TWI429608B - The manufacturing method of the layered body - Google Patents

Description

Method for manufacturing laminated body Field of invention

The present invention relates to a method for producing a laminated body comprising a pair of substrates and a cured layer of a curable resin composition existing between the pair of substrates.

The laminate produced by the method of the present invention is suitable for use as a front panel such as a laminated glass or image display device, and more particularly, for an EL such as a liquid crystal display device (LCD), an organic EL or an inorganic EL. A light-emitting panel display device, a plasma display device, a front panel of a flat panel display (FPD) such as an electronic ink type image display device, and a protective plate such as a thin-film solar cell device or a touch panel.

Background of the invention

A pair of glass substrates are formed into an integrated laminated glass via an adhesive layer. Since the damaged glass fragments adhere to the film without scattering, they are used as windshields for automobiles, and because they are difficult to penetrate and have strength. A window glass (safety glass, anti-theft glass) which is excellent in use as a building (refer to Patent Documents 1 and 2).

Further, from the viewpoint of preventing damage of the liquid crystal panel and preventing light reflection, a liquid crystal display device in which a front panel is provided on the front surface of the liquid crystal panel is known, and the front panel is sealed with a transparent interlayer film between the transparent protective plate and the polarizing plate. (refer to Patent Document 3).

In addition, a solar cell module having a solar cell device is known which is sealed between a transparent surface material and a back surface material which are light-receiving surfaces, and is sealed with a sealing material such as resin (see Patent Document 4).

Accordingly, there is a need in various technical fields for a laminate having a pair of substrates and a cured layer of a curable resin composition existing between the pair of substrates.

There are many proposals for the production method of the laminate. The methods described in Patent Documents 1 and 2 do not limit the type of the substrate to be used, and the type of the curable resin composition which is interposed between the substrates and becomes an intermediate layer has a large degree of freedom and can be effectively utilized. The resources for forming the intermediate layer are excellent in terms of excellent productivity and small environmental load.

In this method, a sealing portion for sealing a curable resin composition is formed on a peripheral portion of one of the substrates, and then a curable resin composition is supplied to a region surrounded by the sealing portion on the substrate. Next, the other substrate is superposed on one of the substrates in a reduced pressure environment to sandwich and seal the curable resin composition between the pair of substrates.

Next, the pair of substrates which are held by the curable resin composition and sealed are placed under a pressure environment higher than the above-described reduced pressure environment (for example, at atmospheric pressure). When the environmental pressure rises, the pair of transparent substrates are pressed in the direction in which they are in close contact with each other, and since the void volume remaining in the sealed space is reduced in accordance with the environmental differential pressure, the curable resin composition flows into the pair of substrates and is sealed. In the decompression space in the sealed space in which the portion is sealed, the entire sealed space is uniformly filled with the curable resin composition. Then, the laminate is obtained by hardening the curable resin composition.

Advanced technical literature Patent literature

Patent Document 1: International Publication WO2008/081838

Patent Document 2: International Publication WO2009/016943

Patent Document 3: Japanese Patent Laid-Open Publication No. 2009-205065

Patent Document 4: Japanese Patent Laid-Open No. Hei 11-87743

As described above, in the method for producing a laminate according to Patent Documents 1 and 2, the curable resin composition is held between a pair of transparent substrates in a reduced pressure environment, and after being sealed, it is placed at a higher level than the above-mentioned reduction. In a pressure environment under a pressurized environment (for example, at atmospheric pressure), the entire sealed space is uniformly filled with the curable resin composition. However, depending on the viscosity of the curable resin composition to be used and the layer thickness of the curable resin composition present in the sealed space, it may be difficult to uniformly exhibit a state in which the entire sealed space is uniformly filled with the curable resin composition.

In other words, when the viscosity of the curable resin composition to be used is high (for example, the viscosity of the curable resin composition is 0.2 Pa‧s or more), and the layer thickness of the curable resin composition existing in the sealed space is large. When the layer thickness of the curable resin composition is 30 μm or more, the pair of substrates which are held by the curable resin composition and sealed are placed under a pressure environment higher than the above-described reduced pressure environment (for example, at atmospheric pressure). ), and then to reduce the voids remaining in the confined space, the time required may increase. Therefore, it takes a long time to present a state in which the entire sealed space is uniformly filled with the curable resin composition.

The present invention has been made to solve the problems of the above-described conventional techniques, and an object thereof is to provide a method for producing a laminated body by curing a sealed curable resin composition held between a pair of substrates, thereby shortening to A novel method of making the entire space of the sealed space uniformly filled with the curable resin composition.

In order to achieve the above object, the method for producing a laminate according to the present invention comprises the steps of: preparing two substrates; forming a sealing portion on a peripheral portion of one of the substrates, the sealing portion for sealing the curable resin composition Supplying a curable resin composition to a region surrounded by the sealing portion on one of the substrates; and superposing another substrate on the supplied curable resin composition under a reduced pressure environment to be between the pair of substrates Holding and curing the curable resin composition; and placing a pair of substrates holding the curable resin composition in a second pressure environment higher than the reduced pressure environment, and curing the resin in the second pressure environment The composition is cured to produce a laminate, and the method for producing the laminate is characterized in that a coating state of the curable resin composition supplied onto the substrate is controlled, and a period in which another substrate is superposed on the curable resin composition When the other substrate is superposed on one of the substrates, the layer of the curable resin composition present in the region surrounded by the sealing portion can satisfy (1) to (3);

(1) a void existing in the curable resin composition layer, the projected circle having an equivalent circle diameter D _pore of 10 mm or less;

(2) a portion where the void is not present in the curable resin composition layer, and the equivalence circle diameter D _non-pore of the projected shape is 40 mm or less;

(3) The curable resin composition layer and the voids present in the curable resin composition layer are in a state of being in contact with the sealing portion.

In addition, the above-mentioned "satisfiable (1) to (3)" means that any one of the requirements described in (1), (2), and (3) can be satisfied.

In the method for producing a laminate according to the present invention, it is preferable that at least one of the pair of substrates is a transparent substrate.

In the method for producing a laminate according to the present invention, the viscosity of the curable resin composition is 0.2 to 50 Pa‧s.

In the method for producing a laminate according to the present invention, the thickness of the curable resin composition layer in the space sealed by the pair of substrates and the sealing portion is 30 to 3000 μm.

In the method for producing a laminate according to the present invention, the sealing portion is formed using a second curable resin composition having a viscosity of 200 to 3,000 Pa s.

In the method for producing a laminate according to the present invention, it is preferred that the pressure-reducing environment is a pressure environment of 0.1 to 1000 Pa.

In the method for producing a laminate according to the present invention, it is preferred that the pressure in the second environment is higher than the pressure in the reduced pressure environment by 50 kPa or more. In the second pressure environment, the pressure-reducing environment in which the other substrate is superposed on the curable resin composition for resin film formation supplied to the region surrounded by the sealing portion and sealed under reduced pressure is equivalent to The first pressure environment.

In the method for producing a laminate according to the present invention, it is preferable that the curable resin composition is supplied to a region surrounded by the sealing portion on one of the substrates, and the curable resin composition is dispersed in a region surrounded by the sealing portion.

In this case, when the curable resin composition is dispersed and dropped, the curable resin composition which is dropped by relatively oscillating the one of the substrates and the nozzle used for dispersion and dropping is preferably used. The diameter of the equivalence circle is forcibly expanded, so that the equivalence circle diameter of the curable resin composition existing in the region surrounded by the sealing portion is uniform.

In the method for producing a laminate according to the present invention, the curable resin composition is supplied onto one of the substrates to form the curable resin composition when the curable resin composition is supplied to a region surrounded by the seal on one of the substrates. The object exhibits a vibration curve satisfying the following (4) to (9);

(4) Repeating the displacement in the vertical direction according to a certain period (X) and amplitude (Y) with respect to the forward direction of the vibration curve;

(5) The displacements of adjacent vibration curves are opposite to each other;

(6) When the thickness of the vibration curve at the time of starting supply is m (mm), the period (X) (mm) and the amplitude (Y) (mm) satisfy the following formula:

2.1×m≦X≦10×m

(2.1×m)/2≦Y≦(10×m)/2

(7) When the thickness of the vibration curve at the time of starting supply is m (mm), the shortest distance d _(sr) (mm) between the vibration curve and the sealing portion satisfies the following formula:

d _(sr) ≦ 2.5 × m

(8) When the thickness of the vibration curve at the start of supply is m (mm), the shortest distance d _(rr) (mm) between the adjacent vibration curves satisfies the following formula:

d _(rr) ≦ 5 × m

(9) When E=2Y-2m, the E(mm) system satisfies the following formula:

(Y+d _(rr) )/10≦E≦Y+d _(rr)

In addition, the above-mentioned "satisfying (4) to (9)" means that any one of the requirements described in (4) to (9) can be satisfied.

Further, in the method for producing a laminate according to the present invention, the curable resin composition is supplied to one of the substrates to supply the region surrounded by the seal on one of the substrates, and the curable resin composition may be used. a vibration curve satisfying the following (10) to (14) and a line advancing in the same direction as the vibration curve are adjacent to each other;

(10) Repeating the displacement in a vertical direction with respect to a certain period (X) and an amplitude (Y) with respect to the direction in which the vibration curve advances;

(11) When the thickness of the vibration curve at the time of starting supply is m (mm), the period (X) (mm) and the amplitude (Y) (mm) satisfy the following formula:

2.1×m≦X≦10×m

(2.1×m)/2≦Y≦(10×m)/2

(12) When the vibration curve is located near the seal portion and the thickness of the vibration curve at the time of starting supply is m (mm), the shortest distance d _(sr) (mm) between the vibration curve and the seal portion satisfies the following formula :

d _(sr) ≦ 2.5 × m

(13) When the thickness of the vibration curve at the start of supply is m (mm), the shortest distance d _(rr) (mm) between the adjacent vibration curve and the straight line satisfies the following formula:

d _(rr) ≦ 2.5 × m

(14) When E=2Y-2m, the E(mm) system satisfies the following formula:

(Y+d _(rr) )/20≦E≦(Y+d _(rr) )/2

In addition, the above-mentioned "satisfaction (10) to (14)" means that any one of the requirements described in (10) to (14) can be satisfied.

Further, in the method for producing a laminate according to the present invention, it is preferable that the time from the start of the dropping of the region surrounded by the sealing portion on one of the substrates from the curable resin composition to the time of lamination is 30 to 1800 seconds.

According to the method for producing a laminated body of the present invention, it is possible to shorten the time required for uniformly filling the space sealed by the pair of substrates and the sealing portion by the curable resin composition, which is carried out during the production of the laminated body, and to improve the laminated body. Productive.

Simple illustration

Fig. 1 is a plan view showing a state in which a sealing portion is formed in a peripheral portion of the substrate.

Fig. 2 is a plan view showing a state in which a curable resin composition layer is formed in a portion of the substrate surrounded by the sealing portion.

Figs. 3(a) to 3(c) are diagrams showing temporal changes of the curable resin composition in which the substrate is dispersed in a dot shape in a region surrounded by the sealing portion.

When the vacuum-curable resin composition of the fourth (a) to (d) is subjected to vacuum lamination in the state shown in Fig. 3(a), the curable resin composition is laminated at the time of vacuum lamination and after the decompression environment is released. State diagram.

When the vacuum-curable resin composition of the fifth (a) to (d) is subjected to vacuum lamination in the state shown in Fig. 3(b), the curable resin composition is laminated at the time of vacuum lamination and after the decompression environment is released. State diagram.

In the case where the vacuum-curable resin composition is subjected to vacuum lamination in the state shown in Fig. 3(c), the curable resin composition is subjected to vacuum lamination and after the decompression environment is released. State diagram.

The seventh (a) to (e) diagrams are time-dependent changes of the curable resin composition in which the substrate is dispersed in a dot shape in a region surrounded by the sealing portion.

Fig. 8 is a sequence diagram in which a hard-pointing resin composition is dispersed and dropped on a substrate surrounded by a sealing portion using a single-point nozzle.

Fig. 9 is a sequence diagram in which a multi-point nozzle is used to disperse and deposit a curable resin composition on a substrate surrounded by a sealing portion.

Fig. 10 is a sequence diagram in which a multi-point nozzle is used to disperse a curable resin composition in a region surrounded by a sealing portion.

Fig. 11 is a sequence diagram in which a multi-point nozzle is used to disperse a curable resin composition in a region surrounded by a sealing portion.

Fig. 12 is a sequence diagram in which a multi-point nozzle is used to disperse a curable resin composition in a region surrounded by a sealing portion.

Fig. 13 is a graph showing the relationship between the elapsed time t (sec) after dropping and the equivalent circle diameter d (mm) of the curable resin composition.

Fig. 14 is a graph showing the relationship between the elapsed time t after dropping, the equivalence circle diameter d of the curable resin composition, and the equivalence circle diameter D _pore of the voids present in the curable resin composition layer.

Fig. 15 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

Fig. 16 corresponds to a partially enlarged view of Fig. 15, showing temporal changes in the shape of the vibration curves 30a, 30b.

