JP6256758B2 - Sealant for photoelectric conversion element - Google Patents

Description

The present invention is a photoelectric conversion element seal that allows a polymerization reaction to proceed rapidly by irradiation with active energy rays such as light such as ultraviolet rays, and that provides a cured product having excellent adhesion to a substrate such as glass and having a high water vapor barrier property. It relates to the agent.

Conventionally, photoelectric conversion elements such as silicon-based solar cells, dye-sensitized solar cells, and organic thin-film solar cells have attracted attention as green energy and energy-saving devices. These photoelectric conversion elements are particularly sensitive to humidity, and when used for a long period of time in an environment such as high temperature and high humidity, deterioration or deterioration occurs due to humidity entering from the outside, and the performance of the element is lowered. For this reason, a photocurable sealing agent having a high sealing property (water vapor barrier property) is frequently used.

As a sealing agent for photoelectric conversion elements, for example, Patent Document 1 discloses a sealing agent for photoelectric conversion elements containing an epoxy resin, a thermosetting agent, an epoxy (meth) acrylate, and a photopolymerization initiator. Has been. Patent Document 2 discloses a dye-sensitized solar cell sealing material containing a monofunctional (meth) acrylate having 10 to 22 carbon atoms, a liquid saturated elastomer, and a photopolymerization initiator.

International Publication Number WO2007 / 007671 JP 2010-138290 A

However, the sealants for photoelectric conversion elements disclosed in Patent Documents 1 and 2 do not satisfy characteristics such as adhesion to a substrate such as glass and water vapor barrier properties.

The sealing agent for a photoelectric conversion element of the present invention has a polymerization reaction that proceeds rapidly by irradiation with an active energy ray such as light such as ultraviolet rays, and a cured product having a high water vapor barrier property is obtained. It aims at providing the sealing agent for photoelectric conversion elements which is excellent.

The gist of the present invention will be described next. The embodiments of the present invention overcome the above-mentioned conventional problems.
(Meth) acrylic compound ((A) component) having a bisphenol structure and an alkylene oxide unit repeating average number of 1 to 8, epoxy (meth) acrylate ((B) component), and photoinitiator ((C) component) Containing
The sealing agent for photoelectric conversion elements, wherein the component (A) is contained in an amount of 25 to 95 parts by mass in 100 parts by mass of the total amount of the component (A) and the component (B).

The sealing agent for a photoelectric conversion element of the present invention has a polymerization reaction that proceeds rapidly by irradiation with an active energy ray such as light such as ultraviolet rays, and a cured product having a high water vapor barrier property is obtained. It is excellent.

The present invention will be described in detail below.
<(A) component>
The component (A) of the present invention is a (meth) acrylic compound having a bisphenol structure and a repeating average number of 1 to 8 alkylene oxide units. Preferably, it is a (meth) acryl compound having a repeating average number of bisphenol structures and alkylene oxide units of 1.5 to 6, particularly preferably having a repeating average number of 2 to 5 (meth) of bisphenol structures and alkylene oxide units. It is an acrylic compound.

The method for synthesizing the component (A) is not particularly limited. For example, 2 is obtained by adding alkylene oxide such as ethylene oxide (hereinafter abbreviated as EO) or propylene oxide (hereinafter abbreviated as PO) to bisphenol A, bisphenol F or bisphenol E. It can be obtained by an ester reaction product of a monohydric alcohol and (meth) acrylic acid. Alternatively, a dihydric alcohol obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to bisphenol A, bisphenol F or bisphenol E is reacted with an epihalohydrin to obtain an alkylene oxide-added bisphenol diglycidyl, and then (meth) acrylic acid and Can be reacted.

As a commercial item of (A) component, for example, light ester BP-2EM, BP-4EM, BP-6EM, BP-4EA, BP-6PA (manufactured by Kyoeisha Chemical Co., Ltd.), A-BPE-4, A-BPP -3 (manufactured by Shin-Nakamura Chemical Co., Ltd.), FA-324A (manufactured by Hitachi Chemical Co., Ltd.) and the like. These may be used independently and 2 or more types may be used together.

<(B) component>
The component (B) of the present invention is epoxy (meth) acrylate. The method for synthesizing the component (B) is not particularly limited, and examples thereof include a reaction product obtained by adding an epoxy resin having at least two epoxy groups in one molecule with (meth) acrylic acid. The reaction product obtained by adding (meth) acrylic acid to an epoxy resin having a repeating unit of alkylene oxide such as ethylene oxide or propylene oxide in the structure and having two or more epoxy groups is In the present invention, it is treated as the component (A).

