid. The filtrate was concentrated to obtain a substantially colorless transparent polymer.

(5) (Methyl) acrylonitrile group introduction step

100 kg of polymer was dissolved in about 100 kg of N,N-Dimethylethylamine (DMAC), potassium acrylate (about 2 molar equivalents relative to the terminal Br group), heat stabilizer (H-TEMPO(4-Hydroxy-2,2,6,6-tetramethyl-piperidine-n-oxyl): 4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl radical) The adsorbent (Kyoword 700SEN) was heated and stirred at about 70 ° C for several hours. The DMAC was distilled off under reduced pressure, the polymer concentrate was diluted with about 100 kg of toluene per 100 kg of the polymer, the solid component was filtered by adding a filter aid, and the filtrate was concentrated to obtain a polymer having an acrylonitrile group at the end [ P1] (Production Example 1), [P2] (Production Example 2). The number of acrylonitrile groups, the number average molecular weight, and the molecular weight distribution introduced per molecule of the obtained polymer are shown in Table 1.

<Manufacture of (meth)acrylic polymer containing hydrolyzable alkylene group> (Manufacturing Example 3)

The amount of each raw material used is shown in Table 2.

(1) Polymerization step

The acrylate (in the case of copolymerization, an acrylate previously mixed in a specific amount) is deoxidized. The inside of a stainless steel reaction vessel equipped with a stirrer was deoxidized, and cuprous bromide and a part of all acrylates (described as initial addition monomers in Table 2) were added and heated and stirred. Adding and mixing acetonitrile (described as acetonitrile for polymerization in Table 2), diethyl 2,5-dibromoadipate as a starter, and adding five to the stage of adjusting the temperature of the mixture to about 80 ° C The polymerization reaction is started by diethyltriamine (hereinafter referred to as triamine). The residual acrylate (described as an additional monomer in Table 2) was added successively, and the polymerization reaction was continued. In the middle of the polymerization, triamine is appropriately added to adjust the polymerization rate. In Table 2, the total amount of the triamine used in the polymerization is represented by a triamine for polymerization. When the polymerization proceeds, the internal temperature rises due to the heat of polymerization, and therefore, The polymerization was carried out while adjusting the internal temperature to about 80 ° C to about 90 ° C.

When the monomer conversion (polymerization rate) is about 95% or more, the volatile component is removed by decompression under reduced pressure to obtain a polymer concentrate.

(2) Diene reaction step

1,7-octadiene (hereinafter referred to as diene or octadiene) and acetonitrile (hereinafter referred to as acetonitrile for diene reaction) are added to the polymer concentrate, and a triamine is added (described in Table 2). For the reaction of the diene with a triamine). The polymer terminal was reacted with octadiene while adjusting the internal temperature to about 80 ° C to about 90 ° C for several hours while heating and stirring. The acetonitrile and unreacted octadiene were removed by evaporation under reduced pressure to obtain a concentrate containing a polymer having an alkenyl group at the end.

(3) crude purification step

The concentrate obtained by the above "(2) diene reaction step" is diluted with toluene, and a filter aid, an adsorbent (Kyoword 700SEN: manufactured by Kyowa Chemical Industry Co., Ltd.), and hydrotalcite (Kyoword 500SH: Kyowa Chemical Industry Co., Ltd.) are added. The company manufactures) and heats and stirs to about 80~100 °C and then filters the solid components. The filtrate was concentrated to obtain a crude crude product.

(4) High temperature heat treatment, adsorption purification step

The above-mentioned crude polymer purified product, a heat stabilizer (Sumilizer GS: manufactured by Sumitomo Chemical Co., Ltd.), and an adsorbent (Kyoword 700SEN, Kyoword 500SH) are added, and the mixture is heated under reduced pressure and heated while stirring, and is heated at about 170 ° C to about The mixture was heated and stirred at a high temperature of 200 ° C for several hours to be decompressed under reduced pressure. Adding an adsorbent (Kyoword 700SEN, Kyoword 500SH), adding about 10 parts by weight of toluene to the polymer, and further heating the stirring number at a high temperature of about 170 ° C to about 200 ° C Hours or so.

