阅读说明：本技术 光固化性树脂组合物、使用该光固化性树脂组合物的燃料电池和密封方法 (Photocurable resin composition, fuel cell and encapsulating method using the Photocurable resin composition ) 是由 曾我哲徳 于 2018-04-13 设计创作，主要内容包括：本发明的目的在于提供一种光固化性树脂组合物,其在浸渍于温水后也维持对作为难粘接的材质的电解质膜的密合力。所述光固化性树脂组合物的特征在于,含有下述的(A)～(C)成分。(A)成分：具有1个以上的(甲基)丙烯酰基并具有包含-[CH<Sub>2</Sub>C(CH<Sub>3</Sub>)<Sub>2</Sub>]-单元的聚异丁烯骨架的聚合物,(B)成分：光自由基聚合引发剂,(C)成分：至少包含(C1)成分和(C2)成分的混合物,作为(C1)成分,是选自分别具有1个以上的烷氧基和(甲基)丙烯酰基的有机硅低聚物以及分别具有1个以上的烷氧基和异氰酸酯基的硅烷单体中的1种以上的化合物,作为(C2)成分,是选自分别具有1个以上的烷氧基和环氧基的有机硅低聚物以及分别具有1个以上的烷氧基和苯基的有机硅低聚物中的1种以上的化合物。(The purpose of the present invention is to provide a kind of Photocurable resin compositions, and the closing force of the dielectric film to the material as hardly possible bonding is also maintained after being impregnated in warm water.The Photocurable resin composition is characterized in that, contains following (A)~(C) ingredient.(A) ingredient: with 1 or more (methyl) acryloyl group and have include-[CH 2 C(CH 3 ) 2 The polymer of the polyisobutene skeleton of]-unit, (B) ingredient: optical free radical polymerization initiator, (C) ingredient: the mixture of (C1) ingredient and (C2) ingredient is included at least, as (C1) ingredient, it is to be selected from the compound for being respectively provided with 1 or more alkoxy and the silicone oligomer of (methyl) acryloyl group and being respectively provided with one or more of 1 or more alkoxy and the silane monomer of isocyanate group, as (C2) ingredient, it is to be selected to be respectively provided with 1 or more alkoxy and the silicone oligomer of epoxy group and the compound for being respectively provided with one or more of 1 or more alkoxy and the silicone oligomer of phenyl.)

1. a kind of Photocurable resin composition, which is characterized in that containing following (A)~(C) ingredient,

(A) ingredient: with 1 or more (methyl) acryloyl group and have include-[CH₂C(CH₃)₂The polyisobutene of]-unit The polymer of skeleton,

(B) ingredient: optical free radical polymerization initiator,

(C) ingredient: including at least the mixture of (C1) ingredient and (C2) ingredient,

It is to be selected to be respectively provided with 1 or more alkoxy and the silicone oligomer of (methyl) acryloyl group as (C1) ingredient And it is respectively provided with the compound of one or more of 1 or more alkoxy and the silane monomer of isocyanate group,

It is to be selected to be respectively provided with 1 or more alkoxy and the silicone oligomer of epoxy group and difference as (C2) ingredient The compound of one or more of silicone oligomer with 1 or more alkoxy and phenyl.

2. Photocurable resin composition according to claim 1, wherein (A) ingredient is to have shown in general formula (1) There is the polymer of polyisobutene skeleton,

In formula (1), R¹Indicate that monovalence or multivalence aromatic hydrocarbyl or monovalence or multivalence aliphatic alkyl, PIB indicate the packet Containing-[CH₂C(CH₃)₂The polyisobutene skeleton of]-unit, R⁴Expression may include the hydrocarbon of the divalent of the carbon atom number 2~6 of oxygen atom Base, R²And R³Each independently represent the alkyl of 1 valence of hydrogen atom or carbon atom number 1~20, R⁵Indicate hydrogen atom, methyl or second Base, n are any integer in 1~6.

3. Photocurable resin composition according to claim 1 or 2, wherein further contain (methyl) acrylate Monomer is used as (D) ingredient.

4. Photocurable resin composition according to claim 3, wherein (D) ingredient be with carbon atom number 5~ (methyl) acrylate monomer of 30 alkyl or the ester ring type group of carbon atom number 5~30.

5. Photocurable resin composition according to any one of claims 1 to 4, wherein relative to (A) ingredient 100 mass parts include 0.1~30 mass parts of (C) ingredient, 0.1~30 mass parts of (D) ingredient.

6. a kind of fuel cell photocurable includes light-cured resin according to any one of claims 1 to 5 Composition.

7. fuel cell photocurable according to claim 6, wherein the fuel cell photo-curable Sealant is the separator as the component in fuel cell, frame, electrolyte, fuel electrode, air electrode and electrolyte Either member periphery fuel cell photocurable in membrane-electrode assembly.

8. fuel cell photocurable according to claim 6, wherein the fuel cell photo-curable Sealant is the frame and dielectric film of the sealant or fuel cell between the adjacent separator in fuel cell Or the sealant between electrolyte film-electrode joint.

9. the fuel cell photocurable according to any one of claim 6~8, wherein the fuel electricity Pond is polymer electrolyte fuel cell.

10. a kind of solidfied material is by Photocurable resin composition according to any one of claims 1 to 5 or claim 6 Made of sealant photocuring described in any one of~9.

11. a kind of fuel cell is comprising the sealing element and fuel electricity between the adjacent separator in fuel cell The fuel cell of any sealing element in sealing element between the frame and dielectric film or electrolyte film-electrode joint in pond, institute Stating any sealing element includes solidfied material described in any one of claim 10.

12. fuel cell according to claim 11, wherein the fuel cell is polymer electrolyte fuel cell.

13. a kind of encapsulating method, which is characterized in that be at least two flange by seal member that will have at least two flange Between at least part sealing method, at least one of described flange is transmissive to the light of active energy beam, described Encapsulating method comprises the following steps: described in any one of surface coating Claims 1 to 5 of in the flange at least one Photocurable resin composition process；A flange for being coated with the Photocurable resin composition is convex with another The process that edge is bonded via the Photocurable resin composition；And active energy is irradiated by the flange for being transmissive to light Amount ray solidifies the Photocurable resin composition, by the work of at least part sealing between at least two flange Sequence.

14. a kind of encapsulating method, which is characterized in that be at least two flange by seal member that will have at least two flange Between at least part sealing method, the encapsulating method comprises the following steps: in the flange at least one is convex The process that edge is coated with Photocurable resin composition according to any one of claims 1 to 5；To the photocuring having been coated with Property resin combination irradiation active energy beam solidify the Photocurable resin composition, formed by the photo-curable tree The process for the gasket that the solidfied material of oil/fat composition is constituted；By the configuration of another flange on the gasket, it is coated with photocuring One flange of property resin combination is crimped with another described flange via the gasket, by least two flange Between at least one sealing process.

15. a kind of encapsulating method, which is characterized in that be at least two flange by seal member that will have at least two flange Between at least part sealing method, the encapsulating method comprises the following steps: in the flange at least one is convex The process of gasket shape die for forming is configured on edge；Sky to the gasket shape die for forming between the flange configured with the mold The process that at least part of gap injects Photocurable resin composition according to any one of claims 1 to 5；To the light Hardening resin composition, which irradiates the active energy beam, solidifies the Photocurable resin composition, is formed by the light The process for the gasket that the solidfied material of hardening resin composition is constituted；The process that the mold is removed from one flange； By the configuration of another flange on the gasket, one flange and another described flange are pressed via the gasket It connects, by the process of at least part sealing between at least two flange.

Technical field

The present invention relates to the Photocurable resin compositions also maintained after being impregnated in warm water to the closing force of dielectric film.

Background technique

In recent years, fuel cell is concerned as automobile, home-use new energy resources system.Fuel cell is by making hydrogen The power generator of electricity is chemically reacted and taken out with oxygen.In addition, fuel cell is since energy efficiency when generating electricity is high, passes through hydrogen With reacting for oxygen and generate water, be clean power generator of new generation therefore.Fuel cell has solid polymer type fuel electric Pond, phosphoric acid type fuel cell, fused carbonate type fuel cell, solid oxide fuel cell this 4 modes, wherein Gu Body high molecular fuel battery due to operating temperature be compared with low temperature (80 DEG C or so) and be high generation efficiency, in automobile Electronic equipments Miniature Power Unit, the emergency power supplies such as power source, home-use power generator, mobile phone etc. are on the way by expectation.

