JP2010144000A - Photocurable resin composition, photocurable moistureproof sealing material for use in electronic paper, electronic paper, and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable resin composition for use in the electronic paper which combines the antithetic characteristics of flexibility and low moisture permeability with the adhesiveness to a PET substrate; and a photocurable moistureproof sealing material using the same. <P>SOLUTION: This photocurable resin composition includes (A) an ethylenically unsaturated double bond-containing urethane compound which is obtained by reacting (a1) a polyolefin polyol compound, (a2) a hydroxyl group-containing ethylenically unsaturated compound and (a3) a compound having two or more isocyanate groups in one molecule, (B) a photopolymerizable monomer, (C) a photopolymerization initiator and (D) a urethane acrylate oligomer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photocurable resin composition, a photocurable moisture-proof sealing material for electronic paper using the photocurable resin composition, an electronic paper sealed with the photocurable moisture-proof sealing material, and a method for producing the same.

  In recent years, electronic paper tends to be thinner and more flexible. With this trend, the base material has shifted from glass, which was mainly used in liquid crystal displays, to PET (polyethylene terephthalate), which is excellent in flexibility, and photocurability. There is also a demand for a moisture-proof sealing material that is low warp and has high followability.

  In addition, it has been found that display elements of electronic paper are deteriorated by moisture and cause display defects, and a sealing material having a low moisture permeability is required more than a conventional photocurable moisture-proof sealing material.

  Many resin compositions that can be cured by irradiation with ultraviolet rays or electron beams have already been developed, and various photo-curable moisture-proof materials have already been put into practical use for use in moisture-proof treatment of electrodes in liquid crystal displays. . As such a resin composition, a urethane-modified acrylate resin composition obtained by reacting a polyester polyol compound, a polyolefin polyol compound, or the like with a polyisocyanate and a hydroxyalkyl (meth) acrylate is known.

  Further, for example, Patent Document 1 discloses a photocurable moisture-proof material containing an acrylic-modified hydrogenated polybutadiene resin that has high adhesion to glass and exhibits excellent characteristics in moisture resistance evaluation.

JP 2001-302946 A

  However, the conventional urethane-modified acrylate resin composition described in Patent Document 1 has excellent adhesion to glass and flexibility, but has a problem of high moisture permeability and poor adhesion to a PET substrate. .

  Moreover, although an epoxy resin composition is low in moisture permeability and excellent in adhesiveness, it has a problem that it is hard and warps greatly.

  Flexibility and low moisture permeability are contradictory properties, and the conventional photocurable resin composition has no moisture-proof sealing material for electronic paper that is excellent in both flexibility and low moisture permeability.

  The present invention has been made to solve the conventional problems as described above, and has a photocurable resin composition having low moisture permeability, flexibility, and adhesion to a PET substrate, and It aims at providing the photocurable moisture-proof sealing material for used electronic paper.

  Another object of the present invention is to provide a highly reliable electronic paper sealed with the photocurable moisture-proof sealing material for electronic paper and a method for producing the same.

  The photocurable resin composition according to the present invention includes [1] (A) (a1) a polyolefin polyol compound, (a2) an ethylenically unsaturated compound having a hydroxyl group, and (a3) two or more isocyanate groups in one molecule. Contains a urethane compound having an ethylenically unsaturated double bond obtained by reacting a compound having, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a urethane acrylate oligomer It is the photocurable resin composition formed by, It is characterized by the above-mentioned.

  In the photocurable resin composition according to the present invention, [2] the component (B) is (B1) a photopolymerizable monomer containing an ethylenically unsaturated double bond and a cyclic aliphatic group. It is characterized by being.

  In the photocurable resin composition according to the present invention, [3] the component (B) is (B2) a photopolymerizable monomer represented by the following general formula (I). And

（一般式（Ｉ）中、Ｒ¹は、水素原子又はメチル基を示し、Ｒ²は炭素数４〜２０のアルキル基を示す。）

(In general formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 4 to 20 carbon atoms.)

  Moreover, in the photocurable resin composition by this invention, [4] The said (B) component contains 30-70 mass% on the basis of the sum total of the said (A) component and (B) component. It is characterized by that.