Further, the treatment liquid was diluted with toluene and the adsorbent was filtered. The filtrate was concentrated to obtain a polymer having an alkenyl group at both terminals.

(5) decaneization step

The polymer obtained in the above "(4) High-temperature heat treatment. Adsorption purification step", MethylDimethoxy Silane (DMS), Ortho-Methyl Formate (MOF), and platinum are mixed in a specific amount. Catalyst [bis(1,3-divinyl-1,1,3,3-tetramethyldioxane) platinum complex catalyst isopropanol solution: hereinafter referred to as platinum catalyst], and Stir under heating to about 100 °C. After heating and stirring for about 1 hour, the volatile component such as unreacted DMS was distilled off under reduced pressure to obtain a polymer [P3] having a methoxydecyl group at both terminals. Table 2 shows the number of alkyl groups, molecular weight, and molecular weight distribution introduced per molecule of the obtained polymer.

(mixing example 1)

20 parts of the polymer [P1] obtained by the production examples 1 and 2 of the component (A), 40 parts of [P2], and 40 parts of the polymer [P3] obtained as the production example 3 of the component (B). (C) component of IBXA (Isobornyl Acrylate) 10% ester, FA-513M (dicyclopentanyl methacrylate, manufactured by Hitachi Chemical Co., Ltd.), 14 parts, DAROCUR 1173 (2-hydroxy-2-methyl-1-phenyl-1-) Propane-1-one (manufactured by Ciba Specialty Chemicals) 0.6 parts, TPO (2,4,6-Trimethyl benzoyl phenyl Phosphine Oxide, 2,4,6-trimethylbenzimidyl-oxyphenylphosphine (Ciba) Specialty Chemicals, Inc.) 0.3 parts, SILQUESTA 171 (vinyl trimethoxy decane; manufactured by Momentive), 6 parts, and KBM-5103 (trimethoxydecyl propyl acrylate, manufactured by Shin-Etsu Chemical Co., Ltd.), 1 part Mixing 2-ethylhexyl phosphate (AP-8, manufactured by the 8th Chemical Industry Co., Ltd.) as a hardening catalyst of [P3], 0.33 parts, 1,8-diazabicyclo[5,4,0]-7- 0.02 parts of undecene was sufficiently stirred and mixed to prepare a liquid curable composition.

(Example 1)

5 kg of the liquid curable composition obtained in Formulation Example 1 was filled in a can of 10 L volume which can be decompressed, and then defoamed for 10 minutes under a reduced pressure of 50 to 200 Pa. 1 kg of the defoamed liquid curable composition is filled in a state of no-void, and the pressure-reducing composition is filled to a pressure of 50 Pa from the side of the filling side, and the filling side connecting portion and the discharge side connecting portion are provided at both end portions in the longitudinal direction. The container for a discharge device (aluminum bag, a laminate of synthetic resin and aluminum foil, having a thickness of about 0.2 mm) which is flexible and stretchable is sealed (further, an aluminum bag filled with a liquid curable composition) It is a structure of the container for the discharge device shown by the symbol 1 in FIG.

(Example 2) (1) dispensing operation

The ME-5000 VT (manufactured by Musashi Engineering Co., Ltd.) is used as the control device of the discharge device (dispensing device), and the container holder shown in Fig. 8 is used so that the discharge side connecting portion is formed in the vertical (vertical) direction. The aluminum bag filled with the liquid curable composition prepared in Example 1 was placed in a container for pressurization and sealed. At this time, the discharge side connecting portion is connected to the liquid supply pipe, and the liquid supply pipe is connected to the liquid side connecting portion of the pressurizing container (the state in the pressurizing container is based on FIG. 7) ). A diaphragm type dispensing valve PCV-12 (manufactured by Musashi Engineering Co., Ltd.) is used as a discharge valve, and a switching valve for exhaust gas (air) is provided between the discharge valve and the liquid side connection portion of the pressure container. The cock is connected to each other by a polyfluorene tube to form a dispensing device (the entire configuration of the ejection device is based on FIG. 7).

