TW201431700A - Transparent face plate with adhesive layer, laminate, display device, and production methods thereof - Google Patents

Abstract

A transparent face plate (1) with an adhesive layer, which is characterized by comprising a transparent face plate (10) and an adhesive layer (14) that is formed on the surface of the transparent face plate (10) and has a layer-like portion (18) and a weir-like portion (20), and which is also characterized in that the difference between the content (W1) of a non-curable oligomer (II) in the layer-like portion (18), said content (W1) being expressed in mass%, and the content (W2) of a non-curable oligomer (II') in the weir-like portion (20), said content (W2) being expressed in mass%, namely (W2) - (W1) is set to be 40 or less. A display device which comprises a display panel and a transparent face plate (1) with an adhesive layer, said transparent face plate (1) being bonded to the display panel so that the adhesive layer is in contact with the display panel.

Description

Transparent surface material with adhesive layer, laminated body, display device, and the like Field of invention

The present invention relates to a transparent face material with an adhesive layer, a laminate, a display device, and the like.

Background of the invention

For example, as a display device that protects a display panel (a surface material to be bonded) with a protective sheet (transparent surface material), a display device in which a display panel and a protective sheet are bonded via an adhesive layer is known. As the display device is similar to the adhesive layer used in the laminated body in which the adhesive layer is sandwiched between the pair of face materials, there is proposed an adhesive layer having a layered portion extending along the surface of the face material and surrounding the periphery of the layered portion. In the ridge portion, the layered portion is composed of a cured product of a curable resin composition, and the curable resin composition contains a curable compound and a non-curable oligomer (see Patent Documents 1 and 2).

Examples of the method for producing a laminate of the above display device include the following methods (i) and (ii).

(i) The curable resin composition forming the layered portion is supplied to a region surrounded by the unhardened weir portion formed on the peripheral edge portion of the surface of the transparent surface material, and then adhered to the protective layer under a reduced pressure atmosphere. Membrane support surface material, and restore The uncured beak and the layered portion are hardened in the atmosphere, and an adhesive layer is formed on the transparent surface material to obtain a laminate in which the adhesive layer is covered by the protective film. Thereafter, the protective film of the laminated body is peeled off at a desired time point, and the laminated body and the bonded surface material are superposed and bonded so that the adhesive layer and the bonded surface material are in contact with each other in a reduced-pressure atmosphere. Return to the atmosphere.

(ii) After supplying the resin composition forming the layered portion to a region surrounded by the unhardened weir portion formed on the peripheral edge portion of the surface of the bonded surface material, the transparent surface material is superposed in a reduced pressure gas atmosphere and restored to The uncured beak and the layered portion are hardened in an atmospheric environment.

In the method (i), when the transparent surface material having the adhesive layer formed on the transparent surface material and the bonded surface material are bonded together under a reduced pressure atmosphere, the interface between the display panel and the adhesive layer is produced. Void. However, when the adherent is returned to the atmosphere, the void volume is reduced due to the pressure difference between the pressure in the gap (maintained in a reduced pressure state) and the pressure (atmospheric pressure) applied to the adhesive layer, so that the void is reduced. disappear. Similarly, in the method (ii), even when a transparent surface material is superposed in a reduced-pressure gas atmosphere, a void is generated, and the void disappears when it returns to the atmosphere.

When the curable resin composition forming the layer portion contains a non-curable oligomer which is not related to the curing reaction, the fluidity of the formed layer portion is lower than that in the case where the non-curable oligomer is not contained. high. Therefore, the layered portion is liable to flow into the gap, so that the gap which has been formed at the interface between the adhesive layer and the face material can disappear in a short time.

Further, by containing a non-curable oligomer, the layered portion becomes low in elasticity. Therefore, the stress applied to the display panel that is in contact with the adhesive layer is small, and the display unevenness of the display device can be suppressed.

Prior technical literature Patent literature

Patent Document 1: International Publication No. 2011/158839

Patent Document 2: International Publication No. 2012/077726

Summary of invention

However, in the transparent surface material with the adhesive layer, the non-hardening oligomer diffuses from the layered portion of the adhesive layer to the beak portion after a predetermined period of time, and is in the vicinity of the interface between the beak portion and the layer portion. The influence of the diffusion of the curable oligomer causes a difference in thickness between the beak portion and the layer portion. Therefore, when the bonding is performed, a void may occur between the bonded surfaces or a bonding failure may occur. In addition, when the laminate of the surface material to which the adhesive layer is attached and the laminated body of the bonded surface material are passed for a predetermined period of time, the volume of the beak portion increases due to the diffusion of the non-curable oligomer to the beak portion. There is a problem that the joint is poor or the gap is formed on the surface to be bonded.

The present invention provides a transparent surface material, a display device, and a laminate having an adhesive layer which is difficult to cause defects in a layer portion and a beak portion even after a predetermined period of time has elapsed. Moreover, the present invention provides a transparent face material and a method of manufacturing a display device which are difficult to cause an adhesive layer in a layered portion and a beak portion even after a predetermined period of time has elapsed.

The transparent surface material with the adhesive layer of the invention has a transparent surface material and An adhesive layer formed on at least one surface of the transparent surface material; wherein the adhesive layer has a layered portion extending along a surface of the transparent surface material and a beak portion surrounding a periphery of the layered portion; the beak portion The curable resin composition for forming a beak portion includes the following curable compound (I') and the following non-curable oligomer (II). The layered portion is composed of a cured product of a curable resin composition for forming a layer portion, and the curable resin composition for forming a layer portion contains the following curable compound (I) and the following non-hardened The oligomer (II); the content W1 expressed by mass% of the non-curable oligomer (II) in the layered portion, and the mass of the non-hardening oligomer (II') in the aforementioned weir portion The difference (W1-W2) of the content W2 indicated by % is 40 or less.

The curable compound (I') contains an urethane acrylate oligomer (A') and a monomer (B') having one or more hardening functional groups and a molecular weight of less than 600. .

The non-curable oligomer (II') is an oligomer having a hydroxyl group, and is hardened in either the curable resin composition for forming a layer portion or the curable resin composition for forming a beak portion. At the time, the hardening reaction (I') does not undergo a hardening reaction.

The curable compound (I) contains an urethane acrylate oligomer (A) and a monomer (B) having one or more curable functional groups and a molecular weight of less than 600.

The non-curable oligomer (II) is an oligomer having a hydroxyl group, and is hardened when either the curable resin composition for forming a layer portion or the curable resin composition for forming a beak portion is cured. , neither with the aforementioned sclerosing Compound (I) undergoes a hardening reaction.

The urethane acrylate oligomers (A) and (A') are preferably urethane acrylate oligomers synthesized from polyoxyalkylene polyols and polyisocyanates.

The non-curable oligomer (II) and (II')-based polyoxyalkylene polyol are preferred.

The number average molecular weight of each of the hydroxyl groups of the non-curable oligomers (II) and (II') is preferably from 400 to 8,000.

The number average molecular weight of the aforementioned urethane acrylate oligomer (A) is preferably from 1,000 to 100,000.

The curable resin composition for forming a layer portion contains a photopolymerization initiator (C1), and the curable resin composition for forming a beak portion preferably contains a photopolymerization initiator (C2).

In the transparent surface material with an adhesive layer according to the present invention, the storage shear modulus at the lobe portion at 35 ° C is higher than the storage shear modulus of the layer portion at 35 ° C and less than 15 times. It is better.

The storage shear modulus of the above-mentioned beak at 35 ° C is preferably from 1 to 150 kPa.

The storage shear modulus of the layered portion at 35 ° C is preferably from 1 to 100 kPa.

In the transparent surface material with an adhesive layer of the present invention, the transparent surface material includes a light-shielding printing portion formed on a peripheral portion of the surface thereof, and at least a part of the layer portion and the weir portion is in the in-plane direction of the surface of the transparent surface material. Preferably, it is placed on the inner side of the light-shielding printing portion.

Further, it is preferred that the weir portion contains a cured product composed of an oligomer having a number average molecular weight of 30,000 to 100,000. It is preferable that the weir portion contains a cured product composed of a monomer having a molecular weight of 125 to 600 and no acid group. The viscosity of the aforementioned beak portion when it is not hardened is preferably from 40 Pa s to 100 Pa s.

The transparent surface material of the adhesive layer of the present invention may further have a protective film covering at least a part of the surface of the adhesive layer and being peelable.

The method for producing a transparent surface material with an adhesive layer of the present invention having a protective film has the following steps (a) to (e): step (a), applying a liquid to the peripheral portion of the surface of the transparent surface material The curable resin composition for forming the weir portion forms an unhardened weir portion, and in step (b), the liquid curable resin composition for forming the layer portion is supplied to the surface of the transparent surface material. a region surrounded by the hardened weir portion; and step (c), the supporting surface material to which the protective film has been attached is brought into contact with the curable resin composition for forming the layer portion in a reduced-pressure gas atmosphere The method is superposed on the curable resin composition for forming a layer portion, and a precursor layer body in which the unhardened layer portion has been sealed by the transparent face material, the protective film, and the unhardened weir portion is obtained, and the unhardened layer is obtained. The layered portion is composed of a curable resin composition for forming a layer portion; and in the step (d), the precursor layer body is placed in a higher pressure gas atmosphere than the step (c) The unhardened layered portion and the beak are hardened to form a layered portion and a crucible The adhesive layer of the portion; in step (e), the support surface material is peeled off from the protective film.

The display device of the present invention has a display panel; and the transparent surface material of the adhesive layer of the present invention is connected to the display panel by an adhesive layer Fitted to the display panel.

The manufacturing method of the display device of the present invention is a method in which a display panel and a transparent surface material with an adhesive layer are laminated and adhered in such a manner that an adhesive layer is in contact with a display panel in a reduced-pressure gas atmosphere of 10 kPa or less.

In the laminated system of the present invention, the transparent surface material with the adhesive layer of the present invention and the laminated body of the bonded surface material are bonded.

As long as the transparent surface material with the adhesive layer of the present invention is used, it is difficult to cause defects in the layered portion and the beak portion even after a predetermined period of time has elapsed.

According to the method for producing a transparent surface material with an adhesive layer according to the present invention, it is possible to obtain a transparent surface material having an adhesive layer which is difficult to cause defects in the layer portion and the beak portion even after a predetermined period of time has elapsed.

The display device of the present invention is difficult to cause defects in the layered portion and the beak portion even after a predetermined period of time has elapsed.

According to the method of manufacturing a display device of the present invention, it is possible to obtain a display device which is difficult to cause defects in the layer portion and the beak portion even after a predetermined period of time has elapsed.

The laminate of the present invention is difficult to cause defects in the layered portion and the beak portion even after a predetermined period of time has elapsed.

1‧‧‧Transparent surface material with adhesive layer

2‧‧‧Display device

3‧‧‧ horizontal moving mechanism

10‧‧‧Transparent surface material (protective plate)

12‧‧‧Lighting Printing Department

14‧‧‧Adhesive layer

16‧‧‧Protective film

18‧‧‧Layered

20(21)‧‧‧堰

20A‧‧‧Unhardened warts

21‧‧‧Second resin composition

24‧‧‧Area

26‧‧‧First composition

28, 44‧‧‧

30‧‧‧Sprapper

31‧‧‧UV-LED light source

32, 34‧‧‧ feed spiral

36‧‧‧Support surface material

38‧‧‧Reducing device

40‧‧‧Sucking pad

42‧‧‧Upright

46‧‧‧ cylinder

48‧‧‧vacuum pump

50‧‧‧ display panel

52‧‧‧ Transparent substrate with color filter

54‧‧‧ Transparent substrate with TFT

56‧‧‧Liquid layer

58‧‧‧Polar plate

60‧‧‧Flexible printed wiring board

Fig. 1 is a cross-sectional view showing an example of a transparent face material with an adhesive layer of the present invention.

Fig. 2 is a plan view showing an example of the aspect of the step (a).

Fig. 3 is a cross-sectional view showing an example of the aspect of the step (a).

Fig. 4 is a plan view showing an example of a specific aspect of the step (a).

Fig. 5 is a cross-sectional view showing an example of a specific aspect of the step (a).

Fig. 6 is a plan view showing another example of the specific aspect of the step (a).

Fig. 7 is a cross-sectional view showing another example of the specific aspect of the step (a).

Fig. 8 is a perspective view showing the main part of the steps shown in Figs. 6 and 7.

Fig. 9 is a plan view showing an example of the aspect of the step (b).

Fig. 10 is a cross-sectional view showing an example of the aspect of the step (b).

Figure 11 is a cross-sectional view showing an example of the aspect of the step (c).

Fig. 12 is a cross-sectional view showing an example of a display device of the present invention.

Figure 13 is a perspective view showing a void pattern in the interface between the display panel and the adhesive layer in the display device of the present invention.

Form for implementing the invention

In the present specification, "transparent" means that the surface material and the display surface of the display panel are bonded together without a gap through the adhesive layer, and the whole or a part of the display image of the display panel can be visually recognized without being affected by the optical strain transmission surface material. . Therefore, even if a part of the light incident on the face material from the display panel is absorbed or reflected by the face material, or the visible light transmittance of the face material is reduced due to an optical phase change or the like, the surface material can be visually recognized without optical strain through the face material. If the display image of the panel is displayed, it can be called "transparent". For example, the transparent facestock also includes a facestock having a polarizing plate.

Moreover, the "curable functional group" means a functional group having a radical polymerizable unsaturated bond. Further, "(meth) acrylate" means acrylate or methacrylate.

