CN107428891B - Curable composition - Google Patents

Abstract

The present invention provides a curable composition containing a radical polymerizable unsaturated compound, a coupling agent, and a condensation reaction acceleration catalyst, which provides a cured product having improved adhesion to a substrate. The curable composition is characterized by containing: (A) a polymer having a (meth) acryloyl group; (B) a silane coupling agent having a (meth) acryloyl group; (C) (C1) a silicon compound having an Si-F bond, and/or (C2) at least one fluorine-based compound selected from the group consisting of boron trifluoride, a complex of boron trifluoride, a fluorinating agent and an alkali metal salt of a polyfluoro compound; and (D) a radical initiator.

Description

Curable composition

Technical Field

The present invention relates to a curable composition, and particularly to a curable composition having excellent adhesion to a substrate.

Background

Radical polymerizable unsaturated compounds are polymerized and cured by the action of radical initiators and/or light, and used for adhesives, coating materials, and the like. Patent document 1 discloses an active energy ray-curable resin composition containing an unsaturated compound, which is useful as a cladding material for an optical fiber, and page 9 of patent document 1 describes that the adhesion to a base material such as glass or plastic is improved by adding a coupling agent. Patent document 2 discloses an active energy ray-curable resin composition containing a reactive monomer, which is useful as a cladding material for an optical fiber, and which is added with a coupling agent and a condensation reaction promoting catalyst, and describes that the use of the condensation reaction promoting catalyst further improves adhesion to a base material.

Patent documents 3 and 4 describe a resin composition to which a polymer having a (meth) acryloyl group, a (meth) acryloylsilane as a coupling agent, and a condensation reaction promoting catalyst are added, which is useful as a binder (adhesive) for an image display device member.

In adhesives and coating materials, adhesion to a substrate is an extremely important property, and further improvement is desired.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 62-250047

Patent document 2: japanese laid-open patent publication No. 5-32712

Patent document 3: japanese laid-open patent publication No. 2013-088455

Patent document 4: japanese patent laid-open publication No. 2013-129754

Disclosure of Invention

Problems to be solved by the invention

The present invention addresses the problem of providing a curable composition containing a radical polymerizable unsaturated compound, a coupling agent, and a condensation reaction acceleration catalyst, which provides a cured product having improved adhesion to a substrate.

Technical scheme

The inventors and others found that: by using a specific compound as a condensation reaction-promoting catalyst, a curable composition which provides a cured product having excellent substrate adhesion can be obtained. That is, the curable composition of the present invention is characterized by containing: (A) a polymer having a (meth) acryloyl group; (B) a silane coupling agent having a (meth) acryloyl group; (C) (C1) a silicon compound having an Si-F bond, and/or (C2) at least one fluorine-based compound selected from the group consisting of boron trifluoride, a complex of boron trifluoride, a fluorinating agent and an alkali metal salt of a polyfluoro compound; and (D) a radical initiator.

The (a) is preferably a polyisobutylene-based polymer having a (meth) acryloyl group. The use of the polyisobutylene polymer having a (meth) acryloyl group can improve the moisture resistance.

The (D) is preferably a photo radical initiator.

The sealing material of the present invention is a sealing material formed from the curable composition of the present invention.

The electric/electronic product of the present invention is an electric/electronic product manufactured using the encapsulating material of the present invention.

The moisture barrier material of the present invention is a moisture barrier material formed from the curable composition of the present invention.

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

Advantageous effects

The curable composition of the present invention has the following effects: a cured product having excellent substrate adhesion is provided by using a specific fluorine compound as a condensation reaction promoting catalyst.

Detailed Description

The embodiments of the present invention will be described below, but these are merely illustrative, and it is needless to say that various modifications can be made without departing from the technical idea of the present invention.

Examples of the polymer having a (meth) acryloyl group used in the composition of the present invention include a polymer having a (meth) acryloyloxy group, a polymer having a (meth) acrylamide group, and a polymer having a (meth) acryloylimino group. Among them, a compound having a (meth) acryloyloxy group is preferably used. The (meth) acryloyl group in the polymer is preferably present in an average of 1.0 or more, more preferably 1.1 or more, and particularly preferably 1.5 or more per 1 molecule of the polymer. The number of the cells may be 2 or more. The (meth) acryloyl group means an acryloyl group and/or a methacryloyl group.

Examples of the polymer having a (meth) acryloyloxy group include an acrylic polymer having a (meth) acryloyloxy group, a hydrocarbon polymer having a (meth) acryloyloxy group, a polyester polymer having a (meth) acryloyloxy group, an epoxy resin having a (meth) acryloyloxy group, a polyurethane polymer having a (meth) acryloyloxy group, and a polyether polymer having a (meth) acryloyloxy group. The introduction of (meth) acryloyloxy groups into the polymer can be achieved by: (meth) acrylic acid derivatives such as (meth) acrylic acid and (meth) acrylic acid halides are reacted with functional groups such as hydroxyl groups, epoxy groups, and halogen atoms present at the ends of the polymer chain.

The acrylic polymer having a (meth) acryloyloxy group is also referred to as an acrylic resin acrylate, and is a polymer having a (meth) acryloyloxy group as a main chain, and a (meth) acrylate polymer. Such a polymer is preferably produced by anionic polymerization or radical polymerization, and radical polymerization is more preferred in view of versatility of monomers or easiness of control. Among the radical polymerization, living radical polymerization or radical polymerization using a chain transfer agent is preferable, living radical polymerization is more preferable, and atom transfer radical polymerization is particularly preferable. When living radical polymerization is used, a polymer having a (meth) acryloyloxy group at a polymer chain end can be produced.

As the skeleton of the acrylic polymer, a polymer such as polymethyl methacrylate (MMA), poly (2-hydroxyethyl methacrylate (HEMA)/MMA), poly (HEMA/Butyl Methacrylate (BMA)), or the like can be used.

Examples of the acrylic polymer having a (meth) acryloyloxy group include poly-n-butyl acrylate having an acryloyl group at both ends as described in production example 1 of WO2012/008127, poly-n-butyl acrylate having an acryloyl group at one end as described in production example 2 of the publication, poly-n-butyl acrylate having an acryloyl group at both ends as described in production example 1 of WO2005/000927, poly-n-butyl acrylate/ethyl acrylate/2-methoxyethyl acrylate having an acryloyl group at both ends as described in production example 2 of WO2006/112420, and poly-2-ethylhexyl acrylate having an acryloyl group at both ends as described in production example 3 of the publication.

As commercially available products of acrylic polymers having a (meth) acryloyloxy group, there may be mentioned, for example, macromonomers AA-6 and AB-6 manufactured by Toyo Synthesis Co., Ltd; RC-100C, RC-200C, RC-300C manufactured by Kaneka, Ltd.

Examples of the hydrocarbon-based polymer include ethylene-propylene-based copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, copolymers of isoprene or butadiene with acrylonitrile and/or styrene, polybutadiene, copolymers of isoprene or butadiene with acrylonitrile and styrene, and hydrogenated polyolefin-based polymers obtained by hydrogenating these polyolefin-based polymers.

Among them, saturated hydrocarbon polymers such as hydrogenated polyolefin polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene are preferable because they have a high gas barrier property and are suitable for applications requiring a gas barrier property, and in particular, polyisobutylene has a high gas barrier property. The polymer can be suitably used for a moisture-proof coating layer for a mirror, such as a back coating layer for a mirror and an end coating layer for a mirror.

The hydrocarbon-based polymer having a (meth) acryloyloxy group may be introduced with a polymer having a hydroxyl group. The polyisobutylene-based polymer having a (meth) acryloyloxy group can be obtained by the method described in Japanese patent laid-open publication No. 2013-035901 and International publication No. WO 2013-047314.

The polyester-based polymer having a (meth) acryloyloxy group is also referred to as a polyester acrylate. Such a polymer can be obtained by dehydrating condensation of a polyester polyol with (meth) acrylic acid. Examples of the polyester polyol include a reaction product of a polyol and a carboxylic acid or an acid anhydride thereof.

Examples of the polyhydric alcohol include low molecular weight polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexanedimethanol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, trimethylolpropane, glycerin, pentaerythritol, and dipentaerythritol, and alkylene oxide adducts thereof.

Examples of the carboxylic acid or its anhydride include dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and trimellitic acid, and anhydrides thereof.

An epoxy resin having a (meth) acryloyloxy group is also referred to as an epoxy acrylate, and can be obtained by addition reaction of an epoxy resin and (meth) acrylic acid. Examples of the epoxy resin include aromatic epoxy resins and aliphatic epoxy resins.