Thereafter, the member was coated (dispensed) by the application pattern shown in Fig. 9 (a), and it was visually confirmed that there was no bubble in the applied liquid resin composition. Produced (biting). Further, VHX-100 (manufactured by Keyence Co., Ltd.) was used as a digital microscope to confirm that no bubbles of 30 μm or more were observed. Further, since it is necessary to perform defoaming before the application of the liquid curable composition in advance, gelation and thickening in the dispensing are not observed. Further, when the liquid curable composition was unable to be discharged, the weight of the liquid curable composition remaining in the aluminum bag was measured and found to be about 35 g.

(2) Fit and harden

Using the discharge apparatus of the above (1), the coating pattern of Fig. 9(b) was applied to the glass (size 100 × 200 × 1 (thickness) mm) so that the thickness of the liquid curable composition was 100 μm. After dispensing, the glass of the same size is adhered to the side of the glass coated with the liquid curable composition, and the UV irradiation device (Light Hammer 6; Fusion UV system, cumulative light amount 6000) is used. mJ/cm ² ) The liquid curable composition between the glasses is cured. Then, it was confirmed that it was left to stand at 23 ° C × 55% RH (Relative Humidity) for 7 days, and as a result, it was good in the absence of bubbles and the like.

(Example 3)

The aluminum bag is placed in the pressurizing container so that the discharge side connecting portion is in the vertical (vertical) direction, and the pressurizing container portion shown in FIG. 10 is used, and the same as in the second embodiment. The way to dispense. The generation of no bubbles (biting) in the applied liquid resin composition was visually confirmed. Further, VHX-100 (manufactured by Keyence Co., Ltd.) was used as a digital microscope, and it was confirmed that there were no bubbles of 30 μm or more. Further, since it is necessary to perform defoaming before the application of the liquid curable composition in advance, it is not The gelation and viscosity increase in the dispensing were observed. Further, when the liquid curable composition was unable to be discharged, the weight of the liquid curable composition remaining in the aluminum bag was measured and found to be about 500 g.

In the discharge device shown in Fig. 7, the discharge device container 1, the container holder 8 and the liquid supply tube 19 are changed to the discharge shown in Fig. 1 . The device container 101, the container holder 108, and the liquid supply tube 119.

(Example 4)

The liquid curable composition was applied to the glass of the same size as in Example 2 by the same method as (1) of Example 2, and then the glass (glass substrate) was coated with the liquid curable composition side. A touch sensor (ITO (Indium Tin Oxides) glass) of the same size was attached and hardened to obtain a bonded sample. Further, a liquid curable composition was applied to the surface of the obtained glass substrate of the bonded sample by the same method as (1) of Example 2, and bonded to a framed liquid crystal module ( The size is 100 x 200 mm) and hardened to obtain a display. The obtained display has no inconvenience such as mixing bubbles.

(Comparative Example 1)

The liquid curable composition of Formulation Example 1 was directly filled in a pressurized container 46 shown in Fig. 11 (the same reference numerals are given to the same configuration as Fig. 7), and defoaming was performed under reduced pressure for 10 minutes at 100 Pa. The liquid curable composition (symbol A in FIG. 11) is directly pressurized by air, and is supplied to the discharge valve 21 via the liquid supply pipe 47 immersed in the liquid curable composition, and is used and implemented. In the same manner as in Example 2, the state of the bubble at the time of dispensing was confirmed, and it was confirmed that the generation of bubbles of about 100 μm to 1 mm was not confirmed in the resin to be supplied. Gelatinized, markedly thickened).

(Comparative Example 2)

The degree of kneading at the time of dispensing and the state of the liquid resin at the time of liquid feeding were confirmed by the same method as in Comparative Example 1, except that the defoaming time was changed to 45 minutes. As a result, no foaming occurred in the bonded sample at the time of dispensing, but gelation was confirmed in one of the remaining resin of the can, and significant thickening was confirmed in the resin liquid in the liquid supply tube.

