Solar cell laminates, solar cell modules, and solar cell varnishes

Abstract

This invention provides a laminate for solar cells with an improved balance of water vapor barrier properties and flexibility. [Solution] A laminate for solar cells comprising a layer (A) containing a perovskite compound and a layer (B) containing a cyclic olefin resin (B1), wherein the glass transition temperature Tg of the cyclic olefin resin (B1) is 45°C or higher and 280°C or lower.

Description

[Technical Field]

[0001] This invention relates to a laminate for solar cells, a solar cell module, and a varnish for solar cells. [Background technology]

[0002] Development of perovskite solar cells, which use perovskite compounds as the photoelectric conversion layer, is progressing.

[0003] Patent Document 1 describes a flexible solar cell having an electrode, a transparent electrode, and a photoelectric conversion layer disposed between the electrode and the transparent electrode on a flexible substrate, wherein the photoelectric conversion layer contains an organic inorganic perovskite compound represented by the general formula RM-X3 (wherein R is an organic molecule, M is a metal atom, and X is a halogen atom or chalcogen atom), and the flexible substrate has a metal foil and a resin layer disposed on the electrode side of the metal foil. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2018 / 139146 [Overview of the project] [Problems that the invention aims to solve]

[0005] This invention provides a laminate for solar cells with an improved balance of water vapor barrier properties and flexibility. [Means for solving the problem]

[0006] According to the present invention, the following solar cell laminate, solar cell module, and solar cell varnish are provided.

[0007] 1. A laminate for a solar cell, comprising a layer (A) containing a perovskite compound and a layer (B) containing a cyclic olefin resin (B1), wherein the glass transition temperature Tg of the cyclic olefin resin (B1) is 45°C or higher and 280°C or lower. 2. The laminate for a solar cell according to 1., wherein the cyclic olefin resin (B1) contains a repeating unit (b) derived from one or more cyclic olefin monomers selected from the group consisting of a repeating unit (AA) represented by the following general formula (II), a repeating unit (AB) represented by the following general formula (III), and a repeating unit (AC) represented by the following general formula (IV). [Chemical formula] (In the general formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R 61 ~R 78 as well as R a1 and R b1 may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring.) [Chemical formula] (In the general formula (III), x and d are 0 or an integer of 1 or more, y and z are 0, 1, or 2, and R 81 ~R 99 may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group, and the carbon atom to which R 89 and R 90 are bonded, and R93 The carbon atom or R to which it is bonded 91 The carbon atom to which it is bonded may be directly bonded or bonded via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R 95 and R 92 or R 95 and R 99 These elements may be bonded to each other to form monocyclic or polycyclic aromatic rings. [ka] (In the above general formula (IV), R 100 , R 101 (These elements may be identical or different from each other, and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, where f is 1 ≤ f ≤ 18.) 3. The laminate for solar cells according to 2., wherein the cyclic olefin resin (B1) includes repeating units (AA) represented by the general formula (II). 4. The laminate for solar cells described in 3., wherein in the general formula (II), u is 0 and v is 0. 5. A laminate for solar cells according to any one of 2. to 4., wherein when the total amount of repeating units constituting the cyclic olefin resin (B1) is set to 100 mol%, the content ratio of repeating units (b) derived from the cyclic olefin monomer in the cyclic olefin resin (B1) is 1 mol% or more and 99 mol% or less. 6. The cyclic olefin resin (B1) comprises repeating units (a) derived from an olefin represented by the following general formula (I), wherein the laminate for solar cells is as described in any of 2. to 5. [ka] (In the above general formula (I), R 300 (This indicates a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.) 7. The cyclic olefin resin (B1) is, The repeating unit (AA) represented by the general formula (II) above, A repeating unit (C) derived from a cyclic olefin containing an aromatic ring, Includes, The aforementioned repeating unit (AA) does not contain an aromatic ring. The cyclic olefin containing the aromatic ring comprises one or more compounds selected from the group consisting of compounds represented by the following general formula (C-1), compounds represented by the following general formula (C-2), and compounds represented by the following general formula (C-3), as described in any of 2. to 6., for use in solar cell laminates. [ka] (In the above general formula (C-1), n ​​and q are each independently 0, 1, or 2, R 1 ~R 17 Each of these is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and R 10 ~R 17 One of them is a bond, and when q=0, R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 10 They may be bonded to each other to form a monocycle or polycycle, and when q=1 or 2, R 10 and R 11 , R 11 and R 17 , R 17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , R 16 and R 10These elements may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring. [ka] (In the above general formula (C-2), n and m are each independently 0, 1, or 2, and q is 1, 2, or 3, R 18 ~R 31 Each of these is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms that may be substituted with a halogen atom other than a fluorine atom, and when q=1, R 28 and R 29 , R 29 and R 30 , R 30 and R 31 They may be bonded to each other to form a monocycle or polycycle, and when q=2 or 3, R 28 and R 28 , R 28 and R 29 , R 29 and R 30 , R 30 and R 31 , R 31 and R 31 These elements may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring. [ka] (In the above general formula (C-3), q is 1, 2 or 3, R 32 ~R 39 Each of these is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms that may be substituted with a halogen atom other than a fluorine atom, and when q=1, R 36 and R 37 , R 37 and R 38 , R 38 and R 39 They may be bonded to each other to form a monocycle or polycycle, and when q=2 or 3, R36 and R 36 , R 36 and R 37 , R 37 and R 38 , R 38 and R 39 , R 39 and R 39 may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic or polycyclic ring may have a double bond, and the monocyclic or polycyclic ring may be an aromatic ring.) 8. The cyclic olefin resin (B1) is the repeating unit (AA) represented by the general formula (II), the repeating unit (a) derived from an olefin represented by the following general formula (I), the repeating unit derived from a cyclic non-conjugated diene represented by the following general formula (Y), and includes the laminate for a solar cell according to 6. or 7.

Chemical formula

Chemical formula

[0008] According to the present invention, it is possible to provide a laminate for solar cells with an improved balance of water vapor barrier properties and flexibility. [Brief explanation of the drawing]

[0009] [Figure 1] This is a schematic diagram showing a cross-section of an example of a laminate for solar cells according to this embodiment. [Figure 2] This is a schematic diagram showing the top view of an example of a solar cell module according to this embodiment. [Figure 3] This is a schematic diagram showing a cross-section of an example of a solar cell module according to this embodiment. [Modes for carrying out the invention]

[0010] In this embodiment, unless otherwise specified, "A~B" indicating a numerical range means A or greater and B or less.

[0011] In this embodiment, "having substituents" of an alkyl group, unless otherwise specified, means that hydrogen atoms present in its structure are substituted by substituents. The position of the substituents and the number of substituents are not particularly limited. Note that if the substituent has carbon atoms, the number of carbon atoms in the substituent is not included in the total number of carbon atoms of the substituted group. For example, an ethyl group having a phenyl group as a substituent is considered an alkyl group with 2 carbon atoms.

[0012] Furthermore, the various monomers in this embodiment may be derived from fossil raw materials, from biological sources such as biomass, or from mixtures thereof.

[0013] 1. Stacked material for solar cells The laminate for solar cells according to this embodiment will be described below.

[0014] The solar cell laminate of this embodiment comprises a layer (A) containing a perovskite compound and a layer (B) containing a cyclic olefin resin (B1), wherein the glass transition temperature Tg of the cyclic olefin resin (B1) is 45°C or higher and 280°C or lower.

[0015] The solar cell laminate of this embodiment may include layers other than the layer (A) containing the perovskite compound and the layer (B) containing the cyclic olefin resin (B1).

[0016] An example of a solar cell laminate according to this embodiment is illustrated in Figure 1. The solar cell laminate 10 includes, in order from the light-receiving surface side, a layer (B) 1 containing a cyclic olefin resin (B1), a transparent electrode 2, an electron transport layer 3, a layer (A) 4 containing a perovskite compound, a hole transport layer 5, and a back electrode 6. Furthermore, in the solar cell laminate 10, layer (A) 4 containing the perovskite compound can function as a photoelectric conversion layer. In addition, in the solar cell laminate 10, layer (B)1 containing the cyclic olefin resin (B1) can function as a protective layer that protects layer (A)4 containing the perovskite compound from water vapor and the like.

[0017] Solar cells are exposed to harsh outdoor environments for extended periods, but perovskite compounds are susceptible to degradation from water vapor. Therefore, water vapor barrier properties are required for perovskite solar cells. Furthermore, because perovskite solar cells can be manufactured by coating or printing, they can be made thinner, opening up possibilities for applications not possible with conventional solar cells, such as attachment to curved surfaces. For this reason, flexibility against bending is also required for perovskite solar cells. In short, perovskite solar cells must possess both water vapor barrier properties and flexibility. However, there was room for improvement in achieving both water vapor barrier properties and flexibility in perovskite solar cells. The inventors of this invention have conducted thorough research in this regard and have found that by using a cyclic olefin resin that satisfies specific requirements, the balance between water vapor barrier properties and flexibility can be improved.

[0018] (1) Layer containing a perovskite compound (A) The layer (A) containing the perovskite compound will be described below.

[0019] Layer (A) can function, for example, as a photoelectric conversion layer.

[0020] The thickness of layer (A) is preferably 5 nm or more, more preferably 10 nm or more, even more preferably 20 nm or more, even more preferably 50 nm or more, even more preferably 100 nm or more, and even more preferably 200 nm or more. This allows for sufficient light absorption and improves photoelectric conversion efficiency. The thickness of layer (A) is preferably 100,000 nm or less, more preferably 10,000 nm or less, even more preferably 5,000 nm or less, even more preferably 2,000 nm or less, even more preferably 1,000 nm or less, and even more preferably 500 nm or less. This suppresses the occurrence of regions where charge separation is not possible, thereby improving the photoelectric conversion efficiency. The thickness of layer (A) is preferably 5 nm to 100,000 nm, more preferably 10 nm to 10,000 nm, even more preferably 20 nm to 5,000 nm, even more preferably 50 nm to 2,000 nm, even more preferably 100 nm to 1,000 nm, and even more preferably 200 nm to 500 nm. This allows for sufficient light absorption, suppresses the occurrence of regions where charge separation is not possible, and improves photoelectric conversion efficiency.