As shown in Figure 1, the battery 1 of polymer electrolyte fuel cell be have electrolyte film-electrode joint 5 (MEA), It supports the frame 6 of the MEA and is formed with the structure of the separator 2 of the flow path of gas, the electrolyte film-electrode joint 5 It is the structure that polyelectrolyte membrane 4 is held between air electrode 3a, fuel electrode 3b.

In order to start polymer electrolyte fuel cell, the fuel containing hydrogen is supplied to anode electrode with needing to be individually insulated Gas supplies containing aerobic oxidizing gas cathode electrode.This is because if the insufficient and gas of isolation and another Gas mixing, it is likely that cause the reduction of generating efficiency.From such background, for preventing fuel gas, oxygen etc. Leakage purpose, mostly use sealant.Specifically, between adjacent separator, between separator and frame, Sealant is used between frame and dielectric film or MEA etc..

As sealant used in polymer electrolyte fuel cell, due to be resistance to gas-premeable, it is low-moisture permeability, resistance to Therefore hot, acid resistance, flexible excellent rubber elastomer have studied the carry out silane using polyisobutene based polymer The being heating and curing property resin combination (referring to patent document 1) of alkylation reaction, the carry out hydrosilanes using perfluoroalkyl polyether compound Change the being heating and curing property resin combination (referring to patent document 2) of reaction, use the carry out hydrosilylation reactions of fluoropolymer Being heating and curing property resin combination (referring to patent document 3), the being heating and curing property tree using Ethylene-Propylene-Diene rubber Oil/fat composition (referring to patent document 4).However, the being heating and curing property resin combination of Patent Documents 1 to 4 needs to solidify Heating process, accordingly, there exist spend activity time and worry deterioration such problems because of the dielectric film caused by heating.

Therefore, it can be realized the light-cured resin combination of the deterioration of dielectric film caused by process shortens, prevents because of heat Object is concerned.It discloses in patent document 5,6 and draws containing polyisobutene diacrylate, (methyl) acrylic monomers, light Send out the photocurable of agent.

Summary of the invention

However, Photocurable resin composition disclosed in patent document 5,6 in order to obtain leakproofness and with polyisobutene Diacrylate is principal component, but photo-curable is insufficient.In addition, light-cured resin disclosed in patent document 5,6 combines Object in order to obtain leakproofness and using the low polyisobutene diacrylate of polarity as principal component, but exist due to its structure and to each Cementability difference such problems of kind component.In turn, since the polyelectrolyte membrane of fuel cell is fluorine system polymer, because This, is the material that previous sealant is extremely hard to bonding, and the Photocurable resin composition of patent document 5,6 is more difficult to glue It connects.

In turn, fuel cell due to warm water there are in the environment of work, to used sealant require soaking Stain maintains the adaptation to dielectric film after warm water.

According to the above, the purpose of the present invention is to provide one kind also maintains to be bonded to as hardly possible after being impregnated in warm water Material dielectric film closing force Photocurable resin composition.

Purport of the invention is as follows.

[1] a kind of Photocurable resin composition, which is characterized in that contain following (A)~(C) ingredient.

(A) ingredient: with 1 or more (methyl) acryloyl group and have include-[CH₂C(CH₃)₂Gathering for]-unit is different The polymer of butylene skeleton

(B) ingredient: optical free radical polymerization initiator

(C) ingredient: the mixture of (C1) ingredient and (C2) ingredient is included at least

It is low with the organosilicon of (methyl) acryloyl group selected from the alkoxy for being respectively provided with 1 or more as (C1) ingredient Polymers and the compound for being respectively provided with one or more of 1 or more alkoxy and the silane monomer of isocyanate group

As (C2) ingredient, be selected from be respectively provided with 1 or more alkoxy and the silicone oligomer of epoxy group and It is respectively provided with the compound of one or more of 1 or more alkoxy and the silicone oligomer of phenyl

[2] Photocurable resin composition according to [1], wherein (A) ingredient is to have shown in general formula (1) There is the polymer of polyisobutene skeleton.

(in formula (1), R¹Indicate that monovalence or multivalence aromatic hydrocarbyl or monovalence or multivalence aliphatic alkyl, PIB indicate institute It states comprising-[CH₂C(CH₃)₂The polyisobutene skeleton of]-unit, R⁴Expression may include the divalent of the carbon atom number 2~6 of oxygen atom Alkyl, R²And R³Each independently represent the alkyl of 1 valence of hydrogen atom or carbon atom number 1~20, R⁵Indicate hydrogen atom, methyl Or ethyl, n are any integer in 1~6)

[3] Photocurable resin composition according to [1] or [2], wherein further contain (methyl) acrylate Monomer is used as (D) ingredient.

[4] Photocurable resin composition according to [3], wherein (D) ingredient be with carbon atom number 5~ (methyl) acrylate monomer of 30 alkyl or the ester ring type group of carbon atom number 5~30.

[5] Photocurable resin composition according to any one of [1]~[4], wherein relative to (A) at Divide 100 mass parts, includes 0.1~30 mass parts of (C) ingredient, 0.1~30 mass parts of (D) ingredient.

[6] a kind of fuel cell photocurable includes photo-curable tree described in any one of [1]~[5] Oil/fat composition.

[7] the fuel cell photocurable according to [6], wherein the fuel cell photo-curable Sealant is the separator as the component in fuel cell, frame, electrolyte, fuel electrode, air electrode and electrolyte Either member periphery fuel cell photocurable in membrane-electrode assembly.

[8] the fuel cell photocurable according to [6], wherein the fuel cell photo-curable Sealant is the frame and dielectric film of the sealant or fuel cell between the adjacent separator in fuel cell Or the sealant between electrolyte film-electrode joint.

[9] the fuel cell photocurable according to any one of [6]~[8], wherein the fuel electricity Pond is polymer electrolyte fuel cell.

[10] a kind of solidfied material is by Photocurable resin composition or [6]~[9] described in any one of [1]~[5] Any one of described in sealant photocuring made of.

[11] a kind of fuel cell, be comprising between the adjacent separator in fuel cell sealing element and combustion Expect the fuel electricity of any sealing element in the sealing element between the frame and dielectric film or electrolyte film-electrode joint of battery Pond, any sealing element include solidfied material described in [10].

[12] fuel cell according to [11], wherein the fuel cell is polymer electrolyte fuel cell.

[13] a kind of encapsulating method, which is characterized in that be will have at least two flange by seal member this at least 2 The method of at least part sealing between a flange, at least one of described flange are transmissive to active energy beam Light, the encapsulating method comprise the following steps: any one of surface coating [1]~[5] of in the flange at least one The process of the Photocurable resin composition；Be coated with a flange of the Photocurable resin composition with it is another The process that a flange is bonded via the Photocurable resin composition；And it is lived by the flange irradiation for being transmissive to light Property energy-ray solidify the Photocurable resin composition, at least part between at least two flange is sealed Process.

[14] a kind of encapsulating method, which is characterized in that be will have at least two flange by seal member this at least 2 The method of at least part sealing between a flange, the encapsulating method comprise the following steps: in the flange at least The process of Photocurable resin composition described in any one of one flange coating [1]~[5]；It is solid to the light having been coated with The property changed resin combination irradiation active energy beam solidifies the Photocurable resin composition, is formed by the photo-curable The process for the gasket that the solidfied material of resin combination is constituted；By the configuration of another flange on the gasket, it is solid to be coated with light One flange of the property changed resin combination is crimped with another described flange via the gasket, and described at least two is convex The process of at least one sealing between edge.

[15] a kind of encapsulating method, which is characterized in that be will have at least two flange by seal member this at least 2 The method of at least part sealing between a flange, the encapsulating method comprise the following steps: in the flange at least The process of gasket shape die for forming is configured on one flange；To the gasket shape die for forming with configured with the mold flange it Between gap at least part injection any one of [1]~[5] described in Photocurable resin composition process；To described Photocurable resin composition, which irradiates the active energy beam, solidifies the Photocurable resin composition, is formed by described The process for the gasket that the solidfied material of Photocurable resin composition is constituted；The work that the mold is removed from one flange Sequence；By the configuration of another flange on the gasket, by one flange and another described flange via the gasket into Row crimping, by the process of at least part sealing between at least two flange.