The "average thickness" in this specification is the average of the thicknesses measured at 10 places.

Transparent surface material with adhesive layer≫

Fig. 1 is a cross-sectional view showing an example of a transparent face material with an adhesive layer of the present invention.

The transparent surface material 1 having the adhesive layer of the protective film 16 has a transparent surface material 10, a light-shielding printing portion 12 formed on the peripheral edge portion of the surface of the transparent surface material 10, and a side surface of the transparent surface material 10 on which the light-shielding printing portion 12 is formed. The adhesive layer 14 and the peelable protective film 16 covering the surface of the adhesive layer 14.

The transparent surface material 1 with an adhesive layer shown in FIG. 1 can be manufactured by bonding the display panel to the display panel after peeling off the protective film 16.

Although the adhesive layer 14 is formed on one side of the transparent surface material 10 in FIG. 1, the adhesive layer 14 may be formed on both sides of the transparent surface material 10. At this time, the surfaces of the adhesive layers 14 are peelable. The protective film 16 is covered.

<Transparent surface material>

It is preferable that the transparent surface material 10 protects the protective panel of the display panel in the image display side provided on the display panel, which will be described later.

As the transparent surface material 10, a glass plate or a transparent resin plate is mentioned. As the transparent surface material 10, it is preferable to have a glass plate from the viewpoint of high transparency with respect to the emitted light and the reflected light from the display panel, and has light resistance, low birefringence, high planar precision, and surface damage resistance. The viewpoint of high mechanical strength also seems to be the best for glass plates. Moreover, it is preferable that the transparent surface material 10 is a glass plate from the viewpoint that the light which can be used for curing the photocurable resin composition is sufficiently transmitted.

As a material of the glass plate, a glass material such as soda lime glass can be mentioned. As the glass plate, a high-transmission glass (whiteboard glass) having a low iron content and a small blue color is preferable. As the glass plate, tempered glass can also be used for the purpose of improving safety. Especially in the case of using a thin glass plate, it is preferred to use a glass plate to which chemical strengthening has been applied.

The material of the transparent resin sheet may, for example, be a resin material (polycarbonate, polymethyl methacrylate or the like) having high transparency.

In order to improve the adhesion to the interface with the adhesive layer 14, the transparent face material 10 may also be subjected to a surface treatment. As a method of surface treatment, a method of treating the surface of the transparent surface material 10 with a decane coupling agent, a method of forming a ruthenium oxide film by an oxidizing flame of a flame burner, and the like can be mentioned.

In order to improve the contrast of the displayed image, an antireflection layer may be provided on the surface of the transparent face material 10 on the side opposite to the side on which the adhesive layer 14 is formed. The method of providing the antireflection layer may be a method of directly forming an inorganic thin film on the surface of the transparent surface material 10, and a method of bonding a transparent resin film provided with an antireflection layer to the protective sheet 10. Further, depending on the purpose, a part or the whole of the transparent surface material 10 may be colored, or a part or the whole of the surface of the transparent surface material 10 may be made into a glass-like shape to scatter light, or may be part of the surface of the transparent surface material 10. Or, fine irregularities or the like are formed as a whole to refract or reflect transmitted light. Further, a colored film, a light-scattering film, a light-refractive film, a light-reflecting film, or the like may be attached to a part or the entire surface of the transparent surface material 10.

The shape of the transparent facestock 10 is generally rectangular for the purpose of conforming to the shape of the display device. A protective plate covering the entire surface of the display surface of the display panel and having an outer shape and having a curved shape may be used depending on the shape of the display device.

The size of the transparent face material 10 may be appropriately set in accordance with the shape of the display device. For example, when the display device is a television receiver, the size of the transparent face material 10 is suitably 0.5 m × 0.4 m or more, and preferably 0.7 m × 0.4 m or more. The upper limit of the size of the transparent face material 10 is determined by the size of the display panel. Moreover, handling of an excessively large display device in setting or the like is likely to be difficult. The upper limit of the size of the transparent face material 10 is usually about 2.5 m x 1.5 m by these constraints.

The thickness of the transparent face material 10 is preferably 0.5 to 25 mm in the case of a glass plate from the viewpoint of mechanical strength and transparency. For applications such as television receivers and PC monitors used in indoors, it is preferably 1 to 6 mm from the viewpoint of weight reduction of the display device, and 3 to 20 mm for public display applications installed outdoors. When chemically strengthened glass is used, the thickness of the glass is preferably about 0.5 to 1.5 mm from the viewpoint of strength. In the case of a transparent resin sheet, the thickness of the transparent resin sheet is preferably 2 to 10 mm.

<Light-shielding printing section>

In the light-shielding printing unit 12, the wiring member or the like connected to the display panel is concealed so that the image display area of the display panel to be described later cannot be visually observed from the side of the transparent surface material 10. The light-shielding printing portion 12 may be formed on the surface on the side where the adhesive layer 14 is formed or the side opposite thereto. From the viewpoint of reducing the parallax between the light-shielding printing portion 12 and the image display region, it is preferable to form the light-shielding printing portion 12 on the surface on the side on which the adhesive layer 14 is formed. When the transparent surface material 10 is a glass plate, it is preferable to use a ceramic printing containing a black pigment in the light-shielding printing part 12, and it is high in light-shielding property. When the light-shielding printing portion is formed on the opposite side to the side on which the adhesive layer has been formed, a transparent film having a light-shielding printing portion in advance may be bonded to the protective sheet to form a light-shielding printing portion. It can also be attached to the surface of the protective sheet. A light-shielding printing portion is provided on the peripheral portion of the film, and a film provided with an anti-reflection layer is bonded to the protective plate on the back surface thereof, that is, the outermost surface of the display device. When the wiring member or the like of the display panel cannot be visually observed from the side where the display panel is viewed or hidden by another member such as the frame of the display device, or the bonded surface material other than the display panel and the adhesive layer are attached. When the transparent surface material 1 is bonded, the light-shielding printing portion 12 may not be formed in the transparent surface material 10.

<adhesive layer>

The adhesive layer 14 has a layer portion 18 that extends along the surface of the transparent surface material 10, and a weir portion 20 that is in contact with and surrounds the periphery of the layer portion 18.

The layered portion 18 is a portion composed of a cured product (transparent resin) formed by curing a layered portion-forming curable resin composition (hereinafter sometimes referred to as "first composition").

The weir portion 20 is a portion composed of a cured product (transparent resin) formed by applying a curable resin composition for forming a weir portion (hereinafter also referred to as "second composition") and hardening it.

The transparent surface material 1 to which the adhesive layer is attached is characterized by the content W1 of the non-hardening oligomer (II) in the layered portion 18 to be described later, and the non-hardening oligomer (II' in the beak 20 The difference (W1-W2) of the content W2 expressed by mass% is 40 or less.

When the difference (W1-W2) is 40 or less, the difference between the content of the non-curable oligomer (II) in the layered portion and the content of the non-curable oligomer (II') in the beak portion is reduced. The diffusion of the non-curable oligomer (II) from the layer portion toward the ridge portion is suppressed. Therefore, it is possible to form a laminate which is difficult to cause defects in the layer portion and the weir portion even after a predetermined period of time has elapsed.

The difference (W1-W2) is preferably 40 or less, preferably 30 or less, more preferably 10 or less, and particularly preferably 5 or less. Further, (W1-W2) is preferably greater than 0 (i.e., W1 > W2).

In the case of the cured product of the curable resin composition, the measurement of the non-curable oligomer (II) content W1 in the layered portion is 2 cm in the layered portion from the outermost peripheral portion of the nearest weir portion. In the above area. Further, the measurement of the non-curable oligomer (II') content W2 in the crotch portion was carried out in a region from the outermost peripheral portion of the crotch portion from the height half of the height of the crotch portion.

By setting the measurement portion of the layer portion as the above region, the diffusion effect of the non-curable oligomer (II) in the vicinity of the interface between the layer portion and the weir portion can be eliminated. Further, by setting the measurement portion of the beak portion as the above-described region, even if the outermost peripheral portion of the beak portion contacts the outside air and becomes insufficiently hardened, the influence thereof can be eliminated.

Further, the non-curable oligomer (II) content in the first composition can be set to the non-curable oligomer (II) content W1 in the layered portion. Similarly, the non-curable oligomer (II') content in the second composition can be set to the non-curable oligomer (II') content W2 in the beak portion.

[Layered part]

The first composition forming the layer portion 18 may be a photocurable resin composition or a thermosetting resin composition. The layered portion 18 is preferably a cured product of a photocurable resin composition containing a curable compound and a photopolymerization initiator (C1) from the viewpoint of being hardenable at a low temperature and having a high curing rate. Moreover, as long as the first composition is a photocurable resin composition, it does not require a high temperature to be cured, and thus, the display panel caused by high temperature is observed. There are also fewer defects such as touch panels.

The first composition which is suitable for photocurability in the present invention will be described. The photocurable first composition contains a composition of a curable compound (I), a non-curable oligomer (II), and a photopolymerization initiator (C1). Further, the first composition may contain an additive as needed.

The viscosity of the first composition at 25 ° C is above 0.05 Pa ‧ and the viscosity at 40 ° C is preferably below 50 Pa ‧ , the viscosity at 25 ° C is above 0.2 Pa ‧ and the viscosity at 40 ° C is 10 Pa ‧ s is preferred below. When the viscosity of the first composition at 25 ° C is at least the lower limit value, when the layered portion is obtained by a vacuum deposition method described later, the coating shape of the first composition to be the layer portion can be maintained until the layer is laminated. And when it is restored to the atmosphere after lamination, it is easy to become an independent void, and the void volume can be reduced by the pressure difference between the pressure (decompression state) in the void and the pressure (atmospheric pressure) applied to the adhesive layer, and the void easily disappears. Therefore, a cured film free from bubble residue can be obtained. When the viscosity of the first composition at 40 ° C is less than or equal to the upper limit, the fluidity of the first composition is increased, so that it is difficult to leave voids in the layer portion. The viscosity of the first composition was measured using an E-type viscometer.

The viscosity of the first composition can be adjusted by the molecular weight and the content ratio of the non-curable oligomer (II). Further, it can also be adjusted by adjusting the molecular weight and the content ratio of the oligomer (A) described later.

(hardening compound (I))

The curable compound (I) in the first composition contains an urethane acrylate oligomer (A) (hereinafter simply referred to as "oligomer (A)") and a monomer (B), which is a monomer ( B) has one or more hardening functional groups and a molecular weight of less than 600. hard The compound (II) is preferably composed of the oligomer (A) and the monomer (B).

The monomer (B) preferably contains a monomer (B1) having a hydroxyl group. The hydroxyl group remains in the layered portion composed of the cured product containing the first component of the monomer (B1). The presence of this hydroxyl group contributes to the stabilization of the non-curable oligomer (II) in the layered portion.

Oligomer (A):

The number average molecular weight of the oligomer (A) is preferably from 1,000 to 100,000, more preferably from 10,000 to 70,000, and particularly preferably from 10,000 to 40,000. When the number average molecular weight of the oligomer (A) is within this range, the viscosity of the first composition is easily adjusted within the above range.

The number average molecular weight of the oligomer (A) is a polystyrene-converted number average molecular weight obtained by gel permeation chromatography (GPC). On the other hand, in the GPC measurement, when there is a spike of an unreacted low molecular weight component (monomer or the like), the peak is excluded to calculate the number average molecular weight.

The oligomer (A) has an acryloxy group.

From the viewpoint of the hardenability of the first composition and the mechanical properties of the layered portion, the average number of the acryloxy groups per one molecule of the oligomer (A) is preferably from 1.8 to 4.

The oligomer (A) may be one type or two or more types.

As the oligomer (A), the following polyurethane acrylate oligomer (A1) (hereinafter referred to as "oligomer (A1)") is preferred.

Oligomer (A1): Polyurethane obtained by reacting a polyol with a polyisocyanate to obtain a prepolymer having an isocyanate group at the end, and reacting the following monomer (a1) with an isocyanate group of the prepolymer Ester acrylate oligomer.

Monomer (a1): a monomer having a molecular weight of from 125 to 600, having one or more acryloxy groups and having one reactive group with an isocyanate group.

The monomer (a1) may, for example, be a group having an active hydrogen group (such as a hydroxyl group or an amine group) and a monomer having an acryloxy group.

Specific examples of the monomer (a1) include a hydroxyalkyl acrylate having a hydroxyalkyl group having 2 to 6 carbon atoms (2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate). , 4-hydroxybutyl acrylate, etc.).

As the monomer (a1) which reacts with the above prepolymer, a hydroxyalkyl acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms is preferred.

As the polyol and the polyisocyanate, a known compound can be used, and the polyol (i) and the diisocyanate described in the raw material of the urethane-based oligomer (a) are described in WO 2009/016943. Ii) Wait.

Specific examples of the polyhydric alcohol include polyoxyalkylene polyols (polyoxyethylene glycol, polyoxypropylene propylene polyol, etc.), polyester polyols, and polycarbonate polyols. Among these, as the polyol, a polyoxyalkylene polyol is preferred, and a polyoxypropylene propylene polyol is preferred. Further, when a part of the oxygen-extended propyl group of the polyoxypropylene propylene polyol is substituted with an oxygen-extended ethyl group, the compatibility between the first composition and other components can be improved, and it is more preferable.

The polyol may be used alone or in combination of two or more.