Examples of the aromatic epoxy resin include resorcinol diglycidyl ether; diglycidyl ethers or polyglycidyl ethers of bisphenol a, bisphenol F, bisphenol S, bisphenol fluorene, or alkylene oxide adducts thereof; phenol novolac epoxy resins such as phenol novolac epoxy resins and cresol novolac epoxy resins; glycidylphthalimide; diglycidyl phthalate, and the like. In addition, compounds described in chapter 2 of epoxy resin, recently introduced ", published in 1990, and in pages 4 to 6 and 9 to 16 of polymer processing and journal 9/22-volume journal-number epoxy resin, published in polymer journal society, published in 48, can be used as the aromatic epoxy resin.

Examples of the aliphatic epoxy resin include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1, 4-butanediol, and 1, 6-hexanediol; diglycidyl ethers of polyalkylene glycols such as diglycidyl ethers of polyethylene glycol and polypropylene glycol; diglycidyl ethers of neopentyl glycol, dibromoneopentyl glycol, and alkylene oxide adducts thereof; polyglycidyl ethers of polyhydric alcohols such as diglycidyl ethers or triglycidyl ethers of trimethylolethane, trimethylolpropane, glycerol and alkylene oxide adducts thereof, and diglycidyl ethers, triglycidyl ethers or tetraglycidyl ethers of pentaerythritol and alkylene oxide adducts thereof; diglycidyl ethers or polyglycidyl ethers of hydrogenated bisphenol a and alkylene oxide adducts thereof; tetrahydrophthalic acid diglycidyl ether; hydroquinone diglycidyl ether, and the like.

In addition, there are also mentioned compounds described on pages 3 to 6 of the epoxy resin in "Polymer processing" journal of the aforementioned document. In addition to these aromatic epoxy resins and aliphatic epoxy resins, there are also included epoxy compounds having a triazine nucleus in the skeleton, for example, TEPIC (Nissan chemical Co., Ltd.), Denacol EX-310(Nagase chemical Co., Ltd.), and the like, and there are also included compounds described in the aforementioned publication "Polymer processing" on pages 289 to 296 of an epoxy resin.

Specific examples of the epoxy resin having a (meth) acryloyloxy group include bisphenol a di (meth) acrylate, ethylene oxide-modified bisphenol a di (meth) acrylate, epichlorohydrin-modified bisphenol a di (meth) acrylate, ethylene oxide-modified bisphenol S di (meth) acrylate and the like.

The urethane polymer having a (meth) acryloyloxy group is also referred to as urethane (meth) acrylate, and can be obtained by reacting an isocyanate group-terminated polyurethane obtained by reacting a polyol with an excess amount of an organic polyisocyanate with a hydroxyl group-containing (meth) acrylate.

Examples of the polyol include low molecular weight polyols, polyether polyols, polyester polyols, and polycarbonate polyols. Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, cyclohexanedimethanol, 3-methyl-1, 5-pentanediol, and the like; examples of the polyether polyol include polyethylene glycol, polypropylene glycol and the like; the polyester polyol includes a reaction product of the low molecular weight polyol and/or the polyether polyol and an acid component such as a dibasic acid or an acid anhydride thereof, for example, adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid.

Examples of the organic polyisocyanate include tolylene diisocyanate, 4 '-diphenylmethane diisocyanate, 4' -dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

These urethane (meth) acrylate polymers can be produced by a known synthesis method. For example, a method in which the organic isocyanate and the polyol component used are heated and stirred in the presence of an addition catalyst such as dibutyltin dilaurate to cause an addition reaction, and a hydroxyalkyl (meth) acrylate is further added thereto and heated and stirred to cause an addition reaction, and the like can be cited.

Examples of the polyether (meth) acrylate polymer include polyalkylene glycol (meth) acrylate and polyalkylene glycol di (meth) acrylate, and the polymer can be obtained by reacting polyalkylene glycol with (meth) acrylic acid and (meth) acrylic acid derivatives.

Examples of the polyalkylene glycol (meth) acrylate include methoxy diethylene glycol (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, 2-ethylhexyl polyethylene glycol (meth) acrylate, methoxy dipropylene glycol (meth) acrylate, nonylphenyl polypropylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate.

Examples of the polyalkylene glycol di (meth) acrylate include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, and the like.

The polymer having a (meth) acrylamide group can be obtained by using a polymer having an amino group instead of a hydroxyl group of a polymer having a hydroxyl group such as a polyol, and reacting (meth) acrylic acid chloride or the like. Wherein the polyol is a raw material of the polymer having a (meth) acryloyloxy group.

The curable composition of the present invention uses (B) a silane coupling agent having a (meth) acryloyl group. The silane coupling agent having a (meth) acryloyl group is a compound having a (meth) acryloyl group and a crosslinkable silicon group. The crosslinkable silicon group is a group having a hydrolyzable group bonded to a silicon atom, and is hydrolyzed by the action of water such as moisture in the air to form a siloxane bond. Examples of the crosslinkable silicon group include groups in which an alkoxy group or a carboxyl group is bonded to a silicon atom as a hydrolyzable group. Specific examples of the crosslinkable silyl group include trimethoxysilyl group and methyldimethoxysilyl group. The silane coupling agent functions as an adhesion imparting agent.

Examples of the silane coupling agent as the component (B) include compounds such as γ -methacryloxypropyltrimethoxysilane and γ -acryloxypropylmethyldimethoxysilane. The amount of the (meth) acryloyl group-containing silane coupling agent of component (B) is 1 to 20 parts by mass, and more preferably 2 to 10 parts by mass, per 100 parts by mass of the (meth) acryloyl group-containing polymer of component (A).

The curable composition of the present invention contains (C) (C1) a silicon compound having an Si-F bond and/or (C2) at least one fluorine-based compound selected from the group consisting of boron trifluoride, a complex of boron trifluoride, a fluorinating agent and an alkali metal salt of a polyfluorinated compound. The curable composition of the present invention contains the component (C), thereby producing a cured product having excellent adhesion to a substrate. (C) The component (B) acts as a condensation reaction promoting catalyst for the crosslinkable silicon group reaction of the silane coupling agent of the component (B).

The silicon compound having an Si — F bond (C1) is a known compound having a group having an Si — F bond (hereinafter, may be referred to as a "fluorosilane group"), and is not particularly limited, and any of a low molecular compound and a high molecular compound can be used. Further, a low-molecular-weight organosilicon compound having a fluorosilane group is preferable in terms of low viscosity of the complex.

The silicon compound having an Si-F bond (C1) includes, as preferred examples, an inorganic compound having a fluorosilyl group represented by the following formula (1), a low-molecular-weight organosilicon compound having the fluorosilyl group, and an organic polymer having the fluorosilyl group.

-SiF_aR¹ _bX_c···(1)

In the formula (1), R¹Represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R² ₃SiO-(R²Each independently is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a fluorine atom). a is any one of 1 to 3, preferably a is 3. In the presence of a plurality of R¹And R²In this case, they may be the same or different. X is a hydroxyl group or a hydrolyzable group other than fluorine, b is any one of 0 to 2, c is any one of 0 to 2, and a + b + c is 3. When a plurality of xs are present, they may be the same or different.

As R in the formula (1)¹Examples thereof include alkyl groups such as methyl and ethyl, cycloalkyl groups such as cyclohexyl, aryl groups such as phenyl, aralkyl groups such as benzyl, and the like, or R²R being methyl, phenyl, or the like² ₃Trisilicoalkyloxy group represented by SiO-, and the like. Among them, methyl is particularly preferable.

Examples of the hydrolyzable group represented by X in the formula (1) include a hydrogen atom, a halogen atom other than fluorine, an alkoxy group, an acyloxy group, a ketoxime ester group (ketoximate), an amino group, an amide group, an acid amide group, an aminoxy group, a mercapto group, and an alkenyloxy group. Among them, preferred are a hydrogen atom, an alkoxy group, an acyloxy group, a ketoxime ester group, an amino group, an amide group, an aminoxy group, a mercapto group, and an alkenyloxy group.

Specifically, when the fluorosilyl group represented by the formula (1) is exemplified, examples of the silicon group having no hydrolyzable group other than fluorine include a silicon group having one fluorine substituted on the silicon group such as a fluorodimethylsilyl group, a fluorodiethylsilyl group, a fluorodipropylsilyl group, a fluorodiphenylsilyl group, and a fluorodibenzylsilyl group; a silicon group substituted with two fluorines such as a difluoromethylsilyl group, a difluoroethylsilyl group, a difluorophenylsilyl group, and a difluorobenzylsilyl group; the silicon group as the trifluorosilane group is substituted with a silicon group having three fluorines.