Fig. 17 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

Fig. 18 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

Fig. 19 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

Fig. 20 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

Fig. 21 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

Fig. 22 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

Fig. 23 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

Fig. 24 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

Form for implementing the invention

Hereinafter, a method of manufacturing a laminated body of the present invention will be described with reference to the drawings.

In the method for producing a laminate according to the present invention, in the pair of substrates, a sealing portion is formed on a peripheral portion of one of the substrates, and the sealing portion is used to seal the curable resin composition. Fig. 1 is a plan view showing a state in which a sealing portion 20 is formed on a peripheral portion of the substrate 10.

[substrate]

In the method for producing a layered product of the present invention, as described later, since the curable resin composition for forming a sealing portion is preferably a photocurable resin composition, at least one of the pair of substrates is preferably transparent. Substrate. In this case, only one of the pair of substrates may be a transparent substrate and the other may be an opaque substrate, or both of the substrates may be transparent substrates. Here, when one of them is a transparent substrate and the other is an opaque substrate, a sealing portion may be formed at a peripheral portion of the transparent substrate, or a sealing portion may be formed at a peripheral portion of the opaque substrate.

Further, the transparent substrate is not particularly limited as long as it is transparent, that is, a substrate having visible light transmittance. Specific examples of the transparent substrate may be, for example, a glass substrate and a transparent resin substrate. Among these, a glass substrate is preferred from the viewpoints of transparency, light resistance, low birefringence, high planar precision, surface scratch resistance, and high mechanical strength.

The material of the glass substrate may be, for example, a high-permeability glass (white plate) or a borosilicate glass having a lower iron content and a smaller blue color than the soda lime glass.

The material of the transparent resin substrate can be, for example, a resin material having high transparency (polycarbonate, polymethyl methacrylate, etc.).

Further, the transparent substrate may be a person who applies fine unevenness to the surface of the substrate for the purpose of scattering or refracting light, or a light-shielding printer for the surface of the substrate, on the premise of at least visible light transmittance.

Further, it is also possible to use a transparent substrate in which a plurality of transparent substrates are bonded together or a transparent substrate to which an optical film or the like is bonded, as a whole.

Further, a structure including a transparent substrate as a part of the constituent elements may be used as the transparent substrate. Such a structure including a transparent substrate as a part of a constituent element may be, for example, an EL (Electro-Excise Light) display device such as a liquid crystal display device (LCD), an organic EL or an inorganic EL, a plasma display device, or an electron. A flat panel display (FPD) such as an ink type image display device, a thin-film solar cell device, a touch panel, or the like.

When one of the pair of substrates is an opaque substrate, a specific example of the opaque substrate may be a substrate made of a metal material such as stainless steel, a substrate made of a ceramic material, or a dispersion of a visible light-absorbing filler in the substrate. A light-shielded resin substrate or the like.

Further, when both of the pair of substrates are transparent substrates, the pair of transparent substrates may be formed of the same material or may be formed of different materials. That is, both of the pair of transparent substrates may be a glass substrate or a transparent resin substrate, and one of the pair of transparent substrates may be a glass substrate and the other may be a transparent resin substrate.

The thickness of the substrate is not particularly limited, and in the case of a transparent substrate, the glass substrate is usually preferably 1 to 6 mm from the viewpoint of mechanical strength and transparency. In particular, in the case where a transparent laminate having a small thickness is required, the thickness of the glass substrate is preferably from 0.3 to 1.5 mm, more preferably from 0.3 to 1 mm. Further, the thickness of the transparent resin sheet is usually 0.1 to 3 mm.

On the other hand, in the case of an opaque substrate, it is usually 0.8 to 4 mm from the viewpoint of mechanical strength and thinness and weight reduction.

Further, the thickness of the pair of substrates may be the same or different.

The surface of the substrate, more specifically, the surface on the side where the sealing portion is formed in the peripheral portion, may be subjected to a surface treatment for enhancing the interface adhesion force with the sealing portion. Here, the surface treatment may be performed only on the peripheral portion of the substrate, or may be performed on the entire surface of the substrate.

The surface treatment method is a method in which the surface of the substrate is treated with a decane coupling agent or the like.

[seal department]

The curable resin composition supplied to the region surrounded by the sealing portion on the substrate is blocked, and then the curable resin composition held between the pair of substrates and sealed in a reduced pressure environment is sealed. In the manufacturing process of the laminated body of the present invention, it is required that the curable resin composition supplied to the region surrounded by the sealing portion has an interface adhesion force which does not occur more than the extent of leakage, and is required to be laminated in the present invention. The manufacturing process of the body should have a firmness that maintains the shape.

A sealing portion that satisfies such a requirement can be formed by providing a sealing member having a surface with an adhesive or an adhesive at a peripheral portion of one of the substrates.

Specific examples of such a sealing member are as follows.

‧ A strip or rod-shaped strip (double-sided tape, etc.) in which an adhesive layer or an adhesive layer is provided on the surface in advance.

‧ An adhesive layer or an adhesive layer is formed on the peripheral portion of one of the substrate surfaces, and a long body is attached thereto.

‧ using a curable resin composition to form a dam-shaped sealing precursor on the peripheral portion of one of the substrate surfaces by printing or dispensing, to harden the curable resin composition, and then forming an adhesive layer on the surface Or adhesive layer.

Further, a high-viscosity curable resin composition which is a second curable resin composition can be formed into a seal satisfying the above requirements by applying a predetermined thickness to a peripheral portion of one of the substrates by using a dispenser or a die coater. unit. In the present specification, the curable resin composition used to form the sealing portion is also referred to as a "second curable resin composition".

Here, in the order of the second curable resin composition described later, when the curable resin composition held between the pair of substrates and sealed is cured, the second curable resin composition may be cured at the same time, or may be sealed. The curable resin composition is hardened before being hardened. Further, one of the constituent elements of the method for producing a laminated body according to the present invention includes: "a sealing portion is formed on a peripheral portion of one of the substrates, and the sealing portion is for sealing a curable resin composition". The "sealing portion" at the position includes a sealing precursor before curing, which is a peripheral portion of the surface of one of the substrates on which the sealing portion is formed, and the curable resin composition is formed into a dam shape.

When the curable resin composition is supplied to the region surrounded by the sealing portion, the second curable resin composition has a strength capable of sealing the curable resin composition for forming the resin film, and performs vacuum lamination in the order described later. When the pressure-reducing environment is released, the thickness of the curable resin composition layer existing in the space sealed by the pair of substrates and the sealing portion can be deformed to deform the sealing portion, and vacuum lamination and release reduction can be performed in the order described later. When the environment is pressed, the sealing portion has a strength capable of withstanding atmospheric pressure, and the viscosity is preferably 200 to 3,000 Pa s, more preferably 500 to 2,000 Å s.

Here, in order to maintain the space between the pair of substrates, spacer particles having a predetermined particle diameter may be incorporated into the second curable resin composition.

In addition, it is preferable that the second curable resin composition is a photocurable resin composition to be described later, and the above-mentioned viscosity is used.

In order to prevent the curable resin composition supplied to the region surrounded by the sealing portion from leaking, the sealing portion preferably forms a layer composed of a curable resin composition supplied from a region surrounded by the sealing portion (hereinafter, In the specification, there is a state in which a predetermined thickness of the "curable resin composition layer" is abbreviated to a certain thickness. For example, the curable resin composition layer is preferably 1.1 times or more and 2 times or less the predetermined thickness.

Further, the width of the sealing portion varies depending on the thickness of the curable resin composition layer, and is preferably about 0.5 to 5 mm and about 0.5 to 3 mm.

When the sealing portion is formed by the application of the second curable resin composition having the viscosity described above, since the second curable resin composition used in the formation of the sealing portion is high in viscosity, such as by the sealing portion The curable resin composition supplied in the surrounding area does not change its shape over time after coating. Therefore, the formed seal portion has a partial defect, or the width of the seal portion is partially thinned, and these defects are not eliminated over time. Therefore, when the formed sealing portion is partially defective or refinished, the curable resin composition supplied to the region surrounded by the sealing portion may be applied before the vacuum lamination is performed in the order described later or when the vacuum lamination is performed. Since it oozes to the outside of this sealing part, there exists a possibility that a large gap exists in the hardening resin composition which exists in the space enclosed by a pair of board|substrate and a sealing part. Further, when the curable resin composition supplied from the region surrounded by the sealing portion oozes to the outside of the sealing portion, the laminated body pattern to be produced may be damaged.

Further, when the formed sealing portion is partially defective or refining, when the decompression environment is released in the order described later, the gas enters the space sealed by the pair of the substrate and the sealing portion, resulting in the presence of the gas. The curable resin composition in a sealed space has a possibility of occurrence of a large void.

In addition, when the sealing portion is formed, the case where the curable resin composition overlaps at the point where the coating is applied is not eliminated over time. Therefore, when the vacuum lamination is performed in the order described later, the thickness of the sealing portion becomes partial. In a uniform case, there is a possibility that a large gap occurs in the curable resin composition existing in the sealed space between the pair of substrates and the sealing portion. Further, the width of the sealing portion where the overlapping portion occurs is increased, which may impair the quality of the laminated body to be produced.

Therefore, when the sealing portion is formed by applying the second curable resin composition, it is preferable that the second curable resin composition is applied, and then it is preferable to cause partial defects such as partial defects, after the second curable resin composition is applied. Shortcomings such as refinement and overlap. However, since the above problem does not occur depending on the size of the defect, it is preferable to check whether or not there is a disadvantage that the predetermined allowable range is exceeded.

The inspection method is a method of confirming the size of the defects existing in the coated curable resin composition by image processing.

Next, the curable resin composition is supplied to the region on the substrate surrounded by the sealing portion.

When the curable resin composition is held between the pair of substrates in the order described below and sealed, the space sealed by the pair of substrates and the sealing portion is set to be a curable resin composition. The amount of fill. At this time, the supply amount of the curable resin composition can be determined only after the volume reduction due to the hardening shrinkage of the curable resin composition is considered in advance.

In the method for producing a laminate according to the present invention, when the curable resin composition is sandwiched between a pair of substrates and sealed in the order described later, the curable resin composition layer exists in a space sealed by the pair of substrates and the sealing portion. The thickness is preferably from 30 to 3000 μm. The reason is that the curable resin composition layer not only functions as an adhesive between a pair of substrates, but also has a function of imparting mechanical strength to the layer, and thus requires a thickness, and on the other hand, generally, such as an opening member or a display The component requirements are thin and lightweight, so it is best not to increase the thickness without any reason.

When the curable resin composition is held between the pair of substrates in the order described below and sealed, the thickness of the curable resin composition layer in the space sealed by the pair of substrates and the sealing portion is preferably 30 to 800 μm. The special system is 100 to 400 μm. In addition, the thickness of the curable resin composition layer may be as small as possible. In this case, the thickness of the curable resin composition layer is preferably 30 to 400 μm, more preferably 100 to 200 μm, and particularly preferably 100. ~160μm.

The method of supplying the curable resin composition is such that the substrate on which the sealing portion is formed in the above-described order is laid flat, and then supplied by a supply mechanism such as a dispenser in a dot shape or a linear shape. Further, the specific supply sequence of the relevant curable resin composition is described later.

In the method of the present invention, a method of injecting a curable resin into a gap of a laminate formed in advance (for example, a method described in JP-A-57-165411, JP-A-2001-339088, In the present specification, a curable resin composition having a higher viscosity can be used. Thereby, when the curable resin composition is cured, the hardening shrinkage can be lowered, and the mechanical strength of the resin layer after curing can be improved.

The viscosity of the curable resin composition for forming a resin film to be used is preferably from 0.2 to 50 Pa s from the viewpoint of easy handling in the steps of industrial production, transfer, and application of a large amount of the curable resin composition.

In addition, the term "viscosity of the curable resin composition for forming a resin film" as used herein means the viscosity in the temperature region at the time of carrying out the method for producing the layered product of the present invention, in particular, the supply of the curable resin composition to After the region surrounded by the sealing portion, the viscosity in the temperature region of the vacuum laminate is carried out in the order described later. For example, when the order is carried out at normal temperature, it is the viscosity of the curable resin composition at normal temperature. Therefore, although it differs according to the temperature at the time of performing these order, it is in the temperature range of 5-80 degreeC in any case. In this regard, the viscosity of the second curable resin composition used in the formation of the sealing portion is also the same.

The viscosity of the curable resin composition to be used is preferably from 1 to 20 Pa s, more preferably from 5 to 20 Pa.

A curable resin composition containing a high molecular weight curable compound (oligomer or the like) as described below can be used as the curable resin composition satisfying the above viscosity.

Since the high molecular weight curable compound can reduce the number of chemical bonds in the curable resin composition, the hardening shrinkage when the curable resin composition is cured becomes small, and the mechanical strength of the cured resin layer is enhanced. On the other hand, many high molecular weight curable compounds are highly viscous. Therefore, from the viewpoint of securing the mechanical strength of the resin layer after curing and suppressing the remaining of the bubbles, it is preferable to adjust the viscosity by dissolving the curable monomer having a small molecular weight in the high molecular weight curable compound. However, the viscosity of the curable resin composition is lowered by using a curable monomer having a small molecular weight, but the curing shrinkage at the time of curing the curable resin composition is increased, and the mechanical strength is liable to lower.