The polyisocyanate is preferably at least one diisocyanate selected from the group consisting of aliphatic diisocyanates, alicyclic diisocyanates, and non-yellowing aromatic diisocyanates.

Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, and 2,4,4-trimethyl-hexa. Methyl diisocyanate and the like.

As the alicyclic polyisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (alias: isophorone diisocyanate), methylene bis(4-cyclohexyl) may be mentioned. Isocyanate) and the like.

The non-yellowing aromatic diisocyanate may, for example, be xylene diisocyanate.

The polyisocyanate may be used alone or in combination of two or more.

As the synthesis of the oligomer (A1), the following monomer (a2) can also be used as a diluent. The diluent remains in the obtained oligomer (A1) and becomes a part of the monomer (B) in the curable compound (I).

Monomer (a2): a monomer having a molecular weight of 125 to 600 and having one or more hardening functional groups and having no reaction with an isocyanate group.

As the monomer (a2), a monomer (B21) to be described later is preferred.

Monomer (B):

The molecular weight of the monomer (B) is less than 600, preferably 125 or more and less than 600, and preferably 140 to 400. The smaller the molecular weight of the monomer (B), the better the adhesion between the transparent face material and the layered portion. When the molecular weight of the monomer (B) is at least the lower limit value, the monomer (B) can be suppressed from volatilizing when the display device is produced by a vacuum deposition method as will be described later.

The monomer (B) may be one type or two or more types.

The number of the curable functional groups per molecule of the monomer (B) is one or more, and the viewpoint of the hardenability of the first resin composition 26 and the mechanical properties of the layered portion 18 obtained by curing the first resin composition 26 is considered. It seems that 1~3 is better. In the curable compound (I), it is preferred to use a monomer having one hardening functional group in combination. (B) and a monomer (B) having two or more curable functional groups.

The curable functional group of the monomer (B) may, for example, be an addition polymerizable unsaturated group (propylene sulfonyl group, methacryl fluorenyl group, acryloxy group, methacryloxy group, etc.), and A combination of a saturated group and a thiol group, and the like. The curable functional group of the monomer (B) is selected from the group consisting of acryloxy group and methacryloxy group from the viewpoint of a fast curing rate and a layer portion having high transparency. Preferably, the methacryloxy group is particularly preferable from the viewpoint of narrowing the difference in reactivity between the oligomer (A) and the curable functional group of the monomer (B) to obtain a homogeneous layered portion.

The monomer (B1) contributes to the stabilization of the non-hardening oligomer (II). Further, by containing the monomer (B1), good adhesion between the transparent surface material and the layered portion can be obtained.

The monomer (B1) preferably has 1 or 2 hydroxyl groups.

Examples of the monomer (B1) having one hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. Base) 4-hydroxybutyl acrylate, 6-hydroxyhexyl methacrylate, and the like.

Examples of the monomer (B1) having two hydroxyl groups include glycerin monomethacrylate and 2,3-dihydroxypropyl acrylate.

As the monomer (B1), a hydroxy methacrylate having a hydroxyl group of 1 to 2 and a carbon number of 3 to 8 (2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, A) Preferably, 4-hydroxybutyl acrylate or the like is preferred, and 2-hydroxybutyl methacrylate is preferred.

The monomer (B1) may be one type or two or more types.

Further, the monomer (B) may also contain the following monomer (B2).

Monomer (B2): a monomer having one or more hardening functional groups, a molecular weight of less than 600, and no hydroxyl group.

The monomer (B2) contributes to the softness of the layered portion.

As the monomer (B2), the following monomer (B21) is preferred. When the content of the monomer (B21) is more than the content of the monomer (B1) by mass ratio, the laminated body in which the adhesive layer is formed on the transparent surface material is attached to the bonded surface material such as a display panel in a reduced-pressure atmosphere. When it is returned to the atmosphere after the combination, the time until the void formed in the adhesive layer disappears tends to be shortened. On the other hand, if the monomer (B21) is contained, the time required for the first composition to harden tends to increase.

Monomer (B21): a methacrylate having no hydroxyl group and having an alkyl group having 8 to 22 carbon atoms or a cyclic alkyl group.

Examples of the monomer (B21) include n-dodecyl methacrylate, n-octadecyl methacrylate, n-xylylene methacrylate, isodecyl methacrylate, and adamantyl methacrylate. As the monomer (B21), n-dodecyl methacrylate or n-octadecyl methacrylate is preferred.

The monomer (B2) may be one type or two or more types.

In the first composition, the ratio of the oligomer (A) is preferably from 20 to 90% by mass, and from 30 to 80% by mass based on the total of the oligomer (A) and the monomer (B) (100% by mass). Preferably. When the ratio of the oligomer (A) is at least the lower limit value, the heat resistance of the layer portion is good. When the ratio of the oligomer (A) is at most the upper limit, the curability of the first composition and the adhesion between the transparent face material and the layer portion are preferable.

In the first composition, the monomer (B) ratio is preferably from 10 to 80% by mass, and from 20 to 70, based on the total of the oligomer (A) and the monomer (B) (100% by mass). The mass % is preferred.

In the first composition, the monomer (B1) ratio is preferably from 10 to 60% by mass, and from 20 to 50% by mass, based on the total of the oligomer (A) and the monomer (B) (100% by mass). good. When the ratio of the monomer (B1) is at least the lower limit value, the stability of the first composition and the adhesion between the transparent surface material and the layer portion are preferable.

In the first composition, the monomer (B2) ratio is preferably from 5 to 50% by mass, and from 15 to 40% by mass, based on the total of the oligomer (A) and the monomer (B) (100% by mass). good. When the ratio of the monomer (B2) is at least the lower limit, it is easy to sufficiently obtain the effect of adding the monomer (B2).

However, in the synthesis of the oligomer (A1), the monomer (a1) which has reacted with the isocyanate group of the prepolymer exists as a part of the oligomer (A), and thus is not contained in the first composition. In the monomer (B) ratio. On the other hand, in the synthesis of the oligomer (A1), a monomer which is added as a diluent at the time of synthesis or after synthesis of the oligomer (A1) (which does not react with the prepolymer) corresponds to a monomer. In the case of (B), the monomer is also contained in the monomer (B) ratio of the first composition.

(non-hardening oligomer (II))

The non-curable oligomer (II) is an oligomer having a hydroxyl group which does not undergo a hardening reaction with the curable compound (I) when the first composition is cured. Further, when the second composition (that is, the curable resin composition for forming a beak portion) to be described later is cured, the oligomer does not react with the curable compound (I) and has a hydroxyl group.

The average number of hydroxyl groups per molecule of the non-curable oligomer (II) is preferably 0.8 to 3, and preferably 1.8 to 2.3.

Number average molecular weight per one hydroxyl group of the non-hardening oligomer (II) (Mn) is preferably 400 to 8000. When the number average molecular weight per one hydroxyl group is 400 or more, the polarity of the non-curable oligomer (II) does not become too high, and good compatibility with the curable compound (I) in the first composition is easily obtained. . When the number average molecular weight per one hydroxyl group is 8000 or less, it is easy to obtain a layered state after hardening by the interaction between the hydroxyl group derived from the curable compound (I) and the hydroxyl group of the non-curable oligomer (II). The effect of stabilizing the non-curable oligomer (II) in the part. This interaction is presumed to be related to hydrogen bonding. Further, the number average molecular weight per one hydroxyl group is preferably 8000 or less, and the first composition can be made to have a low viscosity by being contained in the first composition.

The non-curable oligomer (II) may be used alone or in combination of two or more.

The non-curable oligomer (II) may, for example, be a high molecular weight polyol. As the non-curable oligomer (II), a polyoxyalkylene polyol, a polyester polyol, or a polycarbonate polyol is preferred.

The polyoxyalkylene polyol may, for example, be a polyoxyalkylene glycol such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxypropylene glycerol or polyoxybutylene glycol.

The number average molecular weight (Mn) of each of the hydroxyl groups of the polyoxyalkylene polyol is preferably from 400 to 8,000, more preferably from 600 to 5,000.

Examples of the polyester polyol include residues having an aliphatic diol (ethylene glycol, propylene glycol, 1,4-butanediol, etc.) and an aliphatic dicarboxylic acid (glutaric acid, adipic acid, hydrazine). An aliphatic polyester diol or the like which is a residue of a diacid or the like.

The number average molecular weight (Mn) per one hydroxyl group of the polyester polyol is preferably from 400 to 8,000, more preferably from 800 to 6,000.

The polycarbonate polyol may, for example, be an aliphatic polycarbonate diol having a residue of a diol (such as 1,6-hexanediol) or a ring-opening polymer of an aliphatic cyclic carbonate. An aliphatic polycarbonate diol or the like.

The number average molecular weight (Mn) per one hydroxyl group of the polycarbonate polyol is preferably from 400 to 8,000, more preferably from 800 to 6,000.

In the present specification, the number average molecular weight of the non-curable oligomer (II) is a hydroxyl value P (mgKOH/g) and a non-hardening oligomer (II) measured according to JIS K 1557-1 (2007 edition). The average number of hydroxyl groups Q per molecule is a value calculated by the following formula (1).

Molecular weight of the non-curable oligomer (II) = 56.1 × Q × 1000 / P (1) As a non-curable oligomer (II) from the viewpoint that the elastic modulus of the layered portion after hardening is likely to be low It is preferred to use a polyoxyalkylene polyol, and it is preferred to use a polyoxyalkylene extended polypropyl polyol or a polyoxypropyl propyl polyol having an oxygen extended propyl group and an oxygen extended ethyl group; From a low point of view, it is especially preferred to use a polyoxypropylene propylene polyol.

Further, in the present invention, the oligomer (A) and the non-hardening property are obtained from the viewpoint of stabilizing the layered portion before curing and suppressing separation of the non-curable oligomer (II) from the layered portion after hardening. The oligomer (II) is preferably a molecular chain having the same structure or a similar structure.

Specifically, as a raw material of the oligomer (A) in the first composition, a compound having a hydroxyl group (hereinafter referred to as "hydroxyl-containing compound") is used, and the same hydroxyl group-containing compound is used as a non-hardening oligomer ( II) is better.

In the first composition, the oligomer (A) is an urethane acrylate oligomer synthesized from a polyoxyalkylene polyol and a polyisocyanate in a raw material. From the viewpoint of compatibility, the non-hardening oligomer (II) is preferably a polyoxyalkylene polyol.

Even when the hydroxyl group-containing compound used as the raw material of the oligomer (A) is different from the hydroxyl group-containing compound used as the non-curable oligomer (II), the hydroxyl group-containing compound or the like has a repeating unit having a molecular chain in common with each other or the like. Part of the common structure and the same degree of polarity is preferred. When the oligomer (A) and the non-curable oligomer (II) have the same molecular structure in part, the compatibility of the non-curable oligomer (II) in the composition is improved.

As a method of adjusting the polarity of the hydroxyl group-containing compound, a method of introducing a polar group or a method of preparing a hydroxyl group-containing compound having an oxygen-extended propyl group and an oxygen-extended ethyl group can be mentioned. As long as the polar group is introduced, the polarity of the hydroxyl group-containing compound increases. Further, as long as the oxygen-extended propyl group and the oxygen-extended ethyl group are formed, the polarity of the hydroxyl group-containing compound is increased. These methods can also be used in combination.

The desirable combination of the hydroxyl group-containing compound used as the raw material of the oligomer (A) and the hydroxyl group-containing compound used as the non-curable oligomer (II) is as follows: the oligomer (A) is used as a raw material. A urethane acrylate oligomer synthesized from a polyoxyalkylene polyoxypropyl propyl polyol having an oxygen-extended propyl group and an oxygen-extended ethyl group and a polyisocyanate, the non-hardening oligomer (II) is not The oxygen-extended ethyl polyoxypropyl propylene polyol has a molecular weight per one hydroxyl group which is smaller than a polyoxyl propyl polyol which is a polyol used as the oligomer (A).

The combination of the curable compound (I) and the non-curable oligomer (II) contained in the first composition is a curable compound (I-) containing the oligomer (A12) and the monomer (B1) described below. 1) The combination with the following non-hardening oligomer (II-1) good.

Oligomer (A12): reacting a polyoxyalkylene polyoxypropylene glycol having an oxygen-extended propyl group and an oxygen-extended ethyl group with a polyisocyanate to obtain a prepolymer having an isocyanate group at the end, and the aforementioned monomer (a1) a polyurethane acrylate oligomer obtained by the reaction.

Non-hardening oligomer (II-1): a polyoxyalkylene polyoxypropylene glycol which is the same as the raw material of the oligomer (A12) and has an oxygen-extended propyl group and an oxygen-extended ethyl group.

Further, the combination of the curable compound (I) and the non-curable oligomer (II) contained in the first composition contains the following curable compound of the oligomer (A12) and the monomer (B1) (I) -1) It is also preferred to be combined with the following non-curable oligomer (II-2).

Non-hardening oligomer (II-2): a polyoxypropylene glycol having a polyoxypropylene glycol having no oxygen-extended ethyl group and a smaller molecular weight than polyoxyethylene-extended ethylene polyoxypropylene glycol of the oligomer (A12).

The non-hardening oligomer (II) in the first composition is obtained by laminating a laminate having an adhesive layer formed on a transparent surface material and a bonded surface material in a reduced-pressure atmosphere, and returning to the atmosphere. It helps to shorten the time required for the voids that have been formed at the interface between the bonded face material and the adhesive layer to disappear.