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy. Resin, hydrogenated bisphenol E type epoxy resin, hydrogenated cresol novolak type epoxy resin, hydrogenated phenol novolak type epoxy resin, etc., among which bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin are mentioned. Preferably used. These may be used independently and 2 or more types may be used together.

Although it does not specifically limit as epoxy (meth) acrylate which is (B) component, From the viewpoint that the hardened | cured material which is excellent in the adhesive force to board | substrates, such as glass, and is excellent in water vapor | steam barrier property from a high crosslinking density. Bisphenol A type epoxy (meth) acrylate, bisphenol F type (meth) acrylate, and bisphenol E type (meth) acrylate are preferably used, and examples of such compounds include compounds represented by general formula (1). .

（Ｒは水素原子又は炭素数１〜３のアルキル基を表し、Ｘは、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−ＣＨ（ＣＨ _３ ）−を表し、ｎは１〜１０を表す。好ましくは、ガラス等の基板への接着力及び水蒸気バリア性に優れるという観点から前記Ｘは−Ｃ（ＣＨ_３）_２−であり、前記ｎは１〜５である。）

(R represents an alkyl group having 1 to 3 hydrogen atoms or carbon atoms, X _{is, -CH 2 -, - C (} CH 3) 2 -, - CH (CH 3) - represents, n represents 1 to 10 Preferably, X is —C (CH ₃ ) ₂ — and n is 1 to 5 from the viewpoint of excellent adhesion to a substrate such as glass and water vapor barrier properties.

(B) The acid value of a component becomes like this. Preferably it is 20 KOHmg / g or less, and is 10 KOHmg / g or less. By using the component (B) in the above range, a sealing agent for a photoelectric conversion element having good adhesion to a substrate such as glass and storage stability can be obtained. In addition, the acid value in this invention means the number of mg of potassium hydroxide required in order to neutralize the free fatty acid contained in 1g of (B) component. An example of the test method is a neutralization titration method.

As a commercial item of epoxy (meth) acrylate which is (B) component, for example, Unidic V-5500, V-5502 (manufactured by DIC Corporation), epoxy ester 3000A, epoxy ester 3002M (N), epoxy ester 3002A (N) , (Manufactured by Kyoeisha Chemical Co., Ltd.), lipoxy SP-1506, SP-1509, VR-60, VR-77, VR-90, R802 (manufactured by Showa Polymer Co., Ltd.), Everacryl 3700 (Daicel Cytec Co., Ltd.), Neopole AC5748, 8101, 8250, 8260270, 8318, 8470, 8475, 8319, 8355, 8351, 8335, 8414, 8190, 8195 (manufactured by Nippon Epica Co., Ltd.), BAEA-100, BAEM-100, BAEM-50, BEEM-50 , BF A-50 (manufactured by Keesuemu Co., Ltd.), (manufactured by Nagase Chemtex Co., Ltd.) Dinah call acrylate DA-250, (manufactured by Rahn AG, Inc.) GENOMER2263, BISCOAT 540 (manufactured by Osaka Organic Co., Ltd.), and the like. These may be used independently and 2 or more types may be used together.

In 100 parts by mass of the total amount of component (A) and component (B), component (A) is preferably 25 to 95 parts by mass, more preferably 27 to 90 parts by mass, and particularly preferably 30 to 85 parts. Part by mass. When (A) component is mix | blended within said range, the hardened | cured material with higher water vapor | steam barrier property will be obtained, and the curable resin composition excellent in the adhesive force to board | substrates, such as glass, can be obtained.

<(C) component>
The photopolymerization initiator that is the component (C) used in the present invention is not limited as long as it is a compound that generates radicals by irradiation with active energy rays. Examples of the component (C) include , Acetophenone photo radical polymerization initiator, benzoin photo radical polymerization initiator, benzophenone photo radical polymerization initiator, thioxanthone photo radical polymerization initiator, acylphosphine oxide photo radical polymerization initiator, titanocene photo radical polymerization initiator Of these, acetophenone-based photoradical polymerization initiators and acylphosphine oxide-based photoradical polymerization initiators are preferred from the viewpoint of excellent photocurability and excellent sealing properties. Moreover, these may be used independently and 2 or more types may be used together.

Examples of the acetophenone photoradical polymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- Examples include (4-morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer, but are not limited thereto.