Examples of the silyl group having both fluorine and another hydrolyzable group include fluoromethoxymethylsilyl group, fluoroethoxymethylsilyl group, fluoromethoxyethylsilyl group, fluoromethoxyphenylsilyl group, fluorodimethoxysilyl group, fluorodiethoxysilyl group, fluorodipropoxysilyl group, fluorodiphenoxysilyl group, fluorobis (2-propenyloxy) silyl group, difluoromethoxysilyl group, difluoroethoxysilyl group, difluorophenoxysilyl group, fluorodichlorosilyl group, and difluorochlorosilyl group. Among these, preferred are a silicon group having no hydrolyzable group other than fluorine, and R¹A fluorosilane group which is a methyl group, and more preferably a trifluorosilane group.

Further, from the viewpoint of ease of synthesis, a fluorodimethylsilyl group, a difluoromethylsilyl group, a trifluorosilyl group, a fluoromethoxymethylsilyl group, a fluoroethoxymethylsilyl group, a fluoromethoxyethylsilyl group, a fluorodimethoxysilyl group, a fluorodiethoxysilyl group, a difluoromethoxysilyl group, and a difluoroethoxysilyl group are more preferable. From the viewpoint of stability, a silicon group having no hydrolyzable group other than fluorine, such as a fluorodimethylsilyl group, a difluoromethylsilyl group, or a trifluorosilyl group, is more preferable. From the viewpoint of high reactivity, a silicon group substituted with two or three fluorines on a silicon group such as a difluoromethylsilyl group, a difluoromethoxysilyl group, a difluoroethoxysilyl group, or a trifluorosilyl group is preferable, and a trifluorosilyl group is most preferable.

The compound having a fluorosilane group represented by the above formula (1) may be synthesized from a commercially available reagent or a starting compound. The synthesis method is also not particularly limited, and a compound obtained by reacting a compound having a crosslinkable silicon group represented by the following formula (2) or a compound having a siloxane bond with a fluorinating agent by a known method (for example, Organometallics 1996, 15,2478 (Ishikawa, etc.) or the like) is preferably used.

-SiR¹ _3-aX_a···(2)

(in the formula (2), R¹And X is the same as the formula (1), a is any one of 1 to 3)

Examples of the crosslinkable silyl group represented by the formula (2) include a halosilyl group such as an alkoxysilyl group or a chlorosilyl group, and a hydrosilyl group.

Specific examples of the fluorinating agent for fluorinating an alkoxysilyl group are not particularly limited, and include, for example, NH₄F、Bu₄NF、HF、BF₃、Et₂NSF₃、HSO₃F、SbF₅、VOF₃、CF₃CHFCF₂NEt₂And the like. Specific examples of the fluorinating agent for fluorinating a halosilyl group are not particularly limited, and examples thereof include AgBF₄、SbF₃、ZnF₂、NaF、KF、CsF、NH₄F、CuF₂、NaSiF₆、NaPF₆、NaSbF₆、NaBF₄、Me₃SnF、KF(HF)_1.5～5And the like. Specific examples of the fluorinating agent for fluorinating a hydrosilyl group are not particularly limited, and examples thereof include AgF and PF₅、Ph₃CBF₄、SbF₃、NOBF₄、NO₂BF₄And the like. By BF of compounds having siloxane bonds₃And the like to obtain a fluorosilyl group.

In the method for synthesizing a fluorosilyl group using such a fluorinating agent, BF is preferably used from the viewpoints of simplicity of reaction, high reaction efficiency, high safety and the like₃Fluorination method of alkoxysilane of (2) and use of CuF₂Or ZnF₂A process for fluorinating a chlorosilane.

As BF₃BF may be used₃Gas, BF₃Ether complex, BF₃Thioether complex, BF₃Amine complex and BF₃Alcohol complex and BF₃Carboxylic acid complex, BF₃Phosphoric acid complex, BF₃Hydrate, BF₃Piperidine Complex, BF₃Phenol complex, etc., but BF is preferred from the viewpoint of easy handling₃Ether complex, BF₃Thioether complex, BF₃Amine complex and BF₃Alcohol complex and BF₃Carboxylic acid complex, BF₃A hydrate. Wherein, BF₃Ether complex, BF₃Alcohol complex and BF₃Since the hydrate has high reactivity, BF is particularly preferred₃An ether complex.

Specific examples of the silicon compound having an Si — F bond and having no hydrolyzable group other than fluorine include fluorinated inorganic silicon compounds such as tetrafluorosilane and octafluorotrisilane; fluorotrimethylsilane, fluorotriethylsilane, fluorotripropylsilane, fluorotributylsilane, fluorodimethylvinylsilane, fluorodimethylphenylsilane, fluorodimethylbenzylsilane, fluorodimethyl (3-methylphenyl) silane, fluorodimethyl (4-chlorophenyl) silane, fluorotriphenylsilane, difluorodimethylsilane, difluorodiethylsilane, difluorodibutylsilane, difluoromethylphenylsilane, difluorodiphenylsilane, trifluoroethylsilane, trifluoropropylsilane, trifluorobutylsilane, trifluorophenylsilane, gamma-glycidoxypropyltrifluorosilane, gamma-glycidoxypropyldifluoromethylsilane, vinyltrifluorosilane, vinyldifluoromethylsilane, 3-mercaptopropyltrifluorosilane, octadecylfluorodimethylsilane, fluorotributylsilane, fluorobutylsilane, fluorotriphenylsilane, fluorotrimethylsilane, fluorodimethylsilane, difluorodiethylsilane, difluorobutylsilane, difluorosilane, fluorodiphenylsilane, trifluorosilane, gamma-glycidoxypropylsilane, gamma, And fluorinated low-molecular-weight organosilicon compounds such as octadecyldifluoromethylsilane, octadecyltrifluorosilane, 1, 3-difluoro-1, 1,3, 3-tetramethyldisiloxane, 1,3,5, 7-tetrafluoro-1, 3,5, 7-tetrasilatricyclo [3.3.1.1(3,7) ] decane, 1-difluoro-1-silacyclo-3-pentene, and fluorotris (trimethylsiloxy) silane.

Specific examples of the silicon compound having an Si — F bond and having a hydrolyzable group other than fluorine include fluorinated low molecular weight organosilicon compounds such as fluorotrimethoxysilane, difluorodimethoxysilane, trifluoromethoxysilane, fluorotriethoxysilane, difluorodiethoxysilane, trifluoroethoxysilane, methylfluorodimethoxysilane, methyldifluoromethoxysilane, methyltrifluorosilane, methylfluorodiethoxysilane, methyldifluoroethoxysilane, vinylfluorodimethoxysilane, vinyldifluoromethoxysilane, vinyltrifluorosilane, vinylfluorodiethoxysilane, vinyldifluoroethoxysilane, phenylfluorodimethoxysilane, phenyldifluoromethoxysilane, phenyltrifluorosilane, phenylfluorodiethoxysilane, and phenyldifluoroethoxysilane.

Among them, from the viewpoint of easy availability of raw materials, easy synthesis, and the like, preferred are fluorodimethylvinylsilane, fluorodimethylphenylsilane, fluorodimethylbenzylsilane, vinyltrifluorosilane, vinyldifluoromethylsilane, 3-mercaptopropyltrifluorosilane, octadecylfluorodimethylsilane, octadecyldifluoromethylsilane, octadecyltrifluorosilane, 1, 3-difluoro-1, 1,3, 3-tetramethyldisiloxane, and the like.

The organic polymer having a fluorosilane group (also referred to as a fluorinated polymer in the present specification) is not particularly limited as long as it is an organic polymer having an Si-F bond, and a known organic polymer having an Si-F bond can be widely used. The position of the SiF bond in the organic polymer is not particularly limited, and the SiF bond exerts an effect at any position in the polymer molecule. Examples of the organic polymer having an Si — F bond include a polymer having a fluorosilane group represented by the above formula (1); -Si (CH)₃)F-、-Si(C₆H₅)F-、-SiF₂Polymers in which a fluorosilane group such as-SiF-is embedded in the main chain of the polymer, and the like.

The fluorinated polymer may be a single polymer having the same kind of the fluorosilane group and the main chain skeleton, that is, a single polymer having the same kind of the number of the fluorosilane groups per 1 molecule, the bonding positions thereof, the number of F contained in the fluorosilane groups, and the main chain skeleton, or may be a mixture of a plurality of polymers each having any one or all of them different from each other. The fluorinated silane group contained in the fluorinated polymer is present in an amount of at least 1, preferably 1.1 to 5, and more preferably 1.2 to 3 per 1 molecule of the polymer on average. If the number of the fluorosilane groups contained in 1 molecule is less than 1 on average, the effect of imparting adhesiveness becomes insufficient.