[0021] The perovskite compounds of this embodiment include, for example, compounds represented by the general formula RM-X3 (wherein R represents an organic molecule, M represents a metal atom, and X represents a halogen atom or chalcogen atom).

[0022] In the general formula RM-X3, R is preferably C l N m H n This shows that (l, m, and n are all positive integers). In the general formula RM-X3, R is, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, ethylmethylamine, methylpropylamine, butylmethylamine, methylpentylamine, hexylmethylamine, ethylpropylamine, ethylbutylamine, imidazole, azole, pyrrole, aziridine, azirine, azetidine, azeto, imidazoline, carbazole, methylcarboxyamine, ethylcarboxyamine, propylcarboxyamine The material represents methylamine, ethylamine, propylamine, propylcarboxyamine, formamidinium, guanidine, aniline, or pyridine; ions of these compounds; or phenethylammonium, preferably methylamine, ethylamine, propylamine, propylcarboxyamine, butylcarboxyamine, pentylcarboxyamine, formamidinium, or guanidine; or ions of these compounds, more preferably methylamine, ethylamine, pentylcarboxyamine, formamidinium, or guanidine; or ions of these compounds, and even more preferably methylamine or formamidinium; or ions of these compounds, from the viewpoint of improving photoelectric conversion efficiency.

[0023] In the general formula RM-X3, M represents, for example, lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum, or europium, and from the viewpoint of electron orbital overlap, lead or tin is preferred, and lead is more preferred. These metal atoms may be used individually or in combination of two or more.

[0024] In the general formula RM-X3, X preferably represents a halogen atom from the viewpoint of improving solubility in organic solvents, and preferably represents an iodine atom from the viewpoint of narrowing the energy band gap of the perovskite compound of this embodiment. These halogen atoms or chalcogen atoms may be used alone, or two or more may be used in combination.

[0025] From the viewpoint of improving photoelectric conversion efficiency, the perovskite compound of this embodiment preferably includes a cubic crystal structure in which a metal atom M is arranged at the body center, organic molecules R are arranged at each vertex, and halogen atoms or chalcogen atoms X are arranged at the face centers.

[0026] The perovskite compound of this embodiment preferably contains a crystalline semiconductor, from the viewpoint of improving photoelectric conversion efficiency and suppressing the decrease in photoelectric conversion efficiency (photodegradation) due to continued light irradiation of the solar cell. In this embodiment, a crystalline semiconductor means a semiconductor from which a scattering peak can be detected when the X-ray scattering intensity distribution is measured.

[0027] Crystallinity can be used as an indicator of the crystallization of the perovskite compound in this embodiment. Crystallinity can be determined by separating the scattering peaks originating from the crystalline portion and the halos originating from the amorphous portion, detected by X-ray scattering intensity distribution measurement, by fitting them together, calculating the integral of each intensity, and then calculating the ratio of the crystalline portion to the whole. The crystallinity of the perovskite compound in this embodiment is preferably 30% or higher, more preferably 50% or higher, and even more preferably 70% or higher. This increases the electron mobility in the perovskite compound of this embodiment, thereby improving the photoelectric conversion efficiency. Furthermore, this suppresses photodegradation. Methods for increasing the crystallinity of the perovskite compound in this embodiment include, for example, thermal annealing (heat treatment), irradiation with high-intensity light such as a laser, and plasma irradiation.

[0028] Furthermore, crystallite size can also be evaluated as another indicator of crystallization. Crystallite size can be calculated using the Halder-Wagner method from the full width at half maximum of the scattering peaks originating from the crystalline material, as detected by X-ray scattering intensity distribution measurement. The crystallite size of the perovskite compound in this embodiment is preferably 5 nm or larger, more preferably 10 nm or larger, and even more preferably 20 nm or larger. This increases the electron mobility in the perovskite compound of this embodiment, thereby improving the photoelectric conversion efficiency. Furthermore, this suppresses photodegradation.

[0029] Layer (A) may contain an organic semiconductor or an inorganic semiconductor, etc., as long as it does not impair the effects of the present invention.

[0030] The organic semiconductor of this embodiment includes, for example, one or more selected from the group consisting of compounds having a thiophene skeleton such as poly(3-alkylthiophene); conductive polymers having a poly(p-phenylenevinylene) skeleton, polyvinylcarbazole skeleton, polyaniline skeleton and polyacetylene skeleton and the like; compounds having a porphyrin skeleton such as a phthalocyanine skeleton, naphthalocyanine skeleton, pentacene skeleton and benzoporphyrin skeleton; compounds having a spirobifluorene skeleton and the like; and carbon-containing materials such as carbon nanotubes, graphene and fullerene, which may be surface-modified.

[0031] The inorganic semiconductor of this embodiment includes, for example, one or more selected from the group consisting of titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, zinc sulfide, CuSCN, Cu2O, CuI, MoO3, V2O5, WO3, MoS2, MoSe2, and Cu2S.

[0032] Layer (A) may be a laminate formed by stacking a thin film organic semiconductor or inorganic semiconductor portion and a thin film perovskite compound portion, or it may be a composite film formed by combining an organic semiconductor or inorganic semiconductor portion and a thin film perovskite compound portion. A laminate is preferred in terms of ease of manufacture, while a composite film is preferred in terms of being able to improve the charge separation efficiency in the organic semiconductor or inorganic semiconductor of this embodiment.

[0033] The thickness of the thin film-like perovskite compound portion in this embodiment is preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 20 nm or more. This allows for sufficient light absorption and improves photoelectric conversion efficiency. The thickness of the thin film-like perovskite compound portion in this embodiment is preferably 5,000 nm or less, more preferably 1,000 nm or less, and even more preferably 500 nm or less. This suppresses the occurrence of regions where charge separation is not possible, thereby improving the photoelectric conversion efficiency.

[0034] The thickness of the composite film in this embodiment is preferably 30 nm or more, more preferably 40 nm, and even more preferably 50 nm or more. This allows for sufficient light absorption and improves the photoelectric conversion efficiency. The thickness of the composite film in this embodiment is preferably 3,000 nm or less, more preferably 2,000 nm or less, and even more preferably 1,000 nm or less. This makes it easier for the charge to reach the electrodes, thereby improving the photoelectric conversion efficiency.

[0035] (2) Layer (B) containing cyclic olefin resin (B1) The following describes the layer (B) containing the cyclic olefin resin (B1).

[0036] Layer (B) can function, for example, as a protective layer that protects layer (A) containing the perovskite compound from water vapor or the like.

[0037] The method for forming layer (B) is not particularly limited; for example, pre-formed sheet-like layers (B) may be laminated, or a varnish containing a cyclic olefin resin (B1) may be applied.

[0038] The thickness of layer (B) is preferably 0.1 nm or more, more preferably 0.2 nm or more, even more preferably 0.5 nm or more, even more preferably 1 nm or more, even more preferably 10 nm or more, even more preferably 100 nm or more, even more preferably 1,000 nm or more, and even more preferably 10,000 nm or more, from the viewpoint of further improving the water vapor barrier properties of the solar cell laminate. The thickness of layer (B) is preferably 500,000 nm or less, more preferably 100,000 nm or less, even more preferably 50,000 nm or less, even more preferably 10,000 nm or less, even more preferably 5,000 nm or less, even more preferably 1,000 nm or less, even more preferably 500 nm or less, even more preferably 100 nm or less, and even more preferably 100 nm or less, from the viewpoint of further improving the flexibility of the solar cell laminate and improving the thinness of the solar cell laminate. The thickness of layer (B) is preferably 0.1 nm to 500,000 nm, more preferably 0.2 nm to 100,000 nm, even more preferably 0.5 nm to 50,000 nm, even more preferably 1 nm to 10,000 nm, even more preferably 10 nm to 5,000 nm, even more preferably 10 nm to 1,000 nm, even more preferably 10 nm to 500 nm, and even more preferably 10 nm to 100 nm, from the viewpoint of balancing water vapor barrier properties, flexibility, and thinness of the solar cell laminate.

[0039] The glass transition temperature Tg of the cyclic olefin resin (B1) is preferably 55°C or higher, more preferably 60°C or higher, even more preferably 65°C or higher, even more preferably 70°C or higher, even more preferably 75°C or higher, even more preferably 80°C or higher, even more preferably 85°C or higher, even more preferably 90°C or higher, even more preferably 95°C or higher, even more preferably 100°C or higher, even more preferably 105°C or higher, and even more preferably 110°C or higher, from the viewpoint of improving the heat resistance of the laminate for solar cells. The glass transition temperature Tg of the cyclic olefin resin (B1) is preferably 270°C or lower, more preferably 260°C or lower, even more preferably 250°C or lower, even more preferably 240°C or lower, even more preferably 230°C or lower, even more preferably 220°C or lower, even more preferably 210°C or lower, even more preferably 200°C or lower, even more preferably 190°C or lower, even more preferably 180°C or lower, even more preferably 170°C or lower, and even more preferably 160°C or lower, from the viewpoint of further improving the water vapor barrier properties and flexibility of the laminate for solar cells. The glass transition temperature Tg of the cyclic olefin resin (B1) is preferably 55°C to 270°C, more preferably 60°C to 260°C, even more preferably 65°C to 250°C, even more preferably 70°C to 240°C, even more preferably 75°C to 230°C, even more preferably 80°C to 220°C, even more preferably 85°C to 210°C, even more preferably 90°C to 200°C, even more preferably 95°C to 190°C, even more preferably 100°C to 180°C, even more preferably 105°C to 170°C, and even more preferably 110°C to 160°C, from the viewpoint of balancing heat resistance, water vapor barrier properties, and flexibility of the laminate for solar cells.