The content of the non-curable oligomer (II) in the first composition (100% by mass) is preferably from 10 to 70% by mass, more preferably from 26 to 60% by mass. When the content of the non-curable oligomer (II) is at least the lower limit value, it is difficult to leave voids in the adhesive layer. When the content of the non-curable oligomer (II) is at most the upper limit, the layered portion of the adhesive layer is easily cured sufficiently. As long as the layered portion is sufficiently cured, the protective film is easily peeled off from the adhesive layer after curing.

Further, the chain transfer agent also contributes to shortening the time until the void formed at the interface between the bonded face material and the adhesive layer disappears.

Further, when the first composition contains the monomer (B2) or the chain transfer agent, the curing rate tends to be slow. Therefore, the amount of the monomer (B2) and the chain transfer agent used is preferably a small amount. Non-hardening oligomer (II) in the first composition (100% by mass) when the mass ratio of the monomer (B2) to the monomer (B1) in the first composition is less than 0.6 and the chain transfer agent is not contained The content is preferably from 40 to 70% by mass, more preferably from 50 to 70% by mass.

When the first composition does not contain a chain transfer agent and contains the monomer (B1) and the monomer (B2), and the mass ratio of the monomer (B2) to the monomer (B1) is 0.6 to 2.5, the first composition ( The content of the non-curable oligomer (II) in 100% by mass is preferably from 30 to 70% by mass, more preferably from 40 to 70% by mass.

When the first composition contains 1 part by mass or less of the chain transfer agent per 100 parts by mass of the curable compound (I), and the monomer (B2) content is less than the monomer (B1), the first composition (100% by mass) The content of the non-hardening oligomer (II) in the medium is preferably from 40 to 70% by mass, more preferably from 50 to 70% by mass.

The first composition contains the monomer (B1) and the monomer (B2), and the mass ratio of the monomer (B2) to the monomer (B1) is 1 to 3 and is 1 with respect to 100 parts by mass of the curable compound (I). When the amount of the chain transfer agent is less than the mass part, the content of the non-curable oligomer (II) in the first composition (100% by mass) is preferably 5 to 55% by mass, more preferably 10 to 50% by mass, and more preferably 35. ~50% by mass is especially preferred.

Further, in the case where the first composition is composed of the oligomer (A), the monomer (B), and the non-curable oligomer (II), the oligomer (A): monomer (B) ): ratio of content ratio (% by mass) of non-hardening oligomer (II) is 6 ~80:3~70:10~70 is better.

As long as it is within this range, the first composition can be made to have an appropriate viscosity.

(Photopolymerization initiator (C1))

Examples of the photopolymerization initiator (C1) include acetophenone-based, ketal-based, benzoin or benzoin ether, phosphine oxide, diphenylketone, thioxanthone, and anthraquinone. A photopolymerization initiator. The photopolymerization initiator (C1) is preferably a phosphine oxide-based or thioxanthone-based photopolymerization initiator, and is preferably a phosphine oxide because the surface of the photopolymerization reaction can be suppressed from being colored.

In the photocurable first composition, the photopolymerization initiator (C1) content is preferably 0.01 to 10 parts by mass, and 0.1 to 5 parts by mass based on 100 parts by mass of the total of the oligomer (A) and the monomer (B). The mass portion is preferred.

(additive)

Examples of the additive include a polymerization inhibitor, a photocuring accelerator, a chain transfer agent, a light stabilizer (ultraviolet absorber, a radical scavenger, etc.), an antioxidant, a flame retardant, and an adhesion enhancer (a decane coupling agent, etc.). ), pigments and dyes. As the additive to be added to the first composition, a polymerization inhibitor or a light stabilizer is preferred. In particular, by containing a smaller amount of a polymerization inhibitor than the polymerization initiator, the stability of the first composition can be improved, and the molecular weight of the layered portion after hardening can be adjusted.

Examples of the polymerization inhibitor include hydroquinone (2,5-di-tertiary butylhydroquinone, etc.), catechol (for tertiary catechol), onion, and thiophene. A polymerization inhibitor such as a hydroxytoluene system.

Examples of the light stabilizer include an ultraviolet absorber (such as a benzotriazole-based, diphenylketone-based, and salicylate-based) and a radical scavenger (hindered amine-based).

The antioxidant may, for example, be a phosphorus-based or sulfur-based compound.

In the first composition, the additive content is preferably 10 parts by mass or less, and preferably 5 parts by mass or less, based on 100 parts by mass of the total of the oligomer (A) and the monomer (B).

When the first composition contains a chain transfer agent, the time until the void formed when the bonded surface material having the adhesive layer formed on the transparent surface material is bonded is likely to be shortened. Therefore, as long as a chain transfer agent is used, the amount of addition of the non-curable oligomer (II) required to obtain an effect of achieving good disappearance of the void can be reduced. When the amount of the non-curable oligomer (II) is small, the difference between the hardening shrinkage ratio of the beak portion and the layer portion is easily reduced. On the other hand, from the viewpoint of obtaining a good hardening speed, it is preferred that the chain transfer agent is not contained or only a small amount is contained.

When the chain transfer agent is contained, the amount of addition is preferably 1 part by mass or less, and preferably 0.5 part by mass or less, based on 100 parts by mass of the total of the oligomer (A) and the monomer (B).

The thickness of the layer portion 18 is preferably 0.03 to 2 mm, and more preferably 0.1 to 0.8 mm. When the thickness of the layered portion 18 is equal to or greater than the lower limit value, the layered portion 18 can effectively buffer the punching or the like from the external force on the side of the transparent surface material 10, and the display panel can be protected. Moreover, when the bonded surface material such as a display panel is bonded to the transparent surface material 1 to which the adhesive layer is attached, even if the foreign matter does not exceed the thickness of the layered portion 18, the layered portion 18 is not formed. The thickness varies greatly and has little effect on light transmission performance. When the thickness of the layer portion 18 is equal to or less than the upper limit value, it is difficult to leave a void in the layer portion 18, and when the display device is used, the entire thickness is not increased to more than necessary.

The storage shear modulus of the layered portion 18 at 35 ° C is preferably 1.0 to 100 kPa. The upper limit of the storage shear modulus of the layer portion 18 is preferably 25 kPa, more preferably 12 kPa. When the storage shear modulus is 1.0 kPa or more, the shape of the layer portion 18 is easily maintained. Moreover, even when the thickness of the layered portion 18 is thick, the entire thickness of the layered portion 18 can be maintained, and when the transparent surface material 1 with the adhesive layer is bonded to the bonded body, it is difficult to adhere to the bonded body and adhere thereto. It is desirable that a gap occurs at the interface of the layer 14. On the other hand, when the storage shear modulus is 100 kPa or less, when the transparent surface material 1 with an adhesive layer is bonded to the bonded body in a reduced-pressure atmosphere, and it is returned to the atmosphere, it is already formed. It is desirable that the void at the interface between the bonded body and the adhesive layer 14 disappears in a short time and is difficult to remain.

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The second composition forming the weir portion 20 may be a photocurable resin composition or a thermosetting resin composition. The beak portion 20 is preferably a cured product of a photocurable resin composition containing a curable compound and a photopolymerization initiator (C2) from the viewpoint of being hardenable at a low temperature and having a high curing rate. In addition, as long as the second composition is a photocurable resin composition, it does not require a high temperature during curing, and thus the damage of the bonded surface material such as a display panel or a touch panel due to high temperature is caused. There are also few.

Further, a second composition having the same composition as that of the first component formed in the layered portion may be applied to the peripheral portion of the surface of the transparent surface material and semi-hardened, thereby being formed in the step (d) described later. Unhardened braid before hardening.

A suitable photocurable second composition in the present invention will be described. The photocurable second composition contains a curable compound (I'), which is not hard. The composition of the oligomer (II') and the photopolymerization initiator (C2).

Further, the second composition may contain an additive as needed.

The viscosity of the second composition at 25 ° C is preferably from 10 to 3,000 Pa s, preferably from 300 to 3,000 Pa s, preferably from 500 to 2,800 Pa s, more preferably from 800 to 2,500 Pa s, and at 1000 Å. 2000Pa‧s is especially good. When the viscosity of the second composition at 25 ° C is at least the lower limit value, the shape of the unhardened weir portion is easily maintained for a long period of time, and the height of the unhardened weir portion is easily maintained. When the viscosity of the second composition is less than or equal to the upper limit, the unhardened weir portion can be formed by coating.

Further, even if the second composition forming the uncured weir portion has a viscosity at the time of coating of less than 300 Pa‧s, and the second composition is a photocurable composition, it can be irradiated with light after the coating application. The viscosity of the unhardened weir portion after the light irradiation may be within the above-described appropriate range. In the ease of coating, the viscosity of the second composition at the time of coating is preferably 300 Pa ‧ or less, and more preferably 200 Pa ‧ or less. The lower limit of the viscosity of the second composition at this time is not particularly limited, and is preferably 0.01 Pa·s or more.

The viscosity of the second composition was measured at 25 ° C using an E-type viscometer.

(hardening compound (I'))

The curable compound (I') contains an urethane acrylate oligomer (A') (hereinafter simply referred to as "oligomer (A')") and a monomer (B'), which is a monomer (B'). ) having one or more hardening functional groups and having a molecular weight of less than 600. The curable compound (II') is preferably composed of an oligomer (A') and a monomer (B').

Examples of the oligomer (A') and the monomer (B') include those exemplified as the oligomer (A) and the monomer (B).

Further, the oligomer (A') has an average of 1.8 to 4 per molecule from the viewpoint of the curability of the second composition and the mechanical properties of the weir portion 20 obtained by curing the second composition. A hardening base is preferred.

The monomer (B') preferably contains a monomer having a hydroxyl group (B'1). The hydroxyl group remains in the weir portion composed of the cured product containing the second composition of the monomer (B'1). The presence of the hydroxyl group contributes to the stabilization of the non-hardenable oligomer (II') in the beak. Further, as the curable functional group of the monomer (B'1), an acryloxy group is preferred.

Further, the monomer (B') may contain a monomer (B'2) other than the monomer (B'1). The monomer (B'2) may be the same compound as the monomer (B2), but the methacrylate may be a preferred compound as the acrylate, similarly to the monomer (B2). Further, the monomer (B'2) may be used as a diluent in the synthesis of the oligomer (A') in the same manner as the monomer (B2).

As the monomer (B'2), a monomer having one or more (meth)acryloxycarbonyl groups and having a molecular weight of less than 600 and having no hydroxyl group is preferred. Specifically, it may, for example, be a (meth) acrylate having a carbon number of 8 to 22 or a cyclic alkyl group (n-dodecyl (meth)acrylate, n-octadecyl (meth)acrylate, (A) Base) yttrium acrylate, isodecyl (meth) acrylate, adamantyl (meth) acrylate, etc.).

The curable compound (I') used in the second composition is preferably the same as the curable compound (I) used in the first composition, but may be different.

The number average molecular weight of the oligomer (A') is preferably from 30,000 to 100,000, preferably from 40,000 to 80,000, more preferably from 50,000 to 70,000, and 50,000, from the viewpoint of easily controlling the viscosity of the uncured ridge portion to the above range. ~65000 is better.

The oligomer (A') having a number average molecular weight of 30,000 to 100,000 has a high viscosity, so that it is difficult to synthesize in a usual manner, and it is difficult to mix with the monomer (B') even if the synthesis is successful. Therefore, when the oligomer (A') is synthesized, it is synthesized by diluting the monomer (B'2) and having a reduced viscosity, and the obtained product is preferably used as it is, or it is preferably produced. Further, the monomer (B'1) diluted as described later is used as the curable compound (I').

As the monomer having a hydroxyl group (B'1), a hydroxy acrylate having a hydroxyalkyl group having 1 to 2 hydroxyl groups and 3 to 8 carbon atoms (2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, acrylic acid 4) - hydroxybutyl ester, 6-hydroxyhexyl acrylate, etc.), or hydroxy methacrylate (2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, methyl Preferably, 6-hydroxyhexyl acrylate or the like is preferred, and 4-hydroxybutyl acrylate or 2-hydroxybutyl methacrylate is preferred. One type of the monomer (B) may be used alone or two or more types may be used.

The non-curable oligomer (II') is an oligomer having a hydroxyl group which does not undergo a curing reaction with the curable compound (I') when the second composition is cured. Further, it is an oligomer having a hydroxyl group which does not undergo a hardening reaction with the curable compound (I) when the first composition is cured.

Further, the non-curable oligomer (II') is preferably the same or similar oligomer as the non-curable oligomer (II), and is preferably the same oligomer. For example, in the case where the repeating unit is an oxygen-extended alkyl polyalkylene polyol, the same means that the types and amounts of the repeating units are the same. When the oligomer is composed of different kinds or numbers of repeating units, a similar oligomer is preferred. Similar oligomers are those in which the major repeating units are identical and the amounts are different. As a similar oligomer, it is desirable to contain 30% by mass or more of the phase. The same repeating unit is more preferably contained in an amount of 50% by mass or more. When the polyoxyalkylene polyol is used as the non-curable oligomer (II), the elastic modulus of the beak portion 20 after curing tends to be low.

The ratio of the oligomer (A') to the total amount (100% by mass) of the oligomer (A') and the monomer (B') in the second composition is preferably from 20 to 90% by mass, and is 30%. 80% by mass is preferred. When the ratio of the oligomer (A') is at least the lower limit value, the heat resistance of the beak portion is good. When the ratio of the oligomer (A') is at most the upper limit, the curability of the second composition and the adhesion between the transparent face material and the layer portion are preferable.