The fluorinated polymer may contain a substituent other than the fluorosilyl group, such as a silyl group (e.g., methyldimethoxysilyl group) having only a hydrolyzable group other than fluorine as a hydrolyzable group, in addition to the fluorosilyl group. Examples of such fluorinated polymers include polymers in which one main chain end is a fluorosilane group and the other main chain end is a silicon group having only hydrolyzable groups other than fluorine as hydrolyzable groups. Examples of fluorinated polymers are described in International patent publication No. WO 2008/032539.

In the fluorinated polymer, any method can be used for introducing the fluorosilane group, but examples thereof include a method of introducing the fluorosilane group by a reaction between a low-molecular-weight silicon compound having a fluorosilane group and the polymer (method (i)), and a method of modifying a silicon group of a crosslinkable silicon group-containing polymer having a hydrolyzable group other than fluorine (hereinafter, sometimes referred to as "polymer (X)") into a fluorosilane group (method (ii)).

Specific examples of the method (i) include the following methods.

(a) A method of reacting a polymer having a functional group such as a hydroxyl group, an epoxy group, or an isocyanate group in a molecule with a compound having a functional group reactive with the functional group and a fluorosilane group. For example, a method of reacting a polymer having a hydroxyl group at the terminal with isocyanatopropyldifluoromethylsilane, or a method of reacting a polymer having a SiOH group at the terminal with difluorodiethoxysilane can be mentioned.

(b) A method of subjecting a polymer having an unsaturated group in the molecule to hydrosilylation by allowing a hydrosilane having a fluorosilane group to act thereon. For example, a method of reacting a polymer having an allyl group at the terminal with difluoromethylhydrosilane is exemplified.

(c) A method of reacting an unsaturated group-containing polymer with a compound having a mercapto group and a fluorosilane group. For example, a method of reacting a polymer having an allyl group at the terminal with mercaptopropyldifluoromethylsilane is exemplified.

Examples of the crosslinkable silyl group-containing polymer (X)) having a hydrolyzable group other than fluorine used in the above method (ii) include saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene having a crosslinkable silyl group having a hydrolyzable group other than fluorine, or polyoxyalkylene polymers, (meth) acrylate polymers, and polysiloxane polymers as preferred polymers.

In the method (ii), as a method for converting a crosslinkable silyl group having a hydrolyzable group other than fluorine into a fluorosilyl group, a known method can be used, and for example, a method for converting a hydrolyzable silyl group represented by the above formula (2) into a fluorosilyl group by a fluorinating agent can be mentioned. Examples of the fluorinating agent include the above-mentioned fluorinating agents, and among them, BF₃Ether complex, BF₃Alcohol complex and BF₃The dihydrate is more preferably BF because it has high activity, efficiently undergoes fluorination, does not produce salts or the like in by-products, and is easy to handle₃An ether complex. Further, for the utilization of BF₃The fluorination by the ether complex proceeds even without heating, but heating is preferred for more efficient fluorination. The heating temperature is preferably 50 ℃ or higher and 150 ℃ or lower, and more preferably 60 ℃ or higher and 130 ℃. If the temperature is 50 ℃ or lower, the reaction may not proceed efficiently, and the fluorination may take a long time. When the temperature is 150 ℃ or higher, the fluorinated polymer may be decomposed. In the utilization of BF₃In the fluorination of the complex, coloration may occur depending on the type of the polymer (X) used, but it is preferable to use BF in view of suppressing coloration₃Alcohol complex and BF₃A dihydrate.

The fluorinating agent used for producing the fluorinated polymer may also function as a curing catalyst for the fluorinated polymer, and when moisture is present in the production of the fluorinated polymer by the method (ii), a silanol condensation reaction proceeds, and the viscosity of the obtained fluorinated polymer may be increased. Therefore, it is desirable to produce the fluorinated polymer in an environment free of moisture as much as possible, and it is preferable to perform a dehydration operation such as azeotropic dehydration of the polymer (X) to be fluorinated with toluene, hexane or the like before the fluorination. However, when BF is used₃In the case of an amine complex, fluorination is difficult after dehydration and reactivity tends to be improved by adding a small amount of water, and therefore, it is preferable to add water in a range that allows an increase in viscosityAnd (4) dividing. In addition, from the viewpoint of stability of the fluorinated polymer, it is preferable to remove the fluorinating agent and by-product components derived from the fluorinating agent by filtration, decantation, liquid separation, devolatilization under reduced pressure, or the like after the fluorination. In the use of the above-mentioned BF₃When a fluorinated polymer is produced using a fluorinating agent of the type, BF remaining in the produced fluorinated polymer₃And BF derived by reaction₃Preferably less than 500ppm, more preferably less than 100ppm, particularly preferably less than 50ppm, based on B. By removing BF₃And from BF₃The component (4) can suppress an increase in viscosity of the obtained fluorinated polymer itself or a mixture of the fluorinated polymer and the polymer (X). Taking this into account, BF is used₃Ether complex, BF₃The fluorination method of an alcohol complex is preferred because it can relatively easily remove the boron component by vacuum devolatilization, and BF is particularly preferably used₃Ether complex method.

Here, in the case where the polymer (X) has two or more hydrolyzable groups other than fluorine, all of the hydrolyzable groups may be fluorinated, or the fluorination may be partially performed by adjusting the fluorination conditions by a method such as reducing the amount of the fluorinating agent. For example, in the method (ii), when the polymer (X) is used to produce a fluorinated polymer, the amount of the fluorinating agent used is not particularly limited, and the molar amount of the fluorine atom in the fluorinating agent may be equal to or more than the molar amount of the polymer (X). When it is desired to fluorinate all the hydrolyzable groups contained in the polymer (X) by the method of (ii), it is preferable to use a fluorinating agent in which the molar amount of fluorine atoms in the fluorinating agent is equal to or more than equimolar with respect to the total molar amount of hydrolyzable groups in the crosslinkable silicon group contained in the polymer (X). Here, the "fluorine atom in the fluorinating agent" means a fluorine atom effective for fluorination in the fluorinating agent, and specifically means a fluorine atom capable of substituting for a hydrolyzable group in a crosslinkable silicon group of the polymer (X).

The low-molecular weight compound having a fluorosilane group in the above-mentioned method (i) can also be synthesized from a general-purpose crosslinkable silyl group-containing low-molecular weight compound by the above-mentioned fluorination method.

In the method (i), since the fluorinated polymer has a reactive group for reacting the polymer with a silicon-containing low-molecular-weight compound in addition to the fluorosilane group, it is preferable to obtain the fluorinated polymer by the method (ii) when the reaction is complicated.

The glass transition temperature of the fluorinated polymer is not particularly limited, but is preferably 20 ℃ or lower, more preferably 0 ℃ or lower, and particularly preferably-20 ℃ or lower. When the glass transition temperature is higher than 20 ℃, the viscosity in winter or in cold regions becomes high, and the handling may become difficult. The glass transition temperature can be determined by DSC measurement.

The fluorinated polymer may be linear or may have a branch. The number average molecular weight of the fluorinated polymer is preferably 3000 to 100000, more preferably 3000 to 50000, and particularly preferably 3000 to 30000 in terms of polystyrene of GPC.

In the present invention, (C2) one or more fluorine-based compounds selected from the group consisting of boron trifluoride, a complex of boron trifluoride, a fluorinating agent and an alkali metal salt of a polyfluoro compound can be used as component (C).

Examples of the complex of boron trifluoride include an amine complex, an alcohol complex, an ether complex, a thiol complex, a thioether complex, a carboxylic acid complex, and a water complex of boron trifluoride. Among the above complexes of boron trifluoride, amine complexes having both stability and catalytic activity are particularly preferable.