  Moreover, in the photocurable resin composition by this invention, [5] The said (C) component contains 1-10 mass% with respect to the total amount of the said (A) component and the said (B) component. It is characterized by that.

  Moreover, in the photocurable resin composition by this invention, [6] The said (D) component contains 1-15 mass% on the basis of the sum total of the said (A) component and (B) component. It is characterized by that.

  Moreover, in the photocurable moisture-proof sealing material for electronic paper by this invention, [7] It contains the said photocurable resin composition, It is characterized by the above-mentioned.

  Moreover, in the electronic paper by this invention, it is sealed using [8] the photocurable moisture-proof sealing material for said electronic paper, It is characterized by the above-mentioned.

  In the method for producing electronic paper according to the present invention, [9] the photocurable moisture-proof sealing material for electronic paper is applied to the electronic paper, and then the photocurable moisture-proof sealing material for electronic paper applied. Is cured and sealed.

  The photo-curable resin composition according to the present invention is a photo-curable moisture-proof sealing material for electronic paper having both flexibility and low moisture permeability, which are contradictory properties, and adhesion to a PET substrate. By applying and curing the moisture-proof sealing material, it is possible to produce highly reliable electronic paper.

  Hereinafter, the photocurable resin composition according to the present invention, a photocurable moisture-proof sealing material for electronic paper, electronic paper, and a method for producing the same will be described in detail by embodiments. In addition, this invention is not restrict | limited by this embodiment.

[Photocurable resin composition]
The photocurable resin composition according to the present invention comprises (a1) a polyolefin polyol compound, (a2) an ethylenically unsaturated compound having a hydroxyl group, and (a3) two or more isocyanate groups in one molecule as the component (A). A urethane compound having an ethylenically unsaturated double bond obtained by reacting a compound having a photopolymerizable monomer as the component (B), a photopolymerization initiator as the component (C), and (D) As a component, a urethane acrylate oligomer is contained. Hereinafter, each component will be described.

[Component (A)]
(A1) Component Among the urethane compounds having an ethylenically unsaturated double bond as the component (A), as the (a1) polyolefin polyol compound (hereinafter referred to as “(a1) component”), for example, various commercially available compounds Polyol compounds of saturated and unsaturated alkyl compounds can be used, and specific examples thereof include polyethylene polyol, polypropylene polyol, polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol and the like. Can be mentioned.

  The number average molecular weight of the component (a1) is preferably 500 to 5000, and preferably 1000 to 3000 from the viewpoint of the balance between the flexibility of the obtained cured product (film, coating film), that is, the elongation of the cured product and the properties. It is more preferable that it is 1,500 to 2500.

  When the number average molecular weight of the component (a1) is less than 500, the resulting cured product tends to be brittle, and the tacky surface (stickiness) tends to remain on the surface of the resulting cured product. On the other hand, when the number average molecular weight of the component (a1) exceeds 5,000, the viscosity of the resulting photocurable resin composition increases, so that the workability when formed into a paint is significantly reduced. In addition, the number average molecular weight in this invention is the value which measured by the gel permeation chromatography method and was calculated | required using the standard polystyrene calibration curve.

Component (a2) Next, as (a2) an ethylenically unsaturated compound having a hydroxyl group (hereinafter referred to as “component (a2)”), for example, a hydroxyalkyl acrylate having an alkyl group with 2 to 7 carbon atoms. Specific examples of these include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and the corresponding methacrylates of these acrylates.

  Examples of the component (a2) also include compounds having a hydroxyl group and an ethylenically unsaturated double bond obtained by ring-opening polymerization of an ε-caprolactone monomer. Among these compounds, 2-hydroxyethyl acrylate is preferable because the surface of the obtained cured product has no tackiness and is extremely excellent in curability. Each of the components (a2) is used alone or in combination of two or more.

Component (a3) Next, as (a3) a compound having two or more isocyanate groups in one molecule (hereinafter referred to as “component (a3)”), for example, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, Examples include diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, and hydrogenated products thereof. Each of the components (a3) is used alone or in combination of two or more.