The oligomer (A') ratio in the second composition when the non-curable oligomer (II) in the first composition and the polyol used in the oligomer (A') are the same kind of polyol It is easier to suppress the diffusion of the non-curable oligomer (II) from the layer portion to the weir portion in a small amount.

In the second composition, the ratio of the monomer (B') to the total of the oligomer (A') and the monomer (B') (100% by mass) is preferably from 15 to 70% by mass, and from 15 to 50%. The mass % is preferably from 20 to 45% by mass, more preferably from 25 to 40% by mass.

The content of the non-curable oligomer (II') in the second composition is such that the difference (W1-W2) is equal to or less than the aforementioned predetermined difference in accordance with the content of the non-curable oligomer (II) in the first composition. Mode setting. The content of the non-curable oligomer (II') in the second composition is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 5% by mass or more. The non-curable oligomer (II') is contained in the beak portion formed of the second composition, whereby the diffusion of the non-curable oligomer (II) from the layer portion can be suppressed. Non-hardening oligomer in the second composition The content of (II') is determined by the content of the non-hardening oligomer (II) in the first composition such that the aforementioned difference (W1-W2) is 40 or less, but from the viewpoint of adhesion to the face material It is preferably 65 mass% or less.

Further, when the second composition contains the non-curable oligomer (II'), the refractive index of the beak portion and the layer portion becomes similar in the formed adhesive layer, so that the beak portion can be The boundary of the layered part cannot be seen clearly.

(Photopolymerization initiator (C2))

The photopolymerization initiator (C2) contained in the photocurable second composition may, for example, be an acetophenone system, a ketal system, a benzoin or a benzoin ether system, a phosphine oxide system or a diphenyl group. A photopolymerization initiator such as a ketone system, a thioxanthone system or a fluorene system. Among them, a photopolymerization initiator (C2) is preferably a photopolymerization initiator of an acetophenone type, a ketal type or a benzoin ether type. When hardening with visible light having a short wavelength, a phosphine oxide photopolymerization initiator is preferred from the viewpoint of absorption wavelength region. By using two or more kinds of photopolymerization initiators (C2) having different absorption wavelength regions in combination, the hardening time can be made faster, or the surface hardenability in the beak portion can be improved.

In the photocurable second composition, the photopolymerization initiator (C2) content is preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the total of the oligomer (A') and the monomer (B'). ~5 parts by mass is preferred.

(additive)

The additive to be added to the second composition may be the same as those listed in the first composition. As the additive to be added to the second composition, a polymerization inhibitor or a light stabilizer is preferred. In particular, the stability of the second composition can be improved by containing a polymerization inhibitor in a smaller amount than the polymerization initiator. The molecular weight of the beak after hardening can also be adjusted.

The total amount of the additives is preferably 10 parts by mass or less, and preferably 5 parts by mass or less, based on 100 parts by mass of the total of the oligomer (A') and the monomer (B').

Since the outer region of the image display area of the display panel is narrow, it is preferable to narrow the width of the beak portion 20 in this application. At this time, the width of the beak portion 20 is preferably 0.5 to 2 mm, and preferably 0.8 to 1.6 mm.

The thickness of the beak portion 20 is preferably slightly larger than the thickness of the laminar portion 18 from the viewpoint that it is difficult to form a void that is open to the outside when the bonded face material is bonded to the transparent face material 1 to which the adhesive layer is attached.

When the thickness of the beak portion 20 is thicker than the thickness of the layer portion 18, as shown in FIG. 13, when the display panel 50 and the laminated body 1 are bonded together, even the display panel 50 and the adhesive layer are formed on the peripheral portion of the adhesive layer 14. A gap 110 remains in the interface of the layer 14, and the gap 110 is still shielded by the beak 20, whereby the void 110 does not open to the outside and becomes an independent void 110. Therefore, when the display panel 50 is bonded to the transparent surface material 1 to which the adhesive layer is attached in a reduced-pressure atmosphere, the pressure in the void 110 (decompressed state) and the adhesive layer are applied. The differential pressure of the pressure (atmospheric pressure) of 14 reduces the volume of the void 110 and causes the void 110 to disappear.

The difference between the thickness of the beak portion 20 and the thickness of the layer portion 18 is preferably 0.05 mm or less from the viewpoint of suppressing the occurrence of voids due to the step difference between the beak portion 20 and the layer portion 18, and is preferably 0.03 mm or less. Preferably.

The difference between the thickness of the beak portion 20 and the thickness of the layer portion 18 is measured by using a laser displacement gauge, and the transparent face material 10 and the layered portion 18 or the beak portion formed thereon are measured. The total thickness of 20 is calculated from the difference. Further, the thickness of the layer portion 18 is the thickness of the peripheral portion of the layer portion 18 that is in contact with the weir portion 20.

The storage shear modulus of the beak 20 at 35 ° C is the lower limit of the shear modulus of the beak 20 which can be self-standing, and the upper limit of the storage shear modulus of the layer portion 18 at 35 ° C is 15 times. It is better, specifically 1~150kPa is better. The beak portion 20 can be made self-supporting by setting the shear elastic modulus of the beak portion 20 at 35 ° C to 1 kPa or more.

Further, the storage shear modulus of the beak portion 20 at 35 ° C is preferably larger than the storage shear modulus of the layer portion 18 at 35 ° C. When the storage shear modulus of the beak portion 20 is larger than the storage shear modulus of the layer portion 18, even when the display panel and the transparent surface material 1 with the adhesive layer are bonded together, even in the peripheral portion of the adhesive layer 14 There is a gap between the panel and the adhesive layer 14, and the gap is still difficult to open to the outside, and it is easy to become an independent gap. Therefore, when the display panel is bonded to the transparent surface material 1 with the adhesive layer in a reduced-pressure atmosphere, and the atmosphere is restored to the atmosphere, the pressure in the void (maintaining the reduced pressure state) and the adhesion layer 14 are applied. The differential pressure of the pressure (atmospheric pressure) allows the void volume to be reduced and the voids to easily disappear.

Further, by making the storage shear modulus of the beak portion 20 at 35 ° C 15 times or less the storage shear modulus of the layer portion 18 at 35 ° C, the transparent surface material 1 with the adhesive layer is When the bonded body is bonded, the display unevenness due to the difference in the storage shear modulus of the beak portion 20 and the layer portion 18 can be suppressed.

Further, the storage shear modulus at a temperature of 35 ° C of the enamel portion composed of the cured product of the photocurable resin composition was measured by the following method. Moreover, the storage shear modulus of the layered portion at 35 ° C is also in the same square The value determined by the law.

The storage shear modulus of the crotch portion 20 after hardening at 35 ° C was measured using a rheometer (manufactured by Anton Paar Co., Ltd., modulus rheometer Physica MCR-301) to measure the rotation axis and the light transmittance. The fixed plate gap is the same as the thickness of the beak portion 20, and an unhardened second resin composition is disposed in the gap, and the unhardened second resin composition is irradiated with light required for hardening, and the storage shear of the hardening process is measured. The elastic modulus is cut, and the measured value in the hardening conditions at the time of forming the weir portion 20 is set as the storage shear modulus of the weir portion 20.

<Protective film>

The protective film 16 is not required to be firmly adhered to the adhesive layer 14, and can be attached to the supporting surface material in the manufacturing method of the present invention to be described later. Therefore, the protective film 16 is preferably a self-adhesive protective film having a surface of a base film having low adhesion such as polyethylene, polypropylene or a fluorine-based resin as an adhesive surface.

The adhesive force of the adhesive surface of the protective film 16 is preferably 180 to 0.01 N, preferably 0.02 to 0.06 N, in a 180-degree peeling test at a peeling speed of 300 mm/min with respect to the acrylic sheet. If the adhesive force is at least the lower limit value, the support surface material can be attached. When the adhesive force is at most the upper limit value, the protective film 16 can be easily peeled off from the support surface material.

The thickness of the protective film 16 varies depending on the resin to be used. When a soft film such as polyethylene or polypropylene is used, it is preferably 0.04 to 0.2 mm, and preferably 0.06 to 0.1 mm. When the thickness of the protective film 16 is at least the lower limit value, deformation of the protective film 16 can be suppressed when the protective film 16 is peeled off from the adhesive layer 14. When the thickness of the protective film 16 is equal to or less than the upper limit value, the protective film 16 is easily deflected at the time of peeling, and the protective film 16 can be easily peeled off from the adhesive layer 14.

Further, since the back surface layer is provided on the back surface opposite to the adhesive surface of the protective film 16, the adhesive layer 14 can be more easily peeled off. A film having a low adhesion such as polyethylene, polypropylene or a fluorine-based resin is preferably used for the back layer. In order to facilitate the peeling of the protective film 16, a release agent such as an anthrone may be applied to the protective film 16 in a range that does not adversely affect the adhesive layer 14. Further, it is preferable to provide a barrier layer in one of the protective films, and the barrier layer prevents gas (oxygen, nitrogen, water vapor, etc.) from being mixed into the adhesive layer 14 through the protective film 16 from the outside.

<Action effect>

In the transparent surface material of the adhesive layer of the present invention, the content W1 (% by mass) of the non-curable oligomer (II) contained in the layer portion and the non-hardening oligomer contained in the beryllium portion are Since the difference (W1-W2) of the content W2 (% by mass) of II') is 40 or less, it is difficult to cause a problem in the layered portion and the beak portion even after a predetermined period of time has been adhered to the bonded surface material. Improve the reliability of the product.

<Other forms>

For example, the transparent surface material 1 with a transparent layer of the adhesive layer is an example of a protective plate of the display device, but the transparent surface material of the adhesive layer of the present invention is not limited by the illustrated example, as long as it is a transparent surface material. At least one surface may be formed with a transparent surface material with an adhesive layer of a specific adhesive layer.

For example, the transparent surface material of the adhesive layer of the present invention may be a transparent surface material with an adhesive layer formed with a specific adhesive layer on both sides of the transparent surface material.

Further, in the transparent surface material with an adhesive layer of the present invention, a polarizing mechanism (a film-shaped absorbing polarizer, a wire grid polarizer, etc.) may be provided between the transparent surface material (protective plate) and the specific adhesive layer. ), optical modulation mechanism (1/4 wavelength plate) Such as a retardation film and a phase difference film which has been patterned into a stripe shape, etc.).

制造How to make transparent surface material with adhesive layer≫

The method for producing a transparent surface material with an adhesive layer of the present invention having a protective film has the following steps (a) to (e).

In the step (a), a liquid second composition is applied to the peripheral portion of the surface of the transparent surface material to form an unhardened weir portion.

In the step (b), the liquid first composition is supplied to a region where the surface of the transparent surface material is surrounded by the unhardened weir portion.

In the step (c), the support surface material to which the protective film has been attached is superposed on the first composition in such a manner that the protective film is in contact with the first composition in a reduced-pressure atmosphere, thereby obtaining the first composition. The unhardened layered portion is composed of a transparent face material, a protective film, and a precursor layered body sealed by an unhardened weir portion, and the unhardened weir portion is composed of a second composition.

In the step (d), the unhardened layered portion and the beak portion are hardened to form the layered portion and the crucible in a state in which the precursor laminate is placed in a higher pressure gas atmosphere than the step (c). Adhesive layer of the shape.

In step (e), the support face material is peeled off from the protective film.

The manufacturing method of the present invention encloses the first composition between the transparent surface material and the protective film which has been attached to the supporting surface material under a reduced pressure gas atmosphere, and is made in a high pressure gas environment under atmospheric conditions. A method in which the sealed first composition is hardened to form a layered portion. As a method of enclosing the first composition under reduced pressure, the first composition is supplied to substantially the entire surface of the transparent surface material, and then the protective film attached to the supporting surface material is overlapped, and A method of encapsulating a composition between a transparent face material and a protective film that has been attached to a support face material, rather than applying a first composition to the gap between the transparent face material and the protective film that has been attached to the support face material The method of narrow and wide space.

An example of a method of producing a transparent laminate by encapsulation of a curable resin composition under reduced pressure and curing by a curable resin composition in an air atmosphere is known. For example, a method for producing a transparent laminate and a curable resin composition used in the method are described in International Publication No. 2008/81838 and International Publication No. 2009/16943. In the production of the transparent surface material with the adhesive layer of the present invention, the production methods described in these documents can also be employed.

Hereinafter, a method of manufacturing the transparent face material 1 having the adhesive layer of the protective film 16 of Fig. 1 will be described as an example with reference to the drawings.

<Step (a)>

As shown in FIG. 2 and FIG. 3, the light-shielding printing portion 12 along the peripheral edge portion of the transparent surface material 10 is coated with a light-curable liquid second composition by a spreader 30 or the like to form an unhardened crucible. Shape 20A.

The coating of the second composition is carried out using a printing machine, a spreader or the like.

Step (a), for example, as shown in Figs. 4 and 5, can be carried out using a device having a configuration in which the spreader 30 can be horizontally moved over substantially the entire surface of the surface of the protective sheet 10 by the horizontal moving mechanism 3, The horizontal moving mechanism 3 is composed of a pair of feed spirals 32 and a feed screw 34 orthogonal to the pair of feed spirals 32.

The unhardened weir portion 20A may be in an unhardened state in which no hardening reaction is performed at all, or may be a semi-hardened state in which partial hardening has been performed. Unhardened Partial hardening in the weir portion 20A is performed by light irradiation in the case where the second composition is a photocurable resin composition. For example, ultraviolet light or short-wavelength visible light is irradiated from a light source (ultraviolet lamp, high-pressure mercury lamp, UV-LED, etc.) to partially cure the photocurable resin composition.