The present invention provides a kind of also maintained after being impregnated in warm water to the closely sealed of the dielectric film of the material as hardly possible bonding The Photocurable resin composition of power.In addition, be capable of providing it is a kind of by using Photocurable resin composition of the invention into Row seals and the fuel cell with high reliability.

Detailed description of the invention

Fig. 1 is the schematic section of the monocell of fuel cell.

Fig. 2 is the schematic diagram for indicating fuel cell entirety.

Specific embodiment

Hereinafter, the detailed content to invention is illustrated.

< Photocurable resin composition >

The present invention relates to a kind of Photocurable resin compositions, which is characterized in that containing following (A)~(C) ingredient and Arbitrarily (D) ingredient.

(A) ingredient: with 1 or more (methyl) acryloyl group and have include-[CH₂C(CH₃)₂Gathering for]-unit is different The polymer of butylene skeleton

(B) ingredient: optical free radical polymerization initiator

(C) ingredient: the mixture of (C1) ingredient and (C2) ingredient is included at least

It is low with the organosilicon of (methyl) acryloyl group selected from the alkoxy for being respectively provided with 1 or more as (C1) ingredient Polymers and the compound for being respectively provided with one or more of 1 or more alkoxy and the silane monomer of isocyanate group

As (C2) ingredient, be selected from be respectively provided with 1 or more alkoxy and the silicone oligomer of epoxy group and It is respectively provided with the compound of one or more of 1 or more alkoxy and the silicone oligomer of phenyl

(D) ingredient: (methyl) acrylate monomer.

Each (A)~(D) ingredient and any ingredient of Photocurable resin composition of the invention can be combined arbitrarily Use the substance for meeting following either conditions.It should be noted that each (A)~(D) ingredient is mutually different ingredient.

< (A) ingredient >

(A) used in the present invention as long as ingredient with 1 or more (methyl) acryloyl group and have comprising- [CH₂C(CH₃)₂The polymer of the polyisobutene skeleton of]-unit is just not particularly limited.As (A) ingredient, as long as such as tool There is-[CH₂C(CH₃)₂]-unit (polyisobutene skeleton), or include "-[CH₂C(CH₃)₂Its other than]-unit The polymer of its Component units ".(A) ingredient is relative to Component units total amount, it is proper that excellent including, for example, 70 mass % or more Choosing include 75 mass % or more, more preferably comprising 80 mass % or more-[CH₂C(CH₃)₂]-unit.In addition, (A) ingredient is appropriate Be including, for example, 100 mass % it is below-[CH₂C(CH₃)₂]-unit, in another way, comprising 95 mass % hereinafter, In It include 90 mass % or less in another mode.(A) ingredient suitably have preferably 1~12, it is 2~8 more preferable, into one Walk preferably 2~4, particularly preferred 2 (methyl) acryloyl groups.It should be noted that in the present invention, polymer is not only restricted to limit System, such as can be defined as referring to main chain in polymer with the structure of the repetitive unit of monomer and by 100 or more weights The compound that multiple unit is constituted.In addition, (methyl) acryloyl group can reside in any one of side chain or end of molecule, but From the viewpoint of caoutchouc elasticity, it is preferably in the end of molecule.

As above-mentioned (A) ingredient, from the viewpoint of photo-curable and to the bonding force of dielectric film it is excellent, it is preferably following Shown in shown in general formula (1) with the polymer of polyisobutene skeleton.As the concrete example of (A) ingredient, can enumerate has (first Base) acryloxy alkoxyl phenyl polyisobutene.It should be noted that the main framing of (A) ingredient in the present invention is poly- isobutyl Alkene skeleton, but in addition to mainly using monomer of the isobutene as the composition polyisobutene skeleton, as long as not damaging the present invention Effect range, then can also be copolymerized other monomers.In addition, the coating operations from Photocurable resin composition are excellent Aspect is set out, and (A) ingredient is liquid preferably under room temperature (25 DEG C).

In formula (1), R¹Indicate monovalence or multivalence aromatic hydrocarbyl or monovalence or multivalence aliphatic alkyl, preferably multivalence Aromatic hydrocarbyl, the particularly preferably phenylene of divalent.PIB indicates above-mentioned comprising-[CH₂C(CH₃)₂]-unit (or-by [CH₂C(CH₃)₂What]-unit was constituted) polyisobutene skeleton.R⁴Expression may include the divalent of the carbon atom number 2~6 of oxygen atom Alkyl, the preferably alkyl of the divalent of carbon atom number 2 or 3.R²And R³Each independently represent hydrogen atom or carbon atom number 1~20 The alkyl of 1 valence, preferably hydrogen atom.R⁵Indicate hydrogen atom, methyl or ethyl, preferably hydrogen atom or methyl.N is in 1~6 Any integer, particularly preferably 2~4 integer.

The molecular weight of (A) ingredient in the present invention is not particularly limited, but goes out from the physical property etc. after mobility, solidification Hair, the number-average molecular weight such as preferably 200~500000, further preferably 1000 obtained by chromatography determination~ 100000, particularly preferably 3000~50000.It should be noted that above-mentioned number-average molecular weight is unless otherwise specified, then by making It is calculated with the standard polystyren scaling method of size exclusion chromatography (SEC).

Viscosity of (A) ingredient at 25 DEG C in the present invention is not particularly limited, but from workability etc., such as For 5Pas or more, preferably 50Pas or more, more preferably 100Pas or more, for example, 3000Pas hereinafter, it is preferred that For 2500Pas hereinafter, more preferably 2000Pas or less.Particularly preferred viscosity is 1550Pas.As long as it should be noted that It is not particularly illustrated, then the measurement of viscosity measures the viscosity at 25 DEG C using cone plate type viscometer.

As the manufacturing method of above-mentioned (A) ingredient, it is not particularly limited, well known method can be used.Such as it can enumerate Polymer Bulletin, volume 6, page 135~141 (1981), T.P.Liao and J.P.Kennedy and Polyer Bulletin, page 253~260 (1988), makes terminal hydroxyl polyisobutene and third disclosed in Puskas et al. at volume 20 Method obtained from alkene acyl chlorides or methacrylic chloride reaction etc..In addition, the manufacturing method as other (A) ingredients, can enumerate Method obtained from reacting terminal hydroxyl polyisobutene with the compound with (methyl) acryloyl group and isocyanate group；Make Terminal hydroxyl polyisobutene, the compound with isocyanate group are reacted with the compound with (methyl) acryloyl group and hydroxyl Obtained from method；Make terminal hydroxyl polyisobutene and (methyl) acrylic acid or (methyl) using dehydration esterification method or ester-interchange method Method obtained from acrylic acid lower ester is reacted etc..

In addition, the manufacturing method as polyisobutene shown in above-mentioned general formula (1), is not particularly limited, can preferably enumerate Make shown in halogen end thereof polyisobutene and general formula (2) as shown below this disclosed in Japanese Unexamined Patent Publication 2013-216782 bulletin The method of the compound reaction with (methyl) acryloyl group and phenoxy group of sample.In addition, above-mentioned halogen end thereof polyisobutene can It is obtained by well known method, such as is obtained by cationic polymerization, more preferably obtained by living cationic polymerization.

In formula (2), R²、R³、R⁴And R⁵It can be defined such as above-mentioned formula (1).Specifically, R⁴Indicate carbon atom number 2~6 can With the alkyl of the divalent comprising oxygen atom.R²And R³Each independently represent the alkyl of 1 valence of hydrogen atom or carbon atom number 1~20. R⁵Indicate hydrogen atom, methyl or ethyl.As above-mentioned formula (2) compound represented, such as (methyl) acrylic acid benzene oxygen can be enumerated Base methyl esters, (methyl) phenoxyethyl acrylate, (methyl) acrylic acid phenoxy-propyl etc., preferably (methyl) acrylic acid benzene oxygen Base ethyl ester.

< (B) ingredient >

Used in the present invention as (B) as long as the optical free radical polymerization initiator of ingredient pass through irradiation light (active energy Amount ray) and generating makes the compound of cured free radical of (A) ingredient of the invention etc. there is no limit.Here, active-energy Ray includes the radioactive ray such as alpha ray, β ray, and the electromagnetic waves such as gamma-rays, X-ray, electron beam (EB), wavelength is 100~400nm The ultraviolet light of left and right, wavelength are the light of all broad sense such as the luminous ray of 400~800nm or so, preferably ultraviolet light.As (B) ingredient, such as acetophenone system optical free radical polymerization initiator, benzoin system optical free radical polymerization initiator, hexichol can be enumerated Ketone system optical free radical polymerization initiator, thioxanthones system optical free radical polymerization initiator, the polymerization of acylphosphine oxide system optical free radical Initiator, titanocenes system optical free radical polymerization initiator etc., wherein obtain surface cure from by irradiating active energy beam From the perspective of property and deep excellent curability solidfied material are such, preferably acetophenone system optical free radical polymerization initiator, acyl group Phosphine oxide system optical free radical polymerization initiator.In addition, they can be used alone, also two or more kinds may be used.