  The component (A) in the present invention is a mixture containing the components (a1) to (a3), wherein the hydroxyl group of the component (a1) is 0.5 to 0. 75 equivalents, the hydroxyl group of component (a2) is 0.25 to 0.5 equivalents, and the total of hydroxyl groups of component (a1) and component (a2) is 1 to 1.1 equivalents, A polymer obtained by addition reaction is preferred.

  When the hydroxyl group of the component (a1) is less than 0.5 equivalent with respect to 1 equivalent of the isocyanate group of the component (a3), the resulting cured product has poor flexibility, and when it exceeds 0.75 equivalent, the resulting cured product is obtained. A tactile sensation occurs on the object surface. Further, when the hydroxyl group of the component (a2) is less than 0.25 equivalent with respect to 1 equivalent of the isocyanate group of the component (a3), a tacky feeling is generated on the surface of the obtained cured product, and when it exceeds 0.5 equivalent, The flexibility of the resulting cured product is poor. Furthermore, when the total of the hydroxyl groups of the component (a1) and the component (a2) is less than 1 equivalent with respect to 1 equivalent of the isocyanate group of the component (a3), the storage stability of the resulting photocurable resin composition is inferior. When the resin composition gels and exceeds 1.1 equivalents, the resulting photocurable resin composition has poor curability.

  The component (A) in the present invention can be obtained by blending the components (a1), (a2) and (a3) in the above proportions and subjecting them to an addition reaction (urethanization reaction). ) Component, (a2) component and (a3) component are mixed in the above proportions, and preferably reacted at 60 to 80 ° C. for 5 to 12 hours.

  In that case, an organic solvent can be utilized as needed. Examples of the organic solvent include ester-based, ketone-based, and aromatic-based organic solvents. Examples of the ester-based organic solvent include butyl acetate and ethyl acetate. Examples thereof include methyl ethyl ketone, and examples of the aromatic organic solvent include toluene, xylene and the like. When using these organic solvents, it is used individually or in combination of 2 or more types.

  Further, (B1) a photopolymerizable monomer such as a photopolymerizable monomer having an ethylenically unsaturated double bond and a cycloaliphatic group, which will be described later, is used as a reactive diluent instead of the organic solvent. You can also. When using a photopolymerizable monomer, it is used individually or in combination of 2 or more types, and may be used in combination with an organic solvent.

  The number average molecular weight of the component (A) is preferably 1000 to 20,000, preferably 1500 to 10,000, from the viewpoint of the properties of the obtained cured product (surface curability and flexibility of the coating film). Is more preferable, and 2,000 to 5,000 is even more preferable. When the number average molecular weight of the component (A) is less than 1000, the obtained cured product tends to be brittle and the cured coating film does not have sufficient elongation, and the number average molecular weight of the component (A) exceeds 20,000. And the viscosity at the time of making into a paint increases remarkably.

[(B) component]
The photopolymerizable monomer (B) is a component (B1), that is, a photopolymerizable monomer containing an ethylenically unsaturated double bond and a cyclic aliphatic group, or the component (B2), ie, the following general It is a photopolymerizable monomer represented by the formula (I).

Component (B1) Component (B1) in the present invention, ie, a photopolymerizable monomer having an ethylenically unsaturated double bond and a cycloaliphatic group, is saturated with a vinyl group, an acryloyl group, a methacryloyl group, etc. Monofunctional or polyfunctional photopolymerizable monomers having a monocyclic or heterocyclic ring composed of unsaturated hydrocarbons can be used alone or in combination of two or more. By having an ethylenically unsaturated double bond and a cyclic aliphatic group, the strength and adhesiveness of the cured product tend to be improved.

  Among these photopolymerizable monomers having an ethylenically unsaturated double bond and a cycloaliphatic group, examples of the (meth) acrylate compound having an acryloyl group or a methacryloyl group include cyclohexyl (meth) acrylate and norbornyl. (Meth) acrylate, isobornyl (meth) acrylate, norbornanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (Meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, and the like. Moreover, what has vinyl groups, such as vinyl norbornene and vinyl norbornane, can also be used. Of these photopolymerizable monomers, an isobornyl (meth) acrylate compound is preferred from the viewpoint of the strength and adhesiveness of the cured product.