When the uncured beak portion 20A is partially cured, for example, as shown in FIGS. 6 to 8 , a plurality of the UV-LED light sources 31 are disposed so as to surround the sprinkler 30, whereby the transparent surface material can be applied. The second resin composition 21 on the (protective sheet) 10 is uniformly exposed and hardened after the coating.

Further, in order to maintain the distance between the transparent face material 10 and the display panel, the spacer particles having a predetermined particle diameter may be blended into the second composition.

After the second composition is applied, the light that hardens the second composition is irradiated for a short period of time, whereby the second composition is partially hardened or thickened, so that the shape of the unhardened beak portion 20A can be maintained, which is ideal. .

<Step (b)>

Next, as shown in FIG. 9 and FIG. 10, the liquid first composition 26 is supplied to the rectangular region 24 of the transparent surface material 10 surrounded by the unhardened weir portion 20A.

The supply of the first composition 26 is as shown in Figs. 9 and 10 by feeding the transparent surface material 10 to the lower fixed plate 28, and the first composition 26 is supplied in a line shape by the spreader 30 moving in the horizontal direction. Implemented in strips or dots. The spreader 30 of this example is horizontally movable in the entire range of the region 24 by a known horizontal moving mechanism constituted by a pair of feed spirals 32 and a feed screw 34 orthogonal to the feed screw 32.

The supply amount of the first composition 26 is previously set to be uncured The space formed by the weir portion 20A, the transparent surface material 10, and the protective film 16 is filled with the first composition 26 so that the transparent surface material 10 and the protective film 16 are spaced apart from each other (even if the layer portion 18 becomes a predetermined thickness). The weight of the). At this time, it is preferable to consider in advance the volume reduction caused by the hardening shrinkage of the first composition 26. Therefore, the supply amount of the first composition 26 is preferably such that the thickness of the layer portion 18 before hardening is slightly thicker than the predetermined thickness of the layered portion 18 after hardening.

By having the unhardened weir portion 20A, the peripheral portion of the first composition 26 can be prevented from expanding outward, and the peripheral portion can be thinned, and the entire thickness of the first composition 26 can be uniformly maintained. It is preferable to make the thickness of the layered portion 18 uniform as a whole, and it is easy to prevent voids from remaining at the interface during bonding to the adherend.

<Step (c)>

Next, as shown in FIG. 11, the transparent surface material 10 and the support surface material 36 which adhered the protective film 16 are carried in the pressure-reduction apparatus 38. The adhesion of the protective film 16 to the support surface material 36 is performed by bonding a protective film 16 supplied with a rolled roll to the support surface material 36 using a rubber roller or the like. At this time, the rubber roller is brought into contact with the support surface material 36 so that the gap between the support surface material 36 and the protective film 16 does not occur, and it can be bonded in a decompression space. In order to easily hold the end portion of the protective film 16 when peeling from the adhesive layer 14, it is preferable to use the protective film 16 which is larger than the support surface material 36.

A fixed plate 42 having a plurality of suction pads 40 is disposed on the upper portion of the pressure reducing device 38, and a lower fixed plate 44 is disposed at a lower portion thereof. The upper plate 42 is movable in the vertical direction by the air cylinder 46.

The support face material 36 is attached to the face with the protective film 16 attached thereto. The pad 40 is sucked. The transparent face material 10 is fixed on the lower fixed plate 44 with the surface on which the first composition 26 has been supplied. In this way, the first composition 26 on the transparent face material 10 can be made to face without facing the protective film 16 on the surface of the support face material 36.

The surface material 36 is a transparent surface material such as a glass plate or a resin plate. The thickness of the glass plate used as the support face material 36 is preferably 0.5 to 10 mm, and more preferably 1.0 to 5.0 mm. When the thickness of the glass sheet is at least the lower limit value, it is difficult to cause warpage and deflection of the support surface material 36. When the thickness of the glass sheet is less than or equal to the upper limit, the quality of the support surface material 36 is not necessarily increased, and the support surface material 36 is hard to be peeled off when the precursor layer body before the adhesion layer 14 is cured.

After the transparent surface material 10 and the support surface material 36 are disposed at predetermined positions, the air in the decompression device 38 is sucked by the vacuum pump 48, and the inside of the decompression device 38 is depressurized to become a predetermined decompressed gas atmosphere.

The reduced-pressure gas atmosphere is preferably 1 kPa or less, more preferably 10 to 100 Pa, and even more preferably 15 to 40 Pa. When the pressure-reduced gas atmosphere is at least the lower limit value, each component (curable compound, photopolymerization initiator, polymerization inhibitor, chain transfer agent, light stabilizer, etc.) contained in the first composition is not easily vaporized. Moreover, the time required to achieve a reduced pressure gas environment can be shortened.

After the gas ambient pressure in the decompression device 38 is, for example, a reduced-pressure gas atmosphere of 15 to 40 Pa, the cylinder 46 is oriented while the support surface material 36 is sucked and held by the suction pad 40 of the upper plate 42. The transparent surface material 10 that is in standby below operates and descends. Then, the transparent surface material 10 and the supporting surface material 36 to which the protective film 16 has been attached are laminated via the unhardened weir portion 20A, whereby the uncured layer portion composed of the first composition 26 is transparent. Face material 10, The protective film 16 and the precursor laminate sealed by the unhardened weir portion 20A are held for a predetermined time in a reduced pressure gas atmosphere.

In the precursor laminate, the first composition 26 is extruded by the weight of the support face material 36 itself and the extrusion from the moving support mechanism, so that the space is filled by the first composition 26 An unhardened layered portion is formed.

The time from when the transparent surface material 10 and the support surface material 36 are overlapped to when the decompression gas atmosphere is released is not particularly limited, and the decompressed gas atmosphere can be released immediately after the first composition 26 is sealed, or the first After the composition 26 is sealed, the reduced pressure state is maintained for a predetermined time. By maintaining the reduced pressure state for a predetermined period of time, the first composition can be caused to flow in the sealed space, and the interval between the transparent face material 10 and the protective film 16 attached to the supporting face member 36 can be made uniform even if the gas environment pressure is increased. It is still easy to maintain a sealed state.

The time for maintaining the reduced pressure state may be several hours or longer, but it is preferably within 1 hour from the viewpoint of production efficiency, and preferably within 10 minutes.

In the manufacturing method of the present invention, when the second composition having a high viscosity is applied to form the unhardened weir portion 20A, the first composition 26 in the previously assembled layer body obtained in the step (c) is obtained. The thickness can be made thicker as 0.03~2mm.

<Step (d)>

The vacuum gas environment is removed in step (c) and the precursor laminate is placed in a higher pressure gas environment than step (c). For example, after the inside of the decompression device 38 is, for example, an atmospheric environment, the precursor laminated body is taken out from the decompression device 38.

The precursor layer is placed in a higher pressure gas environment than step (c), that is, the transparent surface material 10 and the support surface material 36 are densely closed by the elevated pressure. Squeeze in the direction. Therefore, even if there is a void in the sealed space in the precursor layer, the unhardened layered portion flows toward the gap, and the entire sealed space is uniformly filled with the unhardened layered portion.

The pressure gas environment in step (d) may be an atmospheric environment or a higher pressure. The pressure gas environment in step (d) is preferably 80 to 120 kPa. Further, from the viewpoint of performing operations such as hardening of the layer portion 18 without special equipment, the pressurized gas atmosphere in the step (d) is optimal in the atmospheric environment.

The time from when the precursor laminate is placed in a higher pressure gas atmosphere than in the step (c) to when the unhardened layer portion starts to harden (hereinafter referred to as "high pressure holding time") is not particularly limited. In the case where the process of taking out the precursor laminate from the decompression device and moving it to the hardening device until the hardening starts is performed in an atmospheric environment, the time required for the treatment is the high pressure holding time. Therefore, if there is no gap in the sealed space of the precursor layer at the time point placed in the atmosphere, or if the gap disappears between the processes, the unhardened layer can be immediately formed. hardening. If it takes time for the void to disappear, the precursor laminate is maintained in a higher pressure gas atmosphere than step (c) until the void disappears. Moreover, it is also possible to increase the constant high pressure holding time from the other necessity of the processing, even if the high pressure holding time is still not hindered. The high pressure holding time can be longer than one day, but from the viewpoint of production efficiency, it is preferably within 6 hours, preferably within 1 hour; and from the viewpoint of improving production efficiency, it is preferably within 10 minutes. .

Next, the unhardened beak inside the precursor laminate The 20A and the layer portion are hardened to form the adhesive layer 14 having the layer portion 18 and the layer portion 20.

The hardening of the unhardened weir portion 20A may be performed simultaneously with the hardening of the unhardened layer portion, or the unhardened weir portion 20A may be hardened before the unhardened layer portion is hardened.

When the unhardened layered portion and the uncured beak portion 20A are composed of a photocurable resin composition, the unhardened weir portion 20A and the unhardened layer portion are formed from the side of the supporting surface material 36. Irradiation light (ultraviolet light or short-wavelength visible light) hardens it. For example, ultraviolet light or short-wavelength visible light is irradiated from a light source (ultraviolet lamp, high-pressure mercury lamp, UV-LED, etc.) to harden the layer portion 18 and the weir portion 20.

In terms of light, ultraviolet light or visible light of 450 nm or less is preferred.

When the transparent surface material is formed with a light-shielding printed portion or when the transparent surface material is provided with an anti-reflection layer, light is irradiated from the support surface material side.

When the layered portion 18 is composed of the photocurable first composition and is sufficiently photocurable, that is, when a suitable shear modulus is not obtained, the light irradiation may be interrupted during the curing and the surface material to be bonded (display panel or the like) After the bonding, the layer portion 18 is again irradiated with light or heated, thereby promoting the hardening of the layer portion 18. When the curing is promoted by heating, the photocurable first composition may contain a trace amount of a thermal polymerization initiator. Further, even when the thermal polymerization initiator is not used in combination, heating can be maintained after incomplete photocuring, whereby the hardened state of the layer portion 18 can be stabilized.

As long as the first composition and the second composition are photocurable, the transparent surface material 1 with the adhesive layer can be produced at a low temperature that the film can withstand, so The protection of the film is quite advantageous from the viewpoint of protection.

<Step (e)>

Next, the support face material 36 is peeled off from the protective film 16. Thereby, the transparent face material 1 with the adhesive layer of the protective film 16 can be obtained.

In order to easily peel off the protective film, the adhesive layer may also be cooled. By cooling the adhesive layer, deformation of the adhesive layer when the protective film is peeled off can be suppressed, thickness uniformity of the adhesive layer after peeling off the protective film can be improved, and occurrence of voids when bonded to the display panel can be suppressed.

The temperature of the cooling adhesive layer varies depending on the glass transition temperature of the resin used as the adhesive layer, and when the glass transition temperature is set to a temperature indicating the maximum value of the loss elastic modulus in the measurement of the shear modulus, the ratio is set to The glass transition temperature is preferably 40 ° C or higher. Although the lower limit temperature is not particularly specified, the resin used for the protective film may be brittle at a low temperature to cause the film to break at the time of peeling, and therefore it is preferably -30 ° C or higher. The cooling time is preferably divided into 5, but it can be adjusted according to the ease of stripping.

The transparent surface material 1 with an adhesive layer of this embodiment can be manufactured without any problem by the manufacturing method similar to Embodiment 1.

[other]

In the present embodiment, at least one of the layered portion 18 and the beak portion 21 constituting the adhesive layer 14 may contain the non-hardening component, or both.

Moreover, the difference between the non-hardening component (W1) contained in the layered portion 18 and the non-hardening component (W2) contained in the beak portion 21 is 40 or less.

≪层层≫

The laminated system of the present invention is a laminated body in which a transparent surface material (without a protective film) with an adhesive layer of the present invention is bonded to a bonded surface material. In the laminated body of the present invention, the adhesive surface layer of the adhesive layer is bonded to the bonded surface material such that the adhesive layer of the transparent surface material with the adhesive layer is in contact with the bonded surface material.

In the laminated body of the present invention, since at least one of the face material and the face material is a transparent face material, the photocurable resin composition can be cured from the side of the transparent face material. The bonded face material may be transparent or opaque.

As the laminate of the present invention, a display device is preferred.

<display device>

Fig. 12 is a cross-sectional view showing an example of a display device.

The display device 2 includes a display panel 50 to which a face material is bonded, a transparent face material 1 (without a protective film) attached to an adhesive layer of the display panel 50, and a flexible printed wiring board 60 connected to the display panel 50. (FPC) The transparent surface material 1 with an adhesive layer is in contact with the display panel 50 with the adhesive layer 14, and the flexible printed wiring board 60 (FPC) is equipped with the drive IC which operates the display panel 50. In this manner, the display device 2 has the transparent face material 10, the display panel 50, and the adhesive layer 14 sandwiched between the transparent face material 10 and the display panel 50.

The bonded surface material 50 of the illustrated example is a display panel, and a transparent substrate 52 provided with a color filter and a transparent substrate 54 provided with a TFT (thin film transistor) are bonded together via a liquid crystal layer 56, and a pair is bonded An example of a liquid crystal panel in which the polarizing plate 58 is sandwiched.

In the display device of this example, the bonded surface material is a display panel, but the bonded surface material is not limited to the display panel, and may be, for example, a touch panel.