As above-mentioned acetophenone system optical free radical polymerization initiator, such as diethoxy acetophenone, 2- hydroxyl -2- can be enumerated Methyl-1-phenyl-propan-1- ketone, benzyl dimethyl ketal, 4- (2- hydroxyl-oxethyl) phenyl-(2- hydroxyl-2- propyl) ketone, 1- hydroxy-cyclohexyl-phenyl -one, 2- methyl -2- morpholinyl (4- thiomethylphenyl) propane -1- ketone, 2- benzyl -2- diformazan Base amino -1- (4- morpholino phenyl) butanone, 2- hydroxy-2-methyl -1- [4- (1- methyl ethylene) phenyl] acetone oligomer Deng, but not limited to this.As the commercially available product of above-mentioned acetophenone system optical free radical polymerization initiator, can enumerate IRGACURE184, IRGACURE1173, IRGACURE2959, IRGACURE127 (BASF AG's system), ESACURE KIP-150 (Lamberti S.p.a. corporation).

As above-mentioned acylphosphine oxide system optical free radical polymerization initiator, such as bis- (2,4,6- trimethylbenzene first can be enumerated Acyl)-phenyl-phosphine oxide, 2,4,6- trimethylbenzoy-diphenies-phosphine oxide etc., but not limited to this.As above-mentioned acyl group The commercially available product of phosphine oxide system optical free radical polymerization initiator, can enumerate IRGACURE TPO, IRGACURE819, IRGACURE819DW (BASF AG's system).

The use level of (B) ingredient of the invention is not particularly limited, from can have both surface cure and deep curability From the perspective of, relative to above-mentioned 100 mass parts of (A) ingredient, preferably 0.1~30 mass parts, more preferably 0.5~20 mass Part, particularly preferably 1~15 mass parts.

< (C) ingredient >

(C) ingredient of the invention is different from (A) ingredient of the invention and (D) ingredient including at least described below (C1) mixture of ingredient and (C2) ingredient.(C1) ingredient is selected from the alkoxy and (methyl) propylene for being respectively provided with 1 or more The silicone oligomer (wherein, do not have epoxy group, phenyl) of acyl group and it is respectively provided with 1 or more alkoxy and isocyanic acid The compound of one or more of the silane monomer of ester group.(C2) ingredient is selected from the alkoxy and epoxy for being respectively provided with 1 or more The silicone oligomer (wherein, do not have (methyl) acryloyl group, phenyl) of base and be respectively provided with 1 or more alkoxy and The compound of one or more of the silicone oligomer (wherein, not having epoxy group, (methyl) acryloyl group) of phenyl.Pass through Will as (C) ingredient and of the invention other at subassembly, have to be impregnated in after warm water and also maintain to the closely sealed of dielectric film Effect as power.(C) ingredient of the invention is liquid at 25 DEG C in the closing force and coating operations to dielectric film Aspect is excellent, thus preferably.It should be noted that the alkoxy in (C) ingredient is not particularly limited, such as methoxyl group, second can be enumerated Oxygroup etc..

In addition, the silicone oligomer of above-mentioned (C1) ingredient, (C2) ingredient (is respectively provided with 1 or more alkoxy and (first Base) acryloyl group silicone oligomer, be respectively provided with 1 or more alkoxy and the silicone oligomer of epoxy group, respectively Silicone oligomer with 1 or more alkoxy and phenyl) it is not particularly limited, but from readily permeable in as Porous Dielectric film, the closing force of material it is excellent in this way from the perspective of, 25 DEG C of kinematic viscosity is preferably smaller than 70mm²/ s, it is especially excellent It is selected as 60mm²/ s or less.In turn, above-mentioned (C1) ingredient, (C2) ingredient silicone oligomer be not particularly limited, but to electricity Solve plasma membrane closing force it is excellent from the perspective of, preferably alcoxyl base unit weight is 10 mass % more than and less than 40 mass %, especially excellent 15 mass % are selected as with and less than 30 mass %.It should be noted that the organosilicon of above-mentioned (C1) ingredient, (C2) ingredient in the present invention Oligomer is not particularly limited, for example, can enumerate weight average molecular weight be 500~7000 range and have dimethyl siloxane, first Base phenyl siloxane, isostructural compound of diphenyl siloxane etc..

Above-mentioned silicone oligomer is not particularly limited, and can enumerate 2 or more the silane lists containing hydrolyzable silyl group Condensation reaction, which occurs, for body is condensed 2 or more organo-silicon compound and the silicone oligomer of formation-Si-O-Si- structure.Make It for the above-mentioned silane monomer containing hydrolyzable silyl group, is not particularly limited, such as dimethyldimethoxysil,ne, two can be enumerated Methyldiethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, methyltrimethoxysilane, methyl Triethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, tetramethoxy-silicane, tetraethoxysilane, 3- ring Oxygen propoxypropyl trimethoxy silane, 3- epoxy propoxy propyl triethoxysilane, 3- glycidoxypropyl two Methoxy silane, 3- glycidoxypropyl diethoxy silane, 3- acryloyloxypropyltrimethoxysilane, 3- first Base acryloxypropyl dimethoxysilane, 3- methacryloxypropyl trimethoxy silane, 3- metering system Methyl diethoxy silane etc..In addition, they can be used alone, also two or more kinds may be used.

The alkoxy for being respectively provided with 1 or more of above-mentioned (C1) ingredient and the silicone oligomer of (methyl) acryloyl group are excellent It is selected as at least being respectively provided with 1 or more alkoxy and the silicone oligomer of (methyl) acryloyl group in side chain.As above-mentioned It is at least respectively provided with the commercially available product of 1 or more alkoxy and the silicone oligomer of (methyl) acryloyl group in side chain, can lift KR-513, X-40-2672B (Shin-Etsu Chemial Co., Ltd's system) etc. out.

As the alkoxy for being respectively provided with 1 or more of above-mentioned (C1) ingredient and the silane monomer of isocyanate group, do not have Be particularly limited to, for example, can enumerate 3- isocyanate propyl triethoxysilane, 3- isocyanates hydroxypropyl methyl diethoxy silane, Isocyanate propyl trimethoxysilane etc..In addition, as 1 or more alkoxy and the silane of isocyanate group is respectively provided with The commercially available product of monomer, can enumerate KBM-9007, KBE-9007, KBE-9207 (Shin-Etsu Chemial Co., Ltd's system), A-1310, Y-5187 (Momentive Performance Materials Japan contract commercial firm) etc..In addition, it is also preferred that using in side chain Silicone oligomer (X-40-9272B, Shin-Etsu Chemial Co., Ltd's system) with methylacryloyl and methoxyl group.

The alkoxy for being respectively provided with 1 or more of above-mentioned (C2) ingredient and the silicone oligomer of epoxy group are preferably at least There is the silicone oligomer of alkoxy and epoxy group in side chain.At least there is alkoxy and epoxy group in side chain as above-mentioned The commercially available product of silicone oligomer can enumerate X-41-1056 (Shin-Etsu Chemial Co., Ltd's system) etc..

The alkoxy for being respectively provided with 1 or more of above-mentioned (C2) ingredient and the silicone oligomer of phenyl are preferably at least Side chain is respectively provided with 1 or more alkoxy and the silicone oligomer of phenyl.As the above-mentioned alcoxyl for being respectively provided with 1 or more The commercially available product of the silicone oligomer of base and phenyl can enumerate KR-213 (Shin-Etsu Chemial Co., Ltd's system) etc..

The use level (total amount of (C1) ingredient and (C2) ingredient) of (C) ingredient of the invention is not particularly limited, relatively In 100 mass parts of (A) ingredient, preferably 0.1~50 mass parts, more preferably 0.5~30 mass parts, particularly preferably 1~20 Mass parts.By (C) ingredient be above-mentioned range in, it is more excellent to the closing force of dielectric film.