Component (B2) In the present invention, from the viewpoint of imparting flexibility to the cured product, the component (B2) preferably contains a photopolymerizable monomer represented by the following general formula (I).

In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 4 to 20 carbon atoms. From the viewpoint of imparting flexibility, R ² is preferably an alkyl group having 6 to 18 carbon atoms, more preferably an alkyl group having 8 to 16 carbon atoms, and particularly preferably an alkyl group having 10 to 14 carbon atoms.

  Examples of the photopolymerizable monomer represented by the general formula (I) include n-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Isodecyl (meth) acrylate, n-hexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.

  In the present invention, it is also possible to use a photopolymerizable monomer having an unsaturated double bond other than the above, and a monofunctional or polyfunctional light having a vinyl group, an acryloyl group, a methacryloyl group, or the like. A polymerizable monomer can be used.

  Of these, a (meth) acrylate compound having an acryloyl group or a methacryloyl group is preferable. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethyl Alkoxyalkyl (meth) acrylates such as (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethoxyethyl (meth) acrylate, 2-ethoxyethoxyethyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl Hydroxyalkyl (meth) acrylates such as (meth) acrylate and 2-hydroxypropyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene Fluorinated alkyl (meth) acrylates such as recall (meth) acrylate, alkoxy (poly) alkylene glycol (meth) acrylate such as methoxydipropylene glycol (meth) acrylate, octafluoropentyl (meth) acrylate, N, N-dimethylamino Dialkylaminoalkyl (meth) acrylates such as ethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, allyl (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,4-butanediol ( Monofunctional (meth) acrylate compounds such as glycol mono (meth) acrylates such as (meth) acrylate, 1,6-hexanediol (meth) acrylate, and 3-methylpentanediol (meth) acrylate Polyethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, hydroxypivalate ester neopentyl glycol di (Meth) acrylate, trimethylolpropane di (meth) acrylate, 1,3-bis (hydroxyethyl) -5,5-dimethylhydantoin di (meth) acrylate, α, ω-di (meth) acrylbisdiethylene glycol phthalate, tri Methylolpropane tri (meth) acrylate, 2-hydroxyethyl (meth) acryloyl phosphate, trimethylolpropane tri (meth) acrylate, ethylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diacryloxy Multifunctional (meth) acrylates such as ethyl phosphate, dipentaerythritol trihydroxy (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate .

  In addition, acrylamide derivatives such as acrylamide, dimethylacrylamide, diethylacrylamide, and (meth) acryloylmorpholine can also be used. Furthermore, what has vinyl groups, such as (alpha), (omega) -tetraallyl bistrimethylol propane tetrahydrophthalate, N-vinyl pyrrolidone, N-vinyl caprolactam, can also be used.

In addition, the content of the component (B1) is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, based on the sum of the component (A) and the component (B). If this content is less than 30% by mass, the adhesion and toughness of the resulting coating film are not sufficient, and if it exceeds 70% by mass, the adhesion of the resulting coating film tends to decrease, and surface curability, elongation In general, properties such as strength are deteriorated.
Further, the content of the component (B2) is preferably 2 to 30% by mass, more preferably 4 to 20% by mass, and more preferably 5 to 15% by mass in the total amount of the component (B) from the viewpoints of adhesiveness, hardness and moisture resistance. % Is particularly preferred.

[Component (C)]
As the component (C) in the present invention, that is, the photopolymerization initiator, for example, a carbonyl-based photopolymerization initiator, a sulfide-based photopolymerization initiator, a quinone-based photopolymerization initiator, an azo-based photopolymerization initiator, a sulfochloride-based light Examples thereof include a polymerization initiator, a thioxanthone photopolymerization initiator, and a peroxide photopolymerization initiator.

