CN107428891A - Solidification compound - Google Patents

Abstract

The present invention provides a kind of solidification compound for promoting catalyst containing free-radical polymerised unsaturated compound, coupling agent and condensation reaction, and the solidification compound provides the solidfied material improved to the adaptation of base material.Solidification compound is characterised by, is contained：(A) there is the polymer of (methyl) acryloyl group；(B) there is the silane coupler of (methyl) acryloyl group；(C) (C1) has the silicon compound of Si F keys, and/or (C2) is selected from one or more of the group being made up of the alkali metal salt of boron trifluoride, the complex compound of boron trifluoride, fluorization agent and polynary fluorine compounds fluorine system compound；And (D) radical initiator.

Description

Solidification compound

Technical field

The present invention relates to a kind of solidification compound, more particularly to a kind of curability group of the excellent adhesion to base material Compound.

Background technology

Free-radical polymerised unsaturated compound and polymerizing curable, is made by the effect of radical initiator and/or light For bonding agent, coating material etc..Patent Document 1 discloses a kind of clad material as optical fiber it is useful contain insatiable hunger With the active energy ray-curable resin composition of compound, page 9 in patent document 1 records by adding coupling Agent, the adaptation with the base material such as glass, plastics can be improved.Patent Document 2 discloses a kind of clad material as optical fiber The useful active energy ray-curable resin composition containing reactive monomer, and the resin combination is added with coupling Agent and condensation reaction promote catalyst, and record due to having used condensation reaction to promote catalyst, therefore can further improve With the adaptation of base material.

In addition, a kind of adhesive as image display device component is recorded in patent document 3 and patent document 4 (bonding agent) it is useful be added with (methyl) acryloyl group polymer, (methyl) acryl silane as coupling agent And condensation reaction promotes the resin combination of catalyst.

In bonding agent, coating material, the adaptation to base material is extremely important characteristic, it is expected further to improve.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Application 62-250047 publications

Patent document 2：Japanese Unexamined Patent Publication 5-32712 publications

Patent document 3：Japanese Unexamined Patent Publication 2013-088455 publications

Patent document 4：Japanese Unexamined Patent Publication 2013-129754 publications

The content of the invention

Problems to be solved by the invention

The problem to be solved in the present invention is, there is provided a kind of to contain free-radical polymerised unsaturated compound, coupling agent And condensation reaction promotes the solidification compound of catalyst, the solidification compound provides to be changed to the adaptation of base material Kind solidfied material.

Technical scheme

The present inventor etc. is found that：Catalyst is promoted as condensation reaction by using specific compound, can be carried For the solidification compound of the solidfied material of base material excellent adhesion.That is, solidification compound of the invention is characterised by, is contained Have：(A) there is the polymer of (methyl) acryloyl group；(B) there is the silane coupler of (methyl) acryloyl group；(C) (C1) has There is the silicon compound of Si-F keys, and/or (C2) is selected from by boron trifluoride, the complex compound of boron trifluoride, fluorization agent and polynary fluorination One or more of the group that the alkali metal salt of compound is formed fluorine system compound；And (D) radical initiator.

(A) is preferably the polyisobutene based polymer with (methyl) acryloyl group.(first is had by using this Base) acryloyl group polyisobutene based polymer, it is possible to increase humidity resistance.

(D) is preferably optical free radical initiator.

The encapsulating material of the present invention is the encapsulating material formed by the solidification compound of the present invention.

The electrical/electronic product of the present invention is using electrical/electronic product made of the encapsulating material of the present invention.

The barrier material of the present invention is the barrier material formed by the solidification compound of the present invention.

The product of the present invention is comprising the product of mirror or glass made of the barrier material using the present invention.

Beneficial effect

The solidification compound of the present invention has the effect that：Promoted by using specific fluorine compounds as condensation reaction Enter catalyst, there is provided the solidfied material of base material excellent adhesion.

Embodiment

Hereinafter, embodiments of the present invention are illustrated, but these are illustratively to show, it goes without saying that as long as not Depart from the technological thought of the present invention, it becomes possible to carry out various modifications.

As the example of the polymer with (methyl) acryloyl group used in the present compositions, can include Polymer with (methyl) acryloxy, the polymer with (methyl) acrylamido or with (methyl) propylene The polymer of imide.Wherein, preferably using the compound with (methyl) acryloxy.In addition, (the first in polymer Base) acryloyl group is average in every 1 Molecularly Imprinted Polymer preferably more than 1.0, and it is further preferred more than 1.1, especially excellent Select more than 1.5.Alternatively, it is also possible to being more than 2.It should be noted that (methyl) acryloyl group represent acryloyl group and/or Methylacryloyl.

As the example of the polymer with (methyl) acryloxy, can include with (methyl) acryloxy Acrylic acid series polymeric compounds, the hydrocarbon system polymer with (methyl) acryloxy, the Polyester with (methyl) acryloxy Polymer, the epoxy system resin with (methyl) acryloxy, the polyurethane series polymer with (methyl) acryloxy Or the polyethers based polymer with (methyl) acryloxy.Importing (methyl) acryloxy into polymer can be by such as Under type is realized：Using the functional groups such as the hydroxyl of polymer chain terminal etc., epoxy radicals, halogen atom are present in, make (methyl) propylene (methyl) acrylic acid derivatives such as acid, (methyl) acrylic acid halide react.

Acrylic acid series polymeric compounds with (methyl) acryloxy are also referred to as acrylic resin acrylate, are main chains For (methyl) acrylic ester polymer, and the polymer with (methyl) acryloxy.This polymer preferably passes through the moon Ionic polymerization or radical polymerization manufacture, and the easiness of versatility or control from monomer considers, more preferably radical polymerization Close.In radical polymerization, preferably active free radical polymerization or the radical polymerization of chain-transferring agent is used, it is more preferably active Radical polymerization, particularly preferred ATRP.If using active free radical polymerization, can manufacture in polymer chain End has the polymer of (methyl) acryloxy.

As the skeleton of acrylic acid series polymeric compounds, polymethyl methacrylate (MMA), poly- (metering system can also be used Sour 2- hydroxyl ethyl esters (HEMA)/MMA), the polymer such as poly- (HEMA/ butyl methacrylates (BMA)).

In addition, as the acrylic acid series polymeric compounds with (methyl) acryloxy, it is, for example, possible to use WO2012/ Polyacrylic acid N-butyl, the system of the publication in two ends with acryloyl group described in the Production Example 1 of No. 008127 publication Make polyacrylic acid N-butyl, the Production Example of WO2005/000927 publications in an end with acryloyl group described in example 2 Poly- (the n-butyl acrylate/ethyl acrylate/acrylic acid 2- methoxyl group second in two ends with acryloyl group described in 1 Ester), poly- (the positive fourth of acrylic acid in two ends with acryloyl group described in the Production Examples 2 of WO2006/112420 publications Ester/2-EHA), poly- (the acrylic acid 2- in two ends with acryloyl group described in the Production Example 3 of the publication Ethylhexyl) etc..

As the commercially available product of the acrylic acid series polymeric compounds with (methyl) acryloxy, for example, East Asia conjunction can be included Into macromonomer AA-6, AB-6 of (strain) system；(strain) kaneka RC-100C, RC-200C, RC-300C etc..

As the example of hydrocarbon system polymer, ethylene-propylene based copolymer, polyisobutene, isobutene and isoamyl can be included Copolymer, polychlorobutadiene, polyisoprene, isoprene or the butadiene of diene etc. and acrylonitrile and/or styrene etc. The copolymer of copolymer, polybutadiene, isoprene or butadiene and acrylonitrile and styrene etc., by these polyolefins The hydrocarbon system polymer such as hydrogenated polyolefins based polymer obtained from polymer is hydrogenated with.

Wherein, the saturation such as hydrogenated polyolefins based polymer such as polyisobutene or hydrogenated polyisoprene, hydrogenated butadiene polymer The barrier properties for gases of hydrocarbon system polymer is big, is suitable for needing the gas barrier of the purposes of barrier properties for gases, particularly polyisobutene Property is big, therefore preferably.As the purposes of this polymer, go for end coating of the back coating of mirror, mirror etc. The moisture barrier coatings of mirror.

Hydrocarbon system polymer with (methyl) acryloxy can be imported (methyl) using the polymer with hydroxyl Acryloxy.In addition, the polyisobutene based polymer with (methyl) acryloxy can pass through Japanese Unexamined Patent Publication 2013- Method described in No. 035901 publication, International Publication WO2013-047314 publications obtains.

Polyester based polymer with (methyl) acryloxy is also referred to as polyester acrylate.This polymer can be with Obtained by making PEPA with (methyl) acrylic acid dehydrating condensation.Here, as PEPA, can include polynary Reactant of alcohol and carboxylic acid or its acid anhydrides etc..

As polyalcohol, can include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propane diols, DPG, tripropylene glycol, polypropylene glycol, butanediol, polytetramethylene glycol, tetramethylene glycol, hexamethylene glycol, new penta 2 Alcohol, cyclohexanedimethanol, 3- methyl isophthalic acids, 5- pentanediols, 1,6-HD, trimethylolpropane, glycerine, pentaerythrite and two The low molecular weight polyols such as pentaerythrite and their alkylene oxide adduct etc..

As carboxylic acid or its acid anhydrides, phthalic acid, M-phthalic acid, terephthalic acid (TPA), adipic acid, amber can be included The binary acid such as acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trihemellitic acid or its acid anhydrides Deng.

Epoxy system resin with (methyl) acryloxy is also referred to as epoxy acrylate, can be by making asphalt mixtures modified by epoxy resin Fat carries out addition reaction with (methyl) acrylic acid and obtained.As epoxy resin, aromatic epoxy resin and fat can be included Fat race epoxy resin etc..