The ratio (additive amount of (C1) ingredient/(C2) ingredient additive amount) of (C1) ingredient of the invention and (C2) ingredient does not have It is particularly limited to, preferably 0.1~5, more preferably 0.15~3, particularly preferably 0.2~2.By in above-mentioned range, It is more excellent to the closing force of dielectric film.

< (D) ingredient >

(D) ingredient can also be further included in the present invention.(methyl) acrylate list as (D) ingredient of the invention Body is the compound that free radical kind caused by (B) ingredient through the invention is polymerize, and is used as reactive diluent. But (D) ingredient of the invention does not include (A) ingredient of the invention, (C1) ingredient.As (D) ingredient, list can be used for example Functionality, difunctionality, trifunctional and multi-functional monomer etc., among these, from compatible with (A) ingredient of the invention And from the aspect of photo-curable is excellent, the ester ring type base of alkyl or carbon atom number 5~30 preferably with carbon atom number 5~30 (methyl) acrylate monomer of group.Here, as above-mentioned carbon atom number, for example, 2 or more, preferably 3 or more, more preferably 5 or more, further preferably 7 or more, in addition, for example, 30 hereinafter, preferably 20 hereinafter, more preferably 15 hereinafter, further Preferably 10 or less.

As (methyl) acrylate monomer of the above-mentioned alkyl with carbon atom number 5~30, it is not particularly limited, such as (methyl) 2-EHA, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid can be enumerated Last of the ten Heavenly stems ester, (methyl) dodecylacrylate, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) propylene Sour n-octadecane base ester, (methyl) acrylic acid isooctadecane base ester, (methyl) acrylic acid nonadecane base ester, 3- heptyl decyl -1- (methyl) acrylate, (methyl) stearyl acrylate etc..In addition, as the above-mentioned ester ring type base with carbon atom number 5~30 (methyl) acrylate monomer of group, can enumerate (methyl) cyclohexyl acrylate, (methyl) dicyclopentanyl acrylate, (methyl) third Olefin(e) acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl oxygen ester, (methyl) isobornyl acrylate, (methyl) acrylic acid gold Rigid Arrcostab, dicyclopentenyl two (methyl) acrylate etc., (D) ingredient can be used alone or with two or more mixing The form of object uses.

The use level of (D) ingredient is somebody's turn to do relative to 100 mass parts of (A) ingredient, preferably 3~300 mass parts, more preferably 5 ~200 mass parts, particularly preferably 10~100 mass parts.If (D) ingredient is 3 mass parts or more, also without surface cure Property reduce misgivings, below the mass if it is 300, the moisture permeability of Photocurable resin composition will not reduce, thus It is preferred that.

< any ingredient >

It, can be in the range of not damaging the purpose of the present invention using with (methyl) propylene for composition of the invention Oligomer (not including (A) ingredient and (D) ingredient of the invention), the thermal free radical initiator, multi-thioalcohol compound, tertiary amine of acyl group It is the various elastomers such as compound, styrene based copolymer, packing material, preserving stabilizer, antioxidant, light stabilizer, closely sealed The additives such as imparting agent (not including (C) ingredient of the invention), plasticizer, pigment, fire retardant and surfactant.

As the above-mentioned oligomer (not including (A) ingredient and (D) ingredient of the invention) with (methyl) acryloyl group, do not have There are carbamate (methyl) acrylate, the hydrogenated butadiene polymer skeleton for being particularly limited to, can for example enumerating polybutadiene skeleton Carbamate (methyl) acrylate, carbamate (methyl) acrylate of polycarbonate backbone, polyether skeleton Carbamate (methyl) acrylate, carbamate (methyl) acrylate of polyester backbone, castor oil skeleton amino Formic acid esters (methyl) acrylate, isoprene (methyl) acrylate, hydrogenated isoprene system (methyl) acrylate, ring Oxygen (methyl) acrylate, acrylate copolymer etc. containing (methyl) acrylic, wherein from (A) ingredient of the invention, (D) the excellent aspect of COMPONENTS COMPATIBILITY is set out, and preferably carbamate (methyl) acrylate of polybutadiene skeleton, hydrogenation is poly- Carbamate (methyl) acrylate, different of carbamate (methyl) acrylate of butadiene skeletal, castor oil skeleton Pentadiene system (methyl) acrylate, hydrogenated isoprene system (methyl) acrylate.It should be noted that in the present invention, it is oligomeric Object refers in main chain with the structure of the repetitive unit of monomer and the compound that is made of 2~100 repetitive units.

Above-mentioned thermal free radical initiator is not particularly limited, such as can enumerate ketone peroxide, ketal peroxide, dialkyl group Peroxide, hydrogen peroxide, peroxyester, diacyl peroxide, peroxy dicarbonate etc..These compounds can be distinguished It is used alone, in addition can also be used in mixed way two or more.

It as above-mentioned multi-thioalcohol compound, is not particularly limited, such as trimethylolpropane tris (3- mercaptopropionic acid can be enumerated Ester), pentaerythrite four (3-thiopropionate), trimethylolpropane tris (3- mercaptobutylate), trimethylolethane trimethacrylate (3- mercapto Base butyrate), trimethylolethane trimethacrylate (3- mercaptobutylate), ethylene glycol bis- (3- thioglycolates), bis- (the 3- mercaptos of butanediol Base ethyl glycolate), trimethylolpropane tris (3- thioglycolate), pentaerythrite four (3- thioglycolate), three-[(3- Mercaptopropionyl oxygroup)-ethyl]-isocyanuric acid ester, pentaerythrite four (3-thiopropionate), bis- (the 3- mercaptopropionic acids of tetraethylene glycol Ester), dipentaerythritol six (3-thiopropionate), pentaerythrite four (3- mercaptobutylate), bis- (the 3- sulfydryl butyryl oxygen of 1,4- Base) butane, 1,3,5- tri- (3- sulfydryl butoxyethyl group) -1,3,5-triazines -2,4,6 (1H, 3H, 5H)-triketones etc., these chemical combination Object can use individually, and in addition can also be used in mixed way two or more.

As the commercially available product of above-mentioned multi-thioalcohol compound, for example, can enumerate TMTP, PETP (shallow lake Chemical Co., Ltd. system), TEMPIC, TMMP, PEMP, PEMP-II-20P, DPMP (SC organic chemistry Co. Ltd. system), MTNR1, MTBD1, MTPE1 are (clear With electrician's Co. Ltd. system) etc., but it is not limited to these.These compounds can use individually, and in addition can also mix It closes using two or more.

For the purpose for improving photo-curable, tertiary amine compound can be cooperated to the present invention.As tertiary amine compound, do not have It is particularly limited to, such as Trimethylamine, triethylamine, tri-butylamine, N can be enumerated, N '-diethanol amine, N, N '-dimethyl is to toluene Amine, N, N '-dimethyl-aniline, N- metil-diethanolamine, N- methyl-dimethanolamine, N, N '-dimethyl amino-acetophenone, N, N '-dimethyl aminobenzophenone, N, N '-diethylamino-benzophenone, triisopropanolamine etc..

It, can be to styrene based copolymer of the present invention for the purpose of the rubber physical property of adjustment solidfied material.As benzene Vinyl copolymer is not particularly limited, such as can enumerate styrene-butadiene copolymer, styrene-isoprene copolymer (SIP), styrene-butadiene copolymer (SB), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-isobutyl Alkene-styrol copolymer (SIBS), acrylonitritrile-styrene resin (AS), Acrylnitrile-Butadiene-Styrene (ABS) Deng.

It is steady can not damage preservation to present invention addition for the purpose of elasticity modulus, mobility for improvement solidfied material etc. The packing material of qualitative degree.Specifically, organic matter powder, inanimate matter powder, metallic powder etc. can be enumerated.As nothing The packing material of machine matter powder can enumerate glass, fumed silica, aluminium oxide, mica, ceramics, silicon rubber powder, carbonic acid Calcium, aluminium nitride, carbon dust, kaolin, dry clay mineral, dring silicon diatomaceous earth etc..The use level of inanimate matter powder relative to (A) at Divide 100 mass parts, preferably 0.1~100 mass parts or so.More than 0.1 mass parts, it can expect adequately to imitate Fruit will not below the mass if it is 100 impact the mobility of Photocurable resin composition, workability It will not reduce, thus preferably.