Examples of the acylphosphine oxide photo radical polymerization initiator include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and the like. But this is not the case.

The blending amount of the component (C) in the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 20 parts per 100 parts by mass of the total amount of the components (A) and (B). It is a mass part, Most preferably, it is 0.5-15 mass part. If it is less than 0.1 parts by mass, the photocuring property of the sealing agent for photoelectric conversion elements is lowered, so that there is a possibility that the water vapor barrier property of the cured product is lowered, and the adhesive force to a substrate such as glass is lowered, When it exceeds 30 mass parts, there exists a possibility that transparency of the hardened | cured material of the sealing compound for photoelectric conversion elements may be impaired.

<(D) component>
In the present invention, (meth) acrylate having a group represented by the following general formula (2) or (3) may be added as the component (D).

Examples of the component (D) include 2-hydroxymethyl (meth) acrylate acid phosphate, 2-hydroxyethyl (meth) acrylate acid phosphate, 2-hydroxypropyl (meth) acrylate acid phosphate, ethylene oxide-modified phosphate diacrylate, Examples thereof include ethylene oxide-modified phosphoric acid triacrylate, ethylene oxide-modified phosphoric acid dimethacrylate, and caprolactone-modified ethylene oxide-modified phosphoric acid dimethacrylate. These may be used independently and 2 or more types may be used together. In addition, (D) component of this invention differs from the (A) component and (B) component of this invention.

As a commercial item of (D) component, light ester PA, P-1M, P-2M (Kyoeisha Chemical Co., Ltd.), Kayamar PM-1 (made by Nippon Kayaku Co., Ltd.), etc. are mention | raise | lifted, for example.

Although the compounding quantity of the said (D) component is not specifically limited, It is 0.1-50 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, More preferably, it is 0.5. It is -25 mass parts, Most preferably, it is 1-10 mass parts. If the amount is less than 0.1 parts by mass, the adhesive strength to the glass substrate may be inferior, and if it exceeds 50 parts by mass, the water vapor barrier property may be deteriorated and further storage stability may be obtained.

  To the present invention, a compound having a (meth) acryloyl group other than the silane coupling agent, filler, component (A), component (D), tris-[(3-mercapto, as long as the object of the present invention is not impaired. Polythiols such as propionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) Compound, Epoxy resin, Tackifier, Thermoplastic elastomer, Rubber polymer fine particle, Storage stabilizer, Antioxidant, Light stabilizer, Adhesion aid, Plasticizer, Dye, Pigment, Flame retardant, Sensitizer, Thermal radical Initiator, organic solvent, heavy metal deactivator, ion trapping agent, emulsifier, water dispersion stability , Defoamers, release agents, leveling agents, waxes, rheology control agents, additives such as a surfactant may be appropriate amount.

Examples of the silane coupling agent include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldipropyloxysilane, and 3-glycidoxypropyldimethyl. Monomethoxysilane, 3-glycidoxypropyldimethylmonoethoxysilane, 3-glycidoxypropyldimethylmonopropyloxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltriethoxy Glycidyl group-containing silane coupling agents such as silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyl Vinyl group-containing silane coupling agent such as rutrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyldimethylmonomethoxysilane, 3-methacryloxypropyldimethylmonoethoxy Silane, 3-acryloxypropylmethyldipropyloxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldipropyloxysilane, 3-acryloxypropyldimethylmono Propyloxysilane, 3-acryloxypropyldimethylmonomethoxysilane, 3-acryloxypropyldimethylmonoethoxysilane, 3-acryloxypropyldimethylmolybdenum (Meth) acrylic group-containing silane coupling agents such as nopropyloxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane And amino group-containing silane coupling agents such as N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane and the like. Among these, a glycidyl group-containing silane coupling agent, a vinyl group-containing silane coupling agent, and a (meth) acryl group-containing silane coupling agent are preferable from the viewpoint of excellent adhesion to a glass substrate. These may be used independently and 2 or more types may be used together.

It is preferable that the compounding quantity of a silane coupling agent is 0.1-20 mass parts with respect to 100 mass parts of total amounts of (A) component of this invention, and (B) component. If the amount is less than 0.1 parts by mass, the adhesion to the glass substrate may be inferior, and if it exceeds 20 parts by mass, the storage stability may be inferior.

The mass ratio of the silane coupling agent to the component (D) (silane coupling agent / (D) component) is not particularly limited, but is 0.01 to from the viewpoint of excellent adhesion to a substrate such as glass and storage stability. 500, more preferably 0.05 to 200, and particularly preferably 0.1 to 50.