As the example of aromatic epoxy resin, resorcinolformaldehyde resin can be included；It is bisphenol-A, Bisphenol F, double Phenol S, bisphenol fluorene or its alkylene oxide adduct diglycidyl ether or polyglycidyl ether；Phenol novolac type epoxy resin And the novolac type epoxy resin such as cresol novalac type epoxy resin；Glycidol phthalimide；Adjacent benzene two Formic acid 2-glycidyl ester etc..In addition, can also be by document《The progress of epoxy resin-nearest-》(clear rolling hall, nineteen ninety Distribution) 2 chapters, document《Process Technology of Polymer》(macromolecule prints and publishes meeting to the supplementary issue epoxy resin of volume 22 of supplementary issue 9/, and Showa is sent out for 48 years Described in page 4~6, page 9~16 OK) etc compound be used as aromatic epoxy resin.

As the example of aliphatic epoxy resin, can include ethylene glycol, propane diols, BDO and 1,6- oneself two The diglycidyl ether of the aklylene glycols such as alcohol；The PAGs such as the diglycidyl ether of polyethylene glycol and polypropylene glycol Diglycidyl ether；The diglycidyl ether of neopentyl glycol, dibromoneopentyl glycol and its alkylene oxide adduct；Trihydroxy methyl second Alkane, trimethylolpropane, the diglycidyl ether or triglycidyl ether and pentaerythrite of glycerine and its alkylene oxide adduct And its more glycidols of the polyalcohol such as diglycidyl ether, triglycidyl ether or four glycidol ethers of alkylene oxide adduct Ether；The diglycidyl ether or polyglycidyl ether of hydrogenated bisphenol A and its alkylene oxide adduct；Tetrahydrophthalic acid two is shunk Glycerin ether；Hydroquinones diglycidyl ether etc..

In addition, can also enumerate in foregoing document《Process Technology of Polymer》Described in page 3~6 of supplementary issue epoxy resin Compound.In addition to these aromatic epoxy resins and aliphatic epoxy resin, can also include has in skeleton The epoxide of triazine core, such as TEPIC (Nissan Chemical (strain)), Denacol EX-310 (Nagase is melted into (strain)) etc., In addition, it can include in foregoing document《Process Technology of Polymer》Described in page 289~296 of supplementary issue epoxy resin etc change Compound etc..

As the concrete example of the epoxy system resin with (methyl) acryloxy, bisphenol-A two (methyl) third can be included Olefin(e) acid ester, ethylene-oxide-modified bisphenol-A two (methyl) acrylate, epoxychloropropane modified bisphenol-A two (methyl) acrylate, Ethylene-oxide-modified bisphenol S two (methyl) acrylate etc..

Polyurethane series polymer with (methyl) acryloxy is also referred to as carbamate (methyl) acrylate, Can the isocyanate-terminated polyurethane as obtained from making polyalcohol with excessive organic multiple isocyanate reaction enter one Step with (methyl) acrylate reactions containing hydroxyl and obtain.

Here, as polyalcohol, there are low molecular weight polyols, PPG, PEPA, polycarbonate polyol Deng.As low molecular weight polyols, ethylene glycol, propane diols, cyclohexanedimethanol and 3- methyl isophthalic acids, 5- pentanediols can be included Deng；As PPG, polyethylene glycol and polypropylene glycol etc. can be included；As PEPA, these can be included Low molecular weight polyols or/and PPG and adipic acid, butanedioic acid, phthalic acid, hexahydrophthalic acid and to benzene The reactant of the sour composition such as the binary acid such as dioctyl phthalate or its acid anhydrides.

As organic multiple isocyanate, toluene di-isocyanate(TDI), 4 can be included, 4 '-methyl diphenylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanate, hexamethylene diisocyanate and IPDI etc..As containing There is (methyl) acrylate of hydroxyl, (methyl) acrylic acid 2- hydroxyl ethyl esters and (methyl) acrylic acid 2- hydroxypropyl acrylates etc. can be included (methyl) acrylic acid hydroxy alkyl ester etc..

These carbamate (methyl) acrylic ester polymers can be manufactured based on known synthetic method.Example Such as, can include in the presence of the addition catalysts such as dibutyl tin laurate, to used organic isocyanate and more First alcohol composition, which carries out heating stirring, makes it carry out addition reaction, further adds (methyl) acrylic acid hydroxy alkyl ester, is heated Stirring makes it carry out method of addition reaction etc..

As polyethers (methyl) acrylic ester polymer, there are PAG (methyl) acrylate, polyalkylene Glycol two (methyl) acrylate, the polymer can be by making PAG and (methyl) acrylic acid, (methyl) propylene Acid derivatives reaction and obtain.

As the example of PAG (methyl) acrylate, methoxyl group diethylene glycol (methyl) propylene can be included Acid esters, ethoxydiglycol (methyl) acrylate, 2- ethylhexyls polyethylene glycol (methyl) acrylate, polyethylene glycol It is (methyl) acrylate, methoxyl group DPG (methyl) acrylate, nonyl phenyl polypropylene glycol (methyl) acrylate, poly- Propane diols (methyl) acrylate etc..

As the example of PAG two (methyl) acrylate, diethylene glycol two (methyl) acrylic acid can be included Ester, triethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, DPG two (methyl) acrylic acid Ester, tripropylene glycol two (methyl) acrylate, (methyl) acrylate of polypropylene glycol two and the (first of polytetramethylene glycol two Base) acrylate etc..

Polymer with (methyl) acrylamido can be by using polymer with hydroxyl such as replacement polyalcohols Hydroxyl and polymer with amino, and obtain the reactions such as (methyl) acrylic acid chloride.Wherein, above-mentioned polyalcohol is The raw material of the above-mentioned polymer with (methyl) acryloxy.

The solidification compound of the present invention uses the silane coupler of (B) with (methyl) acryloyl group.With (methyl) The silane coupler of acryloyl group is the compound with (methyl) acryloyl group and bridging property silicon substrate.Bridging property silicon substrate be with With silicon atom bond the water such as hydrolization group, moisture through the air effect and hydrolyze, the base of siloxanes key can be formed Group.As the example of bridging property silicon substrate, can include bond on the silicon atoms has the alkoxy as hydrolization group, carboxyl Group.As the concrete example of bridging property silicon substrate, trimethoxy silane base, methyl dimethoxysilane base can be included.Silane is even Connection agent is worked as cementability imparting agent.

As the example of the silane coupler of (B) composition, γ-methacryloxypropyl trimethoxy silicon can be included The compounds such as alkane, γ-acryloxypropyl dimethoxysilane.There is (methyl) acryloyl relative to (A) composition The mass parts of polymer 100 of base, the silane coupler with (methyl) acryloyl group of (B) composition is 1~20 mass parts, enters one Walk preferably 2~10 mass parts.

The solidification compound of the present invention contains the silicon compound that (C) (C1) has Si-F keys, and/or (C2) is selected from by three One or more of the group that boron fluoride, the complex compound of boron trifluoride, the alkali metal salt of fluorization agent and polynary fluorine compounds are formed fluorine Based compound.In the solidification compound of the present invention, by the solidification that base material excellent adhesion is generated containing (C) composition Thing.(C) composition promotes catalyst to act as the condensation reaction that the bridging property silicon substrate for the silane coupler for making (B) composition is reacted With.

As (C1) have Si-F keys silicon compound, can widely use containing have Si-F keys group (with Under, sometimes referred to as silicon fluoride base) known compound, be not particularly limited, low molecular compound and macromolecule can be used Compound it is any, but preferably have silicon fluoride base organo-silicon compound, have silicon fluoride base organic polymer peace Quan Xinggao, therefore more preferably.In addition, from the aspect of complex is low viscosity, the low molecule preferably with silicon fluoride base has Organic silicon compound.

There is the silicon compound of Si-F keys as (C1), the silicon fluoride base shown in following formula (1) can be included Inorganic compound, the low molecule organo-silicon compound with the silicon fluoride base, organic polymer with the silicon fluoride base etc. As preferable example.

-SiF_aR¹ _bX_c···(1)

In formula (1), R¹Represent the alkyl or R of substituted or unsubstituted carbon number 1~20² ₃SiO-(R²It is each independent Ground be carbon number 1~20 substituted or unsubstituted alkyl or fluorine atom) shown in organosilan epoxide it is any.a For any one in 1~3, preferably a is 3.Multiple R be present¹And R²In the case of, they both can be the same or different.X For the hydrolization group beyond hydroxyl or fluorine removal, b is any one in 0~2, and c is any one in 0~2, a+b+c 3. In the case of multiple X being present, they both can be the same or different.

As the R in the formula (1)¹, for example, the cycloalkyl such as the alkyl such as methyl, ethyl, cyclohexyl, phenyl can be included Deng the aralkyl such as aryl, benzyl, or R²For the R of methyl, phenyl etc.² ₃Three organosilan epoxides shown in SiO- etc..Wherein, it is special Not preferred methyl.

In addition, the hydrolization group shown in as the X in the formula (1), the halogen that can be included beyond hydrogen atom, fluorine removal is former Son, alkoxy, acyloxy, ketoxime ester group (ketoximate), amino, amide groups, sour amide groups, aminooxy group, sulfydryl, alkenyloxy group Deng.Wherein, preferably hydrogen atom, alkoxy, acyloxy, ketoxime ester group, amino, amide groups, aminooxy group, sulfydryl and alkenyloxy group.

If the specifically silicon fluoride base shown in the exemplified formula (1), do not have water-disintegrable base in addition as fluorine removal Group silicon substrate, can include fluorine dimethylsilyl, fluorine diethylsilyl, fluorine dipropyl silylation, fluorine diphenyl silane base, Substitution has the silicon substrate of a fluorine in the silicon substrates such as fluorine dibenzyl silylation；Difluoromethyl silylation, difluoro ethylsilane base, difluorobenzene Substitution has the silicon substrate of two fluorine in the silicon substrates such as base silane base, difluorobenzyl silylation；Substitute in silicon substrate as silicofluoroform base There is the silicon substrate of three fluorine.