(Comparative Example 3)

An aluminum bag having only one connecting portion was used as a container for a discharge device, and the same operations as in Examples 1 and 2 were carried out except that the liquid curable composition was filled and discharged from the same connection portion. The residue of the liquid curable composition at the time of filling is moisture-cured, but it is a problem that it is mixed into the bonded sample at the time of dispensing, and remains as a foreign matter and bubbles are mixed around the periphery. Further, there is also a problem that the needle at the tip end of the diaphragm valve of the discharge valve is blocked and the dispensing efficiency is lowered.

In the comparison between Examples 1 and 2 and Comparative Examples 1 and 2, a system in which an aluminum bag was used and liquid-feeding and dispensing were carried out without directly contacting the liquid curable composition with a pressurized fluid (air) (Example) In the case of the generation of the bubble immediately after the dispensing and the occurrence of the bubble of the bonded sample over time, the dispensing characteristics are good, and the gelation and thickening of the resin are stable during the liquid feeding. There is no problem with sex.

In the comparison between the second embodiment and the third embodiment, the second embodiment in which the discharge side connecting portion is provided on the lower side in the vertical direction is smaller than the upper side in the vertical direction, and the liquid in the container for the discharge device (aluminum bag) is lowered. Residual amount of the curable composition, The contents are further ejected efficiently.

[Industrial availability]

According to the present invention, it is possible to provide a container for a discharge device filled with a liquid curable composition which has a specific structure and can be applied to mass production of various display devices and has excellent storage stability. In addition, by using such a container for a discharge device filled with a liquid curable composition, visibility of a display device such as a liquid crystal touch panel, an organic EL touch panel, a liquid crystal module, or a PDP can be improved. The impact resistance is such that when the air gap portion is filled with the curable resin, the liquid curable composition is not directly pressurized by air, and the liquid is supplied from another connection portion dedicated to the discharge at the time of filling, whereby the liquid can be supplied. Prevents the generation of bubbles after hardening during coating. In addition, when the liquid curable composition is filled in the container for a discharge device, the defoaming is performed in advance and the filling is performed without voids, thereby eliminating the liquid curable composition caused by defoaming during use. Adverse conditions such as modification of components or gelation during coating. As a result, a display device such as a liquid crystal type touch panel, an organic EL touch panel, a liquid crystal module, a PDP, a digital and analog tachometer, which is excellent in appearance, display accuracy, and sharpness can be provided. As described above, the present invention can be suitably applied to various display devices and their manufacture for mounting on electric or electronic equipment or two-wheeled or four-wheeled vehicles.