[0040] The cyclic olefin resin (B1) preferably contains one or more repeating units (b) derived from cyclic olefin monomers selected from the group consisting of repeating units (AA) represented by the following general formula (II), repeating units (AB) represented by the following general formula (III), and repeating units (AC) represented by the following general formula (IV), and more preferably contains repeating units (AA) represented by the following general formula (II).

[0041] [ka]

[0042] In general formula (II), u is 0 or 1, v is 0 or a positive integer, preferably an integer between 0 and 2, more preferably 0 or 1, w is 0 or 1, R 61 ~R 78 Furthermore, R a1 and R b1 These may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 75 ~R 78 These elements may be bonded to each other to form a monocycle or polycycle.

[0043] [ka]

[0044] In general formula (III), x and d are integers of 0 or greater than or equal to 1, preferably integers of 0 or greater than or equal to 2, more preferably 0 or 1, and y and z are 0, 1 or 2, R 81 ~R 99These may be the same or different from each other, and are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group which is an aromatic hydrocarbon group which is a 6 to 20 carbon atom or an alkoxy group, and R 89 and R 90 The carbon atom to which it is bonded, and R 93 The carbon atom or R to which it is bonded 91 The carbon atom to which it is bonded may be directly bonded or bonded via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R 95 and R 92 or R 95 and R 99 These elements may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

[0045] [ka]

[0046] In general formula (IV), R 100 , R 101 These elements may be identical or different from each other, and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, where f is 1 ≤ f ≤ 18.

[0047] In general formula (II), from the viewpoint of further improving the water vapor barrier properties and flexibility of the solar cell laminate, it is preferable that u is 0 and v is 0.

[0048] The repeating unit (AA) represented by general formula (II) can be derived from the cyclic olefin monomer represented by general formula (IIa) below, the repeating unit (AB) represented by general formula (III) can be derived from the cyclic olefin monomer represented by general formula (IIIa) below, and the repeating unit (AC) represented by general formula (IV) can be derived from the cyclic olefin monomer represented by general formula (IVa) below.

[0049] [ka]

[0050] In general formula (IIa), u is 0 or 1, v is 0 or a positive integer, preferably an integer between 0 and 2, more preferably 0 or 1, w is 0 or 1, R 61 ~R 78 Furthermore, R a1 and R b1 These may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 75 ~R 78 These elements may be bonded to each other to form a monocycle or polycycle.

[0051] [ka]

[0052] In general formula (IIIa), x and d are integers of 0 or greater than or equal to 1, preferably integers of 0 or greater than or equal to 2, more preferably 0 or 1, and y and z are 0, 1 or 2, R 81 ~R 99 These may be the same or different from each other, and are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group which is an aromatic hydrocarbon group which is a 6 to 20 carbon atom or an alkoxy group, and R 89 and R 90 The carbon atom to which it is bonded, and R 93 The carbon atom or R to which it is bonded 91 The carbon atom to which it is bonded may be directly bonded or bonded via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R 95 and R 92 or R 95 and R 99 These elements may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

[0053] [ka]

[0054] In general formula (IVa), R 100 , R 101 These elements may be identical or different from each other, and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, where f is 1 ≤ f ≤ 18.

[0055] By using an olefin monomer represented by general formula (Ia), or a cyclic olefin monomer represented by general formula (IIa), (IIIa), or (IVa) as a polymerization component, the solubility of the cyclic olefin resin (B1) in the solvent is further improved, resulting in better moldability and increased product yield.

[0056] Specific examples of cyclic olefin monomers represented by general formulas (IIa), (IIIa), or (IVa) can be found in paragraphs 0037-0063 of International Publication No. 2006 / 118261. The above cyclic olefin monomers are obtained from dicyclopentadiene and ethylene, but the ethylene may include repeating units derived from biomass-derived monomers (ethylene).

[0057] Specifically, bicyclo-2-heptene derivatives (bicyclohept-2-ene derivatives), tricyclo-3-decene derivatives, tricyclo-3-undecene derivatives, tetracyclo-3-dodecene derivatives, pentacyclo-4-pentadecene derivatives, pentacyclopentadecadiene derivatives, pentacyclo-3-pentadecene derivatives, pentacyclo-4-hexadecene derivatives, pentacyclo-3-hexadecene derivatives, hexacyclo-4-heptadecene derivatives, heptacyclo-5-eicosene derivatives Examples include conductors, heptacyclo-4-eicosene derivatives, heptacyclo-5-heneicosene derivatives, octacyclo-5-docosene derivatives, nonacyclo-5-pentacosene derivatives, nonacyclo-6-hexacosene derivatives, cyclopentadiene-acenaphthylene adducts, 1,4-methano-1,4,4a,9a-tetrahydrofluorene derivatives, 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene derivatives, and cycloalkylene derivatives having 3 to 20 carbon atoms.

[0058] Among the cyclic olefin monomers represented by general formulas (IIa), (IIIa), or (IVa), the cyclic olefin represented by general formula (IIa) is preferred. Furthermore, it is preferable to use either a cyclic olefin represented by general formula (IIa) or a cyclic olefin represented by general formula (IIIa) or (IVa).

[0059] The cyclic olefin monomer represented by general formula (IIa) is preferably bicyclo[2.2.1]-2-heptene (also called norbornene) and tetracyclo[4.4.0.1 2,5 .1 7,10 It comprises one or more selected from the group consisting of ]-3-dodecene (also called tetracyclododecene), and more preferably contains tetracyclododecene. The rigid ring structure of these cyclic olefin monomers has the advantage of making it easier to maintain the elastic modulus of the cyclic olefin resin (B1).

[0060] When the total amount of repeating units constituting the cyclic olefin resin (B1) is taken as 100 mol%, the content of repeating units (b) derived from cyclic olefin monomers in the cyclic olefin resin (B1) is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, even more preferably 7 mol% or more, even more preferably 10 mol% or more, even more preferably 12 mol% or more, even more preferably 15 mol% or more, even more preferably 18 mol% or more, and even more preferably 20 mol% or more, and from the viewpoint of further improving the water vapor barrier properties of the solar cell laminate, it is preferably 99 mol% or less, more preferably 95 mol% or less, and even more preferably 90 mol% or more. The amount is preferably 1 mol% to 99 mol%, more preferably 3 mol% to 95 mol%, more preferably 5 mol% to 90 mol%, more preferably 7 mol% to 70 mol%, more preferably 15 mol% to 50 mol%, more preferably 18 mol% to 40 mol%, and more preferably 20 mol% to 40 mol%. Furthermore, the content of repeating units (b) derived from cyclic olefin monomers is as follows: 13 It can be measured by 13C-NMR.

[0061] From the viewpoint of further improving the water vapor barrier properties and flexibility of the solar cell laminate, the cyclic olefin resin (B1) preferably contains repeating units (a) derived from an olefin represented by general formula (I).

[0062] [ka]

[0063] In general formula (I), R 300 This represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.

[0064] The repeating unit (a) represented by general formula (I) can be derived from the olefin monomer represented by the following general formula (Ia).

[0065] [ka]

[0066] In general formula (Ia), R 300 The group represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. Examples of olefin monomers represented by general formula (Ia) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. From the viewpoint of obtaining molded articles with superior moisture and heat resistance, mechanical properties, and optical properties, ethylene and propylene are preferred among these, with ethylene being more preferred. Two or more types of olefin monomers represented by general formula (Ia) may be used. Furthermore, the olefin monomer may include at least one biomass-derived monomer (ethylene, propylene, α-olefin).

[0067] When the total amount of repeating units constituting the cyclic olefin resin (B1) is taken as 100 mol%, the content of repeating units (a) derived from olefin monomers in the cyclic olefin resin (B1) is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, even more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, and even more preferably 50 mol% or more, and from the viewpoint of further improving the flexibility of the solar cell laminate, preferably 90 mol% or less, more preferably 85 mol% or less. More preferably, the amount is 80 mol% or less, more preferably 75 mol% or less, more preferably 70 mol% or less, more preferably 65 mol% or less, and more preferably 60 mol% or less. Furthermore, from the viewpoint of balancing the flexibility and water vapor barrier properties of the laminate for solar cells, it is preferably 5 mol% to 90 mol%, more preferably 10 mol% to 85 mol%, more preferably 15 mol% to 80 mol%, more preferably 20 mol% to 75 mol%, more preferably 30 mol% to 70 mol%, more preferably 40 mol% to 65 mol%, and more preferably 50 mol% to 60 mol%. Furthermore, the content of repeating units (a) derived from olefin monomers is as follows: 13 It can be measured by 13C-NMR.

[0068] The cyclic olefin resin (B1) preferably comprises a repeating unit (AA) represented by general formula (II) and a repeating unit (C) derived from a cyclic olefin containing an aromatic ring, wherein the repeating unit (AA) does not contain an aromatic ring, and the cyclic olefin containing an aromatic ring comprises one or more compounds selected from the group consisting of the compound represented by the following general formula (C-1), the compound represented by the following general formula (C-2), and the compound represented by the following general formula (C-3).

[0069] [ka]

[0070] In general formula (C-1), n ​​and q are each independently 0, 1, or 2. n is preferably 0 or 1, and more preferably 0. q is preferably 0 or 1, and more preferably 0. R 1 ~R 17 Each of these is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and R 10 ~R 17 One of them is a bonding hand, R 15 It is preferable that the coupling is a joint. R 1 ~R 17 Each of these is preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom. Also, when q=0, R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 10 They may be bonded to each other to form a monocycle or polycycle, and when q=1 or 2, R 10 and R 11 , R 11 and R 17 , R 17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , R 16 and R 10These elements may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring. Among the compounds represented by the above general formula (C-1), the compound represented by the following general formula (C-1A) is preferred.