The curable resin composition to be used is preferably a photocurable resin composition. The photocurable resin composition can be hardened in a short time by using less heat energy than the thermosetting resin composition. Therefore, in the present invention, by using the photocurable resin composition, the environmental load at the time of manufacturing the laminated body can be reduced. Further, since the photocurable resin composition can be substantially cured by using several to several tens of parts, the production efficiency of the laminated body is high.

The "photocurable resin composition" refers to a material that is cured by the action of light to form a resin layer. The photocurable resin composition is, for example, the following, and can be used in a range in which the hardness of the resin layer after curing is not excessively high.

‧ A composition containing a compound having an addition polymerizable unsaturated group and a photopolymerization initiator.

‧ a polyolefin compound having 1 to 6 unsaturated groups (triallyl isocyanurate, etc.) and 1 to 6 thiols in a ratio approximately equal to the molar number of the thiol group A polythiol compound (triethylene glycol dithiol) having a composition of a photopolymerization initiator.

‧ A composition containing an epoxy compound having two or more epoxy groups and a photocationic generator.

The photocurable resin composition preferably has a group selected from the group consisting of acryloxy group and methacryloxy group from the viewpoint that the curing rate is fast and the transparency of the cured resin layer is high. At least one of the above compounds (hereinafter referred to as "(meth)acryloxy)" and a photopolymerization initiator are used.

A compound having a (meth) acryloxy group (hereinafter also referred to as "(meth) acrylate compound") is preferably a compound having 1 to 6 (meth) acryloxy groups per molecule. From the viewpoint that the resin layer after curing does not become excessively hard, it is more preferably a compound having 1 to 3 (meth) acryloxy groups per molecule.

The (meth) acrylate-based compound is preferably an aliphatic or alicyclic compound which does not contain an aromatic ring as much as possible from the light resistance of the resin layer after curing.

Further, the (meth) acrylate-based compound is more preferably a compound having a hydroxyl group from the viewpoint of enhancing the adhesion force at the interface with the substrate. The content of the (meth) acrylate-based compound having a hydroxyl group in the total amount of the (meth) acrylate-based compound is preferably 25% by mass or more, and more preferably 40% by mass or more. On the other hand, a compound having a hydroxyl group tends to cause an excessively high modulus of elasticity of the resin layer after curing, and in particular, when a (meth)acrylate having a hydroxyl group is used, the resin layer after hardening becomes used depending on the use of the laminate. The possibility of being strong. For example, when used in a front panel of a flat panel display (FPD), since the resin layer after hardening is preferably a low modulus of elasticity, a hydroxyl group-containing (meth) acrylate is contained in the total amount of the (meth) acrylate compound. The content is preferably 40% by mass or less, more preferably 30% by mass or less.

Further, for example, a laminate of a substrate made of a different material such as a glass substrate and a resin substrate such as polycarbonate may be laminated on the surface of the substrate having different surface energies so that the resin layer can exhibit a proper adhesion to any of the substrates. A resin layer having an adhesive state of a low modulus of elasticity can be used.

On the other hand, when a thin glass substrate and a thick glass substrate are laminated, the mechanical strength of the laminated body can be improved by providing a resin layer having a high modulus of elasticity and being as thin as 0.1 mm or less. The (meth) acrylate content having a hydroxyl group is set to 60% by mass or more.

The (meth) acrylate-based compound may be a compound having a relatively low molecular weight (hereinafter referred to as "acrylate monomer"), or a compound having a higher molecular weight having a repeating unit (hereinafter referred to as "(meth) acrylate-based oligo) Polymer").

The (meth) acrylate type compound may be one composed of one or more (meth) acrylate monomers, one or more (meth) acrylate oligomers, and one or more. The (meth)acrylate monomer and one or more (meth)acrylate oligomers are preferably composed of one or more acrylate oligomers or one or more acrylates. The oligomer is composed of one or more (meth)acrylate monomers. More preferably, the urethane-based oligomer (which is a curable functional group composed of one or both of an acryloxy group and a methacryloxy group) is contained for the purpose of improving the adhesion to the substrate. A curable resin composition having an average of 1.8 to 4 per molecule and a hydroxyalkyl methacrylate having a hydroxyalkyl group having 1 or 2 hydroxyl groups and 3 to 8 carbon atoms .

Furthermore, when the use of the laminate is a front panel of a flat panel display (FPD), in order to prevent the resin shrinkage during the hardening process from adversely affecting the display performance of the flat panel display (FPD), it is preferred that the cured resin layer belongs to Lower elastic modulus. Therefore, it is preferred to contain an oligomer (having an average of 1.8 to 4 hardening functional groups composed of a (meth) acryloxy group per molecule), and a hydroxyalkyl methacrylate (having a hydroxyl group number) One or two hydroxyalkyl groups having 3 to 8 carbon atoms) and one or more curable resin compositions of a (meth) acrylate monomer having no hydroxyl group. Further, the total content of the (meth) acrylate monomer having no hydroxyl group is preferably more than the above-mentioned hydroxy group-containing (meth) acrylate monomer content. Further, instead of the (meth)acrylate monomer having no hydroxyl group, a hydroxyalkyl (meth)acrylate hydroxyl group having one hydroxyl group and a hydroxyalkyl group having 12 to 22 carbon atoms may be used instead.

In the case where the (meth)acrylate-based single-system is placed under a reduced pressure in a decompression device, it is preferable to have a low vapor pressure which can sufficiently suppress the degree of volatility. When the curable resin composition contains a (meth) acrylate monomer having no hydroxyl group, for example, an alkyl (meth) acrylate having a carbon number of 8 to 22, a polyethylene glycol having a lower molecular weight or A mono(meth)acrylate or a di(meth)acrylate of a polyether diol such as polypropylene glycol is preferably an alkyl methacrylate having 8 to 22 carbon atoms.

The (meth) acrylate-based oligomer preferably has a chain (polyurethane chain, polyester chain, polyether chain, polycarbonate chain, etc.) having two or more repeating units, and (meth) A (meth) acrylate-based oligomer having a molecular structure of propylene methoxy group. The (meth) acrylate-based oligomer has a urethane bond (generally further including a polyester chain or a polyether chain) as commonly referred to as a "urethane acrylate oligomer", and two A (meth) acrylate-based oligomer of the above (meth) acryloxy group. The urethane acrylate oligomer is preferable because it can adjust the mechanical properties of the cured resin layer and the adhesion to the substrate in a wide range according to the molecular design of the urethane chain. .

The number average molecular weight of the (meth) acrylate-based oligomer is preferably from 1,000 to 100,000, more preferably from 10,000 to 70,000. When the number average molecular weight is less than 1,000, the crosslinking density of the resin layer after curing is increased, which may impair the flexibility of the resin layer. On the other hand, if the number average molecular weight is more than 100,000, the viscosity of the uncured curable resin composition may become excessive. When the viscosity of the (meth) acrylate-based oligomer is too high, it is preferable to use a (meth) acrylate-based monomer in combination to reduce the viscosity of the entire curable resin composition.

On the other hand, in the case where the second curable resin composition used for forming the sealing portion is used, it is preferable to adjust the viscosity to the range of 200 to 3000 Pa‧s, preferably containing a hardening group. One or more of the curable oligomers having an average molecular weight of 30,000 to 100,000, and one or more of the curable groups and the (meth)acrylate monomers, and the total of the oligomers and monomers (100) In the mass%), the monomer ratio is 15 to 50% by mass.

The (meth) acrylate-based oligomer is more preferably an acrylate-based oligomer capable of improving reactivity during curing.

The photopolymerization initiator may, for example, be an acetophenone-based, ketal-based, benzoin or benzoin ether-based, phosphine oxide-based, diphenylketone-based, thioxanthone-based or fluorene-based photopolymerization system. The initiator is preferably an acetophenone-based or phosphine oxide-based photopolymerization initiator. When hardening is performed by using short-wavelength visible light, it is more preferably a phosphine oxide-based photopolymerization initiator from the viewpoint of the absorption wavelength of the photopolymerization initiator. By using two or more kinds of photopolymerization initiators having different absorption wavelength bands in combination, the curing time can be shortened, and the second curable resin composition used in the formation of the sealing portion can be improved in surface hardenability.

The photocation generator can be, for example, a phosphonium salt compound or the like.

The curable resin composition may contain, for example, a polymerization terminator, a photohardening accelerator, a chain transfer agent, a light stabilizer (ultraviolet absorber, a radical scavenger, etc.), an antioxidant, a flame retardant, and then Various additives such as a property enhancer (such as a decane coupling agent), a pigment, and a dye preferably contain a polymerization terminator and a light stabilizer. In particular, the polymerization terminator contains less than the amount of the polymerization initiator, and the stability of the curable resin composition can be improved, and the molecular weight of the resin layer after curing can be adjusted.

However, depending on the use of the laminate, it is preferable to avoid the inclusion of an additive which may hinder the possibility of light penetration of the resin layer after hardening. As an example, when the laminated body is used as a front panel of a flat panel display (FPD) or a thin-film solar battery device, the former is emitted light and reflected light from a flat panel display (FPD) forming a display image, and the latter is sunlight. It will penetrate the hardened resin layer and it is therefore preferable to avoid the inclusion of additives which would impede the possibility of such light penetration. For example, the ultraviolet absorber absorbs the ultraviolet component of sunlight that penetrates the resin layer, resulting in a decrease in the amount of light incident on the thin-film solar cell device or a possibility of adversely affecting the color tone of the display image of a flat panel display (FPD). However, on the other hand, the resin layer which is transparent to sunlight is required to have light resistance, and particularly is durability against short-wavelength light such as ultraviolet rays. Therefore, in the case where an ultraviolet absorber or the like is contained, it is preferred to appropriately adjust the absorption characteristics, the blending amount, and the like.

Further, in order to improve the adhesion to the substrate and adjust the elastic modulus of the resin layer after curing, it is preferred to contain a chain transfer agent, and more preferably a chain transfer agent having a thiol group in the molecule.

Examples of the polymerization terminator include hydroquinone (2,5-di-t-butylhydroquinone, etc.), catechol-based (for tert-butylcatechol), lanthanide, and phenolthiophene. A polymerization terminator such as a hydroxytoluene system.

The photosensitizer may, for example, be a UV absorber (such as a benzotriazole-based, diphenylketone-based or salicylate-based) or a radical scavenger (hindered amine-based).

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

Since the photopolymerization initiator and various additives are placed under a reduced pressure environment, the curable resin composition is preferably a compound having a large molecular weight and a small vapor pressure under reduced pressure.

Next, in the reduced pressure environment, the other substrate is superposed on the curable resin composition supplied from the region surrounded by the sealing portion on the substrate in the above-described order. In order to achieve this step, in a state in which the surface on one side of the curable resin composition is supplied to the other substrate in the above-described order, the pair of substrates may be overlapped with the other substrate. Thereby, the curable resin composition is held between the pair of substrates and sealed.

In the present specification, the order in which the other substrate is superposed on the curable resin composition supplied to the region surrounded by the sealing portion in a reduced pressure environment is simply referred to as "vacuum lamination".

In the method for producing a laminated body of the present invention, the curable resin composition layer in the region surrounded by the sealing portion of one of the substrates is subjected to vacuum lamination in a state satisfying the following (1) to (3).

(1) The voids present in the curable resin composition layer have a contour circle diameter D _pore of a projection shape of 10 mm or less.

(2) A portion where no void is present in the curable resin composition layer, and the equivalent circle diameter D _non-pore of the projected shape is 40 mm or less.

(3) The curable resin composition layer and the void existing in the curable resin composition layer are in a state of being in contact with the sealing portion.

2 is a plan view of a substrate, a sealing portion 20 is formed on a peripheral portion of the substrate 10, and a curable resin composition layer 30 is formed in a portion surrounded by the sealing portion 20. The voids 40 are uniformly present in the curable resin composition layer 30.

In the production method of the present invention, the reason why the curable resin composition layer in the region surrounded by the sealing portion is subjected to vacuum lamination in the state satisfying the above (1) to (3) will be described below.

As described above, in the manufacturing method of the present invention, when the curable resin composition is supplied to the region surrounded by the sealing portion of the substrate, the substrate having the sealing portion is laid flat, and the substrate is sealed by a supply mechanism such as a dispenser. The resin composition is supplied in a dot or a line. When the dispenser is used in the supply mechanism, the nozzle form to which the curable resin composition is supplied is not particularly limited, and for example, the single-point nozzle 100 shown in Fig. 8 can be used, and the multi-point nozzle shown in Figs. 9 to 11 can be used. (Branch nozzles) 101, 102, 103, any one of the multi-point nozzles (branch nozzles) 104 shown in Fig. 17. In Fig. 17, a multi-point nozzle (branching nozzle) 104 is used to form a plurality of vibration curves 30b, but a multi-point nozzle (branch nozzle) may be used to form one vibration curve having a large thickness. Further, a slit nozzle may be attached to the multi-point nozzles (branch nozzles) 101, 102, and 103 as shown in Figs. 9 to 11 or the tip end of the multi-point nozzle (branching nozzle) 104 as shown in Fig. 17. In the above-mentioned "single-point nozzle", the front end nozzle of the curable resin composition supply means (dispenser) in which the curable resin composition is dropped on the substrate is composed of one; the "multi-point nozzle" means hardenability. The front end nozzle of the curable resin composition supply means (dispenser) on which the resin composition is dropped on the substrate is composed of a plurality of members; the "branch nozzle" is a curable resin which drops the curable resin composition onto the substrate. The front end portion of the composition supply mechanism (dispenser) is branched into a plurality of nozzles.