The filler may be included. Examples of the filler include glass, silica, alumina, talc, mica, silicone rubber powder, calcium carbonate, aluminum nitride, carbon powder, kaolin clay, dry clay mineral, and dry diatomaceous earth. Among these, water vapor Glass, silica, and talc are preferable because a sealing agent for photoelectric conversion elements having excellent barrier properties can be obtained.

The average particle diameter of the filler is preferably 0.001 to 100 μm, more preferably 0.01 to 50 μm, and particularly preferably 0.1 to 20 μm. If the average particle diameter is less than 0.001 μm, the viscosity of the sealing agent for photoelectric conversion elements may be inferior in workability such as coating, and if it exceeds 100 μm, the cured product may have a water vapor barrier property. . In addition, the measuring method of an average particle diameter is a laser diffraction method. In addition, the compounding quantity of a filler is although it does not specifically limit, 0.1-300 mass parts is preferable in 100 mass parts of total amounts of (A) component and (B) component, More preferably, it is 1-200 mass parts. Yes, and particularly preferably 5 to 100 parts by mass.

  A silica type filler is mix | blended in order to improve the mechanical strength of hardened | cured material. Preferably, dimethyldichlorosilane, hexamethylsilazane, silicone oil, aminosilane, alkyl silane having 1 to 12 carbon atoms, silane having a (meth) acryloyl group, and the like are used.

Examples of commercially available silicas include Aerosil R974, R972, R9200, R976, R976S, RX50, NAX50, NX90, RX200, R8200, RX300, R812, R812S, RY50, NY50, RY200S, R202, RY200, RY300, R104, R106. RA200H, RA200HS, R805, R816, RM50, R711, R7200 (manufactured by Nippon Aerosil Co., Ltd.).

  For the present invention, examples of the compound having a meth) acryloyl group other than the components (A), (B) and (D) include, for example, monofunctional, bifunctional, trifunctional and polyfunctional monomers and oligomers. Etc. can be used. These can be used alone or as a mixture of two or more.

  Examples of the monofunctional monomer include lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl ( (Meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, nonylphenoxyethyl (meth) ) Acrylate, butoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, glycerol (meth) acrylate, modified butyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, morpholino (meth) acrylate.

  Examples of the bifunctional monomer include neopentyl glycol di (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, dicyclopentenyl diacrylate, di (meth) acryloyl isocyanurate, and the like.

  Examples of the trifunctional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (acryloyloxyethyl) isocyanurate, and the like.

  Examples of the polyfunctional monomer include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol pentaacrylate, dipentaerythritol hexa ( And (meth) acrylate. These polymerizable monomers can be used alone or as a mixture of two or more.

  The thermoplastic elastomer is used for the purpose of relaxing internal stress or improving the adhesive force of the sealing agent for photoelectric conversion elements of the present invention. Examples of the thermoplastic elastomer include a styrene thermoplastic elastomer, an olefin thermoplastic elastomer, a urethane thermoplastic elastomer, and a polyester thermal copolymer that are block copolymers composed of a polystyrene block and a polybutadiene block, a polyisoprene block, a polyisobutylene, and the like. Examples thereof include a plastic elastomer and an amide thermoplastic elastomer. Among these, a styrene thermoplastic elastomer or a urethane thermoplastic elastomer is particularly preferable. These may be used alone or in combination of two or more.

  The rubber-like polymer fine particles may be added for the purpose of relaxing internal stress or improving adhesive strength of the sealing agent for photoelectric conversion elements. These rubber-like polymer fine particles include, for example, acrylic rubber-based rubbery polymers, silicone rubber-based rubbery polymers, olefin rubber-based rubbery polymers, polyester rubber-based rubbery polymers, urethane rubber-based rubbery polymers, Of these, a silicone rubber-based rubber polymer and an olefin rubber-based rubber polymer are preferable. It may be used alone or in combination.