  Examples of the carbonyl photopolymerization initiator include benzophenone, benzyl, benzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylamino. Acetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, p, p'-dichlorobenzophenone, p, p'-bisdiethylaminobenzophenone, Michler's ketone, benzoin methyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzylmethyl Ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4-isopropylphenyl) -2- Droxy-2-methylpropan-1-one, methylbenzoylformate, 2,2-diethoxyacetophenone, 4-N, N′-dimethylacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholinopropan-1-one and the like.

  Examples of the sulfide photopolymerization initiator include diphenyl disulfide, dibenzyl disulfide, tetraethylthiuram disulfide, and tetramethylammonium monosulfide. Examples of the quinone photopolymerization initiator include benzoquinone and anthraquinone. Examples of the azo photopolymerization initiator include azobisisobutyronitrile, 2,2′-azobispropane, hydrazine, and the like. Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone. Examples of the peroxide photopolymerization initiator include benzoyl peroxide and di-t-butyl peroxide. Among these photopolymerization initiators, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one is used from the viewpoint of solubility in the obtained photocurable resin composition. preferable. These photoinitiators are used individually or in combination of 2 or more types.

  The content of the component (C) is such that the balance between the photocurability and the properties of the resulting cured product (curability, flexibility (elongation), adhesion, etc.) is the difference between the components (A) and (B). It is preferable to set it as 1-10 mass% with respect to the total amount, and it is more preferable to set it as 2-5 mass%. If this content is less than 1% by mass, photocuring tends to be insufficient. If it exceeds 10% by mass, properties of the resulting cured product (curability, flexibility (elongation), adhesion, etc.) There is a general trend of decline.

[Component (D)]
Examples of the urethane acrylate oligomer as component (D) include, for example, trade names of Arakawa Chemical Co., Ltd. products, beam set 502H, beam set 504H, beam set 505A-6 (above bifunctional), beam set 550B (trifunctional). , Beam set 575 (6 functional), trade name of Kayaku Sartomer Co., Ltd., CN-983, CN-985, CN-963, CN-9893, CN-9788, CN-964, CN-965, CN-966 CN-9178, CN-961, CN-962, CN-980, CN-973, CN-9783, CN-977, CN-978, CN-9782 (above bifunctional), CN-970, CN-971, CN-972 (more than trifunctional), CN-968, CN-975 (more than 6 functional), etc. are mentioned.

[Photocurable moisture-proof sealing material for electronic paper]
The photocurable moisture-proof sealing material for electronic paper of this invention contains the photocurable resin composition mentioned above. In other words, the photocurable resin composition described above is preferably used for a photocurable moisture-proof sealing material for electronic paper. In that case, a filler, a polymerization inhibitor, a modifier, an antifoaming agent, a colorant, a coupling agent, and the like can be arbitrarily added to the photocurable resin composition of the present invention as necessary.

  Examples of the filler include finely powdered silicon oxide, magnesium oxide, aluminum hydroxide, calcium carbonate, and the like. Usually, 0.01 to 100 parts by mass may be added to 100 parts by mass of the photocurable moisture-proof insulating sealing material. it can.

  Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, benzoquinone, p-tert-butylcatechol, 2,6-di-tert-butyl-4-methylphenol, and usually a photocurable moisture-proof insulating seal. 0.01-10 mass parts can be added with respect to 100 weight part of materials.

  Examples of the modifier include a leveling agent for improving leveling properties. Examples of leveling agents include polyether-modified dimethylpolysiloxane copolymers, polyester-modified dimethylpolysiloxane copolymers, polyether-modified methylalkylpolysiloxane copolymers, and aralkyl-modified methylalkylpolysiloxane copolymers. In addition, 0.01 to 10 parts by mass can be added to 100 parts by mass of the photocurable moisture-proof insulating sealing material.

  Examples of the antifoaming agent include known antifoaming agents such as silicon-based oil, fluorine-based oil, and polycarboxylic acid-based polymer. Usually, 0.001 to 5 with respect to 100 parts by mass of the photocurable moisture-proof sealing material. A part by mass can be added.