The third (a) to (c) diagrams are time-dependent changes of the curable resin composition in which the substrate is dispersed in a dot shape in a region surrounded by the sealing portion.

In the third (a), a state in which the curable resin composition is dropped from a single-point nozzle at the tip end of the curable resin composition supply means (dispenser), and the substrate 10 is surrounded by the sealing portion 20 In the middle, the curable resin composition 30 is dispersed in a dot shape.

When the curable resin composition collapses over time, the curable resin composition dispersed in a dot shape is in contact with each other, and as shown in FIG. 3(b), a void is formed inside. In the state of 40, the area surrounded by the sealing portion 20 will expand in a planar shape.

Then, if the elapsed time elapses, the void 40 is destroyed, and as shown in Fig. 3(c), the curable resin composition 30 is uniformly present in the region surrounded by the sealing portion 20.

The inventors of the present invention found that when the vacuum laminate is applied, the curable resin composition which is dispersed and dropped in the region surrounded by the sealing portion exists in any of the states (3) to (c), and at this time, The state of the curable resin composition affects the state of the subsequent curable resin composition layer, and more specifically, the laminated body after vacuum lamination (that is, the curable resin composition layer is sandwiched between a pair of substrates and sealed When it is placed in a pressure environment higher than a reduced pressure environment, it affects the presence or absence of voids in the curable resin composition layer. The inventors of the present invention have found that the voids disappear in a state in which the laminated body is placed in a pressure environment higher than a reduced pressure environment, and it is preferable to look at the state in the third (c) state. Fig. 3(b), but not the case, but as shown in Fig. 3(b), it is preferable to carry out vacuum lamination in the presence of a certain size of void.

Although detailed later, the laminated body after the vacuum lamination is placed under a higher pressure environment than the vacuum-decompressed pressure-reduced environment (for example, at atmospheric pressure. In the present specification, the vacuum-decomposed environment is implemented. In the next step, that is, in a pressure environment higher than the above-described decompression environment, it is referred to as "in the second pressure environment" as compared with the above-described decompression environment (hereinafter, in the present specification, the order is referred to as "decompression". The situation of the environment). By increasing the environmental pressure caused by the release of the decompression environment, the pair of substrates are pressed in the direction in which they are in close contact with each other, and the void volume remaining in the curable resin composition layer is reduced by the differential pressure of the environment. The entire sealed space sealed by the pair of substrates and the sealing portion is uniformly filled with the curable resin composition. In addition, in the laminated system after the vacuum lamination is performed, the curable resin composition for forming a resin layer sealed by the two substrates and the sealing portion is not yet cured, and this is a so-called "layer precursor". In addition, a layered state material in which the curable resin composition for forming a resin layer is not cured, and a material in which the resin layer forming composition is cured is also referred to as a "layered body".

However, depending on the state of the curable resin composition at the time of performing the vacuum lamination, the above-described action due to the release of the decompression environment cannot be sufficiently exhibited, and voids remain in the curable resin composition layer after the decompression environment is released. This point will be described with reference to Figs. 4 to 6 .

In the case where the vacuum-curable resin composition is subjected to vacuum lamination in the state shown in Fig. 3(a), the state of the curable resin composition after vacuum lamination and after the decompression environment is released is shown in the fourth (a) to (d). Fig. 4(a) corresponds to Fig. 3(a). However, the sealing portion formed at the peripheral portion of the substrate is omitted. This point is also the same in the fourth (b) to (d) and the fifth and sixth figures which will be described later. 4(b) is a state diagram of a curable resin composition when vacuum lamination is performed, and 4(c) and (d) are diagrams showing a state of a curable resin composition after the decompression environment is released, showing that the decompression environment is released. The state of the subsequent curable resin composition changes over time.

As shown in Fig. 4(a), when the curable resin composition 30 is vacuum-laminated in a state where the substrate 10 is dot-dispersed, as shown in Fig. 4(b), it is hardened by a dot-like dispersion. The resin compositions 30 are in contact with each other, and the curable resin composition spreads in a planar shape on the substrate 10. However, in the layer of the curable resin composition 30 which spreads on the surface, in addition to the uniformly dispersed small voids 40, there are irregular voids 41 which are irregularly present.

As shown in the fourth (c) and (d), after the pressure reduction environment is released, the voids 40, 41 existing in the layer of the curable resin composition 30 are reduced over time, but the large gaps 41 are irregularly present. It does not eliminate and remains in the state of the layer. The state in which the void remains is not only the state described in the fourth to sixth figures, but also various states.

In the fifth (a) to (d), when the vacuum resin composition is subjected to vacuum lamination in the state shown in Fig. 3(b), the state of the curable resin composition after vacuum lamination and after a reduced pressure environment is shown. The relationship between the curable resin composition in the figure (5) and the void is somewhat different, but corresponds to the third (b) diagram. Fig. 5(b) is a state diagram of the curable resin composition at the time of the vacuum lamination, and the fifth (c) and (d) are diagrams showing the state of the curable resin after the decompression environment is released, and are relieved by the reduced pressure environment. The state of the subsequent curable resin composition changes over time.

As shown in Fig. 5(a), the voids 40 present in the layer of the curable resin composition 30 are small, and the gaps 40 are relatively small, and are uniformly present in the layer. When the vacuum lamination is performed in the state, as shown in Fig. 5(b), the state of the curable resin composition does not change before and after the vacuum lamination, but as shown in Fig. 5(c), In the reduced pressure environment, the voids 40 present in the layer of the curable resin composition 30 are reduced, and then, as shown in Fig. 5(d), the voids present in the layer are eliminated.

In the case where the vacuum-hardened resin composition is subjected to vacuum lamination in the state shown in Fig. 3(c), the state of the curable resin composition after vacuum lamination and after the decompression environment is released is shown in Fig. 6(a) to (d). Fig. 6(a) is equivalent to Fig. 3(c). 6(b) is a state diagram of a curable resin composition when vacuum lamination is performed, and 6th (c) and (d) are diagrams showing a state of a curable resin composition after the decompression environment is released, and after the decompression environment is removed, The state of the curable resin composition changes over time.

As shown in Fig. 6(a), when the hardened resin composition 30 on the substrate 10 is formed into a uniform state without forming a void, as shown in Fig. 6(b), The vacuum lamination is performed to form a large void 41 along the outer edge of the layer of the curable resin composition 30. As shown in the sixth (c) and (d), the large gap 41 is in a state in which the reduced pressure environment is reduced over time, but remains in the layer without being eliminated.

In the production method of the present invention, a curable resin composition for forming a high-viscosity resin film having a viscosity of 0.2 to 50 Pa‧s is used, and the thickness of the curable resin composition layer formed in the region surrounded by the sealing portion is also 30 μm. Since the above is relatively thick, it tends to have voids remaining in the curable resin composition layer after the pressure reduction environment is released. Therefore, in this state, it is important to carry out vacuum lamination in a state in which the above (1) to (3) are satisfied, and it is important that no void remains in the curable resin composition layer after the decompression environment is released.

When the curable resin composition layer satisfies the above (1) to (3), the entire layer of the curable resin composition 30 including the interface with the sealing portion 20 is present in the voids in the layer of the curable resin composition 30. 40 is small, and in a state where the gaps between the gaps 40 are small, they are uniformly present in the layer. Therefore, by performing vacuum lamination and then releasing the decompression environment, the voids existing in the layer of the curable resin composition 30 can be reduced and eliminated.

In the above (1) and (2), the "projection shape of the voids present in the curable resin composition layer" and the "projection shape of the portion where the voids are not present in the curable resin composition layer" means voids. The projected shape of the surface of the curable resin composition layer and the projected shape of the portion where the void is not present on the surface of the layer. Hereinafter, in the present specification, the equivalence circle diameter of the void projection shape is simply referred to as "the equivalence circle diameter of the void", and the equivalence circle diameter of the projection shape in which the void portion is not present is simply referred to as "the equivalence circle in which the void portion is not present". diameter".

Further, the above (1) means all the voids present in the curable resin composition layer, and the projected shape has an equivalence circle diameter D _pore of 10 mm or less. Further, the above (2) means all the void-free portions present in the curable resin composition layer, and the equivalence circle diameter D _{non-pore of} the projected shape is 40 mm or less.

2 is a state diagram of a curable resin composition in which a curable resin composition is dropped onto a substrate in a dot shape using a single-point nozzle of a curable resin composition supply means (dispenser), and in the same figure, D _{non -pore} means "equal diameter of the void portion", and D _pore means "equal diameter of the void".

In addition, the fifteenth figure is a column-shaped multi-point nozzle which uses a curable resin composition supply means (dispenser), and after the multi-point nozzle is swung, the curable resin composition is dropped onto the substrate in a linear form. In the figure of the composition of the curable resin, in the same figure, D _non-pore means "equivalent circle diameter in which no void portion exists", and D _pore means "equal diameter of void". Further, the above-mentioned "equivalent circle" is not limited to a circular shape, and various shapes including a circular shape, an elliptical shape, and a curved surface shape are widely encompassed. When it is not a circular shape, the equivalent circle diameter of the shape refers to the average diameter of the major axis, the minor axis, and the major axis and the minor axis.

When the curable resin composition layer does not satisfy the above (1), since a large void exists in the layer of the curable resin composition 30, even if vacuum lamination is performed and then the decompression environment is released, the existence cannot be made. The voids in the layer of the curable resin composition are eliminated, and a state in which voids remain in the layer remains.

In the production method of the present invention, the voids present in the curable resin composition layer have a contour circle diameter D _{pore of a} projection shape of preferably 3 mm or less.

When the curable resin composition layer does not satisfy the above condition (2), since the voids 40 present in the layer of the curable resin composition 30 are large from each other, and/or because the void 40 does not exist in the layer Since it is evenly distributed, even if the vacuum layer is applied and the pressure-reduced environment is released, the voids existing in the curable resin composition layer cannot be eliminated, and the voids remain in the layer.

In the production method of the present invention, the portion of the curable resin composition layer where no void is present, and the equivalence circle diameter D _{non-pore of} the projected shape is preferably 15 mm or less.

When the curable resin composition layer does not satisfy the above (3), the curable resin composition layer is often in contact with the sealing portion, or the void is often in contact with the sealing portion. In the former case, as described with reference to FIGS. 6(a) to 6(d), a large gap 41 is formed along the outer edge of the layer of the curable resin composition 30 by performing vacuum lamination. Such a large gap cannot be eliminated by the release of the reduced pressure environment, and a state in which a void remains in the layer is exhibited. In the latter case, when the vacuum laminate is applied, a large gap exists along the outer edge of the curable resin composition layer. Therefore, even if vacuum deposition is performed and then the pressure reduction environment is released, the presence of the curable resin composition layer cannot be caused. The voids are eliminated, and a state in which voids remain in the layer is present.

In the production method of the present invention, in order to carry out the vacuum lamination in a state in which the above (1) to (3) are satisfied, the order in which the curable resin composition is dispersed and dropped by using a dispenser may be carried out in the following order.

The curable resin composition in which the substrate is dispersed in a dot shape in a region surrounded by the sealing portion is changed from the time t after the dispersion and the time t, and the state is changed as shown in the seventh (a) to (e). Here, the seventh (a) is a state in which the curable resin composition 30 is dispersed and dropped on the region surrounded by the sealing portion 20 (that is, t=0), and is surrounded by the sealing portion 20. In the region, the curable resin composition 30 is dispersed in a dot shape. Then, the curable resin composition 30 which is dispersed in a dot shape is in contact with each other, and as shown in Fig. 7(b), the curable resin composition 30 is expanded into a planar shape in a region surrounded by the sealing portion 20. in dropping from the time point t ₁ dispersed in curable resin layer 40 to form voids 30 in the elapsed time. Then, the void 40 becomes smaller as time passes, and as the time t ₂ elapses from the dispersion dripping, as shown in Fig. 7(c), the equivalence circle diameter D ₁ of the void 40 satisfies the above (1). State, that is, D _pore = 10mm. Then, the gap 40 becomes smaller again by a further, in dropping point elapsed from the time t ₃ the dispersion, such as section 7 (d), (e) shown in FIG, 40 will eliminate the void. The time t ₂ varies depending on the size of the substrate, but is preferably about 30 to 1800 seconds and 50 to 1000 seconds.