Examples of the amine compound used in the amine complex of boron trifluoride include ammonia, monoethylamine, triethylamine, piperidine, aniline, morpholine, cyclohexylamine, N-butylamine, monoethanolamine, diethanolamine, triethanolamine, guanidine, 2,2,6, 6-tetramethylpiperidine, 1,2,2,6, 6-pentamethylpiperidine, N-methyl-3, 3' -iminobis (propylamine), ethylenediamine, diethylenetriamine, triethylenediamine, pentaethylenediamine, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 2-diaminobutane, 1, 4-diaminobutane, 1, 9-diaminononane, ATU (3, 9-bis (3-aminopropyl) -2,4,8, 10-tetraoxaspiro [5.5] undecane), A compound having a plurality of primary amino groups, such as CTU guanamine, dodecanoic acid dihydrazide, hexamethylenediamine, m-xylylenediamine, dianisidine, 4 '-diamino-3, 3' -diethyldiphenylmethane, diaminodiphenyl ether, 3,3 '-dimethyl-4, 4' -diaminodiphenylmethane, diaminodimethylbiphenyl (tolidine base), m-tolylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, melamine, 1, 3-diphenylguanidine, di-o-tolylguanidine, 1,3, 3-tetramethylguanidine, bis (aminopropyl) piperazine, N- (3-aminopropyl) -1, 3-propanediamine, bis (3-aminopropyl) ether, JEFFAMINE manufactured by Sun Techno Chemical corporation, and the like; compounds having a plurality of secondary amino groups, such as piperazine, cis-2, 6-dimethylpiperazine, cis-2, 5-dimethylpiperazine, 2-methylpiperazine, N ' -di-tert-butylethylenediamine, 2-aminomethylpiperidine, 4-aminomethylpiperidine, 1, 3-bis (4-piperidyl) -propane, 4-aminopropylaniline, homopiperazine, N ' -diphenylthiourea, N ' -diethylthiourea, and N-methyl-1, 3-propanediamine; and methylaminopropylamine, ethylaminopropylamine, ethylaminoethylamine, laurylaminopropylamine, 2-hydroxyethylaminopropylamine, 1- (2-aminoethyl) piperazine, N-aminopropylpiperazine, 3-aminopyrrolidine, 1-o-tolylbiguanide, 2-aminomethylpiperazine, N-aminopropylaniline, ethylaminoethylamine, 2-hydroxyethylaminopropylamine, laurylaminopropylamine, 2-aminomethylpiperidine, 4-aminomethylpiperidine, a compound represented by the formula H2N (C2H4NH) nH (n.apprxeq.5) (trade name: Poly-8, manufactured by Tosoh Co.), N-alkylmorpholine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 6-dibutylamino-1, 8-diazabicyclo [5.4.0] undec-7-ene, Examples of heterocyclic tertiary amine compounds such as 1, 5-diazabicyclo [4.3.0] non-5-ene, 1, 4-diazabicyclo [2.2.2] octane, pyridine, N-alkylpiperidine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene and 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene include γ -aminopropyltriethoxysilane, γ -aminopropylmethyldiethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane, N- (. beta. -aminoethyl) - γ -aminopropyltriethoxysilane, N- (. beta. -aminoethyl) - γ -aminopropylmethyldiethoxysilane, N-3- [ amino (dipropyloxy) ] aminopropyltriethoxysilane, And aminosilane compounds such as (aminoethylaminomethyl) phenethyltriethoxysilane, N- (6-aminohexyl) aminopropyltriethoxysilane, N-phenyl-gamma-aminopropyltriethoxysilane, and N- (2-aminoethyl) -11-aminoundecyltriethoxysilane. Examples of commercially available Products of the above-mentioned boron trifluoride amine complex include Anchor 1040, Anchor 1115, Anchor 1170, Anchor 1222 and BAK1171 manufactured by Air Products Japan.

The fluorinating agent contains a nucleophilic fluorinating agent having a fluorine anion as an active species and an electrophilic fluorinating agent having an electron-deficient fluorine atom as an active species.

Examples of the nucleophilic fluorinating agent include 1,1,2,3,3, 3-hexafluoro-1-dialkylaminopropane compounds such as 1,1,2,3,3, 3-hexafluoro-1-diethylaminopropane, trialkylamine trihydrofluoride compounds such as triethylamine trihydrofluoride, and dialkylaminosulfur trifluoride compounds such as diethylaminosulfur trifluoride.

Examples of the electrophilic fluorinating agent include N-fluoropyridinium salt compounds such as bis (tetrafluoroboric acid) N, N '-difluoro-2, 2' -bipyridinium salt compounds and N-fluoropyridinium salt compounds such as trifluoromethanesulfonic acid N-fluoropyridinium salt compounds, 4-fluoro-1, 4-diazoniabicyclo [2.2.2] octane compounds such as bis (tetrafluoroboric acid) 4-fluoro-1, 4-diazoniabicyclo [2.2.2] octane salts, and N-fluorobis (sulfonyl) amine compounds such as N-fluorobis (phenylsulfonyl) amine. Among these compounds, 1,1,2,3,3, 3-hexafluoro-1-diethylaminopropane compounds are particularly preferable because they are liquid compounds and are easily available.

Examples of the alkali metal salt of the above-mentioned polyfluoro compound include sodium hexafluoroantimonate, potassium hexafluoroantimonate, sodium hexafluoroarsenate, potassium hexafluoroarsenate, lithium hexafluorophosphate, sodium hexafluorophosphate, potassium hexafluorophosphate, sodium pentafluorohydroxy antimonate, potassium pentafluorohydroxy antimonate, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, sodium tetrakis (trifluoromethylphenyl) borate, sodium trifluoro (pentafluorophenyl) borate, potassium trifluoro (pentafluorophenyl) borate, sodium difluoro bis (pentafluorophenyl) borate, and potassium difluoro bis (pentafluorophenyl) borate. Among them, as the polyfluoro compound component in the alkali metal salt of the polyfluoro compound, tetrafluoroboric acid or hexafluorophosphoric acid is preferable. The alkali metal in the alkali metal salt of the polyfluoro compound is preferably at least one alkali metal selected from the group consisting of lithium, sodium, and potassium.

(C) The blending ratio of the component (a) is not particularly limited, but is preferably 0.001 to 80 parts by mass, more preferably 0.001 to 30 parts by mass, and still more preferably 0.005 to 20 parts by mass, based on 100 parts by mass of the (meth) acryloyl group-containing polymer (a). It is sufficient that the larger the content of fluorine atoms in the component (C), the smaller the amount of fluorine atoms incorporated.

The curable composition of the present invention contains the silicon compound having an Si — F bond (C1) and the silicon compound having an Si — F bond (C2) and at least one selected from the group consisting of fluorine compounds, and may be either only one of (C1) and (C2), or both of them may be used in combination. In particular, the curable composition of the present invention preferably contains the silicon compound having an Si-F bond (C1).

The curable composition of the present invention uses a radical polymerization initiator as the component (D). Examples of the radical polymerization initiator include organic peroxides such as diacyl peroxides, ketone peroxides, hydroperoxides, dialkyl peroxides, polyketides, alkyl peresters, and peroxycarbonates. As the initiator, other radical polymerization initiators such as photo radical initiators that generate radicals by light irradiation can be used.

Specific examples of the radical polymerization initiator include benzoyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, dicumyl peroxide, cumene hydroperoxide, and the like. Benzoyl peroxide is most commonly used.

Examples of the photo radical initiator include benzoin ethers such as benzoin ethyl ether, benzoin butyl ether, and benzoin isopropyl ether; benzophenones such as 4,4 '-bisdimethylaminobenzophenones and 4, 4' -bisdiethylaminobenzophenones; acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propanone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-1-propanone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-1-propanone, Acetophenones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -1-butanone, and N, N-dimethylaminoacetophenone; thioxanthones such as 2, 4-diethylthioxanthone, 2-chlorothioxanthone and 2-isopropylthioxanthone; ketals such as benzyl dimethyl ketal and acetophenone dimethyl ketal; phosphine oxides such as 2,4, 6-trimethylbenzoyldiphenylphosphine oxide and phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide; and amine synergists such as ethyl p-dimethylaminobenzoate, 2-dimethylamino ethyl benzoate, bis-4, 4' -dimethylaminobenzophenone, and the like.

Among them, α -aminobenzophenones such as 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -1-butanone are preferable from the viewpoint of deep-cure properties; acylphosphine oxides such as 2,4, 6-trimethylbenzoyldiphenylphosphine oxide and phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide; and photo radical initiators having light absorption at long wavelengths (for example, 300nm) such as amine synergists, and acylphosphine oxides and amine synergists are more preferable.

Further, α -hydroxyacetophenones such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1- [4- (2-hydroxyethoxy) -phenyl- ] -2-hydroxy-2-methyl-1-propanone, and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-1-propanone are preferable because they can improve surface curability.

The radical initiator is generally diluted with an inorganic substance such as calcium sulfate or calcium carbonate, or a diluent such as dimethyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, an aliphatic hydrocarbon, an aromatic hydrocarbon, a silicone oil, a liquid paraffin, a polymerizable monomer, or water.

The radical initiator of component (D) is preferably used in an amount of 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the (meth) acryloyl group-containing polymer (a).

The curable composition of the present invention may contain, as required, various additives such as a reactive diluent, a co-catalyst, a silane coupling agent (adhesion-imparting agent) other than the component (B), a photosensitizer, an extender, a diluent, a plasticizer, a moisture absorber, a condensation reaction-promoting catalyst other than the component (C), a physical property modifier for improving tensile properties, a reinforcing agent, a coloring agent, a flame retardant, a sagging inhibitor, an antioxidant, an antiaging agent, an ultraviolet absorber, a solvent, a perfume, a pigment, and a dye.