As the silicon substrate with fluorine He both other hydrolization groups, fluorine methoxy silylation, fluorine can be included Ethoxyl methyl silylation, fluorine methoxy ethyl silylation, fluorine methoxyphenyl silylation, fluorine dimethoxysilane base, fluorine two Ethoxysilane base, fluorine dipropoxy silylation, fluorine hexichol TMOS base, fluorine double (2- propenyloxy groups) silylation, difluoro first TMOS base, difluoroethoxy silylation, difluorobenzene TMOS base, fluorine dichlorosilane base, difluoro chlorosilyl group etc..Its In, the silicon substrate without hydrolization group, R preferably beyond fluorine removal¹For the silicon fluoride base of methyl, more preferably silicofluoroform base.

In addition, consider from the easiness of synthesis, more preferably fluorine dimethylsilyl, difluoromethyl silylation, silicofluoroform Base, fluorine methoxy silylation, fluorine ethoxyl methyl silylation, fluorine methoxy ethyl silylation, fluorine dimethoxysilane base, Fluorine diethoxy silane base, difluoro-methoxy silylation, difluoroethoxy silylation.From the viewpoint of stability, further It is preferred that do not have the silicon substrate of hydrolization group beyond the fluorine removal such as fluorine dimethylsilyl, difluoromethyl silylation, silicofluoroform base. Consider from the height of activity, preferably difluoromethyl silylation, difluoro-methoxy silylation, difluoroethoxy silylation, trifluoro silicon Substitution has the silicon substrate of two or three fluorine, most preferably silicofluoroform base in the silicon substrates such as alkyl.

Compound with the silicon fluoride base shown in the formula (1) can both use commercially available reagent, can also be by raw material Compound synthesis.As synthetic method it is not also specifically limited, it is preferred that use by using known method (for example, Organometallics 1996, page 15,2478 (Ishikawa etc.) etc.) make the bridging property silicon that has shown in following formula (2) The compound of base, the compound with siloxanes key and compound obtained from fluorization agent reaction.

-SiR¹ _3-aX_a···(2)

(in formula (2), R¹And X is identical with formula (1) respectively, a is any one in 1~3)

As the bridging property silicon substrate shown in above-mentioned formula (2), for example, the halogen such as alkoxysilane group, chlorosilyl group can be included For silylation, hydrosilyl groups etc..

As the concrete example of the fluorization agent for being fluorinated to alkoxysilane group, it is not particularly limited, for example, can arrange Enumerate NH₄F、Bu₄NF、HF、BF₃、Et₂NSF₃、HSO₃F、SbF₅、VOF₃、CF₃CHFCF₂NEt₂Deng.As for halogenated silanes The concrete example for the fluorization agent that base is fluorinated, is not particularly limited, for example, AgBF can be included₄、SbF₃、ZnF₂、NaF、KF、 CsF、NH₄F、CuF₂、NaSiF₆、NaPF₆、NaSbF₆、NaBF₄、Me₃SnF、KF(HF)_1.5~5Deng.As for hydrosilyl groups The concrete example for the fluorization agent being fluorinated, is not particularly limited, for example, AgF, PF can be included₅、Ph₃CBF₄、SbF₃、NOBF₄、 NO₂BF₄Deng.Compound with siloxanes key passes through BF₃Deng and be broken, obtain silicon fluoride base.

In the synthetic method of silicon fluoride base of these fluorization agents has been used, from reaction is simple, reaction efficiency is high, security From the aspect of high, BF has preferably been used₃Alkoxy silane fluoride process, used CuF₂Or ZnF₂Chlorosilane fluorine Change method.

As BF₃, BF can be used₃Gas, BF₃Ether complexes, BF₃Thioether complex compound, BF₃Amine complex, BF₃Alcohol is complexed Thing, BF₃Organic anion complex, BF₃Phosphoric acid complex compound, BF₃Hydrate, BF₃Piperidines complex compound, BF₃Phenol complex compound etc., but hold from operation It is easy etc. to consider, preferably BF₃Ether complexes, BF₃Thioether complex compound, BF₃Amine complex, BF₃Alcohol complex, BF₃Carboxylic acid is complexed Thing, BF₃Hydrate.Wherein, BF₃Ether complexes, BF₃Alcohol complex, BF₃The reactivity of hydrate is high, therefore preferably, it is especially excellent Select BF₃Ether complexes.

As the concrete example for not having hydrolization group beyond fluorine removal in the silicon compound with Si-F keys, for example, The fluorinated inorganic silicon compounds such as tetrafluorosilane, the silane of octafluoro three can be included；Fluorine trimethyl silane, fluorine triethyl silicane, fluorine three Propyl silane, fluorine tributyl silane, fluorine dimethylvinylsiloxy base silane, fluorine dimethylphenylsilaneand, fluorine dimethylbenzyl base silane, fluorine Dimethyl (3- aminomethyl phenyls) silane, fluorine dimethyl (4- aminomethyl phenyls) silane, fluorine dimethyl (4- chlorphenyls) silane, fluorine triphen Base silane, difluorodimethylsilane, difluoro diethylsilane, difluoro dibutyl silane, difluoromethyl phenyl silane, difluorodiphenyl Base silane, trifluoroethyl silane, trifluoro propyl silane, triRuorobutyl silane, trifluorophenyl silane, γ-glycidoxypropyl group Silicofluoroform, γ-glycidoxypropyl group difluoromethyl silane, vinyl silicofluoroform, vinyl difluoromethyl silane, 3- mercaptos Base propyl group silicofluoroform, octadecyl fluorine dimethylsilane, octadecyl difluoromethyl silane, octadecyl silicofluoroform, 1, The fluoro- 1,1,3,3- tetramethyl disiloxanes of 3- bis-, the 1,3,5,7- tetra- fluoro- ring of tetra- silas of 1,3,5,7- three [3.3.1.1 (the 3,7)] last of the ten Heavenly stems Perfluorinated low molecular organo-silicon compound such as the fluoro- 1- silas ring -3- amylenes of alkane, 1,1- bis-, fluorine three (trimethylsiloxy group) silane etc..

In addition, as the concrete example with hydrolization group beyond fluorine removal in the silicon compound with Si-F keys, can enumerate Go out fluorine trimethoxy silane, difluoro dimethoxysilane, trifluoromethoxy silane, fluorine triethoxysilane, difluoro diethoxy Silane, trifluoroethoxy base silane, fluoromethane dimethoxysilane, methyl difluoromethoxy base silane, methyl trifluoro silane, fluoromethane Diethoxy silane, methyl difluoroethoxy silane, vinyl fluoride dimethoxysilane, vinyl difluoromethoxy base silane, second Alkenyl silicofluoroform, vinyl fluoride diethoxy silane, vinyl difluoroethoxy silane, phenyl-fluoride dimethoxysilane, benzene Base difluoromethoxy base silane, phenyl-trifluoro-silane, phenyl-fluoride diethoxy silane, phenyl difluoroethoxy silane etc. are fluorinated low point Sub- organo-silicon compound.

Wherein, raw material is obtained, it is readily synthesized etc. and considers from easy, preferably fluorine dimethylvinylsiloxy base silane, fluorine diformazan Base phenyl silane, fluorine dimethylbenzyl base silane, vinyl silicofluoroform, vinyl difluoromethyl silane, 3- mercaptopropyi trifluoros Silane, octadecyl fluorine dimethylsilane, octadecyl difluoromethyl silane, octadecyl silicofluoroform, 1,3- bis- fluoro- 1,1, 3,3- tetramethyl disiloxanes etc..

As the organic polymer (in this manual, also referred to as fluorinated polymer) with the silicon fluoride base, if Organic polymer with Si-F keys, then be not particularly limited, and can widely use the known organic polymer with Si-F keys Thing.Position of the SiF keys in organic polymer is it is not also specifically limited, any one position in polymer molecule can play Go out effect.As the organic polymer with Si-F keys, the polymerization with the silicon fluoride base shown in foregoing formula (1) can be included Thing；-Si(CH₃)F-、-Si(C₆H₅)F-、-SiF₂-, polymer in the main chain of the silicon fluoride base such as ≡ SiF insertion polymer etc..

The single polymer that the fluorinated polymer can be silicon fluoride base and main chain backbone is identical type, i.e. every 1 The quantity of the silicon fluoride base of molecule, the quantity of its binding site and F possessed by the silicon fluoride base and main chain backbone are phase Congener single polymer, or the mixture of either of which kind or all different multiple polymer. Contained silicon fluoride base is average in every 1 Molecularly Imprinted Polymer in fluorinated polymer at least has 1, preferably in the presence of 1.1~5, Further preferably there are 1.2~3 preferably.If the quantity of contained silicon fluoride base is averagely less than 1 in 1 molecule, cementability Assigning effect becomes insufficient.

Removed in addition, fluorinated polymer while containing silicon fluoride base, can also contain only to have as hydrolization group Substituent beyond the fluorine removal silylation such as the silicon substrate (for example, methyl dimethoxysilane base etc.) of the hydrolization group beyond fluorine. As this fluorinated polymer, such as it is silicon fluoride base that can include the main chain terminal of a side, and the main chain terminal of the opposing party is makees Only there is the polymer of the silicon substrate of the hydrolization group beyond fluorine removal for hydrolization group.The example of fluorinated polymer is international public Open on the books in patent WO2008/032539 publications.

In fluorinated polymer, the importing of silicon fluoride base can utilize any method, but can include by with fluorine silicon The introduction method (method (i)) of the reaction progress of the low molecule silicon compound and polymer of alkyl, it will contain with beyond fluorine removal The silicon-based modifying of polymer (following, sometimes referred to as " polymer (X) ") of bridging property silicon substrate of hydrolization group be silicon fluoride The method (method (ii)) of base.

As the concrete example of method (i), following method can be included.

(a) make polymer in the molecule with functional groups such as hydroxyl, epoxy radicals, NCOs with to the function Group shows the functional group of reactivity and the method that the compound of silicon fluoride base is reacted.Sent as an envoy to for example, can enumerate at end Hold method that polymer with hydroxyl and NCO propyl group difluoromethyl silane reacted, make in end with SiOH The method that the polymer of base is reacted with difluoro diethoxy silane.