<Method of Manufacturing Display Device>

A method of manufacturing a display device will be described as an example of a method for producing a laminate of the present invention. In the manufacturing method of the display device of the present invention, the display panel and the transparent surface material (without the protective film) having the adhesive layer are superposed on each other so as to be in contact with the display panel in a reduced-pressure gas atmosphere of 10 kPa or less. method.

When the transparent surface material 1 with an adhesive layer shown in FIG. 1 covers the surface of the adhesive layer with a protective film, the display panel is bonded to the transparent surface material with the adhesive layer after peeling off the protective film.

The pressure-reduced gas atmosphere when the display panel is bonded to the transparent surface material with the adhesive layer is 10 kPa or less, preferably 1 to 100 Pa, and preferably 5 to 50 Pa.

The laminate of the present invention can also be produced by a method other than the above method. For example, the display device 2 may be manufactured by the following methods (f) to (i).

In the step (f), the liquid second composition is applied to the peripheral portion of the surface of the display panel 50 to form an uncured beak.

In the step (g), the liquid first composition is supplied to a region of the surface of the display panel 50 which has been surrounded by the unhardened weir.

In the step (h), the transparent surface material 10 is superposed on the first composition under a reduced pressure gas atmosphere, and the uncured layer portion composed of the first composition is obtained from the display panel 50, the transparent surface material 10, and the The precursor layer body sealed by the hardened weir.

In the step (i), the precursor layer is placed in a higher pressure gas atmosphere than the step (h), and the uncured layer portion and the uncured layer portion are hardened to form the layer portion 18. And the adhesive layer 14 of the beak 20.

[Step (f)]

In the step (f), the display panel 50 is used in place of the transparent face material 10 (protective sheet) in the above step (a), and otherwise, it can be carried out in the same manner as the above step (a).

[Step (g)]

Step (g) can be carried out in the same manner as the above step (b).

[Step (h)]

The step (h) is carried out in the same manner as in the above step (c), except that the transparent surface material 10 (protective plate) is used instead of the support surface material 36 to which the protective film 16 is bonded in the above step (c).

[Step (i)]

Step (i) can be carried out in the same manner as the above step (d).

The connection of the flexible printed wiring board 60 (FPC) may be performed before the step (a) or after the step (a).

Example

Hereinafter, the present invention will be described in detail by way of examples, but the invention should not be construed as limited.

[Examples 1 to 6 and Comparative Example 1]

[Transparent surface material]

The peripheral portion of the surface of one of the soda lime glass having a length of 100 mm, a width of 100 mm, and a thickness of 1.3 mm was printed with a black pigment-containing ceramic to form a peripheral-shaped light-shielding portion, and the light-transmitting portion was made 68 mm long and 68 mm wide. Transparent surface material - i.

[Support surface material]

A protective film (Totello Co., Ltd., Puretect VLH-9) having a length of 130 mm, a width of 130 mm, and a thickness of 0.75 mm was used as a protective film on a transparent plate made of soda lime glass having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm. The glass is attached by means of a rubber roller, and a support surface material -ii to which a protective film has been attached is produced.

[fitted surface material]

As a bonded surface material, a polarizing plate (KN-18240T, manufactured by Polatechno Co., Ltd.) having an adhesive layer attached to one side of a soda lime glass having a length of 100 mm, a width of 100 mm, and a thickness of 1.7 mm is used, and a liquid crystal display panel is used instead of the liquid crystal display panel. Fitting face material - iii.

[First composition]

A bifunctional polypropylene glycol having a molecular end modified with ethylene oxide (a number average molecular weight calculated from a hydroxyl value: 4000) and 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl The isocyanate was mixed at a molar ratio of 4:5 and reacted at 70 ° C in the presence of a tin catalyst to obtain a prepolymer. The obtained prepolymer was added with 2-hydroxyethyl acrylate at a molar ratio of 1:2, and reacted at 70 ° C to obtain an urethane acrylate oligomer (A-1) (hereinafter referred to as " Oligomer (A-1)"). The oligomer (A-1) had two hardening functional groups of 2, a number average molecular weight of about 24,000, and a viscosity at 25 ° C of about 830 Pa‧s.

40 parts by mass of the oligomer (A-1), 30 parts by mass of 2-hydroxybutyl methacrylate (manufactured by Kyoei Chemical Co., Ltd., Lightester HOB), and 30 parts by mass of n-dodecyl methacrylate were uniformly mixed, and 0.3 parts by mass of bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE 819) was uniformly dissolved in 100 parts by mass of the mixture. And 2,5- Bis-tert-butylhydroquinone (polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.) 0.04 parts by mass, ultraviolet absorber (manufactured by Ciba Specialty Chemicals Co., Ltd., TINUVIN 109) 0.3 parts by mass, and n-dodecyl mercaptan (chain transfer agent) 0.3 parts by mass of THIOKALCOL 20) manufactured by Kao Corporation, and the matrix composition -iv was obtained.

40 parts by mass of the oligomer (A-1), 40 parts by mass of 2-hydroxybutyl methacrylate (manufactured by Kyoei Chemical Co., Ltd., Lightester HOB), and 20 parts by mass of n-dodecyl methacrylate were uniformly mixed, and 0.3 parts by mass of bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE 819) was uniformly dissolved in 100 parts by mass of the mixture. And 0.04 parts by mass of 2,5-di-tertiary butylhydroquinone (polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.3 parts by mass of a UV absorber (manufactured by Ciba Specialty Chemicals Co., Ltd., TINUVIN 109) to obtain a matrix composition Object-v.

Next, the matrix composition -iv or the matrix composition-v and the non-hardening oligomer (II-i) are uniformly dissolved at a ratio shown in Table 1, and are set in an open state in a state of being placed in a container. In the decompression device, the inside of the decompression device was depressurized to about 20 Pa and held for 10 minutes, thereby performing defoaming treatment to obtain the first composition-1 and the first composition-2.

As the non-curable oligomer (II-i), the same molecular end used in the synthesis of the oligomer (A-1) has been modified with ethylene oxide as a 2-functional polypropylene glycol (by hydroxyl value). Calculated number average molecular weight: 4000).

[Second composition]

The bifunctional polypropylene glycol (the number average molecular weight calculated by the hydroxyl value: 4000) and the hexamethylene diisocyanate which have been modified with ethylene oxide at the molecular end are mixed at a molar ratio of 6:7, followed by isoindole Acrylate (Osaka Organic After dilution by IBXA), it was reacted at 70 ° C in the presence of a tin catalyst to obtain a prepolymer. The obtained prepolymer was added with 2-hydroxyethyl acrylate at a molar ratio of 1:2 and reacted at 70 ° C to obtain an urethane acrylate oligomer which had been diluted with 30% by mass of isodecyl acrylate. Polymer (A'-2) (hereinafter referred to as "oligomer (A'-2)"). The oligomer (A'-2) had two hardening functional groups of 2, a number average molecular weight of 55,000, and a viscosity at 60 ° C of 580 Pa ‧ .

90 parts by mass of the oligomer (A'-2) and 10 parts by mass of 2-hydroxybutyl methacrylate (Lightester HOB, manufactured by Kyoei Chemical Co., Ltd.) were uniformly mixed to obtain a mixture. 100 parts by mass of this mixture, 1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, Ciba Specialty Chemicals, IRGACURE 184) 0.9 parts by mass, and bis(2,4,6-trimethyl) Benzyl fluorenyl)-phenylphosphine oxide (photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE 819) 0.1 parts by mass, 2,5-di-tertiary butylhydroquinone (polymerization inhibitor, Tokyo Chemical Industry Co., Ltd.) 0.04 parts by mass of the company and 0.3 parts by mass of a UV absorber (manufactured by Ciba Specialty Chemicals Co., Ltd., TINUVIN 109) were uniformly mixed to obtain a matrix composition -vi.

70 parts by mass of the oligomer (A'-2) and 30 parts by mass of 2-hydroxybutyl methacrylate (Lightester HOB, manufactured by Kyoei Chemical Co., Ltd.) were uniformly mixed to obtain a mixture. 100 parts by mass of this mixture, 1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, Ciba Specialty Chemicals, IRGACURE 184) 0.9 parts by mass, and bis(2,4,6-trimethyl) Benzyl fluorenyl)-phenylphosphine oxide (photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE 819) 0.1 parts by mass, 2,5-di-tertiary butylhydroquinone (polymerization inhibitor, Tokyo Chemical Industry Co., Ltd.) Company made) 0.04 parts by mass, and UV absorber (made by Ciba Specialty Chemicals Co., Ltd., TINUVIN 109) 0.3 The mass parts were uniformly mixed to obtain a matrix composition -vii.

The matrix composition-vi or the matrix composition-vii is placed in a state of being placed in a container, and is placed in a decompression device in an open state, and the inside of the decompression device is depressurized to about 20 Pa for 10 minutes to perform defoaming treatment. The second composition-1 was obtained.

Further, the matrix composition-v or the matrix composition-vii and the non-curable oligomer (II'-i) were uniformly dissolved at a ratio shown in Table 1, and placed in a state of being in an open state. The pressure-reducing device was placed in a decompression device, and the pressure-reducing device was depressurized to about 20 Pa for 10 minutes to carry out a defoaming treatment to obtain a second composition-2 to a second composition-7.

As the non-curable oligomer (II'-i), the same as the non-curable oligomer (II-i) is used.

[Example 1]

(Step (a))

The second composition-1 was coated with a spreader from the inner edge of the light-shielding printing portion of the transparent face material-i to a position of about 7 mm and coated with a width of about 1 mm. The cloth has a thickness of about 0.6 mm and forms an uncured weir.

Next, the uncured enamel portion formed on the transparent surface material -i was uniformly irradiated with ultraviolet light and 450 nm from a chemical lamp (manufactured by Nippon Electric Co., Ltd., FL15BL, peak wavelength: 365 nm, irradiation intensity: 2 mW/cm ² ). The following visible light is 30 seconds. Thereby the uncured beak is viscous.

(Step (b))

The first composition-1 was supplied to a plurality of places on the inner side region of the unhardened weir portion of the transparent face material-i using a spreader in a total mass of 2.5 g.

During the supply of the first composition-1, there is no damage such as cracking and the shape of the unhardened weir portion is maintained.

(Step (c))

The transparent face material-i is placed flat on the lower plate in the decompression device provided with the lifting device of the pair of fixed plates in such a manner that the face of the first composition-1 faces upward.

The support face material -ii to which the protective film had been attached was held under the upper plate of the lifting device in the decompression device using an electrostatic chuck, and the distance from the transparent face material -i was 10 mm in the vertical direction.

The pressure reducing device was sealed and the pressure in the pressure reducing device was evacuated until it reached about 40 Pa. The upper and lower fixed plates are brought close to each other by the lifting device in the decompression device, and the transparent surface material -i and the supporting surface material -ii to which the protective film has been attached are pressed under the pressure of 2 kPa through the first composition-1, and Hold for 10 seconds. The electrostatic chuck is de-energized so that the supporting surface material -ii is separated from the upper fixing plate, and the inside of the decompression device is restored to the atmospheric environment in about 15 seconds, and the uncured layer portion composed of the first composition-1 has been obtained. Transparent surface material -i, protective film and unhardened beak Sealed precursor layer-1.

In the precursor laminate-1, the shape of the unhardened weir portion is maintained substantially in the initial state.

(Step (d))

The uncured ridge portion and the layer portion of the precursor layer-1 were uniformly irradiated from the support surface material -ii side from a chemical lamp (manufactured by Nippon Electric Co., Ltd., FL15BL, peak wavelength: 365 nm, irradiation intensity: 2 mW/cm ^{2 )} Ultraviolet rays and visible light of 450 nm or less for 10 minutes, and the unhardened enamel portion and the layer portion are hardened to form an adhesive layer.

The irradiation intensity was measured using an illuminometer (manufactured by USHIO Electric Co., Ltd., ultraviolet intensity meter UNI METER UIT-101).

The thickness of the layered portion after hardening was substantially uniform at 0.4 mm.

(Step (e))

The support face material -ii was peeled off from the protective film while the adhesive layer was cooled to about -20 ° C to obtain a transparent face material-1 to which an adhesive layer of the protective film was attached.

[Examples 2 to 6 and Comparative Example 1]

In the same manner as in Example 1, except that the types of the first composition and the second composition were changed as shown in Table 2, a transparent surface material with an adhesive layer-2 to a transparent surface material with an adhesive layer was obtained. 7.

[Segment difference evaluation]

(1) Accelerated test

The protective film was peeled off from the transparent surface material with the adhesive layer obtained in each example, and stored in a thermostat at 80 ° C for 5 days.

(2) Evaluation of the shape of the adhesive layer

The shape evaluation of the adhesive layer was performed using a digital microscope VHX-1000 manufactured by Keyence Co., Ltd., and the depth of focus was used to measure the shape. The measurement portion is from the outer peripheral end portion of the beak portion at the central portion of one of the adhesive layers on the transparent face material-i, covering a portion of a distance of about 5 mm across the adhesive layer of the layer portion. In the measurement, a thin silver paste is applied to the surface of the adhesive layer for the purpose of improving the sensitivity of the measurement. The measurement was carried out before (1) the accelerated test. The step difference between the weir and the layer before and after the accelerated test was evaluated as a shape change.

The step difference evaluation calculates the height difference between the highest point and the lowest point in the measurement area as the step difference.