Reactive diluents may also be used in the compositions of the present invention. As the reactive diluent, various monomers such as a monofunctional monomer and/or a polyfunctional monomer having a low molecular weight can be used. Specific examples of the monomer usable as the reactive diluent include a compound having a (meth) acryloyloxy group, a compound having a (meth) acrylamide group, and an N-vinyl compound.

The monomer having a (meth) acryloyloxy group is not particularly limited as long as it is a compound having one or more (meth) acryloyloxy groups, and for example, monofunctional (meth) acrylates, polyfunctional (meth) acrylates, and the like can be used.

Examples of the monofunctional (meth) acrylate include (meth) acrylic acid, ethyl (meth) acrylate, 1-methoxyethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth), Dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate, nonylphenoxypentaethylene glycol (meth) acrylate, dimethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, nonylphenoxyethyl (meth), 2-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, epichlorohydrin-modified butyl (meth) acrylate, epichlorohydrin-modified phenoxy (meth) acrylate, ethylene oxide-modified phthalic acid (meth) acrylate, ethylene oxide-modified succinic acid (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, morpholinylethyl (meth) acrylate, ethylene oxide-modified phosphoric acid (meth) acrylate, and the like.

Examples of the polyfunctional acrylates include 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol diacrylate, caprolactone-modified hydroxypivalate neopentyl glycol diacrylate, neopentyl glycol-modified trimethylolpropane di (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, dicyclopentenyl diacrylate, ethylene oxide-modified dicyclopentenyl di (meth) acrylate, di (meth) acryloyl isocyanurate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene oxide-modified ethylene oxide, Ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, and the like. The polyfunctional acrylates are preferred in view of the difficulty in inhibiting polymerization due to oxygen in the air.

Specific examples of the (meth) acrylamide and the N-vinyl compound include N-methyl (meth) acrylamide, N-N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-N-butyl (meth) acrylamide, N-sec-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-N-hexyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-dimethylaminoethyl (meth) acrylamide, N-dimethylaminopropyl (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-di-N-propyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-N-hexyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-dimethylaminoethyl (meth) acrylamide, N, (meth) acrylamide derivatives such as N, N-diisopropyl (meth) acrylamide, N-di-N-butyl (meth) acrylamide, N-dihexyl (meth) acrylamide, and N, N-dibenzyl (meth) acrylamide, and phthalimidoethyl acrylate, N-vinylpyrrolidone, and N-vinylcaprolactam.

The reactive diluent may be used not only as a single monomer but also as a mixture of a plurality of monomers. The amount of the reactive diluent added per unit amount of the polymer having a (meth) acryloyl group of component (a) is preferably a predetermined amount or less. By setting the amount of the reactive diluent added per unit amount of the polymer having a (meth) acryloyl group of component (a) to a predetermined amount or less, the coating properties and printability of the curable composition can be controlled. For example, the reactive diluent is preferably used in an amount of 0.1 to 50 parts by mass, preferably 0.5 to 40 parts by mass, and more preferably 1 to 35 parts by mass of the monomer to 100 parts by mass of the (meth) acryloyl group-containing polymer of the component (a).

In the present invention, a base may be used. And functions as a co-catalyst for improving the catalytic action of the fluorine-containing compound of component (C). The base is not particularly limited, but an organic base such as an amine compound is preferable. Amidines such as 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) and 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN) are particularly preferable as tertiary amines.

Further, a photobase generator which generates a base when irradiated with light may be used as the base. The photobase generator does not act as a base before the light irradiation, and therefore, it is desirable to use the photobase generator when the base does not act as expected in the curable composition. The photobase generator is preferably a photolatent tertiary amine such as a benzylammonium salt derivative, a benzyl-substituted amine derivative, an α -aminoketone derivative, or an α -aminoketone derivative.

When an alkali or an alkali-generating agent is used, the mixing ratio thereof is not particularly limited, but is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, and still more preferably 0.5 to 30 parts by mass, based on 100 parts by mass of the (meth) acryloyl group-containing polymer (a).

The curable composition of the present invention may further contain a silane coupling agent other than the component (B), and particularly preferably contains epoxy group-containing silanes. The silane coupling agent functions as an adhesion imparting agent. Examples of the silane coupling agent include epoxy group-containing silanes such as γ -glycidoxypropyltrimethoxysilane, γ -glycidoxypropyltriethoxysilane, γ -glycidoxypropylmethyldimethoxysilane and β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane; amino group-containing silanes such as γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane, γ -aminopropylmethyldimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltriethoxysilane, N- (β -aminoethyl) - γ -aminopropylmethyldimethoxysilane, and 1, 3-diaminoisopropyltrimethoxysilane; ketimine-type silanes such as N- (1, 3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine and N- (1, 3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propylamine; mercapto group-containing silanes such as γ -mercaptopropyltrimethoxysilane and γ -mercaptopropylmethyldimethoxysilane; silanes containing a vinyl-type unsaturated group such as vinyltrimethoxysilane and vinyltriethoxysilane; silanes containing chlorine atoms such as gamma-chloropropyltrimethoxysilane; silanes containing an isocyanate group such as γ -isocyanatopropyltriethoxysilane and γ -isocyanatopropylmethyldimethoxysilane; alkylsilanes such as hexyltrimethoxysilane, hexyltriethoxysilane and decyltrimethoxysilane; and phenyl-containing silanes such as phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane, but are not limited thereto. Further, the amino group-containing silanes may be modified with an amino group by reacting the amino group-containing silanes with the silane-containing epoxy group-containing compound, isocyanate group-containing compound, or (meth) acryloyl group-containing compound.

The mixing ratio of the silane coupling agent is not particularly limited, but is preferably 0.01 to 20% by mass, more preferably 0.025 to 10% by mass in the composition. These silane coupling agents may be used alone, or two or more of them may be used in combination.

As the photosensitizer, a carbonyl compound having a triplet energy of 225-310kJ/mol is preferable, for example, examples thereof include xanthone, thioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, isopropylthioxanthone, phthalimide, anthraquinone, 9, 10-dibutoxyanthracene, acetophenone, propiophenone, benzophenone, acylnaphthalene, 2 (acylmethylene) thiazoline, 3-acylcoumarin and 3, 3' -carbonylbiscoumarin, perylene, coronene, tetracene, benzanthracene, phenothiazine, flavin, acridine, and coumarone, with thioxanthone, 3-acylcoumarin and 2 (acylmethylene) thiazoline being preferred, and thioxanthone and 3-acylcoumarin being more preferred.

The compounding ratio of the photosensitizer is not particularly limited, but is preferably 0.01 to 5% by mass, more preferably 0.025 to 2% by mass in the composition. These photosensitizers may be used alone or in combination of two or more.

Examples of the additive include talc, clay, calcium carbonate, magnesium carbonate, anhydrous silicon, hydrous silicon, calcium silicate, titanium dioxide, and carbon black. These may be used alone or in combination of two or more.

The curable composition of the present invention may further contain a diluent. The physical properties such as viscosity can be adjusted by blending a diluent. The diluent is not particularly limited, and examples thereof include various solvents such as saturated hydrocarbon solvents such as normal paraffin and isoparaffin, α -olefin derivatives such as リニアレンダイマー (trade name, manufactured by shinko corporation), aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol and diacetone alcohol, ester solvents such as ethyl acetate, butyl acetate, amyl acetate and cellosolve acetate, citrate solvents such as triethyl acetylcitrate and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. The blending ratio of the diluent is not particularly limited, but is preferably 0.01 to 20% by mass, more preferably 0.025 to 10% by mass in the composition. These diluents may be used alone or in combination of two or more.

Examples of the plasticizer include phosphoric acid esters such as tributyl phosphate and tricresyl phosphate, phthalic acid esters such as dioctyl phthalate, aliphatic monocarboxylic acid esters such as glycerol monooleate, aliphatic dibasic acid esters such as dioctyl adipate, hydrocarbon plasticizers such as polypropylene glycols, liquid polybutene, liquid polyisobutylene, and low molecular weight polybutadiene. These may be used alone or in combination of two or more.

The moisture absorbent is preferably the aforementioned silane coupling agent or silicate. The silicate is not particularly limited, and examples thereof include tetraalkoxysilanes and partial hydrolysis condensates thereof, more specifically tetraalkoxysilanes (tetraalkylsilicates) such as tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, and tetra-t-butoxysilane, and partial hydrolysis condensates thereof.