[0071] [ka]

[0072] In the general formula (C-1A), n is 0, 1, or 2, preferably 0 or 1, and more preferably 0.

[0073] [ka]

[0074] In general formula (C-2), n and m are each independently 0, 1, or 2, and q is 1, 2, or 3. m is preferably 0 or 1, and more preferably 1. n is preferably 0 or 1, and more preferably 0. q is preferably 1 or 2, and more preferably 1. R 18 ~R 31 Each of these is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms that may be substituted with a halogen atom other than a fluorine atom. R 18 ~R 31 Each of these is preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom. Also, when q=1, R 28 and R 29 , R 29 and R 30 , R 30 and R 31 They may be bonded to each other to form a monocycle or polycycle, and when q=2 or 3, R 28 and R 28 , R28 and R 29 , R 29 and R 30 , R 30 and R 31 , R 31 and R 31 These elements may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

[0075] [ka]

[0076] In general formula (C-3), q is 1, 2, or 3, preferably 1 or 2, and more preferably 1. R 32 ~R 39 Each of these is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms that may be substituted with a halogen atom other than a fluorine atom. R 32 ~R 39 Each of these is preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom. Also, when q=1, R 36 and R 37 , R 37 and R 38 , R 38 and R 39 They may be bonded to each other to form a monocycle or polycycle, and when q=2 or 3, R 36 and R 36 , R 36 and R 37 , R 37 and R 38 , R 38 and R 39 , R 39 and R 39 These elements may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

[0077] Furthermore, examples of hydrocarbon groups having 1 to 20 carbon atoms include, independently, alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 15 carbon atoms, and aromatic hydrocarbon groups. More specifically, alkyl groups include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl groups; cycloalkyl groups include cyclohexyl groups; and aromatic hydrocarbon groups include aryl or aralkyl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl groups. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms.

[0078] The cyclic olefin containing the aromatic ring in this embodiment preferably comprises one or more selected from the group consisting of benzonorbornane, indenenorbornene, and methylphenylnorbornene, and more preferably comprises indenenorbornene, from the viewpoint of improving the mechanical properties of the solar cell laminate.

[0079] When the total amount of repeating units constituting the cyclic olefin resin (B1) is set to 100 mol%, the content of repeating units (C) derived from cyclic olefins containing aromatic rings in the cyclic olefin resin (B1) is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, even more preferably 7 mol% or more, even more preferably 10 mol% or more, even more preferably 12 mol% or more, even more preferably 15 mol% or more, and even more preferably 18 mol% or more, and from the viewpoint of further improving the flexibility of the solar cell laminate, it is preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably The amount is 70 mol% or less, more preferably 60 mol% or less, more preferably 50 mol% or less, more preferably 40 mol% or less, more preferably 30 mol% or less, and more preferably 25 mol% or less. Furthermore, from the viewpoint of balancing the mechanical properties and flexibility of the laminate for solar cells, it is preferably 1 mol% to 90 mol%, more preferably 3 mol% to 80 mol%, more preferably 5 mol% to 70 mol%, more preferably 7 mol% to 60 mol%, more preferably 10 mol% to 50 mol%, more preferably 12 mol% to 40 mol%, more preferably 15 mol% to 30 mol%, and more preferably 18 mol% to 25 mol%. Furthermore, the content of repeating units (C) derived from cyclic olefins containing aromatic rings is as follows: 13 It can be measured by 13C-NMR.

[0080] The cyclic olefin resin (B1) preferably comprises a repeating unit (AA) represented by general formula (II), a repeating unit (a) derived from an olefin represented by general formula (I), and a repeating unit derived from a cyclic non-conjugated diene represented by the following general formula (Y).

[0081] [ka]

[0082] In the general formula (Y), u is 0 or 1, v is 0 or a positive integer, preferably an integer between 0 and 2, more preferably 0 or 1, w is 0 or 1, R 61 ~R 76 Furthermore, R a1 and R b1 These may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 104 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer from 0 to 10, and R 75 and R 76 These elements may be bonded to each other to form a monocycle or polycycle.

[0083] The heat resistance of the solar cell laminate of this embodiment can be improved by including repeating units derived from a cyclic non-conjugated diene represented by the general formula (Y) in the cyclic olefin resin (B1). Specifically, even after the cyclic olefin resin (B1) exceeds its glass transition temperature, the elastic modulus of layer (B) is less likely to decrease, thereby improving the shape retention and impact resistance of the solar cell laminate during heating. Furthermore, the cyclic olefin resin (B1) can form a crosslinked structure by incorporating carbon-carbon double bonds in its side chains. This increases the glass transition temperature of the crosslinked cyclic olefin resin (B1), thereby improving the heat resistance of the solar cell laminate.

[0084] The solubility of the cyclic olefin resin (B1) can be improved by including repeating units derived from a cyclic non-conjugated diene represented by general formula (Y). This makes it easier to increase the concentration of the varnish and to easily increase the thickness of the layer (B).

[0085] By including repeating units derived from a cyclic non-conjugated diene represented by general formula (Y) in the cyclic olefin resin (B1), layer (B) can be formed by applying a varnished cyclic olefin resin (B1) and then crosslinking it. This improves adhesion to layers that are difficult to adhere to, such as inorganic layers containing layer (A). Furthermore, by adjusting the varnish composition, it becomes possible to adjust the difference in the coefficient of thermal expansion between layers, thereby suppressing delamination. Furthermore, improving the adhesion of layer (B) can improve the power generation stability of the solar cell module.

[0086] By including repeating units derived from a cyclic non-conjugated diene represented by general formula (Y) in the cyclic olefin resin (B1), the variety of selectable crosslinking agents can be increased, thereby allowing for easy adjustment of the physical properties of layer (B).

[0087] The repeating units derived from cyclic non-conjugated dienes represented by general formula (Y) can be derived from cyclic non-conjugated dienes represented by the following general formula (Ya).

[0088] [ka]

[0089] In the general formula (Ya), u is 0 or 1, v is 0 or a positive integer, preferably an integer between 0 and 2, more preferably 0 or 1, w is 0 or 1, R 61 ~R 76 Furthermore, R a1 and R b1 These may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 104 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer from 0 to 10, and R 75 and R 76 These elements may be bonded to each other to form a monocycle or polycycle.

[0090] The cyclic non-conjugated dienes represented by the general formula (Ya) are not limited to these, but examples include the cyclic non-conjugated dienes represented by the following chemical formulas. Among these, 5-vinyl-2-norbornene and 8-vinyl-9-methyltetracyclo[4.4.0.1 2,5 .1 7,10 A species selected from the group consisting of ]-3-dodecene is preferred, and 5-vinyl-2-norbornene is more preferred.

[0091] [ka]

[0092] [ka]

[0093] The cyclic non-conjugated diene represented by the general formula (Ya) can also be specifically represented by the following general formula (Yb).

[0094] [ka]

[0095] In the general formula (Yb), n is an integer between 0 and 10, R1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0096] When the total amount of repeating units constituting the cyclic olefin resin (B1) is set to 100 mol%, the content of repeating units derived from the cyclic non-conjugated diene represented by general formula (Y) in the cyclic olefin resin (B1) is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, even more preferably 7 mol% or more, even more preferably 10 mol% or more, even more preferably 15 mol% or more, even more preferably 20 mol% or more, and even more preferably 23 mol% or more, from the viewpoint of improving the heat resistance of the solar cell laminate of this embodiment, improving the solubility of the cyclic olefin resin (B1), and improving the adhesion of the layer (B), and from the viewpoint of further improving the flexibility of the solar cell laminate of this embodiment, it is preferably 80 mol% or less, more preferably The amount is 70 mol% or less, more preferably 60 mol% or less, more preferably 50 mol% or less, more preferably 40 mol% or less, more preferably 35 mol% or less, and more preferably 30 mol% or less. Furthermore, from the viewpoint of balancing the heat resistance of the solar cell laminate of this embodiment, the solubility of the cyclic olefin resin (B1), the adhesion of the layer (B), and the flexibility of the solar cell laminate, it is preferably 1 mol% to 80 mol%, more preferably 3 mol% to 70 mol%, more preferably 5 mol% to 60 mol%, more preferably 7 mol% to 50 mol%, more preferably 10 mol% to 40 mol%, more preferably 15 mol% to 35 mol%, more preferably 20 mol% to 30 mol%, and more preferably 23 mol% to 30 mol%. Furthermore, the content of repeating units derived from cyclic non-conjugated dienes represented by general formula (Y) is: 13 It can be measured by 13C-NMR.

[0097] The cyclic olefin resin (B1) includes, for example, one or two selected from the group consisting of random copolymers and block copolymers, and preferably includes a random copolymer from the viewpoint of further improving the water vapor barrier properties and flexibility of the solar cell laminate.

[0098] The cyclic olefin resin (B1) is preferably composed of ethylene and tetracyclo[4.4.0.1 2,5 .1 7,10 Random copolymer with ]-3-dodecene; ethylene and tetracyclo[4.4.0.1 2,5 .1 7,10 It comprises one or two selected from the group consisting of a random copolymer of ]-3-dodecene and 5-vinyl-2-norbornene, and a random copolymer of ethylene and bicyclo[2.2.1]-2-heptene.

[0099] The cyclic olefin resin (B1) may also contain a ring-opening polymer of a cyclic olefin. Examples of ring-opening polymers of cyclic olefins include ring-opening polymers of norbornene monomers, ring-opening polymers of norbornene monomers and other monomers copolymerizable therewith, and their hydrides.