When a dispenser having a nozzle having a number of dropping portions of the curable resin composition is used, when the curable resin composition is dropped onto a predetermined region, the pressure-reducing layer may be applied in the range of time t shown by the following formula.

t ₂ ≦t≦t ₃

However, according to the size of the substrate, it is not possible to realize the dripping curable resin composition, and as shown in Fig. 8, the nozzle 100 is dropped while the substrate 10 is moved by the region surrounded by the sealing portion 20, and the curable resin composition is dropped. 30. In this case, as a result of the time difference from the start of the dropping to the end of the dropping, the shape of the curable resin composition is changed depending on the period of the dropping, and as a result, it may be present in the layer of the curable resin composition 30. The void 40 has a problem that the equivalence circle diameter D _pore becomes uneven.

When the single-point nozzle 100 shown in Fig. 8 is used instead of the multi-point nozzles (branch nozzles) 101 and 102 as shown in Figs. 9, 10, the time required from the start of the dropping to the end of the dropping is shortened. Therefore, the above problems can be alleviated, but the problem cannot be completely solved.

Therefore, as shown in FIGS. 8 to 10, when the curable resin composition 30 is dropped while the nozzles 100, 101, and 102 are moved while the substrate 10 is surrounded by the sealing portion 20, the sealing portion 20 is formed by the sealing portion 20. In the entire area enclosed, it is necessary to pay attention to satisfying the above (1) to (3). Specifically, it is necessary to carry out vacuum lamination in a time period from the initial dropping to t ₃ and from the last dropping to t ₂ or more. For this purpose, it is necessary to set the dropping condition so that the required time ts from the start of the dropping to the end of the dropping is satisfied by the following formula:

t _s <(t ₃ -t ₂ )

In the above-mentioned problem that occurs when the curable resin composition is dropped while the nozzle is moved by the nozzle, the shape of the curable resin composition to be dropped is forcibly changed by the dripping period. More specifically, the above-mentioned problem can be solved by the equivalent circle diameter of the projected shape of the mandatory expansion-curable resin composition (hereinafter referred to as "the equivalent circle diameter of the curable resin composition" in the present specification).

As shown in Fig. 11, when the multi-point nozzle (branch nozzle) 103 is moved while the multi-point nozzle (branch nozzle) 103 is moved, the hard resin composition 30 is dropped, and the hardening is performed in accordance with the period of dropping. The shape of the resin composition may be in a different state. When focusing on the equivalence circle diameter of the curable resin composition, the curable resin composition dropped at an earlier stage becomes larger in diameter than the curable resin composition dropped at a later stage. Since the substrate 10 has various sizes, it is difficult to prepare a nozzle that can be dropped on the entire surface of the substrate on the cost side, and therefore, a multi-point nozzle is often used.

On the other hand, by forcibly expanding the equivalence circle diameter of the curable resin composition dropped at a later stage, the difference in the equivalence circle diameter of the curable resin composition due to the dropping period can be reduced, and even more It is also possible to make the equivalence circle diameter of the dripped curable resin composition uniform. In Fig. 12, the curable resin composition 30 existing in the region surrounded by the sealing portion 20 of the substrate 10 can be made by forcibly expanding the equivalence circle diameter of the curable resin composition dropped at a later stage. The contour circle has a uniform diameter.

The method of forcibly expanding the equivalence circle diameter of the hardened resin composition that has been dropped, as shown by the arrow in Fig. 12, is mandatory by causing the substrate 10 to be relatively oscillated with the multi-point nozzle (branching nozzle) 103. A method of expanding the equivalent circle diameter of a curable resin composition. In this case, the substrate 10 may be oscillated, or the multi-point nozzle (branch nozzle) 103 may be oscillated. Further, by bringing the curable resin composition after the dropping into contact with any projection such as a stirrer, it is possible to forcibly expand the equivalence circle diameter of the curable resin composition.

The extent to which the equivalence circle diameter of the hardened resin composition that has been dropped is expanded can be carried out by following the following ideas.

Fig. 13 is a graph showing the elapsed time t (sec) after dropping, when a certain curable resin composition is dropped, at the time point (i.e., t = 0), the equivalence circle diameter of the curable resin composition is d ₀ . A graph showing the relationship between the equivalence circle diameter d (mm) of the curable resin composition. As shown in the figure, the curable resin composition which has been dropped when the time t _a , t _b , and t _n have elapsed from the start of the dripping, is expanded by the equivalence circle diameter of the curable resin composition to d _a Further, d _b and d _n can make the equivalent circle diameter of the curable resin composition at the time of completion of the dropping uniform.

The inventors of the present invention experimentally confirmed that the elapsed time t after the dropping and the increment (d-d0) of the equivalence circle diameter d of the curable resin composition establish the following relationship:

Dd ₀ =α×t ^1/2

In the formula, α is a coefficient determined by the viscosity of the curable resin composition, the wettability of the substrate surface to the curable resin composition, and the volume of each of the curable resin compositions that have been dropped.

According to this formula, by expanding the diameter of the equivalence circle of the hardened resin composition to be dropped, the equivalence circle diameter of the curable resin composition at the time of completion of the dropping can be made uniform. Further, when the substrate 10 and the nozzle 103 are relatively oscillated, when the equi-circular diameter of the deposited curable resin composition is expanded, the amplitude S of the wobble is set to the equivalent circle obtained by the above formula. The increment of diameter d (dd ₀ ) can be.

The relationship between the elapsed time t after the dropping, the equivalence circle diameter d of the curable resin composition, and the equivalence circle diameter D _pore of the voids present in the curable resin composition layer will be further described.

Fig. 14 is a graph showing the relationship between the elapsed time t after dropping, the equivalence circle diameter d of the curable resin composition, and the equivalence circle diameter D _pore of the voids present in the curable resin composition layer. As is apparent from the figure, as the elapsed time t after the dropping increases, the equivalence circle diameter d of the curable resin composition also increases, and the equivalence circle diameter D _{pore of the} voids decreases. The t ₁ , t ₂ and t ₃ in the graph are synonymous with the seventh graph. That is, the elapsed time t _1, a gap 40 is formed in the layer of curable resin composition 30 is dropped from the dispersion since, when the elapsed time t _2, the equivalent circular diameter of the void of D _pore 40 = 10mm, the elapsed time At t ₃ , the gap 40 will be eliminated.

As described above, when the curable resin composition is dripped, the pressure-reducing layer may be applied in the time t shown by the following formula.

t ₂ ≦t≦t ₃

According to the pattern of Fig. 14, when the pressure reduction laminate is applied, the equivalence circle diameter d of the curable resin composition and the equivalence circle diameter D _{pore of the} voids may be within the following ranges.

d ₂ ≦d≦d ₃

D ₃ ≦D _pore ≦D ₂

When the curable resin composition is dropped while moving the nozzle while the substrate is moved by the sealing portion, the substrate and the nozzle are relatively oscillated, and the equivalent of the curable resin composition that has been dropped is obtained. The diameter of the circle is appropriately expanded in accordance with the period of the dropping, so that the equivalence circle diameter of the curable resin composition at the end of the dropping can be made uniform. Here, the time difference between the first drop and the Xth drop is set to T _x-1 , and the hardened resin composition dropped for the first time has an equivalence circle diameter expansion due to the elapse of time T _x-1 . When Δd _x-1 and the X-th swing amplitude are S _x , when the X-th swing amplitude S _{x is} S _x =Δd _x-1 , the curable resin composition can be obtained at the end of the dropping. The equivalent circle diameter is uniform.

Here, from the viewpoint of shortening the time from the start of the dripping to the time of performing the vacuum lamination, it is preferable to make the equivalence circle diameter of all the curable resin compositions d ₂ immediately before the vacuum lamination is performed. In order to achieve this, when the equivalence circle diameter of the last dripped curable resin composition is set to d _f , it is preferable to use the difference (d ₂ -d _f ) between d ₂ and d _f as the amplitude from the first time. The drip starts to swing. At this time, the n-th swing amplitude S _n is S _n =Δd _x-1 +(d ₂ -d _f ).

In the case where the curable resin composition is applied in a linear form by using a dispenser, the layer of the curable resin which is present in the region surrounded by the sealing portion of the substrate must satisfy the above (1) to the case of performing vacuum lamination. (3).

In the production method of the present invention, in order to carry out the vacuum lamination in a state in which the above (1) to (3) are satisfied, the order in which the curable resin composition is applied in a line may be carried out in the following order.

Fig. 15 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

In Fig. 15, the application pattern of the curable resin composition forms vibration curves 30a, 30b which are oriented with respect to the columnar multi-nozzle of the curable resin composition supply means (dispenser) ( In the case of Fig. 15, the longitudinal direction of the substrate 10 is repeated in the vertical direction (the short-side direction of the substrate 10 in the case of Fig. 15) by a constant period X and an amplitude Y. This vibration curve is a pattern coating film having a predetermined cycle period and amplitude of a curable resin composition obtained by applying a curable resin composition to the substrate by relatively swinging the substrate and the nozzle. By applying the curable resin composition to the vibration curves 30a and 30b, the substrate 10 can be uniformly dispersed in a small gap 40 in the region surrounded by the sealing portion 20. Here, it should be noted that, as will be described later using Fig. 16, the formation period of the vibration curves 30a, 30b and the formation period of the gap 40 are generally not coincident, and the shape of the vibration curves 30a, 30b is changed with time. A gap 40 is formed. Here, when the curable resin composition is applied in a line shape, the coating method is preferably applied only from one of the long side or the short side of the substrate. It is preferable to apply the coating from the long side and the short side of the substrate in such a manner that the applied curable resin composition overlaps and the resin thickness is thicker and thinner. Further, there is a possibility that bubbles are caught in the overlapping portion, and as a result, air bubbles are likely to occur in the final product, and thus it is preferable to avoid them.

Further, in order to uniformly disperse the small gaps 40 in the region surrounded by the sealing portion 20, it is understood from Fig. 15 that the displacements of the mutually adjacent vibration curves 30a, 30b must be opposite to each other.

Here, from the viewpoint that the small gap 40 in the region surrounded by the sealing portion 20 of the substrate 10 is in a uniformly dispersed state, when the thickness of the vibration curve 30a at the time of starting supply is set to m (mm), the period X ( Mm) and the amplitude Y (mm) preferably satisfy the following formula:

2.1×m≦X≦10×m

(2.1×m)/2≦Y≦(10×m)/2

Better system cycle X and amplitude Y satisfy the following formula:

3×m≦X≦6×m

(3×m)/2≦Y≦(6×m)/2

Further, in the above description, the preferred range of the period X and the amplitude Y is described by the relationship with the thickness of the vibration curve 30a, and the relationship between the thickness and the thickness of the vibration curve 30b is also the same. For this point, the preferred ranges of d _(sr) and d _(rr) described below are also the same.

In addition, when vacuum lamination is carried out, since it is necessary to satisfy the above (2), that is, a portion where no void exists in the curable resin composition layer, the equivalence circle diameter D _{non-pore of} the projected shape must be 40 mm or less. The period X is preferably 40 mm or less, more preferably 15 mm or less. Further, the amplitude Y is preferably 20 mm or less, more preferably 7.5 mm or less.

Further, from the viewpoint that the sealing portion 20 does not cause a large gap, the shortest distance d _(sr) between the vibration curve 30a and the sealing portion 20 preferably satisfies the following formula:

d _(sr) ≦ 2.5 × m

At this time, the shortest distance d _(sr) between the vibration curve 30a and the sealing portion 20 is required to satisfy the above equation in relation to the respective portions of the sealing portion 20. That is, the shortest distance between the upper sealing portion 20 and the vibration curve 30a in the figure, and the shortest distance between the sealing portion 20 and the vibration curve 30b on the lower side in the drawing, the sealing portion 20 on the left side or the right side in the drawing, and the vibration curve are required. The shortest distance between 30a or the vibration curve 30b all satisfies the above formula.

The shortest distance d _(sr) between the vibration curve 30a and the sealing portion 20 preferably satisfies the following formula:

d _(sr) ≦0.5×m

The lower limit of the shortest distance d _(sr) between the vibration curve 30a and the sealing portion 20 is not particularly limited, and the vibration curve 30a may be in contact with the sealing portion 20. However, if the vibration curve 30a overlaps with the sealing portion 20, since only the thickness of the portion of the curable resin composition layer becomes large, it is preferable that the vibration curve 30a and the sealing portion 20 do not overlap.

Further, from the viewpoint of not causing a large gap between the vibration curves 30a and 30b, it is preferable that the shortest distance d _{(rr) of the} adjacent vibration curves 30a and 30b satisfies the following formula:

d _(rr) ≦ 5 × m

In this case, the relationship between the vibration curves 30a and 30b and the thickness m at the time of starting supply preferably satisfies the above formula.

The shortest distance d _{(rr) of the} adjacent vibration curves 30a, 30b preferably satisfies the following formula:

d _(rr) ≦m

The shortest distance d _(rr) lower limit value of the adjacent vibration curves 30a and 30b is not particularly limited, and the adjacent vibration curves 30a and 30b may be in contact with each other. However, if the vibration curves 30a and 30b are overlapped, since only the thickness of the portion of the curable resin composition layer becomes large, it is preferable that the vibration curves 30a and 30b do not overlap.

Fig. 16 is a view corresponding to a partially enlarged view of Fig. 15. Here, in order to show the temporal change of the shape of the vibration curves 30a and 30b, the state in which the interval between the adjacent vibration curves 30a and 30b is widened is shown. The vibration curves 30a and 30b of Fig. 16 are indicated by broken lines, and the thickness thereof is enlarged over time, so that the adjacent vibration curves 30a and 30b are in contact with each other to form the gap 40.