As the condensation reaction promoting catalyst other than the component (C), a known condensation reaction promoting catalyst can be widely used, and examples thereof include, but are not particularly limited to, organometallic compounds, acids, and bases such as amines. Examples of the organic metal compounds include organic tin compounds such as stannous octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin bisacetylacetonate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin dioctadecyloxy, tin octoate and tin naphthenate; dialkyltin oxides such as dimethyltin oxide, dibutyltin oxide and dioctyltin oxide; a reactant of dibutyltin oxide and phthalic acid ester, etc.; titanates such as tetrabutyl titanate and tetrapropyl titanate; organoaluminum compounds such as aluminum triacetylacetonate, aluminum triethylacetoacetate and diisopropoxyaluminum ethylacetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead organic acids such as lead octoate and lead naphthenate; bismuth octoate, bismuth neodecanoate, bismuth abietate and other organic acid bismuth. Examples of the silanol condensing catalyst include other known acidic catalysts and basic catalysts. However, depending on the amount of the organotin compound added, the toxicity of the resulting curable composition may become strong.

The method for producing the curable composition of the present invention is not particularly limited, and for example, the curable composition can be produced by mixing predetermined amounts of the components (a), (B), (C), and (D) and, if necessary, other components, and then degassing and stirring the mixture. The order of mixing the components and other components is not particularly limited and may be appropriately determined.

The curable composition of the present invention may be either a one-pack type or a two-pack type, if necessary, but it is particularly preferably used as a one-pack type.

The curable composition of the present invention is cured by active energy ray or heat. Thus, the photocurable composition can be used as a photocurable composition for curing by light irradiation, and can be cured at normal temperature (for example, 23 ℃), but can be accelerated by heating if necessary.

When the curable composition of the present invention is used as a photocurable composition, the conditions of irradiation are not particularly limited, but when active energy rays are irradiated at the time of curing, in addition to rays such as ultraviolet rays, visible rays, and infrared rays, electromagnetic waves such as X-rays and γ -rays, electron beams, proton beams, and neutron beams can be used as the active energy rays, but from the viewpoints of curing speed, ease of acquisition and price of an irradiation apparatus, ease of handling under sunlight or general illumination, and the like, curing by irradiation with ultraviolet rays or electron beams is preferable, and curing by irradiation with ultraviolet rays is more preferable. The ultraviolet light also includes g-line (wavelength of 436nm), h-line (wavelength of 405nm), i-line (wavelength of 365nm), and the like. The active energy ray source is not particularly limited, but examples thereof include a high-pressure mercury lamp, a low-pressure mercury lamp, an electron beam irradiation device, a halogen lamp, a light-emitting diode, a semiconductor laser, and a metal halide lamp, depending on the nature of the photobase generator used.

The irradiation energy is preferably 10 to 20000mJ/cm in the case of ultraviolet ray, for example²More preferably 50 to 10000mJ/cm². If less than 10mJ/cm²When the amount is more than 20000mJ/cm, the curability may be insufficient²Even if the light is irradiated to a required level or more, time and cost are wasted, and the substrate may be damaged.

When the curable composition of the present invention is cured by heat, the curing temperature is preferably 30 to 200 ℃, more preferably 80 to 180 ℃.

The curable composition of the present invention is excellent in adhesion to a substrate and moisture resistance of a cured product, and is suitable as a moisture-proof material. In particular, the use of a polyisobutylene polymer having a (meth) acryloyl group as (a) the polymer having a (meth) acryloyl group can significantly improve the moisture resistance of the coating film.

The moisture barrier material of the present invention is formed from the curable composition of the present invention. The method of using the moisture-proof material of the present invention is not particularly limited, but when high moisture resistance is required, the coating thickness to an adherend is preferably 100 μm or more, more preferably 200 μm or more. The moisture-proof material of the present invention is excellent in adhesion to a substrate such as glass or metal in addition to moisture-proof performance, and is suitable for sealing mirrors and glass, particularly suitable for sealing the edge or outer periphery of mirrors and laminated glass.

The laminated glass is laminated with a plurality of glasses. The laminated glass is sufficient if a plurality of transparent materials are laminated, but generally, glass, a resin layer, and glass are laminated in this order. The material constituting the resin layer has adhesiveness to glass, and is not particularly limited if the resin layer is transparent.

In the present invention, a laminated glass can be obtained in the following manner. First, a moisture-proof material made of the curable composition of the present invention is applied around a laminated glass whose outer periphery is not sealed. The coating method is not particularly limited, and examples thereof include methods known in the art, which are performed by brush coating, extrusion, spray coating, gravure coating, kiss roll, dispenser, and air knife.

The moisture barrier material is then cured. The moisture barrier material of the present invention can be cured by an active energy ray or heat, and can be cured by the same method as that for the curable composition of the present invention described above.

The curable composition of the present invention can be suitably used as a sealing material, an adhesive, a sealing material, an adhesive material, a coating material, a potting material, a coating material, a putty material, a primer, and the like. The curable composition of the present invention can be suitably used, for example, as an encapsulating material for use in electric/electronic products, for example, as an encapsulating material for an organic EL element protecting agent for products including organic EL elements; coating agents used for coatings for the purpose of moisture proofing and insulation, for mounting circuit boards and the like, for coating mirrors, solar power panels, and for coating the outer peripheral portions of panels; sealants for building and industrial use, such as sealants for laminated glass and sealants for vehicles; electric/electronic component materials such as solar cell back encapsulant; an electric insulating material such as an insulating coating material for electric wires/cables; a binder; an adhesive; an elastic adhesive; contact adhesives, and the like.

When the curable composition of the present invention is used as an encapsulating material, the method of applying the composition to an adherend is not particularly limited, and for example, known application methods such as brush coating, extrusion, spray coating, gravure coating, kiss roll, dispenser, and air knife can be used. When moisture resistance is required for the sealing material, the coating thickness is preferably 100 μm or more, and more preferably 200 μm or more.

When the curable composition of the present invention is used as an adhesive, the method of applying the composition to an adherend is not particularly limited, but an application method such as screen printing, stencil printing, roll printing, or spin coating is preferably used. When used as a photocurable composition, the coating thickness to an adherend is as thin as possible, and the curing is easy, and is 500 μm or less, preferably 200 μm or less, more preferably 100 μm or less, and particularly preferably 50 μm or less.

When the curable composition of the present invention is used as a coating agent, the method of applying the composition to an adherend is not particularly limited, but a coating method such as brush coating, extrusion, spray coating, gravure coating, kiss roll, dispenser, air knife coating, and a method of coating with a disk (for example, international publication No. 2010/137418) is preferable. When moisture resistance is required for the coating agent, the coating thickness is preferably 100 μm or more, and more preferably 200 μm or more.

Examples

The present invention will be described more specifically with reference to examples, but these examples are illustrative and should not be construed as limiting.

1) Determination of number average molecular weight

The number average molecular weight was measured by Gel Permeation Chromatography (GPC) under the following conditions unless otherwise specified. In the present invention, the molecular weight of the maximum frequency measured by GPC under the measurement conditions and converted to standard polyethylene glycol is referred to as the number average molecular weight.

An analysis device: alliance (Waters corporation), model 2410 refractive index detector (Waters corporation), model 996 multi-wavelength detector (Waters corporation), Milleniam data processing unit (Waters corporation)

Column chromatography: plgel GUARD + 5. mu. mMixed-Cx 3 roots (50X 7.5mm, 300X 7.5 mm; manufactured by Polymer Lab)

Flow rate: 1 mL/min

Converted polymer: polyethylene glycol

Measurement temperature: 40 deg.C

Solvent in GPC measurement: THF (tetrahydrofuran)

2) Measurement of NMR

NMR was measured using the following measurement apparatus.

FT-NMR measurement apparatus: synthesis of a polyisobutylene polymer having an acryloyl group at the end thereof, JNM-ECA500(500MHz) manufactured by JEOL Ltd (Synthesis example 1)

After nitrogen gas was replaced in a container of a 5L separable flask, 280mL of n-hexane (after drying with a molecular sieve) and 2500mL of butyl chloride (after drying with a molecular sieve) were added thereto, and the mixture was cooled to-70 ℃ under stirring in a nitrogen atmosphere. Next, 1008mL (10.7mol) of isobutylene, 27.4g (0.119mol) of p-dicumyl chloride and 1.33g (0.014mol) of α -picoline were added thereto. After the reaction mixture was cooled to-70 degrees, 5.2mL (0.047mol) of titanium tetrachloride was added and polymerization was started. After the start of the polymerization, the residual isobutylene concentration was measured by gas chromatography, and about 200g of methanol was added at a stage where the residual isobutylene amount was less than 0.5%. After the solvent and the like were distilled off from the reaction solution, the product was dissolved in 2L of n-hexane, and washed with 1L of pure water three times. The solvent was distilled off under reduced pressure, and the resulting polymer was vacuum-dried at 80 ℃ for 24 hours, whereby a chlorine-terminated polyisobutylene-based polymer A-1 was obtained. The molecular weight of polymer A-1 obtained by Size Exclusion Chromatography (SEC) was determined by polystyrene conversion, and as a result, Mw: 5800, Mn: 5200, Mw/Mn: 1.12.