[0100] Examples of norbornene monomers include bicyclo[2.2.1]hepto-2-ene (common name: norbornene) and its derivatives (those with substituents on the ring), tricyclo[4.3.0 1,6 .1 2,5 Deca-3,7-diene (common name dicyclopentadiene) and its derivatives, 7,8-benzotricyclo[4.3.0.1 2,5 Deca-3-ene (common name methanotetrahydrofluorene: also called 1,4-methano-1,4,4a,9a-tetrahydrofluorene) and its derivatives, tetracyclo[4.4.0.1 2,5 .1 7,10 Examples include ]-3-dodecene (common name: tetracyclododecene) and its derivatives. Substituents that can be substituted on the rings of these derivatives include alkyl groups, alkylene groups, vinyl groups, alkoxycarbonyl groups, alkylidene groups, and the like. The derivatives may have one or more substituents. An example of a derivative having substituents on such a ring is 8-methoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10] Dodeca-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, 8-ethylidene-tetracyclo[4.4.0.1 2,5 .1 7,10 Examples include dodeca-3-en. These norbornene monomers can be used individually or in combination of two or more.

[0101] The cyclic olefin resin (B1) is preferably tetracyclo[4.4.0.1 2,5 .1 7,10 It contains a hydride of a ring-opening copolymer of ]-3-dodecene, dicyclopentadiene, and indene norbornene.

[0102] The water vapor transmission coefficient, measured in accordance with JIS K 7129:2008, at a measurement temperature of 40°C and a measurement humidity of 90%RH, is preferably 1.0 g·mm / m², from the viewpoint of further improving the water vapor barrier properties and flexibility of the solar cell laminate. 2 / 24h or less, more preferably 0.8g·mm / m 2 / 24h or less, more preferably 0.6 g·mm / m 2 / 24h or less, more preferably 0.5g·mm / m 2 / 24h or less, more preferably 0.4g·mm / m 2 / 24h or less, more preferably 0.3g·mm / m 2 / 24h or less, more preferably 0.2g·mm / m 2 It is less than / 24h, and for example, 0.0001g·mm / m 2 / 24h or longer is acceptable, and 0.001g·mm / m 2 / 24h or longer is acceptable, and 0.01g·mm / m 2 It may be 24 hours or more, and from the viewpoint of further improving the water vapor barrier properties and flexibility of the solar cell laminate, it is preferably 0.0001 g·mm / m 2 / 24h or more 1.0g·mm / m 2 / 24h or less, more preferably 0.0001 g·mm / m 2 / 24h or more 0.8g·mm / m 2 / 24h or less, more preferably 0.0001 g·mm / m 2 / 24h or more 0.6g·mm / m 2 / 24h or less, more preferably 0.0001 g·mm / m 2 / 24h or more 0.5g·mm / m 2 / 24h or less, more preferably 0.0001 g·mm / m 2 / 24h or more 0.4g·mm / m 2 / 24h or less, more preferably 0.001 g·mm / m 2 / 24h or more 0.3g·mm / m 2 / 24h or less, more preferably 0.01 g·mm / m 2 / 24h or more 0.2g·mm / m 2 It is less than 24 hours.

[0103] Layer (B) may contain resins other than the cyclic olefin resin (B1), additives, etc., as long as they do not impair the effects of the present invention.

[0104] (3) Other layers The solar cell laminate of this embodiment may include layers other than layer (A) and layer (B). The other layers will be described below.

[0105] The solar cell laminate of this embodiment may include, for example, transparent electrodes. The solar cell laminate of this embodiment may include, for example, a back electrode. In this embodiment, either the transparent electrode or the back electrode may be the cathode or the anode. The transparent electrode and back electrode of this embodiment include, for example, one or more selected from the group consisting of metals such as FTO (fluorine-doped tin oxide), sodium, sodium-potassium alloy, lithium, magnesium, aluminum, magnesium-silver mixture, magnesium-indium mixture, aluminum-lithium alloy, Al / Al2O3 mixture, Al / LiF mixture, and gold; conductive transparent materials such as CuI, ITO (indium tin oxide), SnO2, AZO (aluminum zinc oxide), IZO (indium zinc oxide), and GZO (gallium zinc oxide); and conductive transparent polymers.

[0106] The solar cell laminate of this embodiment may include, for example, an electron transport layer. The electron transport layer of this embodiment includes, for example, one or more selected from the group consisting of N-type conductive polymers, N-type low molecular weight organic semiconductors, N-type metal oxides, N-type metal sulfides, alkali metal halides, alkali metals, and surfactants, and preferably one or more selected from the group consisting of cyano group-containing polyphenylene vinylene, boron-containing polymers, vasocuproin, vasophenanthrene, hydroxyquinolinatoaluminum, oxadiazole compounds, benzimidazole compounds, naphthalenetetracarboxylic acid compounds, perylene derivatives, phosphine oxide compounds, phosphine sulfide compounds, fluoro group-containing phthalocyanines, titanium dioxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, and zinc sulfide. The thickness of the electron transport layer in this embodiment is preferably 1 nm or more, more preferably 3 nm or more, and even more preferably 5 nm or more. This allows for sufficient hole blocking. The thickness of the electron transport layer in this embodiment is preferably 2000 nm or less, more preferably 1000 nm or less, and even more preferably 500 nm or less. This reduces resistance during electron transport and improves photoelectric conversion efficiency.

[0107] The solar cell laminate of this embodiment may include, for example, a hole transport layer. The hole transport layer of this embodiment comprises, for example, one or more selected from the group consisting of P-type conductive polymers, P-type low molecular weight organic semiconductors, P-type metal oxides, P-type metal sulfides, and surfactants, preferably a compound having a thiophene skeleton such as poly(3-alkylthiophene); a conductive polymer having a triphenylamine skeleton, poly(p-phenylenevinylene) skeleton, polyvinylcarbazole skeleton, polyaniline skeleton, and polyacetylene skeleton; a phthalocyanine skeleton, naphthalocyanine skeleton, pentacene skeleton, benzoporin The material comprises one or more selected from the group consisting of: compounds having porphyrin skeletons such as pyline skeletons and spirobifluorene skeletons; oxides such as molybdenum oxide, vanadium oxide, tungsten oxide, nickel oxide, copper oxide, and tin oxide; sulfides such as molybdenum sulfide, tungsten sulfide, copper sulfide, and tin sulfide; phosphonic acid compounds such as fluoro group-containing phosphonic acid and carbonyl group-containing phosphonic acid; copper compounds such as CuSCN and CuI; and carbon-containing materials such as carbon nanotubes and graphene. In this embodiment, the thickness of the hole transport layer when it exists as a thin film is preferably 1 nm or more, more preferably 3 nm or more, and even more preferably 5 nm or more. This allows for sufficient blocking of electrons. In this embodiment, the thickness of the hole transport layer when it exists as a thin film is preferably 2,000 nm or less, more preferably 1,000 nm or less, and even more preferably 500 nm or less. This reduces resistance during electron transport and improves photoelectric conversion efficiency.

[0108] 2. Solar cell modules The solar cell module of this embodiment will be described below.

[0109] The solar cell module of this embodiment includes the laminate for solar cells of this embodiment.

[0110] The configuration of the solar cell module in this embodiment is not particularly limited, but for example, it may be a panel-shaped module in which multiple solar cell stacks are arranged.

[0111] According to FIG. 2 showing the upper surface of an example of the solar cell module of the present embodiment, in the solar cell module 100, a plurality of solar cell laminate bodies 10 are arranged in each of the spaces formed by the frame 11. Further, according to FIG. 3 showing a cross section of an example of the solar cell module of the present embodiment, the frame 11 and the solar cell laminate body 10 are arranged on the substrate 13, and a transparent protection member 12 is further arranged thereon.

[0112] The material of the frame 11 is not particularly limited, and any material can be selected as long as the object of the present invention can be achieved.

[0113] The material of the transparent protection member 12 is not particularly limited, and any material can be selected as long as the object of the present invention can be achieved. For example, tempered glass, transparent resin, etc. can be selected.

[0114] The material of the substrate 13 is not particularly limited, and any material can be selected as long as the object of the present invention can be achieved.

[0115] 3. Solar cell varnish Hereinafter, the solar cell varnish of the present embodiment will be described.

[0116] The solar cell varnish of the present embodiment is a solar cell varnish containing a cyclic olefin resin (B1) and a solvent, wherein the solar cell contains a layer (A) containing a perovskite compound, the glass transition temperature Tg of the cyclic olefin resin (B1) is 45°C or higher and 280°C or lower, and the cyclic olefin resin (B1) contains a repeating unit (AA) represented by the following general formula (II), a repeating unit (a) derived from an olefin represented by the following general formula (I), and a repeating unit derived from a cyclic non-conjugated diene represented by the following general formula (Y).

[0117]

Chemical formula

[0118] In general formula (II), u is 0 or 1, v is 0 or a positive integer, preferably an integer between 0 and 2, more preferably 0 or 1, w is 0 or 1, R 61 ~R 78 Furthermore, R a1 and R b1 These may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 75 ~R 78 These elements may be bonded to each other to form a monocycle or polycycle.

[0119] [ka]

[0120] In general formula (I), R 300 This represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.

[0121] [ka]

[0122] In the general formula (Y), u is 0 or 1, v is 0 or a positive integer, preferably an integer between 0 and 2, more preferably 0 or 1, w is 0 or 1, R 61 ~R 76 Furthermore, R a1 and R b1 These may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 104 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer from 0 to 10, and R 75 and R 76 These elements may be bonded to each other to form a monocycle or polycycle.