Fumed silica can be strong for the viscosity of adjustment Photocurable resin composition or the machinery of raising solidfied material The purpose of degree and cooperate.It is carried out it is preferred that can be used with organochlorosilane class, polysiloxane, hexamethyldisilazane etc. The fumed silica etc. of silicic acid anhydride.As the concrete example of fumed silica, such as it can enumerate Japanese Aerosil's Trade name AEROSIL R974, R972, R972V, R972CF, R805, R812, R812S, R816, R8200, RY200, RX200, The commercially available products such as RY200S, R202.

As organic matter powder packing material, can for example enumerate polyethylene, polypropylene, nylon, cross-linked acrylic acid, crosslinking Polystyrene, polyester, polyvinyl alcohol, polyvinyl butyral, polycarbonate.The use level of organic matter powder relative to (A) at Divide 100 mass parts, preferably 0.1~100 mass parts or so.More than 0.1 mass parts, it can expect adequately to imitate Fruit will not below the mass if it is 100 impact the mobility of Photocurable resin composition, workability It will not reduce, thus preferably.

Preserving stabilizer can also be added to the present invention.As preserving stabilizer, benzoquinones, quinhydrones, quinhydrones can also be added The free base absorbant such as monomethyl ether, the metals such as ethylenediamine tetra-acetic acid or its 2- sodium salt, oxalic acid, acetylacetone,2,4-pentanedione, o-aminophenol Chelating agent etc..

Antioxidant can also be added to the present invention.As antioxidant, beta-naphthoquinone, methoxyl group -1 2- can be for example enumerated, 4- naphthoquinones, methylnaphthohydroquinone, quinhydrones, Hydroquinone monomethylether, single tert-butyl hydroquinone, DBH 2,5 di tert butylhydroquinone, 1,4-benzoquinone, 2,5- bis- The oxime-based compounds such as phenyl -1,4-benzoquinone, 2,5- di-t-butyl -1,4-benzoquinone；Phenthazine, 2,2- methylene-bis- (4- methyl-6-tert Butylphenol), catechol, tert-butyl catechol, 2- butyl -4-hydroxyanisol, 2,6- di-t-butyl-paracresol, 2- Tert-butyl -6- (3- tert-butyl -2- hydroxy-5-methyl base benzyl) -4- aminomethyl phenyl acrylate, 2- (1- (2- hydroxyl -3,5- two Tertiary pentyl phenyl) ethyl) -4,6- di-tert-pentyl-phenyl acrylate, 4,4 '-butylidenebis (6- tert-butyl -3- methylphenol), Bis- (2- (3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionyl of 4,4 '-thiobis (6- tert-butyl -3- methylphenol), 3,9- Oxygroup) -1,1- dimethyl ethyl) -2,4,8,10- four oxaspiro (5,5) hendecane, (3- (the tertiary fourth of 3,5- bis- of pentaerythrite four Base -4- hydroxy phenyl) propionic ester), thiodiethylene bis- (3- (3,5- di-tert-butyl-hydroxy phenyl) propionic esters), 18 Alkyl -3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester, N, bis- (3- (the 3,5- di-t-butyls-of N '-hexane -1,6- diyl 4- hydroxy phenyl) propionamide), bis- (1,1- the dimethyl ethyl) -4- hydroxyl-C of benzenpropanoic acid -3,5-_7-C₉Pendant alkyl group ester, 2,4- bis- Methyl -6- (1- methyl pentadecyl) phenol, diethyl ((bis- (1,1- the dimethyl ethyl) -4- hydroxy phenyls of 3,5-) methyl) phosphine Acid esters, 3,3 ', 3 ", 5,5 ', 5 "-six tert-butyl-a, a ', a "-(mesitylene -2,4,6- tolyl) three paracresol, diethyl Bis- ((bis- (1,1- the dimethyl ethyl) -4- hydroxy phenyls of 3,5-) methyl) phosphonic acids calcium, bis- (pungent the butylthiomethyl)-o-cresols of 4,6-, Ethylenebis (oxygen ethylidene) bis- (3- (5- tertiary butyl-4-hydroxy-tolyl) propionic esters), hexamethylene bis (3- (3,5- bis- Tert-butyl-hydroxy phenyl) propionic ester, 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) -1,3,5- triazine -2,4,6 (1H, 3H, 5H)-triketone, 1,3,5- tri- ((4- tert-butyl -3- hydroxyl -2,6- xylyl) methyl) -1,3,5- triazine -2,4,6 Reaction product, the 2,6- di-t-butyl -4- (4,6- of (1H, 3H, 5H)-triketone, N- phenylaniline and 2,4,6- trimethylpentene Bis- (pungent sulfenyl) -1,3,5- triazine -2- base amino) phenols such as phenol, picric acid, citric acid；Three (2,4- di-tert-butyl-phenyls) Phosphite ester, three (2- ((tetra--tert-butyl of 2,4,8,10- dibenzo (d, f) (1,3,2) dioxa phosphine -6- base) oxygroup) ethyls) Bis- (bis- (1,1- the dimethyl ethyl) -6- of 2,4- of amine, bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, phosphorous acid Aminomethyl phenyl) ethyl ester, four (2,4- di-tert-butyl-phenyls) (the bis- phenyl of 1,1-) -4,4 '-diyl biphosphinate, 6- (3- (uncle 3- Butyl -4- hydroxy-5-methyl base phenyl) propoxyl group) -2,4,8,10- tetra-tert dibenzo (d, f) (1,3,2) dioxa phosphine etc. Phosphorus series compound；Dilauryl 3,3 '-thiodipropionate, myristyl 3,3 '-thiodipropionate, distearyl 3, The chalcogenide compounds such as 3 '-thiodipropionates, pentaerythrite four (3- lauryl thiopropionate), 2-mercaptobenzimidazole；Pheno The amine compounds such as thiazine；Lactone based compound；Vitamin E based compound etc..Wherein, preferred phenol system compound.

Light stabilizer can also be added to the present invention.As light stabilizer, such as bis- (2,2,6,6- tetramethyls-can be enumerated 4- piperidyl) sebacate, bis- (1,2,2,6,6- pentamethyl -4- piperidyl) sebacates, 4- benzoyloxy -2,2,6,6- Tetramethyl piperidine, 1- (2- (3- (3,5- di-tert-butyl-hydroxy phenyl) propionyloxy) ethyl) -4- (3- (tertiary fourth of 3,5- bis- Base -4- hydroxy phenyl) propionyloxy) -2,2,6,6- tetramethyl piperidine, 1,2,2,6,6- pentamethyl -4- piperidyl-metering system Acid esters, bis- (1,2,2,6,6- pentamethyl -4- piperidyls) ((bis- (1,1- the dimethyl ethyl) -4- hydroxy phenyls of 3,5-) methyl) fourth Phenyl malonic ester, decanedioic acid bis- ((the octyloxy) -4- of 2,2,6,6- tetramethyl -1 piperidyl) esters, 1,1- dimethyl ethyl peroxidating The reaction product of hydrogen and octane, N, and N ', N ", N " '-four (4,6- is bis--(butyl-(N- methyl -2,2,6,6- tetramethyl piperidine - 4- yl) amino)-triazine -2- base) and -4,7- diaza decane -1,10- diamines, dibutylamine -1,3,5- triazine-N, N '-it is bis- (2, The polycondensation of 2,6,6- tetramethyl -4- piperidyl -1,6- hexamethylene diamine and N- (2,2,6,6- tetramethyl -4- piperidyl) butylamine Object, poly- ((6- (1,1,3,3- tetramethyl butyl) amino -1,3,5- triazine -2,4- diyl) ((2,2,6,6- tetramethyl -4- piperidines Base) imino group) hexa-methylene ((2,2,6,6- tetramethyl -4- piperidyl) imino group)), dimethyl succinate and hydroxyl -2 4-, Polymer, 2,2,4,4- tetramethyl -20- (β-laurel Epoxide carbonyl) ethyl -7- oxygen of 2,6,6- tetramethyl -1- piperidine ethanol Miscellaneous two spiral shell of -3,20- diaza (5,1,11,2) heneicosane -21- ketone, Beta-alanine-N- (2,2,6,6- tetramethyl -4- piperidines Base)-dodecyl ester/tetradecane base ester, N- acetyl group -3- dodecyl -1- (2,2,6,6- tetramethyl -4- piperidyl) pyrroles Alkane -2,5- diketone, two spiral shell (5,1,11,2) heneicosane -21- ketone of 2,2,4,4- tetramethyl -7- oxa- -3,20- diaza, 2, 2,4,4- tetramethyl -21- oxa- -3,20- diazabicylo-(5,1,11,2)-heneicosane -20- propionic acid dodecyl ester/ten Tetraalkyl ester, malonic acid-((4- methoxyphenyl)-methylene)-bis- (1,2,2,6,6- pentamethyl -4- piperidyls) ester, 2,2, Bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzene diformazans of high-grade aliphatic ester, the N of 6,6- tetramethyl -4- piperidine alcohols, N ' - Amide etc. is obstructed amine system；The benzophenone based compounds such as octabenzone；2- (2H- benzotriazole -2- base) -4- (1,1,3,3- tetramethyl Base butyl) phenol, 2- (2- hydroxy-5-methyl base phenyl) benzotriazole, 2- (2- hydroxyl -3- (3,4,5,6- tetrahydro phthalyl Imines-methyl) -5- aminomethyl phenyl) benzotriazole, 2- (3- tert-butyl -2- hydroxy-5-methyl base phenyl) -5- chlorobenzotriazole, 2- (2- hydroxyl -3,5- di-tert-pentyl-phenyl) benzotriazole, 3- (3- (2H- benzotriazole -2- base) -5- tertiary butyl-4-hydroxy benzene Base) methyl propionate and polyethylene glycol reaction product, 2- (2H- benzotriazole -2- base) -6- dodecyl -4- methylphenol Etc. benzotriazole based compound；The benzoic ethers systems such as 2,4- di-tert-butyl-phenyl -3,5- di-tert-butyl-4-hydroxybenzoic acid ester Close object；Triazine based compounds such as 2- (4,6- diphenyl -1,3,5- triazine -2- base) -5- ((hexyl) oxygroup) phenol etc..It is especially excellent It is selected as the amine compound that is obstructed.