Further, when the adjacent vibration curves 30a and 30b are formed, when the vibration curves 30a and 30b are in contact with each other, the gap 40 is formed at the time when the vibration curves 30a and 30b are formed.

Here, the diameter E (mm) of the formed void 40, more specifically, the diameter E (ie, the equivalence circle diameter) of the void 40 in the amplitude Y direction of the vibration curves 30a, 30b, is as follows Shown as follows:

E=2Y-2m

When the vacuum lamination is carried out, it is preferable that the diameter E of the void 40 satisfies the following formula, that is, the state satisfying the above (1) to (3), and the system satisfies the above (1) and (2).

(Y+d _(rr) )/10≦E≦Y+d _(rr)

In addition, the above description is based on the assumption that the amplitude Y and the thickness m of the vibration curves 30a and 30b are equal. When the amplitudes Y _a , Y _b and the thicknesses m _a and m _b of the vibration curves 30a and 30b are different, the diameter E of the gap 40 is expressed by the following formula:

E=Y _a +Y _b -(m _a +m _b )

(Y _a +Y _b +2d _(rr) )/20≦E≦(Y _a +Y _b +2d _(rr) )/2

In addition, from the viewpoint of being easy to industrially high-speed and curved coating, and the ratio between the curable resin composition and the void in the region surrounded by the sealing portion is appropriate, the vibration curve thickness m at the start of supply is started. It is preferably 1 to 40 mm, more preferably 3 to 15 mm.

In order to apply the curable resin composition to the predetermined vibration curves 30a and 30b, as shown in Fig. 17, a nozzle that can move in either of the x-axis and the y-axis in the drawing (multi-point nozzle (including The branch nozzle)) 104 is coated with a curable resin composition.

As described in the case where the curable resin composition is dispersed in a dot shape, the curable resin composition after the dropping is extended with time, and the diameter of the equivalent circle is increased. The same phenomenon is caused when the curable resin composition is applied in a line shape, and the thickness of the vibration curves 30a and 30b becomes thicker with time.

Therefore, as shown in Figs. 18 and 19, it is preferable to apply the coating direction (the arrow shown in Fig. 18) when the vibration curve 30a is formed, and the coating curve 30b adjacent to the vibration curve 30a. The cloth direction (indicated by the arrow in Fig. 19) is set to the opposite direction, and the reason is that the size of the gap 40 existing in the region surrounded by the sealing portion 20 can be made uniform as shown in Fig. 20.

Further, although the amplitudes Y of the vibration curves 30a and 30b are the same in the fifteenth to twenty-fifthth embodiments, the vibration curve 30a' and the amplitude Y of the vibration curve 30b' may be different as shown in Fig. 21.

Further, in the figures 15 to 21, the patterns of the adjacent curable resin composition layers each form a vibration curve, but as shown in Fig. 22, the pattern of the adjacent curable resin composition layer may be Only one of them is the vibration curve 30a", and the other is the straight line 30c.

However, in this case, the closest to the sealing portion 20 must be a non-linear line 30c and must be a vibration curve 30a".

Further, it is preferable that the period X and the amplitude Y of the vibration curve 30a" satisfy the above conditions in accordance with the relationship between the thickness m of the vibration curve at the time of starting supply.

Further, the shortest distance d _(sr) between the vibration curve 30a" and the sealing portion 20 preferably satisfies the above condition in accordance with the relationship between the thickness m of the vibration curve at the time of starting supply.

Furthermore, the shortest distance d _(rr) between the adjacent vibration curve 30a" and the straight line 30c is preferably between the adjacent vibration curves according to the relationship between the thickness m of the vibration curve at the start of supply. The condition described in the shortest distance d _(rr) .

Further, the gap E (mm) formed by the contact of the adjacent vibration curve 30a" with the straight line 30c, more specifically, the diameter E of the gap in the amplitude Y direction of the vibration curve 30a" (ie, Equivalent circle diameter), which preferably satisfies the following formula: (Y+d _(rr) ) / 20 ≦ E ≦ (Y + d _(rr) ) / 2, in Figures 15 to 22, on the substrate 10 A pattern of a layer of the curable resin composition is formed in the longitudinal direction. However, as shown in FIG. 23, a pattern (30e, 30f) of a layer of the curable resin composition may be formed in the short-side direction of the substrate 10.

Further, in the fifteenth to twenty-fifthth drawings, the pattern of the curable resin composition layer forms a vibration curve, but as shown in Fig. 24, the straight lines 30f and 30g of the wide portion 31 may be provided in a predetermined period X. Also in this case, the conditions described when the curable resin composition is applied to the vibration curves 30a and 30b are also applicable. However, the maximum width of the wide portion 31 satisfies the condition of the amplitude Y described in the vibration curve.

In the method for producing a laminate of the present invention, the vacuum laminate can be carried out in the following order. In the present invention, the substrate on the surface on which the sealing portion and the curable resin composition layer are formed is referred to as "one of the substrates", and the substrate on the surface is not formed. It is "another substrate."

One of the substrates was placed in a decompression device, and the substrate was placed flat on the fixed support disk in the decompression device to face up in a state in which the curable resin composition layer was placed.

A moving support mechanism that can move in the vertical direction is provided in an upper portion of the pressure reducing device, and another substrate is attached to the moving support mechanism. Here, when a thin film system solar cell device is formed on the surface of another substrate, the surface on the side on which the thin film system solar cell device is formed faces downward. Further, when the use of the laminated body is a flat panel display (FPD), the surface on the side where the image is displayed faces downward. Further, when the antireflection layer is provided on the surface of the other substrate, the surface on the side where the antireflection layer is not formed faces downward.

The other substrate is placed over one of the substrates and is not in contact with the layer of the curable resin composition. That is, the curable resin composition layer on one of the substrates is not brought into contact with the other substrate but is opposed to each other.

Alternatively, a moving support mechanism movable in the up and down direction may be provided in a lower portion of the decompression device, and one of the substrates may be placed above the moving support mechanism. At this time, the other substrate is mounted on the fixed support disk provided on the upper portion of the pressure reducing device, and one of the substrates is opposed to the other substrate.

Furthermore, one of the substrates and the other of the substrates may be supported by upper and lower moving support mechanisms provided in the decompression device.

After one of the substrates and the other substrate are placed at a predetermined position, the inside of the pressure reducing device is depressurized to form a predetermined reduced pressure environment. If possible, one of the substrates and the other substrate may be placed at a predetermined position in the decompression device after the decompression operation or the formation of the predetermined decompression environment.

After a predetermined decompression environment is formed inside the decompression device, the other substrate supported by the moving support mechanism is moved downward, and the other substrate is superposed on the hard resin composition layer on one of the substrates.

By overlapping, the curable resin composition is sealed in the surface of one of the substrates, the lower surface of the other substrate, and the space surrounded by the sealing portion.

When overlapping, the curable resin composition is squeezed and diffused by the weight of the other substrate itself, the pressing from the moving support mechanism, etc., so that the space is filled with the curable resin composition, and then the decompression is released. In the environment, a void-free curable resin composition layer is formed.

The reduced pressure environment at the time of superposition is 1000 Pa or less, preferably 0.1 Pa or more. When the pressure-reduced environment is excessively low, the components (hardening compound, photopolymerization initiator, polymerization terminator, light stabilizer, etc.) contained in the curable resin composition may be adversely affected. For example, if the decompression environment is excessively low, the components may be vaporized, and it takes time to provide a reduced pressure environment. The pressure in the reduced pressure environment is preferably 1 to 100 Pa. Very good 3 to 30Pa.

The time from when the one substrate overlaps the other substrate to when the pressure-reducing environment is released is not particularly limited, and the pressure-reducing environment can be immediately released after the curable resin composition is sealed, or hardened. After the resin composition is sealed, the reduced pressure state is maintained for a predetermined period of time. By maintaining the reduced pressure state for a predetermined period of time, the curable resin composition flows in the sealed space, so that the interval between one of the substrates and the other substrate can be made uniform even by releasing the decompression environment. The sealing state can be easily maintained even in a second pressure environment which is higher than the pressure reducing environment at the time of performing vacuum lamination. The time for maintaining the reduced pressure state may be a long time of several hours or more, but from the viewpoint of production efficiency, it is preferably within 1 hour, more preferably within 10 minutes.

Then, by releasing the decompression environment and placing the pair of substrates holding the curable resin composition in a second pressure environment higher than the reduced pressure environment, one of the substrates is increased by the increase in the environmental pressure. When the other substrate is pressed in the direction in which it is in contact with each other, the curable resin composition flows in the sealed space, and the entire sealed space is uniformly filled with the curable resin composition to form a curable resin composition having no voids. Floor.

Here, the pressure in the second pressure environment is preferably 50 kPa or more higher than the pressure reduction environment in which the vacuum layer is laminated. The pressure in the second pressure environment is usually preferably from 80 k to 120 kPa. The second pressure environment may be an atmospheric pressure environment or a higher pressure. From the viewpoint of the operation such as hardening of the curable resin composition, it is possible to carry out the operation without requiring special equipment, and it is preferably an atmospheric pressure environment.

In the second pressure environment, the pressure-separating step by pressing one of the substrates and the other substrate can release the decompression of the decompression chamber of the decompression device in the decompression device that performs the vacuum lamination. The pressure-reduction chamber is adjusted to a pressure of 80 k to 120 kPa (for example, atmospheric pressure), and the curable resin composition for forming a resin layer is cured in the pressure environment, or may be decompressed from the vacuum lamination. The apparatus is moved to another chemical processing apparatus, and the inside of the hardening processing apparatus is adjusted to a pressure of 80 k to 120 kPa, and the curable resin composition for forming a resin layer is cured in the pressure environment.

The time during which the pair of substrates holding the curable resin composition is maintained in the second pressure environment higher than the reduced pressure environment is not particularly limited. When a pair of substrates holding the curable resin composition are taken out from the decompression device and moved to the hardening treatment device, and the processes until the start of hardening are performed in an atmospheric pressure environment, the time required for the process is maintained. Time in the second pressure environment. Therefore, when it is placed in an atmospheric pressure environment, there is no gap in the curable resin composition layer in the sealed space, or the void in the curable resin composition layer disappears during the process. The curable resin composition is cured. When it takes time until the void disappears, the pair of substrates holding the curable resin composition are held in the second pressure environment until the void disappears. Further, even if the time elapsed in the second pressure environment is elongated, it is usually not hindered, and the holding time in the second pressure environment can be lengthened from other necessity in the process.

The holding time in the second pressure environment may be a long time of one day or longer, but from the viewpoint of production efficiency, preferably within 6 hours, more preferably within 1 hour, from the viewpoint of further improving production efficiency, Good within 10 minutes.

Then, by curing the curable resin composition in the sealed space, a laminate having a pair of substrates and a cured layer of a curable resin composition existing between the pair of substrates is obtained.

The means for curing the curable resin composition is arbitrarily used for thermal curing or photocuring in accordance with the type of the thermosetting resin composition. However, as described above, the curable resin composition to be used is preferably a photocurable resin composition.

In the case of the photocurable resin composition, for example, a light source (ultraviolet lamp, high pressure mercury lamp, or the like) is irradiated with ultraviolet light or short-wavelength visible light, and the curable resin composition in the sealed space is cured to obtain a pair of substrates. A laminate of a cured layer of a curable resin composition existing between the pair of substrates.

Light is irradiated from the side of the transparent substrate in the pair of substrates. When both of them are transparent substrates, they can be irradiated from both sides.

In the case of a laminated system flat panel display (FPD) manufactured and a case where the flat display device uses a transmissive display device, light transmittance can be obtained by causing the device to generate an action, but most of them belong to In the state in which the operation is performed, the light-transmissive property is not obtained. Therefore, the transparent substrate serving as the protective sheet is irradiated with light that hardens the curable resin composition. On the other hand, when the flat-panel display uses a penetration-scattering type display device which is in a transparent state when it is not in operation, light from the display device side can also be utilized.

The light is preferably ultraviolet light or visible light of 450 nm or less. In particular, an antireflection layer is provided on the transparent substrate, and the antireflection layer or the resin film used in forming the antireflection layer does not penetrate the ultraviolet rays, and it is necessary to be hardened by visible light.

The laminate obtained by the production method of the present invention is suitable for use in a thin-film solar cell device or an image display device. Specific examples of the thin-film solar battery device include, for example, a thin film germanium solar cell device, a compound semiconductor solar cell device such as a chalcopyrite system or a CdTe system, and the like. On the other hand, specific examples of the video display device include, for example, a liquid crystal display device (LCD), an EL (Electrically Excited Light) display device such as an organic EL and an inorganic EL, a plasma display device, and an electronic ink type image display. A flat panel display (FPD) such as a device.

In the case of a thin-film solar cell device, a thin-film solar cell device can be formed only on one of the substrates, and a thin-film solar cell device can be formed on both of the substrates.