1‧‧‧ Container for spouting device

2‧‧‧Sheet shaped body

3‧‧‧Filling side connection

4‧‧‧Spray side connection

5‧‧‧Filled side seals

5'‧‧‧Spray side seal

6‧‧‧ Arms

6'‧‧‧ Arms

7‧‧‧ Hollow

7'‧‧‧ Hollow

8‧‧‧Container support

9‧‧‧Connecting Department

10‧‧‧Mixed cans

11‧‧‧ Valve

12‧‧‧ valve

13‧‧‧Pipe

14‧‧‧Measuring device

15‧‧‧Pressure container

16‧‧‧Base

17‧‧‧ Liquid supply line

18‧‧‧ Liquid supply side connection

19‧‧‧ Liquid supply tube

20‧‧‧ 盖部

21‧‧‧Spray valve

22‧‧‧Liquid Storage Department

23‧‧‧Switching valve

24‧‧‧ Pressurized side connection

25‧‧‧ solenoid valve

26‧‧‧Supply source

27‧‧‧Pipe

28‧‧‧Pipe

29‧‧‧Distribution valve

30‧‧‧Coating head

31‧‧‧ needle

32‧‧‧Piston

33‧‧‧ Space a

34‧‧‧ Space b

35‧‧‧Pipe

36‧‧‧Pipe

37‧‧‧ Pressure Control Agency

38‧‧‧Spray control mechanism

39‧‧‧Spray outlet

40‧‧‧ components

41‧‧‧Bow section

42‧‧‧ hook

43‧‧‧ Spring

44‧‧‧Flange

45‧‧‧ openings

46‧‧‧ Pressurized container

47‧‧‧ Liquid supply tube

101‧‧‧With container for ejection device

103‧‧‧Filling side connection

104‧‧‧Spray side connection

105‧‧‧Filled side seals

107‧‧‧ Hollow

108‧‧‧Container support

109‧‧‧Connecting Department

116‧‧‧Base

119‧‧‧ Liquid supply tube

144‧‧‧Flange

145‧‧‧ openings

151‧‧‧Slit

152‧‧‧Protruding

153‧‧‧Lip face

154‧‧‧ valve body

155‧‧‧Spray side seal

156‧‧‧ Interior Department

157‧‧‧ wing

158‧‧‧ Main body

159‧‧‧ openings

160‧‧‧Spray side seal

161‧‧‧slit

162‧‧‧Protruding

163‧‧‧ valve body

166‧‧‧Internal space

170‧‧‧Spray side connection

171‧‧‧Outer casing

172‧‧‧ openings

173‧‧‧Protruding

174‧‧‧wing

175‧‧‧ Hollow

176‧‧‧Conical surface

177‧‧‧ Main body

178‧‧‧ protruding parts

179‧‧‧ openings

180‧‧‧Spray side seal

181‧‧‧ valve body

182‧‧ ‧ spring

183‧‧‧The Peripheral Department

184‧‧‧ protruding parts

A‧‧‧ liquid hardening composition

B‧‧‧Filling device

C‧‧‧Spray device

Fig. 1 is a view showing an example of a container for a discharge device filled with a liquid curable composition of the present invention in a state of being placed in a container for pressurization of a discharge device.

Fig. 2(a) is a view in which the discharge side connecting portion 104 and the discharge side sealing portion 155 are assembled. A perspective view of the person. Fig. 2(b) is a view showing a cross-sectional view taken along line I-I of Fig. 2(a). Fig. 2 (c) is a perspective view showing the discharge side seal portion 155 shown in Figs. 2 (a) and (b).

Fig. 3 (a) is a perspective view showing another example of the discharge side seal portion which can be used in the present invention. Fig. 3 (b) is a view showing a state in which the discharge side seal portion 160 shown in Fig. 3 (a) extends in the axial direction. Fig. 3 (c) is a combination of the discharge side seal portion 160 shown in Fig. 3 (a) and the discharge side connecting portion 104 shown in Fig. 2, and is connected to the both ends of the slit 161 of Fig. 3 (a). FIG. 2(b) is a cross-sectional view corresponding to FIG. 2(b) when the slit 151 of FIG. 2 is arranged substantially in parallel. (d) of FIG. 3 is a view showing a state in which the discharge-side sealing portion 160 shown in FIG. 3(c) is inserted into the connection portion 109 so as to extend in the axial direction.

Fig. 4 (a) is a perspective view showing still another example of the discharge side connecting portion which can be used in the present invention. Fig. 4 (b) is a cross-sectional view taken along line II-II of Fig. 4 (a) showing a state in which the discharge side seal portion is closed. Fig. 4 (c) is a cross-sectional view taken along line II-II of Fig. 4 (a) showing a state in which the discharge side seal portion is opened.

Fig. 5 is a view showing another example of the container for a discharge device filled with the liquid curable composition of the present invention in a state of being placed in a container for pressurization of a discharge device.

Fig. 6 is a view showing an example of a filling device used when filling a liquid curable composition in a container for a discharge device.

Fig. 7 is a schematic view showing an example of an embodiment of the discharge device of the present invention.

FIG. 8 is a view showing the use of the container for a discharge device filled with the liquid curable composition used in the present invention in a container for pressurization. The device supports a pattern diagram with one example.

Fig. 9(a) is a schematic view showing an example of a coating pattern in the embodiment. Fig. 9(b) is a schematic view showing another example of the coating pattern in the embodiment.

Fig. 10 is a schematic view showing a portion of the container for pressurization of the discharge device used in the third embodiment.

Fig. 11 is a schematic view showing an example of a conventional discharge device.