[0123] The solvents of this embodiment include, for example, aromatic hydrocarbon solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, and decane; alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and decahydronaphthalene; chlorinated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, and tetrachloroethylene; 1-methyl-2-pyrrolidone, ethylene carbonate, propylene carbonate, γ-butyrolactone, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, tributyl acetyl citrate, 2,4-pentadiene, dimethyl sulfoxide, n-alkyl adipate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, and 3-methoxy-3-methyl-1-butyl acetate. The varnish contains one or more solvents selected from the group consisting of ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, and cyclohexanone; alcohol solvents such as benzyl alcohol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-ethyl-1-hexanol, n-propyl alcohol, isopropyl alcohol, ethanol, and methanol; ether solvents such as ethyl ether, ethylene glycol monomethyl ether, anisole, phenyl ether, dioxane, and tetrahydrofuran; and ester solvents such as ethyl acetate and butyl acetate. From the viewpoint of long-term stability, solubility, and versatility of the varnish, it preferably contains at least one or more solvents selected from the group consisting of toluene, xylene, and cyclohexane.

[0124] In this embodiment, the method for preparing the varnish may be any method, but may include, for example, a step of mixing an adhesive resin composition with a solvent. There are no restrictions on the order in which the components are mixed, and it can be done in any way, such as all at once or in stages. There are also no restrictions on the apparatus for preparing the varnish, and it may be carried out using any batch or continuous apparatus capable of stirring and mixing. The temperature when preparing the varnish can be arbitrarily selected within the range from room temperature to the boiling point of the solvent. The reaction solution obtained when the cyclic olefin resin (B1) is acquired may be used as the solvent as is.

[0125] The varnish of this embodiment may contain components other than the cyclic olefin resin (B1) and solvent, for example, one or more selected from the group consisting of thermal radical initiators, photoradical initiators and crosslinking agents such as sulfur compounds; photosensitizers; vulcanization accelerators; vulcanization accelerator aids; crosslinking aids; and antioxidants such as phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants and thioether antioxidants.

[0126] The thermal radical initiators of this embodiment include, for example, dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, 2,5-bis(t-butylperoxy)2,5-dimethylhexane, 2,5-bis(t-butylperoxy)2,5-dimethylhexine-3, di-t-butyl peroxide, isopropylcumyl-t-butyl peroxide and bis(α-t-butylperoxyisopropyl)benzene; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl-4,4-bis(t-butylperoxy)valerate, ethyl-3,3-bis(t-butylperoxy)butyrate and 3, It includes one or more selected from the group consisting of peroxyketals such as 3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxycyclononane; peroxyesters such as bis(t-butylperoxy)isophthalate, t-butylperoxybenzoate, and t-butylperoxyacetate; hydroperoxides such as t-butyl hydroperoxide, t-hexyl hydroperoxide, cumin hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, and p-menthane hydroperoxide; bibenzyl compounds such as 2,3-dimethyl-2,3-diphenylbutane; and 3,3,5,7,7-pentamethyl-1,2,4-trioxepane.

[0127] The photoradical initiator of this embodiment includes, for example, one or more selected from the group consisting of benzoin alkyl ether, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, methylbenzoylformate, and isopropylthioxanthone.

[0128] In addition, a photosensitizer may be used in combination with the photoradical initiator of this embodiment. The photosensitizer of this embodiment includes, for example, one or more selected from the group consisting of carbonyl compounds such as anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzantrone, p,p'-tetramethyldiaminobenzophenone and chloranil; nitro compounds such as nitrobenzene, p-dinitrobenzene and 2-nitrofluorene; aromatic hydrocarbons such as anthracene and chrysene; sulfur compounds such as diphenyl disulfide; and nitrogen compounds such as nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene and tetracyanoethylene.

[0129] The sulfur-based compound of this embodiment comprises one or more selected from the group consisting of sulfur, sulfur monochloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dimethyldithiocarbamate.

[0130] Furthermore, a vulcanization accelerator may be used in combination with the sulfur-based compound of this embodiment. The vulcanization accelerators of this embodiment include, for example, thiazole-based vulcanization accelerators such as N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, N,N-diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio)benzothiazole and benzothiadyl disulfide; guanidine-based vulcanization accelerators such as diphenylguanidine, triphenylguanidine, di-ortho-tolylguanidine, orthotrylbiguanide and diphenylguanidine phthalate; acetaldehyde-aniline reaction products; butyraldehyde-aniline condensates; aldehydeamine or aldehyde-ammonia-based vulcanization accelerators such as hexamethylenetetramine and acetaldehyde ammonia; and 2-mercapto It comprises one or more selected from the group consisting of imidazoline-based vulcanization accelerators such as midazoline; thiourea-based vulcanization accelerators such as thiocarbanilide, diethylthiourea-dibutylthiourea, trimethylthiourea, and diorthotrilthiourea; thiram-based vulcanization accelerators such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, and dipentamethylenethiuram tetrasulfide; dithioate-based vulcanization accelerators such as zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium diethyldithiocarbamate; and xantate-based vulcanization accelerators such as zinc dibutylxanthogenicate.

[0131] Furthermore, a vulcanization accelerator may be used in combination with the vulcanization accelerator of this embodiment. The vulcanization accelerator of this embodiment contains, for example, one or more selected from the group consisting of metal oxide-based vulcanization accelerators such as zinc oxide, active zinc white, zinc carbonate, composite zinc white, magnesium oxide, litharge, red lead, and basic lead carbonate; fatty acid-based vulcanization accelerators such as stearic acid, oleic acid, lauric acid, and lead stearate; and organic amine / glycol-based vulcanization accelerators such as triethanolamine and diethylene glycol.

[0132] The crosslinking aid of this embodiment contains, for example, one or more selected from the group consisting of oximes such as p - quinonedioxime and p,p'-dibenzoylquinonedioxime; acrylates or methacrylates such as ethylene dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, cyclohexyl methacrylate, acrylic acid / zinc oxide mixture, and allyl methacrylate; vinyl monomers such as divinylbenzene, vinyltoluene, and vinylpyridine; allyl compounds such as hexamethylenediallylnadiimide, diallyl itaconate, diallyl phthalate, diallyl isophthalate, diallyl monoglycidyl isocyanurate, triallyl cyanurate, and triallyl isocyanurate; maleimide compounds such as N,N'-m-phenylenebismaleimide and N,N'-(4,4'-methylenediphenylene) dimaleimide; and cyclic non-conjugated dienes such as vinyl norbornene, ethylidene norbornene, and dicyclopentadiene.

[0133] The phenolic antioxidants of this embodiment include, for example, acrylate-based phenolic compounds described in Japanese Patent Publication No. 63-179953 and Japanese Patent Publication No. 1-168643, such as 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate and 2,4-di-t-amyl-6-(1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl)phenylacrylate; 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 4,4'-butylidene-bis(6-t-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-t-butylphenol), bis(3-cyclohexyl-2-hydroxy-5-methylphenyl)methane, 3,9-bis(2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5] Alkyl-substituted phenolic compounds such as undecane, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis(methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenylpropionate)methane [i.e., pentaerythrimethyl-tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenylpropionate)], pentaerythritol=tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, triethylene glycol bis(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate) and tocopherol; Furthermore, it contains one or more triazine group-containing phenolic compounds selected from the group consisting of 6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bisoctylthio-1,3,5-triazine, 6-(4-hydroxy-3,5-dimethylanilino)-2,4-bisoctylthio-1,3,5-triazine, 6-(4-hydroxy-3-methyl-5-t-butylanilino)-2,4-bisoctylthio-1,3,5-triazine, and 2-octylthio-4,6-bis-(3,5-di-t-butyl-4-oxyanilino)-1,3,5-triazine, preferably one or more selected from the group consisting of acrylate-based phenolic compounds and alkyl-substituted phenolic compounds, and more preferably an alkyl-substituted phenolic compound.

[0134] Examples of phosphorus-based antioxidants in this embodiment include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(2-t-butyl-4-methylphenyl) phosphite, tris(cyclohexylphenyl) phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite, and 9,10-dihydro-9-oxa-10-phosphite. Monophosphite compounds such as sphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene; as well as 4,4'-butylidene-bis(3-methyl-6-t-butylphenyl-ditridecyl phosphite), 4,4'-isopropylidene-bis(phenyl-dialkyl(C12~C15) phosphite), 4, 4'-Isopropylidene-bis(diphenyl monoalkyl (C12~C15) phosphite), 1,1,3-Tris(2-methyl-4-di-tridecyl phosphite-5-t-butylphenyl)butane, Tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylenediphosphite, Cyclic neopentanetetraylbis(isodecyl phosphite), Cyclic neopentanetetraylbis(nonylphenyl phosphite), Cyclic neopentanetetraylbis(2,4-di-t-butylphenyl phosphite) The compound comprises one or more diphosphite compounds selected from the group consisting of cyclic neopentanetetraylbis(2,4-dimethylphenyl phosphite) and cyclic neopentanetetraylbis(2,6-di-t-butylphenyl phosphite), preferably a monophosphite compound, and more preferably one or more diphosphite compounds selected from the group consisting of tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, and tris(2,4-di-t-butylphenyl) phosphite.

[0135] The sulfur-based antioxidant of this embodiment includes, for example, one or more selected from the group consisting of dilauryl 3,3-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, laurylstearyl 3,3-thiodipropionate, pentaerythritol-tetrakis-(β-lauryl-thio-propionate), and 3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane.

[0136] The thioether-based antioxidant of this embodiment includes, for example, one or more selected from the group consisting of tetrakis{methylene-3-(laurylthio)propionate}methane, bis[methyl-4-{3-n-alkyl(C12 or C14)thiopropioniodyl}-5-t-butylphenyl]sulfide, and ditridecyl-3,3'-thiodipropionate.