  Examples of the colorant include known inorganic pigments, organic pigments, organic dyes, and the like, and each is blended according to a desired color tone. You may use these in combination of 2 or more types. Usually, the addition amount of these pigments and dyes can be 0.01 to 50 parts by mass with respect to 100 parts by mass of the photocurable moisture-proof sealing material.

  As a coupling agent, a silane coupling agent is mentioned from an adhesive viewpoint with a base material, and 1-5 mass parts can be added with respect to 100 mass parts of photocurable moisture-proof sealing materials.

  In the photocurable resin composition of the present invention, from the viewpoint of heat resistance, the glass transition temperature (Tg) of the coated film after photocuring at 23 ° C is preferably 30 to 50 ° C, and more preferably 35 to 45 ° C.

[Electronic paper]
The electronic paper according to the present invention is an electronic paper that is sealed using the above-described photocurable moisture-proof sealing material.

[Method for manufacturing electronic paper]
The electronic paper by this invention is manufactured by sealing electronic paper using a photocurable moisture proof sealing material. That is, as a method for producing electronic paper, first, the above-described photocurable moisture-proof sealing material is applied to the electronic paper. Next, the electronic paper is obtained by curing the coating film of the photocurable moisture-proof sealing material applied to the electronic paper by irradiating ultraviolet rays using a high pressure mercury lamp, a metal halide lamp, an LED or the like as a light source.

  EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples below, but the present invention is not limited to these examples. “Parts” and “%” indicate “parts by mass” and “% by mass”, respectively.

Synthesis example 1
After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, 53 parts of 2-hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: HEA) (hydroxyl) Group: 2.0 equivalents), hydrogenated polybutadiene diol (manufactured by Nippon Soda Co., Ltd., trade name: GI-1000, number average molecular weight: about 1500) 600 parts (hydroxyl group: 2.0 equivalents), and hydroquinone monomethyl ether ( 0.5 parts of Wako Pure Chemical Industries, Ltd.) was added, heated to 70 ° C., and kept at 70 to 75 ° C. for 30 minutes. Tolylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate) 70 parts of T-65 (isocyanate group: 2.0 equivalents) were uniformly added dropwise over 3 hours to be reacted.

  After completion of the dropwise addition, the reaction was carried out by incubating at 70 to 75 ° C. for about 5 hours. After confirming that the isocyanate had disappeared by IR measurement, the reaction was terminated, and a urethane compound having an ethylenically unsaturated double bond (hereinafter referred to as “the isocyanate compound”). "R-0") was obtained.

Example 1
After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, 4 parts of Irgacure 369, 2 parts of Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.), Isobol 47.5 parts of nyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate IB-XA) was charged, heated to 110 ° C., kept warm for 45 minutes, and stirred and mixed uniformly. Furthermore, 47.5 parts of urethane compound (R-0) having an ethylenically unsaturated double bond, 5 parts of urethane oligomer (trade name; Beam Set 502H, manufactured by Arakawa Chemical Industries, Ltd.), silane coupling agent (trade name) ; KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts), heated at 85-95 ° C. for 140 minutes, stirred uniformly, and a photocurable resin composition (hereinafter referred to as “R-1”). Obtained.

(Example 2)
After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, 4 parts of Irgacure 369, 2 parts of Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.), Isobol Nyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate IB-XA) 45 parts was charged, heated to 110 ° C., kept warm for 45 minutes, and uniformly stirred and mixed. Furthermore, 45 parts of urethane compound (R-0) having an ethylenically unsaturated double bond, 10 parts of urethane oligomer (trade name; Beam Set 502H, manufactured by Arakawa Chemical Industries, Ltd.), silane coupling agent (trade name; KBE) -9007, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts was added, and the mixture was kept at 85 to 95 ° C. for 140 minutes and stirred uniformly to obtain a photocurable resin composition (hereinafter referred to as “R-2”). .