(b) act on the hydrosilanes with silicon fluoride base to carry out with the polymer of unsaturated group in the molecule The method of hydrosilylation.The polymer in end with pi-allyl is sent as an envoy to for example, can enumerate and difluoromethyl hydrosilanes are entered The method of row reaction.

(c) side for making the polymer containing unsaturated group be reacted with the compound with sulfydryl and silicon fluoride base Method.For example, the side sent as an envoy to and there is the polymer of pi-allyl to be reacted with mercaptopropyi difluoromethyl silane in end can be enumerated Method.

As the bridging property silicon substrate with the hydrolization group beyond fluorine removal of containing used in the above method (ii) Polymer (polymer (X)), can include the polyisobutene containing the bridging property silicon substrate with the hydrolization group beyond fluorine removal, The saturated hydrocarbons based polymer such as hydrogenated polyisoprene, hydrogenated butadiene polymer, or polyoxy alkylidene based polymer, (methyl) propylene Acid esters based polymer, polysiloxanes based polymer is as preferable polymer.

In addition, in method (ii), fluorine is converted to as by the bridging property silicon substrate with the hydrolization group beyond fluorine removal The method of silylation, known method can be used, for example, can include shown in the foregoing formula (2) with fluorization agent The method that water-disintegrable silicon substrate is converted to silicon fluoride base.As fluorization agent, for example, foregoing fluorization agent can be included, wherein, BF₃ Ether complexes, BF₃Alcohol complex, BF₃The activity of dihydrate is high, is efficiently fluorinated, and then will not be produced in accessory substance Salt etc., easy post-processing, therefore it is further preferred that particularly preferred BF₃Ether complexes.And then for utilizing BF₃What ether complexes were carried out For fluorination, even if without heating, reaction can also be carried out, but in order to be more efficiently fluorinated, preferably be heated.As Heating-up temperature, preferably more than 50 DEG C and less than 150 DEG C, more preferably more than 60 DEG C and 130 DEG C.It is if less than 50 DEG C, then sometimes anti- Would not efficiently it carry out, fluorination can spend the time.If more than 150 DEG C, then fluorinated polymer can probably decompose.Utilizing BF₃In the fluorination that complex compound is carried out, according to used polymer (X) species, it some times happens that colouring, but coloured from suppression From the aspect of, preferably using BF₃Alcohol complex, BF₃Dihydrate.

For manufacturing the fluorization agent of fluorinated polymer, can also may be worked as the curing catalysts of fluorinated polymer, If moisture be present when manufacturing fluorinated polymer using the method for above-mentioned (ii), silanol condensation reaction can be carried out, gained The viscosity of fluorinated polymer can probably rise.Thus, it is desirable that the manufacture of fluorinated polymer is as far as possible in the ring in the absence of moisture Carried out under border, it is preferred that before fluorination, the polymer (X) that will be fluorinated is taken off using the implementation azeotropic such as toluene, hexane The dehydrating operations of water etc..But, BF is being used₃In the case of amine complex, it is difficult to be fluorinated after dehydrating operations, by adding Add micro moisture, reactivity tends to improve, it is therefore preferable that the scope risen with tolerable viscosity adds moisture.In addition, from fluorination From the aspect of the stability of polymer, it is preferred that after fluorination, by filtering, being decanted, liquid separation, decompression devolatilization etc. go fluorine removal The composition from fluorization agent of agent and by-product.Using above-mentioned BF₃The situation of the fluorization agent manufacture fluorinated polymer of system Under, the remaining BF in manufactured fluorinated polymer₃And what is generated by reacting is derived from BF₃Composition with B gauge, preferably Less than 500ppm, more preferably less than 100ppm, particularly preferably less than 50ppm.By removing BF₃And from BF₃Composition, energy Suppress viscosity rising of fluorinated polymer itself and the mixture of fluorinated polymer and polymer (X) of gained etc..If consider To this point, then BF has been used₃Ether complexes, BF₃The fluoride process of alcohol complex can simply remove boron by vacuum volatilization Composition, therefore preferably, particularly preferably used BF₃The method of ether complexes.

Here, in the case of the hydrolization group that polymer (X) has beyond two or more fluorine removal, both can be to all Hydrolization group be fluorinated, the condition of fluorination can also be adjusted using the methods of the amount for reducing fluorization agent, it is thus local It is fluorinated.For example, in the method for above-mentioned (ii), in the case where using polymer (X) manufacture fluorinated polymer, fluorization agent Usage amount be not specially limited, the mole of the fluorine atom in fluorization agent is equimolar relative to the mole of polymer (X) Amount above.In the feelings for wanting to be fluorinated all hydrolization groups contained by polymer (X) by the method for (ii) Under condition, preferably using the mole of the fluorine atom in fluorization agent relative to the hydrolysis in the bridging property silicon substrate contained by polymer (X) Property group integral molar quantity for more than equimolar such amount fluorization agent.Here, " fluorine atom in fluorization agent " refers to, fluorination In agent to being fluorinated effective fluorine atom, specifically, refer to can be in the bridging property silicon substrate of substituted polymer (X) water-disintegrable base The fluorine atom of group.

The low molecular compound with silicon fluoride base in the above method (i) can also utilize above-mentioned fluorination process, by leading to Low molecular compound synthesis containing bridging property silicon substrate.

In method (i), due to while with silicon fluoride base, also having and being used to make polymer and low point containing silicon The reactive group of sub- compound reaction, therefore, in the case where reacting complicated, fluorinated polymers is obtained preferably by method (ii) Thing.

The glass transition temperature of fluorinated polymer is not particularly limited, but preferably less than 20 DEG C, more preferably 0 DEG C with Under, particularly preferably below 20 DEG C of ﹣.If glass transition temperature be higher than 20 DEG C, in the winter time or cold district viscosity become Height, become to be difficult to operate sometimes.Glass transition temperature can be determined by DSC and obtained.

Fluorinated polymer both can be straight-chain, or can also have side chain.The number-average molecular weight of fluorinated polymer exists Preferably 3000~100000, more preferably 3000~50000, particularly preferably 3000 in GPC polystyrene conversion~ 30000。

In the present invention, as (C) composition, (C2) can be used to be selected from by boron trifluoride, the complex compound of boron trifluoride, fluorine One or more of the group that the alkali metal salt of agent and polynary fluorine compounds is formed fluorine system compound.

As the complex compound of the boron trifluoride, for example, can the amine complex of exemplified boron trifluoride, alcohol complex, Ether complexes, thiol complex, thioether complex compound, organic anion complex, aquo complex etc..In the complex compound of above-mentioned boron trifluoride In, particularly preferably have the amine complex of stability and catalyst activity concurrently.

As the amines used in the amine complex of the boron trifluoride, for example, can include ammonia, mono aminoethane, Triethylamine, piperidines, aniline, morpholine, cyclohexylamine, n-butylamine, MEA, diethanol amine, triethanolamine, guanidine, 2,2,6,6- tetra- Methyl piperidine, 1,2,2,6,6- pentamethvls, N- methyl -3,3 '-imino group double (propylamine), ethylenediamine, diethylenetriamines, Triethylenediamine, five ethylene diamines, 1,2- diaminopropanes, 1,3- diaminopropanes, 1,2- diaminobutanes, 1,4- bis- Butylamine, 1,9- diamino nonanes, ATU (3,9- double (3- aminopropyls) -2,4,8,10- four oxaspiro [5.5] hendecanes), CTU guanamines, the hydrazides of lauric acid/dodecanoic acid two, hexamethylene diamine, m-xylene diamine, dianisidine, 4,4 '-diaminourea -3,3 '-diethyl Diphenyl methane, diamino-diphenyl ether, 3,3 '-dimethyl -4,4 '-diaminodiphenyl-methane, diaminourea dimethyl diphenyl (tolidine base), toluylenediamine, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, melamine, 1,3- diphenylguanidines, Di-o-tolylguanidine, 1,1,3,3- TMGs, double (aminopropyl) piperazines, N- (3- aminopropyls) -1,3- propane diamine, double (3- Aminopropyl) ether, Sun Techno Chemical company systems JEFFAMINE etc. have the compounds of multiple primary amino radicals；Piperazine, Cis -2,6- lupetazins, cis -2,5- lupetazins, 2- methyl piperazines, N, N '-di-t-butyl ethylenediamine, 2- amino Methyl piperidine, 4- aminomethylpiperidines, 1,3- bis- (4- piperidyls)-propane, 4- aminopropyls aniline, homopiperazine, N, N '-hexichol Base thiocarbamide, N,N' diethyl thiourea, N- methyl isophthalic acids, 3- propane diamine etc. have the compound of multiple secondary amino groups；And methylamino Propylamine, ethylamino propylamine, ethylamino ethamine, lauryl amino propylamine, 2- Hydroxy-ethylaminos propylamine, 1- (2- amino second Base) piperazine, N- aminopropylpiperazines, 3- amino-pyrrolidines, 1- neighbour's toluene biguanides, 2- aminomethylpiperazines, N- aminopropyl benzene Amine, ethylamine ethylamine, 2- Hydroxy-ethylaminos propylamine, lauryl amino propylamine, 2- aminomethylpiperidines, 4- amino methyl piperazines Compound (trade name shown in pyridine, formula H2N (C2H4NH) nH (n ≈ 5)：Poly-8, eastern Cao's company system), N- alkyl morpholines, 1, Carbon -7- the alkene of 8- diazabicylos [5.4.0] 11, the carbon -7- alkene of 6- dibutylamino -1,8- diazabicylos [5.4.0] 11, 1,5- diazabicylos [4.3.0] nonyl- 5- alkene, 1,4- diazabicylos [2.2.2] octane, pyridine, N- Alkylpiperidines, 1,5,7- The heterocycle shape such as three azabicyclics [4.4.0] decyl- 5- alkene, 7- methyl isophthalic acids, the azabicyclics of 5,7- tri- [4.4.0] decyl- 5- alkene is tertiary-aminated Compound etc., it can additionally include γ aminopropyltriethoxy silane, gamma-amino hydroxypropyl methyl diethoxy silane, 4- ammonia Base -3- triethoxy silanes, N- (beta-aminoethyl)-γ aminopropyltriethoxy silane, N- (beta-aminos Ethyl)-gamma-amino hydroxypropyl methyl diethoxy silane, N-3- [amino (dipropylene epoxide)] aminopropyl triethoxysilicane Alkane, (aminoethylaminomethyl) phenethyl triethoxysilane, N- (6- Aminohexyls) aminopropyltriethoxywerene werene, N- The amino such as phenyl-γ aminopropyltriethoxy silane, N- (2- amino-ethyls) -11- amino-undecanoic ethyl triethoxy silicane alkane Silane compound.As the commercially available product of the amine complex of the boron trifluoride, for example, Air Products Japan can be included The Anchor 1040 of Co. Ltd. system, Anchor 1115, Anchor 1170, Anchor 1222, BAK1171 etc..