[0137] The preferred embodiment of the cyclic olefin resin (B1) in the solar cell varnish of this embodiment is the same as the preferred embodiment of the cyclic olefin resin (B1) in the solar cell laminate of this embodiment.

[0138] Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted. Furthermore, the present invention is not limited to the embodiments described above, and any modifications, improvements, etc., that can achieve the objectives of the present invention are included in the present invention. [Examples]

[0139] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

[0140] The glass transition temperature (Tg) of the resin in each example was determined from the endothermic curve obtained using a Shimadzu Science DSC-6220 under an N2 (nitrogen) atmosphere and the following temperature conditions. The results are shown in Table 1. (Temperature conditions) The temperature was raised from room temperature to 300°C at a rate of 10°C / min, held for 5 minutes, then cooled to -20°C at a rate of 10°C / min, held for 5 minutes, and then raised to 300°C at a rate of 10°C / min.

[0141] The content ratio of each repeating unit constituting the resin in each example was obtained using a JEOL Corporation ECA500 nuclear magnetic resonance spectrometer under the following conditions. 13 The results were obtained from 1C-NMR spectra. The results are shown in Table 1. Solvent: Deuterated tetrachloroethane Sample concentration: 50-100 g / l-solvent Pulse repetition time: 5.5 seconds Cumulative number of times: 6,000 to 16,000 Measurement temperature: 120℃

[0142] <Examples 1-3> (Preparation of catalyst) Ethyl aluminum sesquichloride (Al(C2H5) 1.5 Cl 1.5 The solution was diluted with cyclohexane to prepare an organoaluminum compound catalyst solution.

[0143] (polymerization) In a stirred polymerizer, the organoaluminum compound catalyst solution prepared by the above method is used as a catalyst to polymerize ethylene and tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene (hereinafter sometimes referred to as TD) was copolymerized to obtain a copolymer solution. Ethylene was supplied into the polymerizer along with hydrogen gas. The amount of each repeating unit was adjusted to the amounts shown in Table 1 by adjusting the supply amounts of ethylene, TD, and hydrogen.

[0144] (Decalcification) Water and an aqueous sodium hydroxide solution were added to the obtained copolymer solution to stop the polymerization reaction and remove catalyst residue from the copolymer solution (decalcification). Pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] was added to the decalcified solution as a stabilizer and mixed in a stirring tank for 1 hour.

[0145] (Solvent removal) The solution, mixed with a stabilizer, was heated to 180°C to remove the solvent and unreacted monomers, thereby obtaining a molten resin (a random copolymer of ethylene and TD).

[0146] (Press forming) The obtained resin was press-molded into a 50 μm thick sheet (temperature: 260°C, pressure: 10 MPa), and these were designated as resins A to C.

[0147] (Formation of layer (A)) CH3NH3I and PbCl2 were dissolved in N,N-dimethylformamide (DMF) in a molar ratio of 3:1 to prepare the perovskite layer formation solution. The total weight concentration of CH3NH3I and PbCl2 in the perovskite layer formation solution was adjusted to 20%. Next, layer (A) was formed on the surface of resins A to C by applying the perovskite layer-forming solution obtained by the above method using a spin-coating method, and this was designated as laminates A to C.

[0148] <Example 4> The raw materials used in the resin synthesis were as follows: Transition metal compound (1) (Synthesized by the method described in Japanese Patent Publication No. 2004-331965.)

[0149] [ka]

[0150] Modified methylaluminoxane (MMAO, manufactured by Tosoh Finechem Co., Ltd.) Toluene (manufactured by Wako Pure Chemical Industries, Ltd.: Wako Special Grade) 5-Vinyl-2-norbornene (hereinafter referred to as VNB) (manufactured by Tokyo Chemical Industry Co., Ltd.) Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene (hereinafter referred to as TD) (manufactured by Mitsui Chemicals, Inc.) Methanol (manufactured by Fujifilm Wako Pure Chemical Industries: Wako Special Grade)

[0151] The procedure for resin synthesis was as follows: In a 1 L stainless steel autoclave that had been thoroughly purged with nitrogen, a hexane solution of 450 mL of toluene, 30 mL of VNB, 16 mL of TD, and MMAO (0.9 mmol in Al equivalent) and 360 mL of hydrogen were added. Then, ethylene was introduced into the system until the total pressure reached 0.6 MPa. Next, a toluene solution of 0.028 mmol of transition metal compound (1) was added, and polymerization was carried out at 35°C for 180 minutes. Next, polymerization was stopped by injecting 1 mL of methanol under pressure. Then, deionized water was added and the mixture was stirred for 1 hour, and the organic layer was filtered through filter paper. This organic layer was then added to acetone to precipitate the resin, stirred, filtered through filter paper, and dried under reduced pressure at 80°C for 10 hours to obtain the resin (a random copolymer of ethylene, VNB, and TD).

[0152] The obtained resin was press-molded under the same conditions as in Examples 1-3, and this was designated as resin D. Next, a layer (A) was formed on the surface of resin D under the same conditions as in Examples 1-3, and this was designated as laminate D.

[0153] <Example 5> To 100 parts by mass of the resin obtained in Example 4, 0.6 parts by mass of the radical initiator DMDPB (2,3-dimethyl-2,3-diphenylbutane, manufactured by Acros Organics) and 0.06 parts by mass of the antioxidant Irganox1010 (pentaerythritol = tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, manufactured by BASF) were added, and the mixture was stirred until it was completely dissolved to obtain the composition. The obtained composition was coated onto a release-treated PET film and dried for 4 minutes in a forced-air dryer under a nitrogen stream at 150°C to obtain a laminated film. Then, another laminated film was obtained using the same procedure. The two resulting laminated films were stacked so that the coated surfaces of the composition were in contact with each other. Under a vacuum controlled to 20 kPa or less, the press pressure was increased to 3.5 MPa using a vacuum press, and the temperature was raised at a constant rate from room temperature (25°C) and held at 180°C for 60 minutes. The PET film was then peeled off to obtain the resin E precursor. Next, the resin E precursor was sandwiched between polyimide films, and under a vacuum controlled to less than 20 kPa using a vacuum press, the press pressure was increased to 3.5 MPa. The temperature was then raised at a constant rate from room temperature (25°C) and held at 220°C for 120 minutes. Subsequently, the polyimide films were peeled off to obtain resin E with a thickness of 50 μm. Next, a layer (A) was formed on the surface of resin E under the same conditions as in Examples 1 to 3, and this was designated as laminate E.

[0154] <Examples 6-8> 2-norbornene, tri-n-octylaluminum, and 2,6-di-tert-butyl-4-hydroxytoluene were supplied to a pressure polymerizer that had been substituted with a nitrogen atmosphere. Then, ethylene was supplied to the polymerizer along with hydrogen gas. The amount of each repeating unit was adjusted to the amounts shown in Table 1 by adjusting the ratio of the supplied amounts of 2-norbornene and ethylene. Next, it was diluted with toluene. Next, a toluene solution of the titanocene catalyst was added to the solution in the polymerizer. The titanocene catalyst used was the one shown in formula (2) below.

[0155] [ka]

[0156] Next, a toluene solution of the borate compound was added. Triphenylmethylium tetrakis(pentafluorophenyl)borate was used as the borate compound. The addition polymerization reaction was initiated by adding a titanocene catalyst and a borate compound. After the reaction, a small amount of 2-propanol was added to the reaction solution to stop the addition polymerization reaction. Hydrochloric acid was added to the reaction solution and stirred for 10 minutes, after which the organic layer was washed with deionized water. Washing with deionized water was repeated until the aqueous layer became neutral, and then the washed organic layer was collected. The collected organic layer was added dropwise to a large amount of acetone to precipitate the resulting resin. After collecting the precipitated resin by filtration, the resin was washed at least twice with methanol and acetone. The washed resin was dried under reduced pressure at 110°C for at least 16 hours to obtain a dried resin (random copolymer of ethylene and norbornene).

[0157] The obtained resins were press-molded under the same conditions as in Examples 1-3, and these were designated as resins F-H. Next, a layer (A) was formed on the surface of resins F-H under the same conditions as in Examples 1-3, and these were designated as laminates F-H.

[0158] <Example 9> In a polymerization reactor whose interior was purged with nitrogen, 7 parts by mass of monomer mixture (tetracyclododecene 40 mol%, dicyclopentadiene 40 mol%, indene norbornene 20 mol%), 1600 parts by mass of anhydrous cyclohexane, 0.6 parts by mass of 1-hexene, 1.3 parts by mass of diisopropyl ether, 0.33 parts by mass of isobutyl alcohol, 0.84 parts by mass of triisobutylaluminum, and 30 parts by mass of a cyclohexane solution of tungsten hexachloride (concentration: 0.66%) were added, and the entire volume was stirred at 55°C for 10 minutes. Next, while continuing to stir, 693 parts by mass of the monomer mixture and 72 parts by mass of a cyclohexane solution of tungsten hexachloride (concentration: 0.77%) were added dropwise at 55°C, each over a period of 150 minutes. After the addition was complete, stirring was continued for another 30 minutes, and then 1.0 part by mass of isopropyl alcohol was added to stop the polymerization reaction. When the polymerization reaction solution was measured by gas chromatography, the conversion rate of the monomers to polymers was 100%. Next, 300 parts by mass of the polymerization reaction solution containing the above polymer was transferred to an autoclave equipped with a stirrer, and 100 parts by mass of cyclohexane and 2.0 parts by mass of diatomaceous earth-supported nickel catalyst (nickel load 58%) were added. After purging the autoclave with hydrogen, the hydrogenation reaction was carried out at 180°C and under a hydrogen pressure of 4.5 MPa for 6 hours. After the hydrogenation reaction was complete, the solution was filtered under pressure at 0.25 MPa using a pressure filter with diatomaceous earth as the filter bed to obtain a colorless, transparent solution. The solution was then added to a beaker containing three times the amount of acetone under stirring to precipitate the resin (a hydride of a ring-opening copolymer of tetracyclododecene, dicyclopentadiene, and indene norbornene).