Example

Hereinafter, the present invention will be more specifically described based on examples. However, the present invention is not limited to this. Further, Examples 1, 7, 7, 8, 10, and 15 are examples, and other examples are comparative examples.

(example 1) (Photocurable resin composition for sealing portion formation)

a difunctional polypropylene glycol having a molecular end modified with ethylene oxide (number average molecular weight calculated from a hydroxyl value: 4000), and hexamethylene diisocyanate mixed at a molar ratio of 6 to 7. Then, it is diluted with isodecyl methacrylate (IBXA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and then subjected to a reaction in the presence of a catalyst of a tin compound to obtain a molar ratio of about 1 to 2. A 2-hydroxyethyl acrylate was added and reacted, whereby a solution of a urethane acrylate oligomer (hereinafter referred to as "UC-1") diluted with 30% by mass of isodecyl methacrylate was obtained. The hardening base of UC-1 is 2, and the number average molecular weight is about 55,000. The viscosity of the UC-1 solution at 60 ° C is about 580 Pa‧s.

90 parts by mass of the UC-1 solution and 10 parts by mass of 2-hydroxybutyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER HOB) were uniformly mixed to obtain a mixture. 100 parts by mass of the mixture, 1 part by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, manufactured by Ciba Specialty Chemicals, IRGACURE 184), 0.1 part by mass of bis(2,4, 6-trimethylbenzimidyl)-phenylphosphine oxide (photopolymerization initiator, manufactured by Ciba Specialty Chemicals, IRGACURE 819), 0.04 parts by mass of 2,5-di-t-butylhydroquinone (polymerization termination) The agent () 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 photocurable resin composition X for forming a sealing portion.

The photocurable resin composition X for sealing portion formation was placed in a container and opened in a decompression device, and the inside of the decompression device was depressurized to about 20 Pa for 10 minutes to perform a defoaming treatment. The viscosity of the photocurable resin composition X (that is, the second curable resin composition) for forming the seal portion at 25 ° C was measured, and it was about 1400 Pa s.

A substrate made of soda lime glass having a length of 1100 mm, a width of 900 mm, and a thickness of 2 mm (hereinafter referred to as "substrate A", which corresponds to one of the substrates of the present invention) is disposed at a position of 5 mm from the outer peripheral portion, and the photocuring property for forming the sealing portion is applied. The resin composition X forms a sealing portion having a thickness of 1 mm.

(Photocurable resin composition for resin layer formation)

1 mole of difunctional polypropylene glycol (number average molecular weight calculated from hydroxyl value: 2000), 1 mole of diethylene glycol modified with ethylene oxide at the end of the molecule (based on hydroxyl value) The calculated number average molecular weight: 4000), and 1 mole of ethylene glycol were uniformly mixed to obtain a polyol mixture. The polyol mixture is mixed with isophorone diisocyanate at a molar ratio of 5 to 6 to obtain a prepolymer in the presence of a tin compound catalyst, and about 1 to 2 in the prepolymer. The molar ratio of 2-hydroxyethyl acrylate was added to the molar ratio to obtain a urethane acrylate oligomer (hereinafter referred to as "UA-2"). The hardening base of UA-2 is 2, the number average molecular weight is about 19,000, and the viscosity at 25 ° C is about 1300 Pa‧s.

60 parts by mass of UA-2 and 40 parts by mass of 2-hydroxybutyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER HOB) were uniformly mixed, and uniformly dissolved in 100 parts by mass of the mixture. 0.2 parts by mass of bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (photopolymerization initiator, manufactured by Ciba Specialty Chemicals, IRGACURE 819), 0.04 parts by mass of 2,5- The photo-curable resin composition Y for forming a resin layer was obtained by using a di-tert-butylhydroquinone (polymerization terminator) and 0.3 parts by mass of a UV absorber (manufactured by Ciba Specialty Chemicals Co., Ltd., TINUVIN 109).

The resin layer-forming photocurable resin composition Y is placed in a container and placed in a decompression device in an open state, and the inside of the decompression device is decompressed to about 20 Pa for 10 minutes, thereby performing defoaming treatment. . The viscosity of the photocurable resin composition Y for forming a resin layer at 25 ° C was measured, and it was about 14 Pa ‧ .

Then, the resin layer-forming photocurable resin composition Y was dispersed and dropped in the region surrounded by the sealing portion in the region surrounded by the sealing portion by using a multi-point nozzle type dispenser as described below.

(Dispersed dropping conditions)

‧ Dropping pitch: 15mm.

‧ Thickness of the curable resin composition layer: 0.8 mm (drop amount: 0.18 cc/dot).

‧ Drop head: Three sets of multi-nozzles (branch nozzles) using 8 × 8 = 64 points are arranged in the longitudinal direction.

‧ Drop time: Drop the beat 3.3 sec × 24 points = 79.2 sec.

The substrate A in which the curable resin composition was dispersed in a dot shape was placed on the lower surface of the lower plate on the lower side of the vacuum processing chamber of the decompression device. A soda lime glass plate (referred to as "substrate B", which corresponds to another substrate of the present invention) having the same shape and the same thickness as the user of the substrate A is electrostatically adsorbed on the lower surface of the upper plate on the upper side of the lifting device.

Next, the vacuum processing chamber was sealed, and evacuation was performed until the treatment chamber became 15 Pa. Then, the upper and lower flat plates are brought closer to each other by the lifting device in the vacuum processing chamber, and the substrate A and the substrate B are laminated. Here, the time from the completion of the dropping of the curable resin composition to the lamination is 120 sec. The vacuum processing chamber is then returned to atmospheric pressure.

Next, the upper and lower flat plates are separated from each other by the lifting device, and are adsorbed on the upper suction pad of the upper plate, and the laminated body (referred to as "layered body C") composed of the substrate A and the substrate B is peeled off from the upper upper plate.

Then, the layered body C was kept horizontal and left to stand for about 10 minutes, and then the presence or absence of voids in the curable resin composition layer was visually observed from the surface side of the substrate B. The results are shown in the table below.

In addition, the meanings of the symbols in the table are as follows:

○: There is no void having a diameter of 100 μm or more in the region surrounded by the sealing portion.

△: The number of voids having a diameter of 100 μm or more is 1 to 30/m ² in a region surrounded by the sealing portion.

x: The number of voids having a diameter of 100 μm or more is 31/m ² or more in a region surrounded by the sealing portion.

Then, ultraviolet rays are uniformly irradiated from the high-pressure mercury lamp from the surface direction of the laminated body C, and the curable resin composition is cured to obtain a laminated glass-like laminated body (referred to as "layered body D").

(Example 2)

The same procedure as in Example 1 was carried out, except that a photocurable resin composition for forming a resin layer having a viscosity of 4 Pa ‧ at 25 ° C was used.

(Example 3)

The same procedure as in Example 1 was carried out except that a photocurable resin composition for forming a resin layer having a viscosity of 1 Pa ‧ at 25 ° C was used.

(Example 4)

The same procedure as in Example 3 was carried out except that the dropping pitch was set to 30 mm.

(Example 5)

The same dimensions as in Example 1 were carried out except that the substrate size was 1300 mm in length, 1100 mm in width, and 2 mm in thickness, and the number of dropping points was 40 points, and the dropping time was 132 sec (3.3 sec × 40 points in dropping beat). order.

(Example 6)

The same procedure as in Example 5 was carried out except that the time from the completion of the dropping to the lamination was 70 sec.

(Example 7)

When the resin layer-forming photocurable resin composition is dropped, the isocratic diameter of the curable resin composition which is dropped by the dropping head (nozzle) under the following conditions is forcibly expanded. The same procedure as in Example 6 was carried out except that the equivalence circle diameter of the curable resin composition present in the region surrounded by the sealing portion was uniform.

(swing condition when dropping)

‧1st to 24th points: no swing

‧25th to 27th: swing amplitude 0.5mm

‧28th to 32nd point: swing amplitude 1.0mm

‧33~40 points: swing amplitude 1.5mm

[Table 1]

In Example 1, in the curable resin composition layer of the laminate after standing for 10 minutes, there was no void in which D _non-pore was 100 μm or more. As a result, when the vacuum layer is formed, the curable resin composition layer in the region surrounded by the sealing portion of the substrate A satisfies the above conditions (1) to (3).

On the other hand, the viscosity of the curable resin composition was lower than that of the example 2 of Example 1, and the number of voids in the layer of the curable resin composition of the laminate after standing for 10 minutes was 1 to 30/m ² . As a result, since the curable resin composition after dispersion and dropping is more rapidly expanded, it is judged that when the vacuum lamination is performed, the portion is formed as shown in Fig. 7(e).

The viscosity of the curable resin composition was lower than that of the example 3 of Example 2, and the number of voids was 31/m ^{2 in the} layer of the curable resin composition of the laminate after standing for 10 minutes. As a result, it has been found that since the curable resin composition after dispersion and dropping is more rapidly expanded, the portion in the state shown in Fig. 7(e) is more increased.

In the case of using the same curable resin composition as in Example 3, the number of voids was 1 to 30/m ^{2 in the} layer of the curable resin composition of the laminate after standing for 10 minutes. . As a result, it was found that the interval between the curable resin compositions dispersed and dispersed was increased, and the portion shown in the seventh (e) diagram was reduced as compared with the case of Example 3.

The substrate size was larger than that of the example 5 of Example 1, and the number of voids was 31/m ² or more in the layer of the curable resin composition of the laminate after standing for 10 minutes. From this result, it is found that as a result of the increase in the number of dropping points, since the dropping time (that is, the time required from the start of the dropping to the completion of the dropping) is increased, when the vacuum lamination is performed, part of it is shown in Fig. 7(e). The gap has been eliminated.

In the example 6 which shortens the time from the completion of the dropping to the lamination, the number of the voids is 1 to 30/m ² in the curable resin composition layer of the laminated body after standing for 10 minutes. As a result, it was found that although the portion shown in the state shown in Fig. 7(e) was not formed, a portion in which D _{pore was} larger than 10 mm as shown in Fig. 7(b) was generated.

In the example 7 in which the dripping head was swayed when the curable resin composition was dropped, the voids having a diameter of 100 μm or more were not present in the curable resin composition layer of the laminate after standing for 10 minutes. As a result, it is found that the equivalence circle diameter of the curable resin composition dispersed and dropped by the swing of the dropping head is enlarged, and the equivalence circle diameter of the curable resin composition at the time of completion of the dropping is uniform. As a result, when the vacuum layer is formed, the curable resin composition layer in the region surrounded by the sealing portion of the substrate A satisfies the above (1) to (3).

(Example 8)

In the same procedure as in Example 1, a sealing portion having a thickness of 1 mm was formed on the substrate A. However, the substrate A was made of a soda lime glass substrate having a length of 1110 mm, a width of 970 mm, and a thickness of 2 mm, and a sealing portion was formed at a position 4 mm from the inner side of the outer peripheral portion of the substrate. In addition, when the sealing portion was formed, the photocurable resin composition X for forming a sealing portion similar to that of Example 1 was used.

Next, the curable resin composition is applied to the vibration curves 30a and 30b as shown in Fig. 15 in the region surrounded by the sealing portion. The curable resin composition is the same as the photocurable resin composition Y for forming a resin layer of Example 1. However, a curable resin composition having a viscosity of 2 Pa ‧ at 25 ° C was used. The coating conditions are as follows.

(coating conditions)

‧Vibration curve: sinusoid

‧Period X: 20mm

‧Amplitude Y: 10mm

‧The thickness of the vibration curve just after coating is m: 6mm

The thickness of the vibration curve is set to a state in which the thickness of the curable resin composition layer is the same as the thickness of Example 1 at the time of vacuum lamination. In this regard, the same applies to Examples 9 to 15.

‧The shortest distance between the vibration curve and the seal d _(sr) : 0mm

‧The shortest distance d _(rr) between adjacent vibration curves: 0mm

‧Coating device: Coating device with a branching head of the dosing pump 16, using 3 sets

(Applicable according to 20×16×3=960mm width)

The void diameter E in the amplitude Y direction of the vibration curve was obtained by the following equation and was 8 mm.

E=2Y-2m

After the curable resin composition was applied, the same procedure as in Example 1 was carried out. However, the time from the completion of the dropping to the lamination is 50 sec.

(Example 9)

The same procedure as in Example 8 was carried out except that the time from the completion of the dropping to the lamination was 25 sec.

(Example 10)

The same procedure as in Example 8 was carried out except that the shortest distance d _(sr) between the vibration curve and the sealing portion was set to 1.5 mm, and the shortest distance d _(rr ) between the adjacent vibration curves was set to 3 mm. order of.

The gap diameter E in the amplitude Y direction of the vibration curve is 2 mm.

(Example 11)

The same procedure as in Example 10 was carried out except that the thickness m of the vibration curve immediately after application was set to 3 mm. Here, the gap diameter E in the amplitude Y direction of the vibration curve is 8 mm.

(Example 12)

The same procedure as in Example 10 was carried out except that the thickness m of the vibration curve immediately after application was set to 9 mm.

The gap diameter E in the amplitude Y direction of the vibration curve is -4 mm. Here, the void diameter E is a negative value, and it means that when the void is formed, the adjacent vibration curves overlap each other.