Closely sealed imparting agent (not including (C) ingredient of the invention) can also be added to the present invention.As closely sealed imparting agent, can Enumerate 3- methacryloxypropylmethyl dimethoxysilane, 3- methacryloxypropyl trimethoxy silane, 3- Methacryloxypropyl methyl diethoxysilane, 3- methacryloxypropyl, 3- acryloyl Oxygroup propyl trimethoxy silicane, methacryloxy octyl trimethoxy silane, vinyltrimethoxysilane, vinyl Trichlorosilane, vinyltriethoxysilane, vinyl-three ('beta '-methoxy ethyoxyl) silane, γ-r-chloropropyl trimethoxyl silicon Alkane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-sulfydryl third Base trimethoxy silane, γ aminopropyltriethoxy silane, N- β-(amino-ethyl)-gamma-amino propyl trimethoxy silicon Alkane, N- β-(amino-ethyl)-gamma-amino hydroxypropyl methyl dimethoxysilane, γ-ureidopropyltriethoxysilane, methyl-prop Olefin(e) acid hydroxy methacrylate phosphate, methacryloxy oxygroup ethyl acid phosphate, methacryloxy oxygroup ethylhexyldithiophosphoric acid Half salt of formula phosphate monoethylamine, 2-hydroxyethyl methacrylate phosphate etc..Among these, preferred methacrylic acid hydroxyl Ethyl ester phosphate, methacryloxy oxygroup ethyl acid phosphate, methacryloxy oxygroup ethyl acid phosphate Half salt of monoethylamine, 2-hydroxyethyl methacrylate phosphate etc..The content of adaptation imparting agent is relative to (A) ingredient 100 Mass parts, preferably 0.05~30 mass parts, further preferably 0.2~10 mass parts.

It can also be to present invention addition plasticizer, pigment, fire retardant and surfactant.As plasticizer, such as can lift Petroleums operation oil, acrylic acid series plasticizer, the adjacent benzene such as paraffin series operation oil, naphthene series operation oil, aromatic system operation oil out The binary such as dicarboxylate, dioctyl phthalate, dibutyl adipate acid dialkyl ester, liquid polybutene, liquid are poly- Low molecular weights liquid polymer such as isoprene etc..As pigment, such as carbon can be enumerated etc..As fire retardant, such as can enumerate Hydrated metal compound system, phosphorus system, organic silicon-type, nitride compound etc..As surfactant, such as anion table can be enumerated Face activating agent, nonionic surfactant, nonionic surfactant etc..They can be used alone or in combination with 2 kinds with On.

Photocurable resin composition of the invention can be manufactured by known method.Such as it can be by as follows Operation manufacture: cooperate specified amount (A) ingredient~(C) ingredient and other any ingredients, it is excellent using mixing arrangements such as mixing machines It is selected in 10~70 DEG C of temperature mixing preferably 0.1~5 hour.Additionally, it is preferred that being manufactured under shading environment.

< coating method >

As the method that Photocurable resin composition of the invention is coated on adherend, well known sealing can be used Agent, bonding agent method.It is, for example, possible to use dispensing, spraying, ink-jet, the silk-screen printings, intaglio process using automatic coating machine The methods of brush, dipping, spin coating.In addition, Photocurable resin composition of the invention is preferably 25 from the viewpoint of coating DEG C be liquid.

< curing method >

Photocurable resin composition of the invention can pass through the light such as irradiation ultraviolet light, visible light, active energy beam And solidify.So-called light refers to comprising the radioactive ray such as alpha ray, β ray, the electromagnetic waves such as gamma-rays, X-ray, electron beam herein (EB), the ultraviolet light of 100~400nm or so, the broad sense of the various active energy beams such as luminous ray of 400~800nm or so Light.Light source when solidification is not particularly limited, such as can enumerate low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultra high pressure mercury Lamp, black light lamp, microwave-excited mercury lamp, metal halide lamp, sodium vapor lamp, halogen lamp, xenon lamp, LED, fluorescent lamp, sunlight, electron beam Irradiation unit etc..From the viewpoint of the characteristic of solidfied material, the exposure of light irradiation is preferably 10kJ/m²More than, more preferably 15kJ/m²More than.

< solidfied material >

Solidfied material of the invention is ultraviolet to Photocurable resin composition irradiation of the invention by above-mentioned curing method Made of the light such as line (active energy beam etc.) solidify it.As long as solidfied material of the invention light-cured resin of the invention Solidfied material made of composition solidification, then its curing method can be any means.

< purposes and sealant >

It is photo-curable sealing as the suitable purposes using Photocurable resin composition of the invention or its solidfied material Agent.Sealant also includes the purposes such as bonding agent, smears, casting agent, embedding agent in the present invention.In addition, such on the way In use, Photocurable resin composition of the invention is preferably liquid at 25 DEG C.

As the specific purposes of sealant, Photocurable resin composition of the invention or its solidfied material are due to for low gas Therefore body permeability, low-moisture permeability, heat resistance, acid resistance, flexible excellent rubber elastomer can enumerate fuel cell, the sun It can battery, dye-sensitized solar cell, lithium ion battery, electrolytic capacitor, liquid crystal display, organic el display, electricity The layers such as sub- paper, LED, hard disk device, photodiode, optical communication circuit, electric wire Cable fiber, optoisolator, IC card Stack, sensor, substrate, medical medical device equipment etc.., on the way, light-cured resin of the invention combines for these Object is due to being impregnated in the closing force being also able to maintain that after warm water to dielectric film, it is therefore especially preferred that fuel cell applications.

< fuel cell >

Fuel cell is the power generator that electricity is taken out and chemically reacting hydrogen and oxygen.In addition, fuel cell has Polymer electrolyte fuel cell, phosphoric acid type fuel cell, fused carbonate type fuel cell, solid oxide fuel cell This 4 modes, wherein polymer electrolyte fuel cell is since operating temperature is compared with low temperature (80 DEG C of front and backs) and is high power generation effect Therefore rate is used for electronic equipments Miniature Power Unit, the emergency power supplies such as automobile power source, home-use power generator, mobile phone etc. Purposes.

As shown in Figure 1, the battery 1 of representative polymer electrolyte fuel cell is that have electrolyte film-electrode joint The structure of the separator 2 of 5 (MEA), the frame 6 of the above-mentioned MEA of support and the flow path for being formed with gas, the electrolyte film-electrode Conjugant 5 is the structure that polyelectrolyte membrane 4 is held between air electrode 3a and fuel electrode 3b.In addition, starting When polymer electrolyte fuel cell, fuel gas (hydrogen) and oxidizing gas (oxygen) pass through oxidizing gas flow passages 8a and fuel Gas flow path 8b is supplied.In addition, for the purpose for mitigating fever when generating electricity, cooling water flows through cooling water flow path 9.It should Illustrate, as shown in Fig. 2, device made of being overlapped the several hundred batteries and being packaged is known as battery pack 10.