2‧‧‧Sheet shaped body

41‧‧‧Bow section

42‧‧‧ hook

43‧‧‧ Spring

101‧‧‧With container for ejection device

103‧‧‧Filling side connection

104‧‧‧Spray side connection

105‧‧‧Filled side seals

108‧‧‧Container support

109‧‧‧Connecting Department

116‧‧‧Base

119‧‧‧ Liquid supply tube

144‧‧‧Flange

145‧‧‧ openings

155‧‧‧Spray side seal

A‧‧‧ liquid hardening composition

Claims (12)

A container for a discharge device filled with a liquid curable composition, which is filled with a liquid curable composition and deformable by a pressing force from the outside, wherein the liquid curable composition has moisture hardening The composition of at least one of the properties and the active energy ray-curing property includes a discharge-side connection portion connectable to the discharge device at one end side in the longitudinal direction of the container for the discharge device, and a discharge-side connection portion that can be freely opened and closed. a discharge side seal portion, and a filling side connection portion for filling the liquid curable composition in an airtight state, and a filling side seal for sealing the filling side connection portion to be opened and closed in a manner different from the discharge side connection portion The filling-side connecting portion is formed on the other end side opposite to the discharge-side connecting portion in the longitudinal direction of the container for the discharge device, and after filling the liquid-curable composition, the filling-side connecting portion is maintained by the filling-side sealing portion. The state of the seal. A container for a discharge device filled with a liquid curable composition according to claim 1, wherein the container for the discharge device is composed of a sheet-shaped molded body containing a synthetic resin. The container for a discharge device filled with a liquid curable composition according to claim 2, wherein the sheet-like molded body containing the synthetic resin has a thickness of 0.05 to 0.5 mm. A method for producing a container for a discharge device filled with a liquid curable composition, which is filled with liquid hardenability according to any one of claims 1 to 3. In the method for producing a container for a discharge device of the composition, the liquid-hardenable composition which has been subjected to the defoaming treatment is filled in the container for the discharge device in an airtight state through the filling-side connecting portion, and then the filling side is The sealing portion seals the filling side connecting portion. A discharge device for a liquid-like curable composition, comprising: a container for pressurization; and a container for a discharge device filled with a liquid curable composition according to any one of claims 1 to 3, which is attached to the filling side a state in which the filling-side sealing portion of the connecting portion is closed and the discharge-side sealing portion of the discharge-side connecting portion is opened, and is disposed in the pressurizing container; and the discharge valve is connected to the discharge side through the discharge-side connecting portion The inside of the container for the discharge device is in communication; and a pressurizing mechanism that applies a pressing force from the outside of the container for the discharge device. The discharge device for a liquid-like curable composition according to claim 5, wherein the container for the discharge device is disposed in the pressurizing container such that the discharge-side connecting portion is located on a lower side in the vertical direction of the container for the discharge device on. The ejection device of the liquid curable composition of claim 5 or 6, wherein the pressurizing mechanism is a pressurized fluid. The discharge device of the liquid curable composition according to claim 7, comprising controlling the liquid curable composition from the container for the discharge device based on the pressure inside the pressurizing container applied by the pressurizing mechanism The pressure control mechanism for the discharge amount. The discharge device for a liquid curable composition according to claim 5 or 6, further comprising a discharge control mechanism for controlling a discharge amount of the liquid curable composition supplied from the container for the discharge device from the discharge valve. The discharge device for a liquid curable composition according to claim 7, further comprising a discharge control mechanism for controlling a discharge amount of the liquid curable composition supplied from the container for the discharge device from the discharge valve. The discharge device for a liquid curable composition according to claim 8, further comprising a discharge control mechanism for controlling a discharge amount of the liquid curable composition supplied from the container for the discharge device from the discharge valve. A display device for applying a liquid to at least one of a protective member, a functional protective member, and a display module, using the ejection device of the liquid curable composition according to any one of claims 5 to 11 The curable composition is obtained by bonding the protective member or the functional protective member to the display module via the liquid curable composition, and curing the liquid curable composition.