(Example 3)
After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, 4 parts of Irgacure 369, 2 parts of Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.), Isobol 47.5 parts of nyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate IB-XA) was charged, heated to 110 ° C., kept warm for 45 minutes, and stirred and mixed uniformly. Furthermore, 47.5 parts of urethane compound (R-0) having an ethylenically unsaturated double bond, 5 parts of rosin urethane acrylate (manufactured by Arakawa Chemical Industries, Ltd., trade name: Beam Set 102), silane coupling agent (product) Name: KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts, heated at 85-95 ° C. for 140 minutes, stirred uniformly, photocurable resin composition (hereinafter referred to as “R-3”) Got.

(Comparative Example 1)
After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, 4 parts of Irgacure 369, 2 parts of Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.), Isobol 50 parts of Nyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate IB-XA) was charged, heated to 110 ° C., kept warm for 45 minutes, and stirred and mixed uniformly. Furthermore, 50 parts of urethane compound (R-0) having an ethylenically unsaturated double bond and 3 parts of a silane coupling agent (trade name: KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) are added, and the temperature is 85 to 95 ° C. The mixture was kept for 140 minutes and stirred uniformly to obtain a photocurable resin composition (hereinafter referred to as “R-4”).

(Comparative Example 2)
After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, 4 parts of Irgacure 369, 2 parts of Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.), Isobol Nyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate IB-XA) 45 parts, lauryl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester LA) was charged and heated to 110 ° C. For 45 minutes, and stirred and mixed uniformly. Furthermore, 50 parts of urethane compound (R-0) having an ethylenically unsaturated double bond and 3 parts of a silane coupling agent (trade name: KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) are added, and the temperature is 85 to 95 ° C. It was kept warm for 140 minutes and stirred uniformly to obtain a photocurable resin composition (hereinafter referred to as “R-5”).

(Comparative Example 3)
After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, 4 parts of Irgacure 369, 2 parts of Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.), Isobol 47.5 parts of nyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate IB-XA) was charged, heated to 110 ° C., kept warm for 45 minutes, and stirred and mixed uniformly. Furthermore, 47.5 parts of urethane compound (R-0) having an ethylenically unsaturated double bond, 5 parts of modified acrylate polymer (Arakawa Chemical Industries, Ltd., trade name: Beam Set 271), silane coupling agent ( Brand name: KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts, heated at 85-95 ° C. for 140 minutes, stirred uniformly, and photocurable resin composition (hereinafter referred to as “R-6”). )

(Comparative Example 4)
After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, 4 parts Irgacure 369, 2 parts Irgacure 907 (manufactured by Ciba Specialty Chemicals), lauryl acrylate 50 parts (trade name: NK ester LA, manufactured by Shin-Nakamura Chemical Co., Ltd.) were charged, heated to 110 ° C., kept warm for 45 minutes, and uniformly stirred and mixed. Furthermore, 50 parts of urethane compound (R-0) having an ethylenically unsaturated double bond and 3 parts of a silane coupling agent (trade name: KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) are added, and the temperature is 85 to 95 ° C. The mixture was kept for 140 minutes and stirred uniformly to obtain a photocurable resin composition (hereinafter referred to as “R-7”).

The photocurable resin compositions (R-1) to (R-7) obtained as described above were prepared using a PET film (Teijin Tetoron Film G2C, 80 mm × 80 mm, manufactured by Teijin Limited) using an applicator so that the film thickness was 270 μm. X50 μm), and the upper surface is covered with a PET film, and then an ultraviolet irradiation device (UV irradiation device 4 kW × 1, manufactured by Nippon Battery Co., Ltd., output: 160 W / cm, metal halide lamp), irradiation distance 12 cm, lamp movement Evaluation with a film thickness of about 270 μm that was cured by irradiating with ultraviolet rays under the conditions of a speed of 20 m / min and an irradiation amount of about 700 mJ / cm ² , cutting the obtained cured film into 1 cm width, and sandwiching and adhering between PET films A test film was obtained.

[Peel strength]
Only one end of the evaluation test film was peeled off to obtain a test piece for measuring adhesive force. The peel strength is fixed to a universal tensile testing machine (manufactured by Shimadzu Corporation, Autograph IM-100) so that the cured film peeled off from the PET film forms an angle of 180 degrees, and at a rate of 20 mm / min at 23 ° C. It was determined by measuring 180 degree peel strength. The results are shown in Table 1.