If supplying oxidizing gas (oxygen to fuel electrode supply fuel gas (hydrogen), to oxygen electrode (air electrode) Gas), then reaction as described below occurs in each electrode, the reaction (H for generating water occurs as a whole₂+1/2O₂→H₂O).If It is described in detail, then as described below, in the proton (H that fuel electrode generates⁺) spread and move in solid polymer membrane To oxygen electrode side, reacted with oxygen and the water (H that generates₂O it) is discharged from oxygen electrode side.

Fuel electrode (anode electrode): H₂→2H⁺+2e^–

Oxygen electrode (cathode electrode): 1/2O₂+2H⁺+2e^-→H₂O

In order to start polymer electrolyte fuel cell, the fuel containing hydrogen is supplied to anode electrode with needing to be individually insulated Gas supplies containing aerobic oxidizing gas cathode electrode.This is because if the insufficient and gas of isolation and another Gas mixing, it is likely that cause the reduction of generating efficiency.From such background, for preventing fuel gas, oxygen etc. Leakage purpose, mostly use sealant.Specifically, between adjacent separator, between separator and frame, Sealant is used between frame and dielectric film or MEA etc..

Above-mentioned polyelectrolyte membrane can enumerate the cation-exchange membrane with ionic conductivity, from chemistry it is stable, From the aspect of work under high temperature is strong, can preferably it enumerate with sulfonic fluorine system polymer etc..As commercially available product, can enumerate Nafion (registered trademark), the Flemion (registered trademark) of Asahi Kasei Corporation, Asahi Glass Co., Ltd of E.I.Du Pont Company Aciplex (registered trademark) of system etc.., can be by using in general, although polyelectrolyte membrane is the material of difficult bonding Photocurable resin composition of the invention is bonded.

Nafion (registered trademark)

Above-mentioned fuel electrode is referred to as hydrogen electrode, anode, and well known electrode can be used.For example, making platinum, nickel, ruthenium Equal catalyst loadings electrode made of carbon.In addition, above-mentioned air electrode is referred to as oxygen electrode, cathode, well known electricity can be used Pole.For example, making the catalyst loadings such as platinum, alloy electrode made of carbon.The surface of each electrode, which can have to have, to be promoted The gas diffusion layers of the effect of diffusion, the moisturizing of electrolyte of air inlet body.Well known gas diffusion layers can be used in gas diffusion layers, Such as carbon paper, carbon cloth, carbon fiber can be enumerated etc..

As shown in Figure 1, above-mentioned separator 2 has the thread road of convex-concave, fuel gas, oxidizing gas pass through the flow path, quilt It is supplied to electrode.In addition, separator is made of aluminium, stainless steel, titanium, graphite, carbon etc..

Said frame is to be supported, enhance in such a way that the dielectric film of film or MEA will not rupture.Said frame Material can enumerate polyvinyl chloride, polyethylene naphthalate, polyethylene terephthalate, polypropylene, polycarbonate Equal thermoplastic resins.In addition, being bonded component, preferably structure to use hardening resin composition or its solidfied material of the invention Part transmitted light.

Fuel cell of the invention is characterized by being sealed by Photocurable resin composition of the invention or its solidfied material Fuel cell.As the component that the needs in fuel cell seal, can enumerate separator, frame, electrolyte, fuel electrode, Air electrode, MEA etc..As more specific sealing station, can enumerate between adjacent separator, separator and frame it Between, between frame and dielectric film or MEA etc..It should be noted that " between separator and frame " or " polyelectrolyte membrane or Between MEA and frame " the purpose of main sealing be to prevent the mixing of gas, leakage, between adjacent separator The purpose of sealing be to prevent the leakage of gas and cooling water from leaking into outside from cooling water flow path.It should be noted that because from Dielectric film generate acid and become strong acid atmosphere, therefore, to sealant require acid resistance.

< encapsulating method >

It as the encapsulating method for using Photocurable resin composition of the invention, is not particularly limited, typically may be used Enumerate FIPG (in-place molding gasket), CIPG (cured in place gasket), MIPG (on-site molding gasket), liquid injection molding etc..

FIPG is following method, that is, light of the invention is being coated with by the flange of seal member using automatic coating device etc. Hardening resin composition irradiates ultraviolet in the state of making it with another lip fits from the flange side for being transmissive to light Line isoreactivity energy-ray solidifies Photocurable resin composition, the method for carrying out adhering and sealing.It more specifically, is a kind of Encapsulating method, which is characterized in that be will have between at least two flange by seal member of at least two flange at least The method of a part sealing, at least one of above-mentioned flange are transmissive to the light of active energy beam, the encapsulating method packet It includes following process: being coated with the process of above-mentioned Photocurable resin composition on the surface of at least one of above-mentioned flange；It will The flange and another flange for being coated with above-mentioned Photocurable resin composition are via above-mentioned Photocurable resin composition The process of fitting；And irradiating active energy beam by the above-mentioned flange for being transmissive to light combines above-mentioned light-cured resin Object solidification, by the process of at least part sealing between above-mentioned at least two flange.

CIPG is following method, that is, applies light of the invention to by the flange pearl of seal member using automatic coating device etc. Hardening resin composition, irradiation ultraviolet light isoreactivity energy-ray make Photocurable resin composition be solidified to form gasket. Then, make itself and another lip fits, the method for carrying out compression seal.It more specifically, is a kind of encapsulating method, feature It is, is the side that there will be at least part sealing between at least two flange by seal member of at least two flange Method, the encapsulating method comprise the following steps: at least one flange in above-mentioned flange is coated with above-mentioned light-cured resin The process of composition；Above-mentioned photo-curable tree is made to the above-mentioned Photocurable resin composition irradiation active energy beam having been coated with Oil/fat composition solidification, the process for forming the gasket being made of the solidfied material of above-mentioned Photocurable resin composition；Another is convex Edge configures on above-mentioned gasket, is coated with a flange of Photocurable resin composition with another above-mentioned flange via upper It states gasket to be crimped, by the process of at least part sealing between above-mentioned at least two flange.

MIPG is following method, that is, mold is crimped on by the flange of seal member in advance, to the material for being transmissive to light Mold and flange between generate chamber injection Photocurable resin composition, irradiation ultraviolet light isoreactivity energy-ray make it Photocuring forms gasket.Then, the method for making it carry out compression seal with another lip fits.It should be noted that mold is excellent It is selected as being transmissive to the material of light, specifically, glass, polymethyl methacrylate (PMMA), polycarbonate, cyclenes can be enumerated Hydrocarbon polymer, alkene etc..In addition, mold is preferably pre-coated with fluorine system, organic in order to be easy to take out from mold after forming gasket The release agent of silicon systems etc..It more specifically, is a kind of encapsulating method, which is characterized in that be will have at least two flange close The method for sealing at least part sealing between at least two flange of component, the encapsulating method comprise the following steps: upper State the process that gasket shape die for forming is configured at least one flange in flange；To above-mentioned gasket shape die for forming be configured with The process that at least part in the gap between the flange of the mold injects above-mentioned Photocurable resin composition；To above-mentioned light Hardening resin composition, which irradiates above-mentioned active energy beam, solidifies above-mentioned Photocurable resin composition, is formed by above-mentioned light The process for the gasket that the solidfied material of hardening resin composition is constituted；The process that above-mentioned mold is removed from said one flange； By the configuration of another flange on above-mentioned gasket, said one flange is pressed with another above-mentioned flange via above-mentioned gasket It connects, by the process of at least part sealing between above-mentioned at least two flange.

Liquid injection molding is following method, that is, by specified pressure by Photocurable resin composition stream of the invention Enter to be transmissive to the mold of the material of light, irradiation ultraviolet light isoreactivity energy-ray makes its photocuring, forms gasket.Then, make Its method for carrying out compression seal with another lip fits.It should be noted that mold is preferably capable the material of transmitted light, tool For body, glass, PMMA, polycarbonate, cyclic olefin polymer, alkene etc. can be enumerated.In addition, in order to be easy after forming gasket It is taken out from mold, mold is preferably pre-coated with the release agent of fluorine system, organic silicon-type etc..