[0159] The obtained resin was press-molded under the same conditions as in Examples 1-3, and this was designated as resin I. Next, a layer (A) was formed on the surface of resin I under the same conditions as in Examples 1-3, and this was designated as laminate I.

[0160] <Comparative Example 1> PET (polyethylene terephthalate) resin sheet (thickness: 50 μm, water vapor transmission coefficient: 1.4 g·mm / m²) 2 A layer (A) was formed on the surface of the material (24h) under the same conditions as in Examples 1-3 to obtain a laminate.

[0161] [Water vapor transmission coefficient] In accordance with JIS K 7129:2008, the water vapor transmission coefficients of laminates A to I were measured using a MOCON PERMATRAN-W3 at a measurement temperature of 40°C and a measurement humidity of 90%RH. In Comparative Example 1, the water vapor transmission coefficient of layer (A) as a single layer was calculated. Specifically, the water vapor transmission coefficient of a laminate formed by creating layer (A) on the surface of a PET resin sheet with a known water vapor transmission coefficient was measured, and the water vapor transmission coefficient of the PET resin sheet was subtracted from this value and multiplied by the thickness of layer (A) to calculate the water vapor transmission coefficient of layer (A) as a single layer. In other words, the water vapor transmission coefficient of layer (A) as a single layer was calculated using the following formula. Water vapor permeability coefficient of layer (A) as a single layer (unit: g·mm / m 2 (24 hours) = {Water vapor transmission rate of laminate (unit: g / m³) 2 (24h) - Calculated water vapor transmission rate of PET resin sheet (unit: g / m²) 2 / 24h)} × Thickness of layer (A) (unit: mm) The results are shown in Table 1.

[0162] [Flexibility] Laminates A through I were folded at a 30-degree angle and evaluated according to the following criteria. In Comparative Example 1, the flexibility of layer (A) as a single layer was evaluated. Specifically, since layer (A) is made of inorganic material, it was given a rating of C because it could not follow the bending of layer (A) and cracks or fissures occurred. The results are shown in Table 1. A: No cracks or fissures, and easily follows the bending direction. B: There were no cracks or fissures, but it did not easily follow the bending direction. C: There were cracks or fissures.

[0163] [Table 1]

[0164] The laminates A to I of the examples showed an improved balance of water vapor barrier properties and flexibility compared to the comparative example (single layer (A)). This indicates that the present embodiment can provide a laminate for solar cells with an improved balance of water vapor barrier properties and flexibility. [Explanation of Symbols]

[0165] 1. Layer (B) containing cyclic olefin resin (B1) (protective layer) 2 Transparent electrode 3 Electron transport layer 4. Layer containing perovskite compound (A) (photoelectric conversion layer) 5. Hole transport layer 6 Back electrode 10. Stacked material for solar cells 11 frames 12 Transparent protective material 13 circuit boards 100 solar modules

Claims

1. A laminate for solar cells comprising a layer (A) containing a perovskite compound and a layer (B) containing a cyclic olefin resin (B1), A laminate for solar cells, wherein the glass transition temperature Tg of the cyclic olefin resin (B1) is 45°C or higher and 280°C or lower.

2. The laminate for solar cells according to claim 1, wherein the cyclic olefin resin (B1) comprises one or more repeating units (b) derived from cyclic olefin monomers selected from the group consisting of repeating units (AA) represented by the following general formula (II), repeating units (AB) represented by the following general formula (III), and repeating units (AC) represented by the following general formula (IV). 【Chemistry 1】 (In the above general formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ６１ ~R ７８ And R ａ１ and R ｂ１ These may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ７５ ~R ７８ These may be bonded to each other to form a monocycle or polycycle. 【Chemistry 2】 (In the general formula (III), x and d are integers of 0 or 1 or more, y and z are 0, 1 or 2, and R ８１ ~R ９９ may be the same as or different from each other, and is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms or an alkoxy group. R ８９ and R ９０ The carbon atom to which is bonded, and R ９３ The carbon atom to which is bonded or R ９１ The carbon atom to which is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. When y = z = 0, R ９５ and R ９２ or R ９５ and R ９９ may be bonded to each other to form a monocyclic or polycyclic aromatic ring.) 【Transformation 3】 (In the above general formula (IV), R １００ , R １０１ (These elements may be identical or different from each other, and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, where f is 1 ≤ f ≤ 18.)

3. The laminate for solar cells according to claim 2, wherein the cyclic olefin resin (B1) includes repeating units (AA) represented by the general formula (II).

4. The laminate for solar cells according to claim 3, wherein in the general formula (II), u is 0 and v is 0.

5. The laminate for solar cells according to any one of claims 2 to 4, wherein when the total amount of repeating units constituting the cyclic olefin resin (B1) is set to 100 mol%, the content ratio of repeating units (b) derived from the cyclic olefin monomer in the cyclic olefin resin (B1) is 1 mol% or more and 99 mol% or less.

6. The laminate for solar cells according to any one of claims 2 to 5, wherein the cyclic olefin resin (B1) includes repeating units (a) derived from olefins represented by the following general formula (I). 【Chemistry 4】 (In the above general formula (I), R ３００ (This represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.)

7. The cyclic olefin resin (B1) is The repeating unit (AA) represented by the general formula (II) above, A repeating unit (C) derived from a cyclic olefin containing an aromatic ring, Includes, The aforementioned repeating unit (AA) does not contain an aromatic ring. The laminate for solar cells according to any one of claims 2 to 6, wherein the cyclic olefin containing the aromatic ring comprises one or more compounds selected from the group consisting of a compound represented by the following general formula (C-1), a compound represented by the following general formula (C-2), and a compound represented by the following general formula (C-3). 【Transformation 5】 (In the above general formula (C-1), n ​​and q are each independently 0, 1, or 2, R １ ~R １７ Each of these is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and R １０ ~R １７ One of them is a bond, and when q = 0, R １０ and R １１ , R １１ and R １２ , R １２ and R １３ , R １３ and R １４ , R １４ and R １５ , R １５ and R １０ They may be bonded to each other to form a monocycle or polycycle, and when q = 1 or 2, R １０ and R １１ , R １１ and R １７ , R １７ and R １７ , R １７ and R １２ , R １２ and R １３ , R １３ and R １４ , R １４ and R １５ , R １５ and R １６ , R １６ and R １６ , R １６ and R １０ These elements may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring. 【Transformation 6】 (In the above general formula (C-2), n and m are each independently 0, 1, or 2, q is 1, 2, or 3, R １８ ~R ３１ Each of these is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and when q = 1, R ２８ and R ２９ , R ２９ and R ３０ , R ３０ and R ３１ They may be bonded to each other to form a monocycle or polycycle, and when q = 2 or 3, R ２８ and R ２８ , R ２８ and R ２９ , R ２９ and R ３０ , R ３０ and R ３１ , R ３１ and R ３１ These elements may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring. 【Transformation 7】 (In the general formula (C-3), q is 1, 2, or 3; R ３２ ~R ３９ are each independently a halogen atom excluding a hydrogen atom or a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom. When q = 1, R ３６ and R ３７ , R ３７ and R ３８ , R ３８ and R ３９ may be bonded to each other to form a monocyclic or polycyclic ring. When q = 2 or 3, R ３６ and R ３６ , R ３６ and R ３７ , R ３７ and R ３８ , R ３８ and R ３９ , R ３９ and R ３９ may be bonded to each other to form a monocyclic or polycyclic ring. The monocyclic or polycyclic ring may have a double bond, and the monocyclic or polycyclic ring may be an aromatic ring.)

8. The cyclic olefin resin (B1) is The repeating unit (AA) represented by the general formula (II) above, A repeating unit (a) derived from an olefin, represented by the following general formula (I), A laminate for a solar cell according to claim 6 or 7, comprising repeating units derived from a cyclic non-conjugated diene represented by the following general formula (Y). 【Transformation 8】 (In the above general formula (I), R ３００ (This represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.) 【Chemistry 9】 (In the general formula (Y), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ６１ ~R ７６ as well as R ａ１ and R ｂ１ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R １０４ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, R ７５ and R ７６ may be bonded to each other to form a monocyclic or polycyclic ring.)

9. The water vapor transmission coefficient, measured according to JIS K 7129:2008, at a measurement temperature of 40°C and a measurement humidity of 90% RH, is 1.0 g / mm / m ２ A laminate for solar cells according to any one of claims 1 to 8, wherein the length is 24 hours or less.

10. A solar cell module comprising a laminate for solar cells according to any one of claims 1 to 9.

11. A varnish for solar cells comprising a cyclic olefin resin (B1) and a solvent, The solar cell includes a layer (A) containing a perovskite compound. The glass transition temperature Tg of the cyclic olefin resin (B1) is 45°C or higher and 280°C or lower. The cyclic olefin resin (B1) is The repeating unit (AA) is represented by the following general formula (II), A repeating unit (a) derived from an olefin, represented by the following general formula (I), Repeating units derived from cyclic non-conjugated dienes represented by the following general formula (Y), Varnish for solar cells, including 【Chemistry 10】 (In the above general formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ６１ ~R ７８ And R ａ１ and R ｂ１ These may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ７５ ~R ７８ These may be bonded to each other to form a monocycle or polycycle. 【Chemistry 11】 (In the above general formula (I), R ３００ (This represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.) 【Chemistry 12】 (In the above general formula (Y), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ６１ ~R ７６ And R ａ１ and R ｂ１ These may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R １０４ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer from 0 to 10, and R ７５ and R ７６ (These may be bonded to each other to form a monocycle or polycycle.)

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