In the fluorization agent, contain nucleophilic fluorination agent of the fluorine anion as spike and the fluorine by electron deficient Electrophilic fluorination agent of the atom as spike.

As the nucleophilic fluorination agent, for example, 1,1,2,3,3,3- hexafluoro -1- diethylamino propane etc. 1 can be included, The hydrofluorinations of trialkylamine three such as 1,2,3,3,3- hexafluoro -1- dialkyl amido propane based compound, the hydrofluoride of triethylamine three Dialkyl amido sulfur trifluoride based compound such as thing based compound, diethylaminosulfur trifluoride etc..

As the electrophilic fluorination agent, for example, double (tetrafluoro boric acid) N, N '-two fluoro- 2,2 '-bipyridine salt can be included The N- fluorine pyridiniujms based compounds such as compound, trifluoromethanesulfonic acid N- fluorine pyridinium compounds, double (tetrafluoro boric acid) 4- fluoro- 1, Double (the phenyl of fluoro- 1,4- diaza-bicyclos [2.2.2] the octane based compounds of the 4- such as 4- diaza-bicyclos [2.2.2] octane salt, N- fluorine Sulfonyl) double (sulfonyl) amine compounds of the N- such as amine fluorine etc..Wherein, 1,1,2,3,3,3- hexafluoro -1- diethylamino propane Based compound is liquefied compound, and is easily obtained, therefore particularly preferably.

As the alkali metal salt of the polynary fluorine compounds, for example, sodium hexafluoroantimonate, potassium hexafluoroantimonate, six can be included Fluorine natrium arsenicum, potassium hexafluoroarsenate, lithium hexafluoro phosphate, sodium hexafluoro phosphate, Potassium Hexafluorophosphate, five fluorine hydroxyl sodium antimonates, five fluorine hydroxyls Potassium antimonate, LiBF4, sodium tetrafluoroborate, potassium tetrafluoroborate, four (trifluoromethyl) Boratexes, trifluoro (pentafluorophenyl group) Double (pentafluorophenyl group) Boratexes of Boratex, trifluoro (pentafluorophenyl group) potassium borate, difluoro, double (pentafluorophenyl group) potassium borates of difluoro etc.. Wherein, as the polynary fluorine compounds composition in the alkali metal salt of polynary fluorine compounds, preferably tetrafluoro boric acid or hexafluorophosphoric acid.Separately Outside, as the alkali metal in the alkali metal salt of polynary fluorine compounds, one kind for being preferably selected from the group that is made up of lithium, sodium and potassium Above alkali metal.

(C) mixing ratio of composition is not particularly limited, but has the polymer of (methyl) acryloyl group relative to (A) 100 mass parts, preferably 0.001~80 mass parts, more preferably 0.001~30 mass parts, further preferred 0.005~20 mass Part.It should be noted that the content of the fluorine atom in (C) composition is bigger, more tend to coordinate just enough on a small quantity.

The solidification compound of the present invention contains (C1), and there is the silicon compound of Si-F keys and (C2) to be selected from One or more of group being made up of fluorine system compound, it can be only any of (C1) and (C2), and this can also be used Both.Particularly, solidification compound of the invention, which preferably comprises (C1), has the silicon compound of Si-F keys.

The solidification compound of the present invention uses radical polymerization initiator to be used as (D) composition.Draw as radical polymerization Agent is sent out, diacyl peroxide class, ketone peroxide class, hydroperoxide type, dialkyl peroxide class, peroxide can be included Change the organic peroxides such as ketal class, alkyl super-acid ester class and peroxycarbonates class.In addition, as initiator, can make With passing through other radical polymerization initiators such as optical free radical initiator of the light irradiation to produce free radical.

As the concrete example of radical polymerization initiator, benzoyl peroxide, methyl ethyl ketone peroxide, mistake can be included Aoxidize lauroyl, cumyl peroxide, cumyl hydroperoxide etc..Most generally use benzoyl peroxide.

In addition, the example as optical free radical initiator, can include benzoin ethyl ether, benzoin butyl ether and benzoin The benzoin ethers such as isopropyl ether；4,4 '-bis- dimethylamino benzophenones and 4,4 '-bis- diethylamino benzophenone etc. two Benzophenone class；Acetophenone, 2,2- dimethoxy -2- phenyl acetophenones, 2,2- diethoxy -2- phenyl acetophenones, 1,1- dichloros Acetophenone, 1- hydroxycyclohexylphenylketones, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- [4- (2- hydroxyl-oxethyls)-benzene Base] -2- hydroxy-2-methyl -1- acetone, 2- hydroxyls -1- { 4- [4- (2- hydroxy-2-methyls-propiono)-benzyl] phenyl } -2- Methyl isophthalic acid-acetone, 2- methyl isophthalic acids-(4- (methyl mercapto) phenyl) -2- morpholinyl -1- acetone, 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls) -1- butanone, 2- dimethylaminos -2- (4- methyl-benzyls) -1- (4- morpholines -4- bases-phenyl) -1- fourths The acetophenones such as ketone and N, N- dimethylamino benzoylformaldoxime；2,4- diethyl thioxanthones, CTX and 2- isopropyls The thioxanthene ketone class such as thioxanthones；The ketal classes such as benzyl dimethyl ketal, acetophenone dimethyl ketal；2,4,6- trimethylbenzoyls The phosphinoxides such as double (2,4,6- trimethylbenzoyls) phosphine oxides of diphenyl phosphine oxide, phenyl；ESCAROL 507 Amine synergists such as ethyl ester, benzoic acid (2- dimethylaminos) ethyl ester, double -4,4 '-dimethylamino benzophenones etc..

Wherein, from the aspect of the curability of deep, preferably 2- methyl isophthalic acids-(4- (methyl mercapto) phenyl) -2- morpholinyls -1- third Ketone, 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls) -1- butanone and 2- dimethylaminos -2- (4- methyl benzyls Base) the alpha-aminoacetophenone class such as -1- (4- morpholines -4- bases-phenyl) -1- butanone；2,4,6- trimethyl benzoyl diphenyl base oxygen Change the acylphosphine oxide class such as double (2,4,6- trimethylbenzoyls) phosphine oxides of phosphine, phenyl；And amine synergist etc. is in long wavelength (for example, wavelength 300nm) has the optical free radical initiator of light absorbs, more preferably acylphosphine oxide class and amine synergist.

In addition, 1- hydroxycyclohexylphenylketones, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- [4- (2- '-hydroxyethoxies Base)-phenyl -] -2- hydroxy-2-methyl -1- acetone, 2- hydroxyls -1- { 4- [4- (2- hydroxy-2-methyls-propiono)-benzyl] benzene Base } the alpha-hydroxyacetophenone class such as -2- methyl isophthalic acids-acetone can improve surface cure, therefore preferably.

Radical initiator generally utilizes the inorganic matters such as calcium sulfate, calcium carbonate, repefral, phthalic acid Dibutyl ester, dicyclohexyl phthalate, aliphatic hydrocarbon, aromatic hydrocarbon, silicone oil, atoleine, polymerizable monomer, water etc. dilute Agent is diluted to use.

Preferably, there is the mass parts of polymer 100 of (methyl) acryloyl group, the free radical of (D) composition relative to (A) Initiator with more than 0.01 mass parts and below 20 mass parts, preferably more than 0.1 mass parts and below 10 mass parts, more preferably 1 Amount more than mass parts and below 10 mass parts is used.

In the solidification compound of the present invention, reactive diluent, co-catalyst can be added as needed, except (B) Silane coupler (cementability imparting agent), sensitising agent, sweetening agent, diluent, plasticizer, moisture absorber beyond composition, remove (C) condensation reaction beyond composition promotes catalyst, the physical property regulator for improving tensile properties etc., reinforcing agent, colouring agent, fire-retardant The various additives such as agent, anti-sagging agent, antioxidant, age resister, ultra-violet absorber, solvent, spices, pigment, dyestuff.

The composition of the present invention can also use reactive diluent.As reactive diluent, low molecule can be used The various monomers such as the monofunctional monomer and/or polyfunctional monomer of amount.As the concrete example for the monomer that can serve as reactive diluent, It is vinylated that the compound with (methyl) acryloxy, the compound with (methyl) acrylamido, N- can be included Compound.

As the monomer with (methyl) acryloxy, if the chemical combination with more than one (methyl) acryloxy Thing is just not particularly limited, it is, for example, possible to use simple function (methyl) esters of acrylic acid, multifunctional (methyl) esters of acrylic acid Deng.