Among the above optional components, addition of an antioxidant and a light stabilizer is preferable for improving the weather resistance of the curable composition. Commercial products can be used as the antioxidant and the light stabilizer. For example, a Summarizer BHT, a Summarizer S, a Summarizer BP-76, a Summarizer MDP-S, a Summarizer GM, a Summarizer BBM-S, a Summarizer WX-R, a Summarizer NW, a Summarizer BP-179, a Summarizer BP-101, a Summarizer GA-80, a Sumizer TNP, Sumilyzer TPP-R, Sumilyzer P-16 (manufactured by Sumitomo Chemical Co., Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK Tab 2112, Adekas tab 260, Adekas tab 522A, Adekas tab 329K, Adekas tab 1500, Adekas tab C, Adekas tab 135A, Adekas tab 3010 (Asahi Denka Kogyo Co., Ltd.), Tinuvin 770, Tinuvin 765, Tinuvin 144, Tinuvin 622, Tinuvin 111, Tinuvin 123, Tinuvin 292 (Ciba Specialty Chemicals Co., Ltd.) Although the compounding quantity of these antioxidants and light stabilizers is not specifically limited, Preferably it is 0.001-10 mass parts with respect to 100 mass parts of (A) component, More preferably, it is 0.01-5 mass parts. is there.

The sealing agent for photoelectric conversion elements of the present invention is cured by rapid polymerization reaction by irradiation with active energy rays such as light such as ultraviolet rays. The active energy ray is preferably irradiated light having a wavelength range of 150 to 750 nm, and an integrated light amount of 1 to 100 kJ / LED using a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp or an LED lamp. It can be cured at the integrated light quantity of cm ^2, preferably integrated quantity of light 5~70kJ / cm ^2.

The sealing agent for a photoelectric conversion element of the present invention has a polymerization reaction that proceeds rapidly by irradiation with an active energy ray such as light such as ultraviolet rays, and a cured product having a high water vapor barrier property is obtained. Since it is excellent, it is suitably used for various sealing applications. Specifically, for use in photoelectric conversion elements such as silicon-based solar cells, dye-sensitized solar cells, and organic thin-film solar cells, which are sealing applications that require water vapor barrier properties and adhesion to substrates such as glass. Preferably used.

The adhesive force to a substrate such as glass in the present invention means a material having a pressure of 1.0 MPa or more, and a photoelectric conversion element sealing agent having this characteristic is suitably used for applications such as a photoelectric conversion element. When a sealing agent having an adhesive strength to a substrate such as glass of less than 1.0 MPa is used for the photoelectric conversion element, it will be peeled off from the glass substrate base, resulting in leakage of the electrolyte, resulting in a decrease in the performance of the photoelectric conversion element. There is a risk that.

In addition, the water vapor barrier property in the present invention means that the moisture permeability is 150 g / m ² · 24 h or less, and the photoelectric conversion element sealing agent having this characteristic is suitably used for applications such as photoelectric conversion elements. It is done. When a sealing agent having a moisture permeability of more than 150 g / m ² · 24 h is used for the photoelectric conversion element, the humidity or the like that enters from the outside may cause alteration or deterioration, and the performance of the photoelectric conversion element may be deteriorated.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

<Preparation of composition>
Each component was sampled in parts by mass shown in Table 1, and mixed for 60 minutes with a mixer under light shielding at room temperature to prepare a photoelectric conversion element sealing agent. All numerical values are expressed in parts by mass.

-(A) component a1: EO-modified bisphenol A diacrylate having an average of 2.3 ethylene oxide structural moiety repeating units (product name BPE-80N, manufactured by Shin-Nakamura Chemical Co., Ltd.)

a2: EO-modified bisphenol A diacrylate having a repeating unit of four ethylene oxide structure parts (product name FA324, manufactured by Hitachi Chemical Co., Ltd.)

(A) Component comparison component a′1: EO-modified bisphenol A diacrylate having a repeating unit of 10 ethylene oxide structure parts (product name A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.)

(B) Component b1: An epoxy (meth) acrylate represented by the formula (1), where n = 4 and X is —C (CH ₃ ) ₂ —, an acid value of 7.9 KOHmg / g (product name) VR-60, manufactured by Showa Denko KK
b2: An epoxy (meth) acrylate represented by the formula (1) in which n = 2 and X is —C (CH ₃ ) ₂ —, an acid value of 6.6 KOHmg / g (product name VR-90, Showa Denko)

(B) Component Comparison Component B'1: Urethane (meth) acrylate (Product name CN 9893, manufactured by Sartomer)

(C) Component c1: 1-hydroxy-cyclohexyl-phenyl-ketone (BASF)
c2: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF)

(D) Component d1: 2-hydroxyethyl methacrylate acid phosphate

<Other ingredients>
Silane coupling agent: 3-acryloxypropyltrimethoxysilane (product name KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
Silica: Spherical silica with an average particle size of 1.5 μm Talc: Scale-like talc

<Characteristic evaluation>
Various characteristics were measured as follows.