[Evaluation of void occurrence]

(1) The transparent surface material-1 of the adhesive layer after the accelerated test and the peeling of the protective film is placed on the pressure-reducing device provided with the lifting device of the pair of fixed plates in such a manner that the adhesive layer faces upward. Inside the fixed plate.

The bonded face material -iii was held under the upper plate of the lifting device in the decompression device using an electrostatic chuck, and was placed at a distance of 10 mm from the transparent face material-1 of the adhesive layer.

The pressure reducing device was sealed and the pressure in the pressure reducing device was evacuated until it reached about 30 Pa. The upper and lower fixed plates were brought close to each other by a lifting device in the decompression device, and the bonded face material -iii and the transparent face material-1 with the adhesive layer were pressure-bonded under pressure of 2 kPa through the adhesive layer for 10 seconds. The electrostatic chuck is de-energized to separate the bonded surface material-iii from the upper plate, and the inside of the pressure-reducing device is returned to atmospheric pressure in about 20 seconds to obtain an adhesive layer-coated transparent surface material-i and a laminated surface material- Iii laminated body-1.

As a result of observing the laminated body-1 in the transient, there were many fine voids (bubbles) at the interface between the bonded surface material -iii and the adhesive layer of the transparent surface material-1 to which the adhesive layer was attached. The laminated body-1 was allowed to stand, and the time until the disappearance of the void (the disappearance time of the void) was measured. The laminates-2 to -7 were produced in the same manner using the transparent surface materials -2 to -7 with an adhesive layer, and the void disappearance time was measured.

The results are shown in Table 1. The void disappearance time averaged the results of the 2 samples.

The evaluation results in each case are shown in Table 2. In addition, "W1-W2" in Table 2 indicates the content W1 (% by mass) of the non-curable oligomer (II-i) in the first composition and the non-hardening oligomer in the second composition (II). The difference in the content of W- (% by mass) of '-i) (W1-W2).

As shown in Table 2, in Comparative Example 1 in which W1-W2 exceeded 40, voids remained even after 2 hours, and the voids did not disappear thereafter. On the other hand, in Examples 1 to 6 in which W1-W2 was 40 or less, the void disappeared within 90 minutes, and the productivity was high and preferable. Further, in the examples 1 to 5 in which W1-W2 is 30 to 0, the voids disappear at 0 minutes, and the productivity is high and preferable.

[Embodiment 7]

[Transparent surface material]

A soda lime glass having a length of 250 mm, a width of 190 mm, and a thickness of 1.3 mm was used as a transparent surface material. In the present embodiment, in order to easily confirm the influence of the display unevenness, the glass substrate on which the light-shielding printing portion is not formed is used as a transparent surface material.

[Support surface material]

A protective film (Tocello, Puretect VLH-9) having a length of 130 mm, a width of 130 mm, and a thickness of 0.75 mm was attached to a length of 100 mm, a width of 100 mm, and a thickness of 3 mm by using a rubber roller so that the adhesive surface of the protective film was in contact with the glass. On one side of the transparent plate made of soda lime glass, a support surface material to which a protective film is attached is produced.

[First resin composition (resin composition for layered portion)]

The same matrix composition -i as the above-mentioned matrix composition -iv was produced except that the amount of n-dodecyl mercaptan was 0.5 parts by mass.

Next, 100 parts by mass of the matrix composition-i, the non-curable oligomer (II-i) is uniformly dissolved in a ratio of 100 parts by mass, and placed in a container to be placed in an open state. In the decompression device, the inside of the decompression device was depressurized to about 20 Pa and held for 10 minutes, thereby performing a defoaming treatment to obtain a first resin composition (in-plane (layered portion) resin composition).

[Second resin composition (resin composition for beak portion)]

55 parts by mass of the above oligomer (A'-2) and 45 parts by mass of 4-hydroxybutyl acrylate (4HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.) were uniformly mixed to obtain a mixture. 100 parts by mass of this mixture, 3.0 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE 184), and bis(2,4,6-trimethyl group) Benzyl fluorenyl)-phenylphosphine oxide (photopolymerization initiator, Ciba Specialty Chemicals Co., Ltd., IRGACURE 819) 0.5 parts by mass, 2,5-di-tertiary butylhydroquinone (polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.), 0.04 parts by mass, and UV absorber (Ciba Specialty Chemicals Co., Ltd. , TINUVIN 109) 0.3 parts by mass was uniformly mixed to obtain a matrix composition -ii.

Next, 75 parts by mass of the matrix composition-ii was used, and the non-curable oligomer (II-i) was uniformly dissolved at a ratio of 25 parts by mass to obtain a second resin composition.

[Third resin composition (resin composition for beak portion)]

As the third resin composition, the aforementioned matrix composition vi is used.

Next, the storage shear modulus of the resin layer obtained by hardening the first to third resin compositions was measured using a rheometer (manufactured by Anton Paar Co., Ltd., Physica MCR301): for forming an uncured resin layer The photocurable resin composition was placed between a soda lime glass workbench and a measuring shaft (D-PP20/AL/S07 manufactured by Anton Paar Co., Ltd.), and was placed at 35 ° C in a nitrogen atmosphere. The black light of the lower part of the stage (FL15BL, manufactured by Nippon Electric Co., Ltd.) was irradiated with light of 2 mW/cm ^{2 for} 10 minutes, and the photocurable resin composition for forming a resin layer was cured by applying a dynamic shear strain of 1%. The storage shear modulus of the resin layer obtained from each resin composition is shown in Table 3 below.

[table 3]

[Embodiment 7]

First, the entire resin composition is covered from the outer periphery of the transparent face material to a position of about 25 mm, and the second resin composition is applied by a spreader to have a width of about 1 mm and a coating thickness of about 0.6 mm, and is attached to the spreader. The LED light source illuminates the UV light to form a partially hardened beak (see FIGS. 4 to 5).

The first resin composition was supplied to a plurality of places on the inner side region of the weir portion by using a spreader with a total mass of 2.5 g. During the supply of the first resin composition, there is no damage such as cracking and the shape of the uncured portion is maintained.

Next, the transparent surface material is placed on the lower plate in the decompression device (refer to FIG. 6) provided with the lifting device of the pair of fixed plates in a face-up manner in which the first resin composition is applied, and will be reduced. The pressure in the pressure device is exhausted until it reaches about 40 Pa. After the pressure is reduced, the upper and lower fixing plates are brought close to each other by the lifting device in the decompression device, and the transparent surface material and the supporting surface material to which the protective film has been attached are pressure-bonded and held at a pressure of 2 kPa through the first resin composition. Fit in seconds. After the bonding, the inside of the decompression device is returned to the atmosphere to obtain a precursor laminate in which the first resin composition has been sealed by the transparent surface material, the protective film, and the beak portion.

The precursor layer body was uniformly irradiated with ultraviolet light from a chemical lamp (made by Nippon Electric Co., Ltd., FL15BL, peak wavelength: 365 nm, irradiation intensity: 2 mW/cm ² ) and visible light of 450 nm or less for 10 minutes from the side of the support surface layer to make the ridge portion ( The second resin composition) and the first resin composition are cured to form an adhesive layer.

The irradiation intensity was measured using an illuminometer (manufactured by USHIO Electric Co., Ltd., ultraviolet intensity meter UNI METER UIT-101).

The thickness of the layered portion after hardening was substantially uniform at 0.4 mm.

Thereafter, the support surface material was peeled off from the protective film while the adhesive layer was cooled to about -20 ° C to produce a transparent surface material having an adhesive layer to which a protective film was attached.

As shown in Table 4, in Example 7 in which the elastic modulus ratio of the layered portion and the beak portion was the lowest, the display unevenness could not be visually recognized. It was confirmed that the flexibility of the layered portion and the beak portion was lowered, and good visibility was maintained.

Although the preferred embodiments of the invention have been described above, the invention is not limited by the embodiments. Additions, omissions, substitutions, and other modifications can be made without departing from the scope of the invention. The invention is not limited by the foregoing description, but is only limited by the scope of the appended claims.

Japanese Patent Application No. 2012-288004, filed on Dec. 28, 2012, and Japanese Patent Application No. 2013-037505, filed on Feb. 27, 2013, The entire contents of the scope, drawings and abstract are included as a disclosure of the specification.

1‧‧‧Transparent surface material with adhesive layer

10‧‧‧Transparent surface material

12‧‧‧Lighting Printing Department

14‧‧‧Adhesive layer

16‧‧‧Protective film

18‧‧‧Layered

20‧‧‧堰

Claims (15)

A transparent surface material with an adhesive layer, comprising a transparent surface material and an adhesive layer formed on at least one surface of the transparent surface material; the adhesive layer has a layered portion extending along a surface of the transparent surface material and surrounding the layered portion a beak-shaped portion of the periphery; the crotch portion is composed of a cured product of a curable resin composition for forming a crotch portion, and the curable resin composition for forming the crotch portion contains the following curable compound (I') and The non-curable oligomer (II'), wherein the layered portion is composed of a cured product of a curable resin composition for forming a layer portion, and the curable resin composition for forming the layer portion contains the following hardening The compound (I) and the following non-curable oligomer (II); and the content W1 of the non-curable oligomer (II) expressed by mass% in the layered portion and the aforementioned non-hardening in the aforementioned weir portion The difference (W1-W2) of the content W2 expressed by mass% (II') is 40 or less; the curable compound (I'): containing urethane acrylate oligomer (A') and single Body (B'), monomer (B') has more than one hardening functional group and molecular weight below 600; non-hard The oligomer (II') is an oligomer having a hydroxyl group, and is cured when either the curable resin composition for forming a layer portion or the curable resin composition for forming a beak portion is cured. Neither the hardening reaction with the hardening compound (I'); the curable compound (I): containing the urethane acrylate oligomer (A) and the monomer (B), the monomer (B) having 1 More than one hardening functional group and The non-curable oligomer (II) is an oligomer having a hydroxyl group, and is not limited to the curable resin composition for forming a layer portion or the curable resin composition for forming a beak portion. When one is cured, it does not undergo a hardening reaction with the curable compound (I). The transparent surface material of the adhesive layer of claim 1, wherein the urethane acrylate oligomers (A) and (A') are amines synthesized from polyoxyalkylene polyols and polyisocyanates. Ethyl formate acrylate oligomer. The transparent surface material of the adhesive layer according to claim 1 or 2, wherein the non-hardening oligomers (II) and (II') are polyoxyalkylene polyols. The transparent surface material of the adhesive layer according to any one of claims 1 to 3, wherein the number average molecular weight of each of the non-curable oligomers (II) and (II') is from 400 to 8,000. The transparent surface material of the adhesive layer according to any one of claims 1 to 4, wherein the urethane acrylate oligomer (A) has a number average molecular weight of from 1,000 to 100,000. The transparent surface material of the adhesive layer according to any one of claims 1 to 5, wherein the curable resin composition for forming a layer portion contains a photopolymerization initiator (C1), and the beryllium portion is formed of a curable resin. The material contains a photopolymerization initiator (C2). The transparent surface material of the adhesive layer according to any one of claims 1 to 6, wherein the storage shear modulus of the beak at 35 ° C is a storage shear modulus at 35 ° C of the layer portion. Above and below 15 times. The transparent surface material of the adhesive layer according to any one of claims 1 to 7, wherein the storage shear modulus of the beak at 35 ° C is 1 to 150 kPa. The transparent surface material with an adhesive layer according to any one of claims 1 to 8, wherein the storage layer has a storage shear modulus of 1 to 100 kPa at 35 °C. The transparent surface material with an adhesive layer according to any one of claims 1 to 9, wherein the transparent surface material includes a light-shielding printing portion formed on a peripheral portion of the surface thereof, and at least a part of the layer portion and the beak portion are transparent The in-plane direction of the surface of the face material is placed on the inner side of the light-shielding printed portion. The transparent surface material of the adhesive layer according to any one of claims 1 to 10, further comprising a protective film covering at least a part of the surface of the adhesive layer and being peelable. A method for producing a transparent surface material with an adhesive layer, which is a method for producing a transparent surface material with an adhesive layer as claimed in claim 11, comprising the following steps (a) to (e): step (a), in a transparent surface material The peripheral portion of the surface is coated with a liquid curable resin composition for forming a weir portion to form an unhardened weir portion, and in step (b), a liquid curable resin composition for forming a layer portion is supplied. a region to the surface of the transparent surface material that has been surrounded by the unhardened weir portion; in step (c), the support surface material to which the protective film has been attached is formed with the protective film and the layered portion in a reduced pressure atmosphere The curable resin composition is superposed on the layered portion to form a curable resin On the object, a precursor layer body in which the unhardened layer portion has been sealed by the transparent surface material, the protective film, and the unhardened weir portion is obtained, and the uncured layer portion is formed by the layer portion. a resin composition; in the step (d), the unhardened layered portion and the beak portion are hardened while the precursor layer body has been placed in a higher pressure gas atmosphere than the step (c); An adhesive layer having a layered portion and a beak portion is formed; and in step (e), the support surface material is peeled off from the protective film. A display device comprising: a display panel; and a transparent face material with an adhesive layer according to any one of claims 1 to 10, which is attached to the display panel such that the adhesive layer is in contact with the display panel. A method of manufacturing a display device, the method of manufacturing the display device of claim 13, wherein the display panel and the adhesive layer are transparent in an adhesive atmosphere of 10 kPa or less in a manner that the adhesive layer is in contact with the display panel. The face materials overlap and fit. A laminated body in which a transparent face material and an attached face material of the adhesive layer as claimed in claims 1 to 10 are bonded.