As simple function (methyl) esters of acrylic acid, for example, (methyl) acrylic acid, (methyl) acrylic acid second can be included Ester, (methyl) acrylic acid 1- methoxy acrylates, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid penta Ester, (methyl) Hexyl 2-propenoate, (methyl) cyclohexyl acrylate, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (first Base) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) acrylic acid nonyl ester, (methyl) decyl acrylate, (first Base) dodecylacrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate base ester, (methyl) acrylic acid tetrahydrochysene Furfuryl group ester, caprolactone modification (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) cyclohexyl acrylate, the ring penta of (methyl) acrylic acid two Base ester, (methyl) acrylic acid dicyclopentenyl base ester, (methyl) acrylic acid dicyclopentenyl epoxide ethyl ester, (methyl) acrylic acid are different Norbornene ester, (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) acrylate, phenoxy group diethyl Glycol (methyl) acrylate, phenoxy group tetraethylene glycol (methyl) acrylate, (methyl) nonylphenol acrylate phenoxy ethyl, nonyl Phenoxyl tetraethylene glycol (methyl) acrylate, dimethyl (methyl) acrylamide, (methyl) dimethyl aminoethyl Ester, (methyl) acrylate propyl ester, (methyl) acrylate, butoxy ethyl, butoxytriglycol (methyl) propylene Acid esters, (methyl) glycidyl acrylate, (methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) acrylic acid 2- hydroxypropyl acrylates, (methyl) Acrylic acid 2- hydroxy butyl esters, (methyl) glycerol acrylate, epoxychloropropane modified (methyl) butyl acrylate, epoxychloropropane change Property (methyl) acrylic acid phenoxy group ester, ethylene-oxide-modified phthalic acid (methyl) acrylate, ethylene-oxide-modified butanedioic acid (methyl) acrylate, caprolactone modification (methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) acrylic acid N, N- dimethylamino ethyl ester, (methyl) acrylic acid N, N- diethylamino ethyl ester, (methyl) acrylic acid morpholinylethyl ester, ethylene-oxide-modified phosphoric acid (methyl) Acrylate etc..

As polyfunctional acrylic ester class, for example, 1,3-BDO two (methyl) acrylate, Isosorbide-5-Nitrae-fourth two can be included Alcohol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, ethylene glycol Two (methyl) acrylate, propane diols two (methyl) acrylate, hydroxy new pentane acid ester neopentylglycol diacrylate, caprolactone Modified hydroxyl pivalate neopentylglycol diacrylate, neopentyl glycol be modified trimethylolpropane two (methyl) acrylate, Stearic acid modified pentaerythrite two (methyl) acrylate, diacrylate dicyclopentenyl base ester, ethylene-oxide-modified two (methyl) Acrylic acid dicyclopentenyl base ester, two (methyl) acryloyl group isocyanuric acid esters, trimethylolpropane tris (methyl) acrylate, season Penta tetrol three (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, pentaerythrite four (methyl) acrylic acid Ester, dipentaerythritol monohydroxy five (methyl) acrylate etc..From being difficult to from the aspect of producing inhibition because of the oxygen in air, It is preferred that polyfunctional acrylic ester class.

As (methyl) acrylamide, the concrete example of N- vinyl compounds, N- methyl (methyl) acryloyl can be included Amine, N- n-propyls (methyl) acrylamide, N- isopropyls (methyl) acrylamide, N- normal-butyls (methyl) acrylamide, N- are secondary Butyl (methyl) acrylamide, the N- tert-butyl groups (methyl) acrylamide, N- n-hexyls (methyl) acrylamide, N- benzyls (methyl) Acrylamide, N- ethoxys (methyl) acrylamide, N, N- dimethyl aminoethyls (methyl) acrylamide, N, N- dimethylaminos Base propyl group (methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, N, N- diethyl (methyl) acrylamide, N, N- bis- N-propyl (methyl) acrylamide, N, N- diisopropyls (methyl) acrylamide, N, N- di-n-butyls (methyl) acrylamide, N, (methyl) acrylamide derivative such as N- dihexyls (methyl) acrylamide, N, N- dibenzyl (methyl) acrylamide, acrylic acid Phthalimide ethyl ester, NVP, N- caprolactams etc..

Reactive diluent can not only use a kind of monomer, can also mix various of monomer to use.It is in addition, reactive Diluent relative to the addition of the unit quantity of the polymer with (methyl) acryloyl group of (A) composition be preferably ormal weight with Under.By making addition of the reactive diluent relative to the unit quantity of the polymer with (methyl) acryloyl group of (A) composition Measure as coating, the printing of solidification compound below ormal weight, can be controlled.For example, it is preferable that relative to (A) composition The mass parts of polymer 100 with (methyl) acryloyl group, using the addition of monomer as more than 0.1 mass parts and 50 mass parts Below, the amount preferably more than 0.5 mass parts and below 40 mass parts, more preferably more than 1 mass parts and below 35 mass parts To use reactive diluent.

In the present invention, alkali can be used.Co-catalyst as the catalytic action for the fluorine system compound for improving (C) composition Work.It is not particularly limited as alkali, but the preferably organic base such as amines.Particularly preferable as the 1,8- diazas of tertiary amine The amidine classes such as the carbon -7- alkene (DBU) of two rings [5.4.0] 11,1,5- diazabicylos [4.3.0] nonyl- 5- alkene (DBN).

Further, it is possible to use the Photobase generator of alkali can be produced when irradiation light as alkali.Photobase generator before light irradiation not It can be worked as alkali, thus, it is desirable that alkali plays a part of using in the case of not being expected in solidification compound Photobase generator.As Photobase generator, preferably benzyl ammonium salt derivatives, benzyl substituted amine derivatives, alpha-amino ketone derivative, α-ammonium The light latency tertiary amine such as ketone derivatives.

In the case where using alkali or generated base alkaline agent, its mixing ratio is not particularly limited, but has (first relative to (A) Base) acryloyl group the mass parts of polymer 100, preferably 0.01~50 mass parts, more preferably 0.1~40 mass parts, further it is excellent Select 0.5~30 mass parts.

The solidification compound of the present invention can further contain the silane coupler in addition to (B) composition, particularly preferably Silanes containing epoxy radicals.Silane coupler works as cementability imparting agent.As the silane coupler, for example, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl group triethoxysilane, γ-epoxy third can be included The silicon containing epoxy radicals such as epoxide hydroxypropyl methyl dimethoxysilane, β-(3,4- expoxycyclohexyls) ethyl trimethoxy silane Alkanes；Gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, gamma-amino hydroxypropyl methyl dimethoxy Silane, N- (beta-aminoethyl)-gamma-amino propyl trimethoxy silicane, N- (beta-aminoethyl)-ethoxy of gamma-amino propyl group three Base silane, N- (beta-aminoethyl)-gamma-amino hydroxypropyl methyl dimethoxysilane, 1,3- diaminourea isopropyl trimethoxy silicon The silanes containing amino such as alkane；N- (1,3- dimethylbutylenes) -3- (triethoxysilicane alkyl) -1- propylamine, N- (1,3- bis- Methylbutylene) the ketimide type silanes such as -3- (trimethoxy silane base) -1- propylamine；γ-mercaptopropyi trimethoxy silicon The silanes containing sulfydryl such as alkane, γ-mercaptopropyi methyl dimethoxysilane；Vinyltrimethoxy silane, vinyl three The silanes containing vinyl-type unsaturated group such as Ethoxysilane；γ-r-chloropropyl trimethoxyl silane etc. contains chlorine atom Silanes；γ-NCO propyl-triethoxysilicane, γ-NCO hydroxypropyl methyl dimethoxysilane etc. contains There is the silanes of NCO；The alkyl such as hexyl trimethoxy silane, hexyl triethoxysilane, decyl trimethoxy silane Silanes；Phenyltrimethoxysila,e, phenyl triethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silicon Silanes containing phenyl such as alkane etc., but it is not limited to this.Alternatively, it is also possible to using by making the silane containing amino Class and the described compound containing epoxy radicals comprising silanes, the compound containing NCO, contain (methyl) third The compound of enoyl- reacted and will be amino modified after the silanes containing modified amido.

The mixing ratio of the silane coupler is not particularly limited, but in the composition, preferably 0.01~20 mass %, More preferably 0.025~10 mass %.These silane couplers both can be used alone, can also and with two or more.

As the carbonyls of the sensitising agent, the preferably triplet energies with 225-310kJ/mol, for example, can Include xanthone, thioxanthones, CTX, 2,4- dimethyl thioxanthones, 2,4- diethyl thioxanthones, 2,4- diisopropyls Thioxanthones, isopropyl thioxanthone, phthalimide, anthraquinone, 9,10- dibutoxies anthracene, acetophenone, propiophenone, hexichol first Ketone, acyl-naphthaline, 2 (Acylmethylene) thiazolines, 3- acyl groups cumarin and 3,3 '-carbonyl bicoumarin, cool, aphthacene, Benzanthracene, phenthazine, flavine, acridine, coumarin ketone etc., preferably thioxanthones, 3- acyl groups cumarin and 2 (Acylmethylene) thiophenes Oxazoline, more preferably thioxanthones and 3- acyl group cumarins.

The mixing ratio of sensitising agent is not particularly limited, but in the composition, preferably 0.01~5 mass %, more preferably 0.025~2 mass %.These sensitising agents both can be used alone, can also and with two or more.

As the sweetening agent, for example, talcum, clay, calcium carbonate, magnesium carbonate, anhydrous silicon, aqueous silicon, silicon can be included Sour calcium, titanium dioxide, carbon black etc..They both can be used alone, can also and with two or more.

The solidification compound of the present invention can further contain diluent.By coordinating diluent, viscosity etc. can be adjusted Physical property.As diluent, known diluent can be widely used, be not particularly limited, for example, can include n-alkane, The saturation hydrocarbon system solvent such as isoparaffin, リ ニ ア レ Application ダ イ マ ー (Idemitsu Kosen Co., Ltd.'s trade name) etc. is alpha-olefin derived The aromatic hydrocarbon series solvent such as thing, toluene, dimethylbenzene, ethanol, propyl alcohol, butanol, amylalcohol, hexanol, octanol, decyl alcohol, DAA etc. The lemons such as the ester series solvent such as alcohol series solvent, ethyl acetate, butyl acetate, pentyl acetate, cellosolve acetate, ATEC The various solvents such as the ketone series solvents such as lemon acid esters series solvent, methyl ethyl ketone, methyl iso-butyl ketone (MIBK).The mixing ratio of diluent does not have Especially limitation, but in the composition, preferably 0.01~20 mass %, more preferably 0.025~10 mass %.These diluents both may be used To be used alone, can also and with two or more.