then, 15.2g of the obtained polyisobutylene polymer A-1100 g, 540ml of butyl chloride, 60ml of n-hexane, and 2-phenoxyethyl acrylate (manufactured by Tokyo chemical Co., Ltd.) were put in a 1L separable flask and cooled to-70 ℃ with stirring. After cooling to below-70 degrees celsius, 22ml of titanium tetrachloride was added. After stirring was continued at-70 ℃ for 6 hours, 200ml of methanol was added to stop the reaction. The supernatant was separated from the reaction solution, the solvent and the like were distilled off, and then the product was dissolved in 650ml of n-hexane, washed with 500ml of pure water three times, reprecipitated from methanol, the solvent was distilled off under reduced pressure, and the resulting polymer was vacuum-dried at 80 degrees for 24 hours, whereby the objective acryloyl group-terminated polyisobutylene-based polymer was obtained. The molecular weight of the polymer obtained by Size Exclusion Chromatography (SEC) was determined by polystyrene conversion, and as a result, Mw: 6000, Mn: 5400, Mw/Mn: 1.11. further, Fn of an acryloyl group introduced into the terminal of the obtained acryloyl group-terminated polyisobutylene (the number of acryloyl groups per 1 molecule of polyisobutylene polymer) was 1.93.

(Synthesis example 2) Synthesis of fluorinated Polymer

In a new flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser, propylene oxide was reacted in the presence of a zinc hexacyanocobaltate-ethylene glycol dimethyl ether complex catalyst using polyoxypropylene glycol having a molecular weight of about 2000 as an initiator to obtain polyoxypropylene glycol having a hydroxyl value-equivalent molecular weight of 14500 and a molecular weight distribution of 1.3. To the resulting polyoxypropylene glycol, a methanol solution of sodium methoxide was added, and methanol was distilled off under heating and reduced pressure to convert the terminal hydroxyl group of the polyoxypropylene glycol into a sodium alkoxide, thereby obtaining a polyoxyalkylene polymer.

Subsequently, the polyoxyalkylene polymer is reacted with allyl chloride to remove unreacted allyl chloride, and the resulting product is purified to obtain a polyoxyalkylene polymer having an allyl group at the terminal. To the polyoxyalkylene polymer having an allyl group at the terminal, 150ppm of an isopropyl alcohol solution of a vinylsiloxane platinum complex having a platinum content of 3 wt% was added, and methyldimethoxysilane as a silicon hydride compound was reacted to obtain a polyoxyalkylene polymer having a methyldimethoxysilyl group at the terminal.

The molecular weight of the resulting polyoxyalkylene polymer having a methyldimethoxysilyl group at the terminal was measured by GPC, and the peak top molecular weight was 15000 and the molecular weight distribution was 1.3. The number of the terminal methyldimethoxysilyl groups was 1.7 per 1 molecule as determined by 1H-NMR.

In a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, degassing under reduced pressure, replacing with nitrogen, and adding BF under a nitrogen stream₃Diethyl ether complex 2.4g, heated to 50 ℃. Subsequently, a mixture of dehydrated methanol (1.6 g) was slowly added dropwise thereto and mixed. 100g of the obtained polymer and 5g of toluene were charged into a new flask equipped with a stirrer, a nitrogen inlet, a thermometer, and a reflux condenser. After stirring at 23 ℃ for 30 minutes, the mixture was heated to 110 ℃ and stirred under reduced pressure for 2 hours to remove toluene. 4.0g of the mixture obtained in the previous step was slowly added dropwise to the vessel under a stream of nitrogen, and after completion of the dropwise addition, the reaction temperature was raised to 120 ℃ to react for 30 minutes. After the reaction, the unreacted product was removed by degassing under reduced pressure. A polyoxyalkylene polymer having a fluorosilane group at the terminal (hereinafter referred to as a fluorinated polymer) was obtained. 1HNMR spectrum of the obtained fluorinated polymer (NMR 400 manufactured by Shimazu Co., Ltd., in CDCl)₃Measurement in solvent), and as a result, the polymer was measured for its silylmethylene group (-CH) with the polymer as the raw material₂-Si) disappears, and a broad peak appears on the low magnetic field side (0.7 ppm-).

(examples 1 to 10)

In accordance with the compounding ratios shown in table 1, a polymer having a (meth) acryloyl group as component (a), a silane coupling agent having a (meth) acryloyl group as component (B), a fluorine-based compound as component (C), a radical initiator as component (D), and other components such as a reactive diluent were added to a flask equipped with a stirrer, a thermometer, a nitrogen gas inlet, a monomer charging tube, and a water-cooled condenser, and stirred and dissolved to obtain a curable composition. The adhesion to an adherend and the moisture permeability of the obtained curable composition were evaluated by the following methods.

In table 1, the amount of each of the compounding ingredients is represented by g, and the details of the compounding ingredients are as follows.

*1: polymer obtained in Synthesis example 1

*2: ultraviolet UV3700B manufactured by Nippon synthetic chemical industry Co., Ltd., urethane acrylate Polymer

*3: IBXA, chemical Co., Ltd

*4: KAYARAD R-684, PRODUCED BY CHEMICAL MEDICINE

*5: 3-Acryloxypropyltrimethoxysilane, KBM5103, manufactured by shin-Etsu chemical Co., Ltd

*6: 3-methacryloxypropyltrimethoxysilane, KBM503, manufactured by shin-Etsu chemical Co., Ltd

*7: 3-glycidoxypropyltriethoxysilane, KBM403, manufactured by shin-Etsu chemical Co., Ltd

*8: tris- (trimethoxysilylpropyl) isocyanurate, KBM9659, from shin-Etsu chemical Co

*9: organic Polymer having SiF bond obtained in Synthesis example 2

*10：BF₃Ether complexes

*11: dioctyltin, NEOSTANN U830, manufactured by Nindong Chemicals Ltd

*12: aluminum Diethylacetoacetate/monoacetylacetone, aluminum chelate D, product of Fine Chemical Co., Ltd

*13: IRGACURE 184 manufactured by BASF corporation

*14: IRGACURE 1173, manufactured by BASF

*15: 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone, IRGACURE379EG, manufactured by BASF

1) Evaluation of adhesion (adhesiveness) to substrate

The curable composition was applied to an adherend (15cm square glass plate) with a thickness of 100 μm using a glass rod, and UV irradiation (irradiation conditions: UV-LED365nm, illuminance: 1000 mW/cm)²The cumulative light quantity: 3000mJ/cm²) The curable composition is cured. After irradiation, at 23 deg.C,Two days at 50% RH. After the aging, a 100-mesh checkerboard test of 2mm square was performed according to the JISK5600 coating general test method. The results are shown in Table 1.

2) Evaluation of moisture permeability

The curable composition obtained in example 1 was coated on a 15cm square Teflon (registered trademark) sheet having a thickness of 220 μm, and UV-irradiated (irradiation conditions: UV-LED365nm, illuminance: 1000 mW/cm)²The cumulative light quantity: 3000mJ/cm²) The curable composition is cured. After irradiation, the mixture was aged at 23 ℃ and 50% RH for two days. After the aging, the moisture permeability at 50 ℃ and 85% RH was measured by the moisture permeability test method of JIS Z0208 moisture-proof packaging material using the cured film, and the moisture permeability was 10.5g/m² 24h。

Comparative examples 1 to 8

Curable compositions were prepared and adhesion was evaluated in the same manner as in examples 1 to 10, according to the compounding ratios shown in table 1. The evaluation results are shown in table 1.

Claims (6)

1. A curable composition characterized by containing:

(A) a polyisobutylene-based polymer having a (meth) acryloyl group;

(B) a silane coupling agent having a (meth) acryloyl group;

(C) (C1) a silicon compound having an Si-F bond, and/or (C2) at least one fluorine-based compound selected from the group consisting of boron trifluoride, a complex of boron trifluoride, a fluorinating agent and an alkali metal salt of a polyfluoro compound; and

(D) a free-radical initiator, which is a free-radical initiator,

the component (B) contains 5 to 20 parts by mass of a (meth) acryloyl group-containing silane coupling agent per 100 parts by mass of the (meth) acryloyl group-containing polymer of the component (A).

2. The curable composition according to claim 1, wherein (D) is a photo radical initiator.

3. An encapsulating material formed from the curable composition according to claim 1 or 2.

4. An electric/electronic product manufactured using the encapsulating material according to claim 3.

5. A moisture barrier material formed from the curable composition of claim 1 or 2.

6. A product comprising a mirror or glass made using the moisture barrier material of claim 5.