[Cross peel adhesion test]
Thickness 5mm x width 25mm x length 50mm Two glass substrates bonded to each other with a sealant for each photoelectric conversion element so as to form a cross are irradiated with an integrated light quantity of 30 kJ / cm ² by an ultraviolet irradiator. Created. And this test piece was pressed with a crosshead using a tensile tester, the stress required until a glass plate and a glass plate isolate | separated was measured, and the result is shown in Table 1.
[Evaluation criteria]
○: 1.0 MPa or more
X: Less than 1.0 MPa

[Water vapor barrier property test (moisture permeability barrier property test)]
Each sealing agent for photoelectric conversion elements in Table 1 was poured into a frame of 200 mm × 200 mm × 0.2 mm. Then, the integrated light quantity 30kJ / cm < ² > was irradiated with the ultraviolet irradiation machine, and the sheet-like hardened | cured material of thickness 0.2mm was created. 5 g of calcium chloride (anhydrous) was put in an aluminum cup having an opening with a diameter of 30 mm, and the cured product was set in the cup. After measuring the “initial total weight” (g), leave it in a constant temperature and humidity chamber maintained at an atmospheric temperature of 85 ° C. and a relative humidity of 85%, and set the “total weight after leaving” (g) every 24 hours. Measured and calculated moisture permeability (g / m ² · 24h). The detailed test method conforms to JIS Z 0208.
[Evaluation criteria]
A: Less than 100 g / m ² · 24 h ○: 100 g / m ² · 24 h or more, less than 150 g / m ² · 24 h ×: 150 g / m ² · 24 h or more

In Comparative Examples 1 and 2, since (A) component is less than 25 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B), glass is compared with Examples 1 to 6 of the present invention. As a result, the adhesive strength to the substrate was poor. Furthermore, the comparative example 2 was a result in which water vapor | steam barrier property is also inferior. Moreover, since the comparative example 3 uses EO modified bisphenol A diacrylate whose EO repetition number is 10 instead of the component (A) of the present invention, it is compared with Examples 1 to 6 of the present invention. The result was poor barrier properties.
Moreover, since the (A) component of this invention is not contained, the comparative example 4 was a result in which water vapor | steam barrier property is inferior compared with Examples 1-6 of this invention. Moreover, since the comparative example 5 does not contain (B) component of this invention, it was a result in which the adhesive force to substrates, such as glass, is inferior compared with Examples 1-6 of this invention.
In Comparative Example 6, since urethane (meth) acrylate was used instead of the component (B) of the present invention, the water vapor barrier property was inferior compared with Examples 1 to 6 of the present invention.

The sealing agent for a photoelectric conversion element of the present invention has a polymerization reaction that proceeds rapidly by irradiation with an active energy ray such as light such as ultraviolet rays, and a cured product having a high water vapor barrier property is obtained. Since it is excellent, it is suitably used for various sealing applications. Specifically, display applications such as liquid crystal displays, organic EL displays, electronic paper, silicon solar cells, and dye-sensitized solar cells, which are sealing applications that require water vapor barrier properties and adhesion to substrates such as glass. It is extremely effective as a sealant for use in photoelectric conversion elements such as organic thin film solar cells and is industrially useful because it can be applied to a wide range of fields.

Claims (4)

(Meth) acrylic compound ((A) component) having a bisphenol structure and an alkylene oxide unit repeating average number of 1 to 8, epoxy (meth) acrylate ((B) component), and photoinitiator ((C) component) And 0.1-20 mass parts of silane coupling agents are contained with respect to 100 mass parts of total amounts of (A) component and (B) component ,
The sealing agent for photoelectric conversion elements, wherein the component (A) is contained in an amount of 25 to 95 parts by mass in 100 parts by mass of the total amount of the component (A) and the component (B). The silane coupling agent is selected from the group consisting of a glycidyl group-containing silane coupling agent, a vinyl group-containing silane coupling agent, and a (meth) acryl group-containing silane coupling agent. The sealing agent for photoelectric conversion elements as described in 2. Furthermore, the sealing material for photoelectric conversion elements of Claim 1 or 2 containing a filler. Furthermore, it contains (meth) acrylate which has group represented by the following general formula (1) or (2) which is (D) component, The any one of Claims 1-3 characterized by the above-mentioned. The sealing agent for photoelectric conversion elements.