As the plasticizer, for example, the phosphoric acid esters such as tributyl phosphate, tricresyl phosphate can be included, adjacent benzene two The fat such as the Aliphatic monoacid esters such as the phthalates such as formic acid dioctyl ester, glycerin mono-fatty acid ester, dioctyl adipate The hydrocarbon-based plasticizers such as race's binary acid esters, polypropylene glycols, liquid polybutene, liquid polyisobutene, low molecular weight polybutadiene Deng.They both can be used alone, can also and with two or more.

As the moisture absorber, preferably foregoing silane coupler, silicate.It is not special as the silicate Do not limit, for example, tetraalkoxysilane or its partial hydrolysis condensate can be included, more specifically, tetramethyl can be included TMOS, tetraethoxysilane, ethyoxyl trimethoxy silane, dimethoxy diethoxy silane, methoxyl group triethoxy Silane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silanes, tetraisobutoxy-silicane alkane, four tert-butoxy silicon The tetraalkoxysilanes such as alkane (tetraalkyl silicate) and their partial hydrolysis condensate.

Promote catalyst as the condensation reaction in addition to (C) composition, known condensation reaction can be widely used Promote catalyst, be not particularly limited, for example, the alkali such as organo-metallic compound, acid, amine can be included.As organometallic The example of compound, stannous octoate, two sad dibutyl tins, dibutyl tin laurate, dibutyitin maleate, two can be included Dibutyltin diacetate, bis-acetylacetonate base dibutyl tin, Dibutyltin oxide, double triethoxy silicic acid dibutyl tins, distearyl The organotin chemical combination such as the new caprinoyl oxygen tin of sour dibutyl tin, tin dilaurate dioctyl tin, dioctyl two, tin octoate and aphthenic acids tin Thing；The dialkyltins such as dimethyl tin oxide, Dibutyltin oxide, dioctyl tin oxide；Dibutyltin oxide and adjacent benzene two Reactant of formic acid esters etc.；The titanate esters such as butyl titanate, metatitanic acid orthocarbonate；Praseodynium aluminium, trimethylacetyl acetic acid The organo-aluminum compound classes such as aluminium, oacetic acid diisopropoxy aluminium；Four acetylacetone,2,4-pentanedione zirconiums, four titanium acetylacetones etc. are sequestration Compound class；Organic lead plumbate such as lead octoate and lead naphthenate；The organic acid bismuths such as Bismuth Octoate, bismuth neodecanoate and rosin acid bismuth.Make For silanol condensation catalyst, known other acidic catalysts and base catalyst etc. can be included.However, according to organic The addition of tin compound, the toxicity change of the solidification compound of gained is strong sometimes.

The method for manufacturing the solidification compound of the present invention is not particularly limited, for example, can be by coordinating ormal weight The composition (A), (B), (C) and (D), further according to needing to coordinate other to coordinate material, stirring is de-gassed to manufacture.Respectively into Divide and other coordinate the cooperation order of materials to be not particularly limited, can suitably determine.

A liquid type can be both made in the solidification compound of the present invention as needed, and two-liquid type can also be made, but especially It is that can be preferably used as a liquid type.

The solidification compound of the present invention is solidified using active energy beam or heat.Thus, it is possible to it is used as passing through light The Photocurable composition solidified is irradiated, can be solidified under normal temperature (for example, 23 DEG C), but can also be as needed Promote to solidify by heating.

In the case where the solidification compound of the present invention is used as into Photocurable composition, the condition as irradiation light does not have There is special limitation, but in solidification in the case of irradiation active energy beam, as active energy beam, except purple can be utilized Beyond the electromagnetic wave such as the light such as outside line, luminous ray, infrared ray, X ray, gamma-rays, can also utilize electron beam, proton beam, Neutron beam etc., but from curing rate, the easiness of the acquisition of irradiation unit and price, the behaviour under sunshine or general illumination Easiness of work etc. considers, the solidification carried out preferably by ultraviolet or electron beam irradiation, more preferably using ultraviolet irradiate into Capable solidification.It should be noted that also comprising g lines (wavelength 436nm), h lines (wavelength 405nm), i line (wavelength in ultraviolet 365nm) etc..As active energy beam source, it is not particularly limited, but according to the property of used Photobase generator, for example, can Include high-pressure mercury-vapor lamp, Cooper-Hewitt lamp, electron beam illuminating device, Halogen lamp LED, light emitting diode, semiconductor laser, gold Belong to halide lamp etc..

As irradiation energy, such as in the case of ultraviolet, preferably 10~20000mJ/cm², more preferably 50~ 10000mJ/cm².If it is less than 10mJ/cm², then curability is insufficient sometimes, if being more than 20000mJ/cm²Even if then needed for irradiation Light more than degree, will also result in the waste of time and cost, and damage base material sometimes.

In the case where making the solidification compound solidification of the present invention using heat, preferably 30~200 DEG C of solidification temperature is more excellent Select 80~180 DEG C.

For the solidification compound of the present invention, the moisture resistance of adaptation and solidfied material to base material is excellent, is adapted to As barrier material.Particularly, by using with (methyl) acryloyl group polyisobutene based polymer as (A) with The polymer of (methyl) acryloyl group, the humidity resistance of film can be significantly improved.

The barrier material of the present invention is formed by the solidification compound of the present invention.The application method of the barrier material of the present invention It is not particularly limited, but in the case where requiring high moisture, to preferably more than 100 μm of the coating thickness of adherend, more preferably More than 200 μm.For the barrier material of the present invention, in addition to humidity resistance, to the adaptation of the base materials such as glass, metal It is excellent, it is suitable for being packaged mirror, glass, particularly suitable for sealing mirror, the end of laminated glass or periphery Dress.

The laminated glass is laminated with multiple glass.If laminated glass is laminated with multiple transparent materials with regard to enough, but generally Order according to glass, resin bed, glass is laminated.The material and glass for forming resin bed have cementability, if resin bed It is transparent, it is not particularly limited.

In the present invention, laminated glass can obtain in the following manner.First, using the solidification compound shape by the present invention Into barrier material, be coated with the barrier material around the unencapsulated laminated glass in periphery.Coating method is not particularly limited, For example, can include using brushing, extrusion, spraying, intaglio plate, touch roller, point gum machine and air knife are carried out, in the technical field In known method.

Then, solidify the barrier material.The barrier material of the present invention is solidified using active energy beam or heat, The method same with foregoing solidification compound of the invention can be utilized to make its solidification.

The solidification compound of the present invention can be suitable as encapsulating material, bonding agent, encapsulant, jointing material, painting Layer material, cast encapsulating material, coating, putty material and priming paint etc..The solidification compound of the present invention can be for example applicable In the encapsulating material used in electrical/electronic product, for example, the organic EL element as the product comprising organic EL element is protected Protect the encapsulating material of agent；In the face of the coating for the purpose of moistureproof, insulation of installation circuit substrate etc., mirror or solar power generation The coating agent used in coating of the outer peripheral portion of plate or panel etc.；Compound glass sealant, vehicle sealant etc. are built With and industrial sealant；The electrical/electronic part material such as rear surface of solar cell encapsulant；Electric wire/cable insulate The electrically insulating materials such as covering material；Adhesive；Bonding agent；Elastic adhesive；Contact the purposes such as bonding agent.

In the case where the solidification compound of the present invention is used as into encapsulating material, to the no spy of coating method of adherend Do not limit, for example, brushing, extrusion can be utilized, spraying, intaglio plate, touch coating side known to roller, point gum machine and air knife etc. Method.In the case where requiring moisture resistance to encapsulating material, coating thickness is preferably more than 100 μm, more preferably more than 200 μm.

It is not special to the coating method of adherend in the case where the solidification compound of the present invention is used as into bonding agent Limitation, but preferably by coating methods such as silk-screen printing, stencilization, roll printing, spin coatings.As Photocurable composition In the case of, the more thin easier solidification of coating thickness to adherend, for less than 500 μm, preferably less than 200 μm, further Preferably less than 100 μm, particularly preferably less than 50 μm.

It is not special to the coating method of adherend in the case where the solidification compound of the present invention is used as into coating agent Limitation, but preferably by brushing, extrusion, spraying, intaglio plate, touch roller, point gum machine, airblade coating and, applied by disk The coating methods such as the method (for example, No. 2010/137418 publication of International Publication) of cloth.The situation of moisture resistance is being required coating agent Under, coating thickness is preferably more than 100 μm, more preferably more than 200 μm.

Embodiment

Hereinafter, enumerate embodiment and more specific description is carried out to the present invention, but these embodiments are to illustrate, and are not sayed And explain, should not the explanation of being defined property.

1) measure of number-average molecular weight

Number-average molecular weight is just carried out under the following conditions as long as no specifying by gel permeation chromatography (GPC) Measure.In the present invention, it will be measured under the condition determination by GPC and use the maximum after the conversion of standard polyethylene glycol The molecular weight of frequency is referred to as number-average molecular weight.

Analytical equipment：Alliance (Waters company systems), 2410 type differential refraction detectors (Waters company systems), 996 type multiwavelength detectors (Waters company systems), Milleniam data processing equipments (Waters company systems)

Chromatographic column：Plgel GUARD+5 μm Mixed-C × 3 piece (50 × 7.5mm, 300 × 7.5mm：PolymerLab Company system)

Flow velocity：1mL/ minutes

Polymer after conversion：Polyethylene glycol

Measurement temperature：40℃

Solvent when GPC is determined：THF

2) NMR measure

NMR measure is carried out using following measure devices.