(Example 13)

The same procedure as in Example 10 was carried out except that the period X of the vibration curve was set to 15 mm and the amplitude Y was set to 7.5 mm.

The gap diameter E in the amplitude Y direction of the vibration curve is -3 mm.

(Example 14)

The same procedure as in Example 10 was carried out except that the period X of the vibration curve was set to 25 mm and the amplitude Y was set to 12.5 mm.

The gap diameter E in the amplitude Y direction of the vibration curve is 7 mm.

(Example 15)

The same procedure as in Example 14 was carried out except that the time from the completion of the dropping to the lamination was 50 sec.

In Example 8, in the curable resin composition layer of the laminate after standing for 10 minutes, voids having a diameter of 100 μm or more were not present. As a result, when the vacuum layer is formed, the curable resin composition layer in the region surrounded by the sealing portion of the substrate A satisfies the above (1) to (3).

On the other hand, in the case of the example 9 which is shorter than the example 8 after the completion of the dropping, the number of the voids is 1 to 30/m in the layer of the curable resin composition of the laminate after standing for 10 minutes. ² . From this result, it is found that as shown in Fig. 7(b), a portion in which D _{pore is} larger than 10 mm is generated.

In Example 10, voids having a diameter of 100 μm or more were not present in the layer of the curable resin composition of the laminate after standing for 10 minutes. As a result, when the vacuum layer is formed, the curable resin composition layer in the region surrounded by the sealing portion of the substrate A satisfies the above (1) to (3).

With respect to Example 10, the thickness of the vibration curve immediately after application was set to be finer in Example 11, and in the layer of the curable resin composition of the laminate after standing for 10 minutes, the number of voids was 1 to 30. /m ² . From this result, it is found that when vacuum lamination is performed, as shown in Fig. 7(b), a portion having a D _{pore of} more than 10 mm is formed.

With respect to Example 10, the thickness m of the vibration curve immediately after application was set to be thicker, and in the case of the curable resin composition layer of the laminate after standing for 10 minutes, the number of voids was 31/ m ² or more. In Example 12, since the gap diameter E in the amplitude (Y) direction of the vibration curve is -4 mm, it is judged that the adjacent vibration curves overlap each other when the void is formed. As a result, it was found that when the vacuum lamination was carried out, the void as shown in Fig. 7(e) was partially eliminated.

With respect to Example 10, in the example 13 in which the period X and the amplitude Y of the vibration curve were reduced, the number of voids in the layer of the curable resin composition of the laminate after standing for 10 minutes was 31/m ² or more. In Example 13, since the gap diameter E in the amplitude Y direction of the vibration curve is -3 mm, it is judged that the adjacent vibration curves overlap with each other when the void is formed. As a result, it was found that when the vacuum lamination was carried out, the void as shown in Fig. 7(e) was partially eliminated.

With respect to Example 10, in Example 14 in which the period X and the amplitude Y of the vibration curve were enlarged, the number of voids in the layer of the curable resin composition of the laminate after standing for 10 minutes was 1 to 30/m ² . From this result, it is found that when vacuum lamination is performed, as shown in Fig. 7(b), a portion having a D _{pore of} more than 10 mm is formed.

In the case of the example 15 in which the time from the completion of the dropping to the lamination was carried out, the voids having a diameter of 100 μm or more were not present in the curable resin composition layer of the laminate after standing for 10 minutes. From this result that, by a more narrow D _pore, when a vacuum laminate occasion, the substrate is present in the A layer surrounded by a sealing portion region curable resin, form satisfies the above (1) to (3) status.

Industrial availability

According to the method for producing a laminated body of the present invention, it is possible to shorten the time required for the entire space sealed by the pair of substrates and the sealing portion to be uniformly filled by the curable resin composition, which can be improved in the process of manufacturing the laminated body. The productivity of the laminate.

In addition, the entire contents of the specification, the scope of the application, the drawings and the abstract of the Japanese Patent Application No. 2009-253984, filed on November 5, 2009, are hereby incorporated by reference.

10. . . Substrate

20. . . Sealing part

30. . . Curable resin composition

30. . . Curable resin composition layer

30a, 30a', 30a", 30b, 30b', 30d, 30e... vibration curve

30c, 30f, 30g. . . straight line

31. . . Wide area

40, 41. . . Void

100, 101, 102, 103, 104. . . nozzle

101, 102, 103, 104. . . Multi-nozzle (branch nozzle)

D _pore . . . The voids present in the layer of the curable resin composition, the equivalent circle diameter of the projected shape

D _non-pore . . . a portion of the layer of the curable resin composition where no void exists, and the equivalent circular diameter of the projected shape

E. . . Diameter of the gap

m, ma, mb. . . Thickness

X. . . cycle

Y, Ya, Yb. . . amplitude

Fig. 1 is a plan view showing a state in which a sealing portion is formed in a peripheral portion of the substrate.

Fig. 2 is a plan view showing a state in which a curable resin composition layer is formed in a portion of the substrate surrounded by the sealing portion.

Figs. 3(a) to 3(c) are diagrams showing temporal changes of the curable resin composition which is dotted and dispersed in a region surrounded by the sealing portion of the substrate.

When the vacuum-curable resin composition of the fourth (a) to (d) is subjected to vacuum lamination in the state shown in Fig. 3(a), the curable resin composition is laminated at the time of vacuum lamination and after the decompression environment is released. State diagram.

When the vacuum-curable resin composition of the fifth (a) to (d) is subjected to vacuum lamination in the state shown in Fig. 3(b), the curable resin composition is laminated at the time of vacuum lamination and after the decompression environment is released. State diagram.

In the case where the vacuum-curable resin composition is subjected to vacuum lamination in the state shown in Fig. 3(c), the curable resin composition is subjected to vacuum lamination and after the decompression environment is released. State diagram.

The seventh (a) to (e) drawings are time-dependent changes of the curable resin composition which is dotted and dispersed in a region surrounded by the sealing portion of the substrate.

Fig. 8 is a sequence diagram in which a hard-pointing resin composition is dispersed and dropped on a substrate surrounded by a sealing portion using a single-point nozzle.

Fig. 9 is a sequence diagram in which a multi-point nozzle is used to disperse and deposit a curable resin composition on a substrate surrounded by a sealing portion.

Fig. 10 is a sequence diagram in which a multi-point nozzle is used to disperse a curable resin composition in a region surrounded by a sealing portion.

Fig. 11 is a sequence diagram in which a multi-point nozzle is used to disperse a curable resin composition in a region surrounded by a sealing portion.

Fig. 12 is a sequence diagram in which a multi-point nozzle is used to disperse a curable resin composition in a region surrounded by a sealing portion.

Fig. 13 is a graph showing the relationship between the elapsed time t (sec) after dropping and the equivalent circle diameter d (mm) of the curable resin composition.

Fig. 14 is a graph showing the relationship between the elapsed time t after dropping, the equivalence circle diameter d of the curable resin composition, and the equivalence circle diameter D _pore of the voids in the curable resin composition layer.

Fig. 15 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

Fig. 16 is a partial enlarged view corresponding to Fig. 15, showing temporal changes in the shape of the vibration curves 30a, 30b.

Fig. 17 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

Fig. 18 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

Fig. 19 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

Fig. 20 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

Fig. 21 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

Fig. 22 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

Fig. 23 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

Fig. 24 is a view showing a preferred coating form when the curable resin composition is applied in a line shape.

10. . . Substrate

20. . . Sealing part

30. . . Curable resin composition layer

40. . . Void

D _pore . . . The voids present in the layer of the curable resin composition, the equivalent circle diameter of the projected shape

D _non-pore . . . a portion of the layer of the curable resin composition where no void exists, and the equivalent circular diameter of the projected shape

Claims (12)

A method for manufacturing a laminated body comprising the steps of: preparing two substrates; forming a sealing portion on a peripheral portion of one of the substrates, the sealing portion for sealing the curable resin composition; and one of the substrates The curable resin composition is supplied to the region surrounded by the sealing portion, and the other substrate is superposed on the supplied curable resin composition under a reduced pressure environment to sandwich the curable resin between the pair of substrates. And sealing the pair of substrates holding the curable resin composition in a second pressure environment higher than the reduced pressure environment, and curing the curable resin composition in the second pressure environment to produce In the laminated body, the method for producing the laminated body is characterized in that the coating state of the curable resin composition supplied onto the substrate and the period in which the other substrate is superposed on the curable resin composition are controlled When the other substrate is superposed on one of the substrates, the curable resin composition layer existing in the region surrounded by the sealing portion satisfies the following (1) to (3); (1) exists in The gap in the curable resin composition layer has a projected circle having an equivalent circle diameter D _pore of 10 mm or less; (2) a portion where the void portion is not present in the curable resin composition layer, and projection thereof equivalent circle diameter D _non-pore shape is 40mm or less; (3) the curable resin composition layer and the contact state is present in the curable resin composition layer, the voids were alternately with the sealing portion. The method for producing a laminate according to the first aspect of the invention, wherein at least one of the two substrates is a transparent substrate. The method for producing a laminate according to claim 1 or 2, wherein the viscosity of the curable resin composition is 0.2 to 50 Pa. s. The method for producing a laminate according to the first aspect of the invention, wherein the thickness of the curable resin composition layer in the space sealed by the pair of substrates and the sealing portion is 30 to 3000 μm. The method for manufacturing a laminate according to claim 1, wherein the sealing portion has a viscosity of 200 to 3000 Pa. The second curable resin composition of s is formed. The method for producing a laminate according to the first aspect of the invention, wherein the reduced pressure environment is a pressure environment of 0.1 to 1000 Pa. The method for producing a laminate according to the first aspect of the invention, wherein the pressure of the second environment is higher than a pressure of the reduced pressure environment by 50 kPa or more. The method for producing a laminate according to the first aspect of the invention, wherein the supply of the curable resin composition to the region surrounded by the sealing portion on one of the substrates means that the curable resin is dispersed and dispersed in a region surrounded by the sealing portion. Composition. The method for producing a laminate according to the eighth aspect of the invention, wherein, in the case where the curable resin composition is dispersed and dropped on one of the substrates, the one of the substrates and the nozzle used for dispersion and dropping are relatively placed Further, the equivalence circle diameter of the hardened resin composition which has been dropped is forcibly expanded, whereby the equivalence circle diameter of the curable resin composition existing in the region surrounded by the sealing portion is made uniform. The method for producing a laminate according to the first aspect of the invention, wherein the hardenable resin composition is supplied to one of the substrates to supply the curable resin composition to a region surrounded by the seal on one of the substrates, The curable resin composition is subjected to a vibration curve satisfying the following (4) to (9); (4) the displacement is repeated in a vertical direction by a constant period (X) and an amplitude (Y) with respect to a direction in which the vibration curve advances; (5) The displacements of the adjacent vibration curves are opposite to each other; (6) when the thickness of the vibration curve at the time of starting supply is m (mm), the period (X) (mm), and the aforementioned amplitude (Y) (mm) is satisfied by the following formula: 2.1 × m ≦ X ≦ 10 × m (2.1 × m) / 2 ≦ Y ≦ (10 × m) / 2 (7) The thickness of the vibration curve when the supply is started In the case of m (mm), the shortest distance d _(sr) (mm) between the vibration curve and the seal portion satisfies the following formula: d _(sr) ≦ 2.5 × m (8) The thickness of the vibration curve at the start of supply is set to For m(mm), the shortest distance d _(rr) (mm) between adjacent vibration curves satisfies the following formula: d _(rr) ≦ 5 × m (9) When E = 2Y - 2 m, the E ( mm) satisfy the following formula _{based: (Y + d (rr)} ) / 10 ≦ E ≦ Y + d (rr) The method for producing a laminate according to the first aspect of the invention, wherein the hardenable resin composition is supplied to one of the substrates to supply a region surrounded by the seal on one of the substrates, and the curable resin is composed. The object can satisfy the following vibration curves of (10) to (14) and a line advancing in the same direction as the vibration curve; (10) with respect to the direction of advancement of the vibration curve, in a vertical direction according to a certain period (X) () repeating the displacement with the amplitude (Y); (11) when the thickness of the vibration curve at the time of starting supply is m (mm), the period (X) (mm) and the amplitude (Y) (mm) are satisfied. Formula: 2.1 × m ≦ X ≦ 10 × m (2.1 × m) / 2 ≦ Y ≦ (10 × m) / 2 (12) When the vibration curve is located near the seal, and the thickness of the vibration curve when the supply starts When m (mm), the shortest distance d _(sr) (mm) between the vibration curve and the sealing portion satisfies the following formula: d _(sr) ≦ 2.5 × m (13) The thickness of the vibration curve when the supply starts When m (mm), the shortest distance d _(rr) (mm) between the adjacent vibration curve and the line satisfies the following formula: d _(rr) ≦ 2.5 × m (14) when E = 2Y-2m, The E (mm) system is satisfied Formula: (Y+d _(rr) ) / 20 ≦ E ≦ (Y + d _(rr) ) /2. The method for producing a laminate according to the first aspect of the invention, wherein the hardening resin composition is completed on one of the substrates by the sealing portion The dripping of the surrounding area starts until the time of lamination is 30 to 1800 seconds.