[Water permeability]
Also, the photocurable resin compositions (R-1) to (R-7) are applied to a polytetrafluoroethylene plate (130 × 130 × 10 mm) using an applicator so that the film thickness is about 270 μm. Then, it was cured using an ultraviolet irradiation device under the above conditions to obtain a 110 × 110 mm test piece for measuring moisture permeability.

  The moisture permeability was obtained by setting the moisture permeability measurement test piece on a water vapor permeability meter (manufactured by LYSSY AG, L80-500 type water vapor permeability meter) and measuring the water vapor permeability at 60 ° C. and 90% RH. The results are shown in Table 1.

[Glass transition point (DMA method)]
Also, the photocurable resin compositions (R-1) to (R-7) are applied to a polytetrafluoroethylene plate (130 × 130 × 10 mm) using an applicator so that the film thickness is about 270 μm. Then, it was cured using an ultraviolet irradiation device under the above conditions to obtain a test piece for measuring viscoelasticity.

  For the glass transition point, a test piece for measuring viscoelasticity is set on RSA-III manufactured by TA instruments, the test mode is tensile, the test temperature is −60 to 150 ° C., the heating rate is 5 ° C./min, and the frequency is 1 Hz. It was measured. The results are shown in Table 1.

  As shown in Table 1, in the photocurable resin compositions according to Examples 1 to 3, a result of excellent balance of adhesiveness, flexibility, and moisture permeability at 23 ° C. was obtained. Moreover, the adhesiveness in 60 degreeC and Tg are also preferable, and it is excellent also in heat resistance. Therefore, it has been found that the photocurable moisture-proof sealing material for electronic paper according to the present invention has both contradictory properties such as flexibility and low moisture permeability, and adhesion to a PET substrate. On the other hand, Comparative Example 1 is excellent in moisture permeability and heat resistance, but is inferior in adhesiveness at 23 ° C., and Comparative Example 2 is excellent in adhesiveness and flexibility at 23 ° C., but has low peel strength at 60 ° C. and heat resistance. Inferior to sex. Further, Comparative Examples 3 and 4 resulted in inferior properties.

  As described above, the photo-curable resin composition according to the present invention is a photo-curable moisture-proof sealing material for electronic paper which has both flexibility and low moisture permeability, which are contradictory properties, and adhesion to a PET substrate. Yes, by applying and curing this photocurable moisture-proof sealing material, highly reliable electronic paper can be provided.

Claims (9)

  (A) (a1) a polyolefin polyol compound, (a2) an ethylenically unsaturated compound having a hydroxyl group, and (a3) an ethylenically unsaturated double compound obtained by reacting a compound having two or more isocyanate groups in one molecule. A photocurable resin composition comprising a urethane compound having a bond, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a urethane acrylate oligomer.   The photocurable resin composition according to claim 1, wherein the component (B) is a photopolymerizable monomer containing (B1) an ethylenically unsaturated double bond and a cyclic aliphatic group. The photocurable resin composition according to claim 1, wherein the component (B) is (B2) a photopolymerizable monomer represented by the following general formula (I).

(In general formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 4 to 20 carbon atoms.)   The said (B) component contains 30-70 mass% on the basis of the sum total of the said (A) component and (B) component, The photocurable resin composition in any one of Claims 1-3. .   The photocurable resin composition according to any one of claims 1 to 4, wherein the component (C) is contained in an amount of 1 to 10 mass% with respect to a total amount of the component (A) and the component (B). object.   The said (D) component contains 1-15 mass% on the basis of the sum total of the said (A) component and (B) component, The photocurable resin composition in any one of Claims 1-5 object.   The photocurable moisture-proof sealing material for electronic paper containing the photocurable resin composition in any one of Claims 1-6.   The electronic paper sealed using the photocurable moisture-proof sealing material for electronic paper of Claim 7.   The manufacturing method of the electronic paper which apply | coats the photocurable moisture-proof sealing material for electronic paper of Claim 7 to electronic paper, and hardens | cures and then seals the applied photocurable moisture-proof sealing material for electronic paper.