FT-NMR determines device：JEOL (strain) JNM-ECA500 processed (500MHz) (synthesis example 1) has third in end The synthesis of the polyisobutylene polymer of enoyl-

After having carried out nitrogen displacement in the container to 5L detachable flask, add n-hexane and (done with molecular sieve After dry) 280mL and butyl chloride (after molecular sieve drying) 2500mL, are stirred while being cooled to ﹣ 70 in a nitrogen atmosphere ℃.Then, isobutene 1008mL (10.7mol) is added, to dicumyl chlorine 27.4g (0.119mol) and α-methylpyridine 1.33g(0.014mol).After reactant mixture is cooled to 70 degree of ﹣, titanium tetrachloride 5.2mL (0.047mol) is added, is started Polymerization.After polymerization starts, remaining isobutylene concentration is measured using gas chromatography, is less than in isobutene remaining quantity In 0.5% stage, add about 200g methanol.After distilling off solvent etc. from reaction solution, make product be dissolved in just oneself In alkane 2L, washed three times using 1L pure water.Distilling off solvent under reduced pressure, by the polymer of gained under 80 degree vacuum Dry 24 hours, thus obtain chlorine terminated polyisobutylene based polymer A-1.Converted using polystyrene to passing through size exclusion color The molecular weight for the polymer A-1 that spectrum (SEC) method obtains is determined, as a result, Mw：5800, Mn：5200, Mw/Mn： 1.12。

Then, by polyisobutene based polymer A-1 100g, butyl chloride 540ml, n-hexane 60ml, the acrylic acid 2- of gained Phenoxy ethyl (Tokyo HuaCheng Industry Co., Ltd's system) 15.2g is fitted into 1L detachable flasks, stirs while cooling down To 70 degree of ﹣.After completing to be cooled to below 70 degree of ﹣, titanium tetrachloride 22ml is added.Then, it is small to continue stirring 6 in the case where 70 degree of ﹣ When after, addition methanol 200ml stop reaction.After supernatant, distilling off solvent etc. are isolated from reaction solution, make production Thing is dissolved in n-hexane 650ml, is washed three times using 500ml pure water, from methanol after reprecipitation, under reduced pressure Distilling off solvent, the polymer of gained is dried in vacuo 24 hours under 80 degree, the acryloyl group end-blocking for thus obtaining target is poly- Isobutylene-based polymer.Converted using polystyrene to the molecular weight of the polymer obtained by size exclusion chromatography (SEC) method It is determined, as a result, Mw：6000, Mn：5400, Mw/Mn：1.11.In addition, the acryloyl group end-blocking in gained is poly- different The Fn (number of the acryloyl group in every 1 molecule polyisobutylene polymer) for the acryloyl group that the end of butylene imports is 1.93.

The synthesis of (synthesis example 2) fluorinated polymer

In possessing the new flask of agitating device, nitrogen ingress pipe, thermometer and reflux condenser, by molecular weight about 2000 polyoxypropylene glycol is as initiator, in the presence of six cyano group cobalt acid zinc-glycol dimethyl ether complex compound catalyst Under, expoxy propane is reacted, and the polyoxy that the hydroxyl value conversion molecular weight for obtaining gained is 14500 and molecular weight distribution is 1.3 is sub- Diglycol.The methanol solution of sodium methoxide is added in the polyoxypropylene glycol of gained, methanol is distilled out in the case where heating is depressurized, The terminal hydroxyl of polyoxypropylene glycol is converted into sodium alkoxide, obtains polyoxy alkylidene based polymer.

Then, polyoxy alkylidene based polymer is reacted with allyl chloride, unreacted allyl chloride is removed, carry out essence System, obtains the polyoxy alkylidene based polymer in end with pi-allyl.There is the polyoxy alkylidene of pi-allyl to this in end Based polymer, the vinylsiloxane platinum complex aqueous isopropanol 150ppm that addition platinum content is 3wt%, makes as silane The methyl dimethoxysilane of compound is reacted, and obtains the polyoxy alkylidene in end with methyl dimethoxysilane base Based polymer.

Molecule using GPC to the polyoxy alkylidene based polymer in end with methyl dimethoxysilane base of gained Amount is determined, as a result, peak top molecular weight is 15000, molecular weight distribution 1.3.Determined using 1H-NMR, end Methyl dimethoxysilane base is 1.7 in every 1 molecule.

It is laggard in decompression degassing in the flask for possessing agitating device, nitrogen ingress pipe, thermometer and reflux condenser Row nitrogen displacement, BF is added under stream of nitrogen gas₃Diethyl ether complexes 2.4g, is heated to 50 DEG C.Then, dehydration first is slowly added dropwise Alcohol 1.6g mixture is mixed.Possessing the new flask of agitating device, nitrogen ingress pipe, thermometer and reflux condensing tube In, the polymer 100g, the toluene 5g that are obtained described in addition.After stirring 30 minutes at 23 DEG C, it is heated to 110 DEG C and carries out decompression stirring Mix 2 hours, remove toluene.The mixture 4.0g obtained just now is slowly added dropwise into the container under stream of nitrogen gas, is tied being added dropwise Shu Hou, reaction temperature is warming up to 120 DEG C, reacted 30 minutes.After the completion of reaction, decompression degassing is carried out, unreacted reactant is entered Row removes.Obtain the polyoxy alkylidene based polymer (hereinafter referred to as fluorinated polymer) in end with silicon fluoride base.To gained Fluorinated polymer 1HNMR spectrum (use Shimazu company systems NMR400, in CDCl₃It is measured in solvent) carry out Measure, as a result, silane the methylene (- CH with the polymer as raw material₂- Si) corresponding to peak (m, 0.63ppm) disappear Lose, in downfield side, broad peak occurs in (0.7ppm~).

(embodiment 1~10)

According to the mixing ratio shown in table 1, attaching have agitator, thermometer, nitrogen inlet, monomer loading tube and In the flask of water cooled condenser, add the polymer with (methyl) acryloyl group of (A) composition, (B) composition with (first Base) silane coupler of acryloyl group, the fluorine system compound of (C) composition, (D) composition radical initiator and reactivity it is dilute Release the other compositions such as agent and be stirred, it is dissolved and is obtained solidification compound.Gained is consolidated using following methods The cementability and moisture permeability to adherend of the property changed composition are evaluated.

In table 1, each use level for coordinating material is represented with g, coordinates material Details as Follows and be described.

*1：The polymer obtained in synthesis example 1

*2：Purple light UV3700B, Japanese synthetic chemical industry (strain) system, urethane acrylate based polymer

*3：IBXA, common prosperity company chemistry (strain) system

*4：KAYARAD R-684, Japanese chemical drug company system

*5：3- acryloyl propyl group trimethoxy silanes, KBM5103, chemical company of SHIN-ETSU HANTOTAI system

*6：3- methyclyloxypropyl trimethoxy silanes, KBM503, chemical company of SHIN-ETSU HANTOTAI system

*7：3- glycidoxypropyl group triethoxysilanes, KBM403, chemical company of SHIN-ETSU HANTOTAI system

*8：Three-(trimethoxysilylpropyl) isocyanuric acid esters, KBM9659, chemical company of SHIN-ETSU HANTOTAI system

*9：The organic polymer with SiF keys obtained in synthesis example 2

*10：BF₃Ether complexes

*11：Dioctyl tin, NEOSTANN U830, day east chemical conversion company system

*12：Fine Chemical company systems are ground in double oacetic acid aluminium/single acetyl acetone, aluminium chelate compound D, river

*13：IRGACURE 184, BASF AG's system

*14：IRGACURE 1173, BASF AG's system

*15：2- (dimethylamino) -2- [(4- aminomethyl phenyls) methyl] -1- [4- (4- morpholinyls) phenyl] -1- butanone, IRGACURE379EG, BASF AG's system

1) base material adaptation (cementability) is evaluated

Solidification compound is coated on by viscous material (15cm square glass plate) using glass bar, thickness is 100 μm, Carry out UV irradiations (irradiation condition：UV-LED365nm, illumination：1000mW/cm², add up light quantity：3000mJ/cm²), make curability Composition solidifies.After irradiation, cured two days under 23 DEG C, 50%RH.It is general according to JISK5600 coating after the curing Test method, carry out 100 mesh checkerboard tests of 2mm square.Show the result in table 1.

2) moisture permeability is evaluated

The solidification compound obtained in embodiment 1 is coated on 15cm square Teflon (registration mark) piece, thickness For 220 μm, UV irradiations (irradiation condition is carried out：UV-LED365nm, illumination：1000mW/cm², add up light quantity：3000mJ/cm²), Solidify solidification compound.After irradiation, cured two days under 23 DEG C, 50%RH.After the curing, using cured film, According to the moisture permeability test method of JIS Z0208 moisture-proof packaging materials, 50 DEG C of 85%RH moisture permeability is determined, it is tied Fruit is moisture permeability 10.5g/m² 24h。

(comparative example 1~8)

According to the mixing ratio shown in table 1, it is prepared as solidification compound with embodiment 1~10 and evaluates Nian Jie Property.Evaluation result is shown in table 1.

Claims (7)

1. a kind of solidification compound, it is characterised in that contain：

(A) there is the polymer of (methyl) acryloyl group；

(B) there is the silane coupler of (methyl) acryloyl group；

(C) (C1) has the silicon compound of Si-F keys, and/or (C2) is selected from by boron trifluoride, the complex compound of boron trifluoride, fluorination One or more of the group that the alkali metal salt of agent and polynary fluorine compounds is formed fluorine system compound；And

(D) radical initiator.

2. solidification compound according to claim 1, it is characterised in that (A) is with (methyl) acryloyl group Polyisobutene based polymer.

3. solidification compound according to claim 1 or 2, it is characterised in that (D) is optical free radical initiator.

4. a kind of encapsulating material, it is formed by solidification compound according to any one of claims 1 to 3.

5. a kind of electrical/electronic product, the encapsulating material described in its usage right requirement 4 is made.

6. a kind of barrier material, it is formed by solidification compound according to any one of claims 1 to 3.

7. a kind of product, it includes mirror or glass made of the barrier material described in usage right requirement 6.