WO2016152392A1 - Curable composition - Google Patents
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- WO2016152392A1 WO2016152392A1 PCT/JP2016/056027 JP2016056027W WO2016152392A1 WO 2016152392 A1 WO2016152392 A1 WO 2016152392A1 JP 2016056027 W JP2016056027 W JP 2016056027W WO 2016152392 A1 WO2016152392 A1 WO 2016152392A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
Definitions
- the present invention relates to a curable composition, and particularly to a curable composition having excellent adhesion to a substrate.
- Patent Document 1 discloses an active energy ray-curable resin composition containing an unsaturated compound that is useful as a cladding material for optical fibers. On page 9 of Patent Document 1, glass or It is described that adhesion to a substrate such as plastic is improved.
- Patent Document 2 discloses an active energy ray-curable resin composition containing a reactive monomer useful as an optical fiber cladding material, and a resin composition to which a coupling agent and a condensation reaction promoting catalyst are added. It is described that since the catalyst is used, the adhesion with the substrate is further improved.
- Patent Document 3 and Patent Document 4 disclose a polymer having a (meth) acryloyl group useful as a bonding agent (adhesive) for an image display device member, (meth) acryloylsilane which is a coupling agent, and acceleration of condensation reaction.
- a resin composition to which a catalyst has been added is described.
- adhesion to the substrate is an extremely important characteristic and further improvement is desired.
- JP 62-250047 A Japanese Patent Laid-Open No. 5-32712 JP 2013-088455 A JP 2013-129754 A
- the problem to be solved by the present invention is a curable composition containing a radical polymerizable unsaturated compound, a coupling agent and a condensation reaction accelerating catalyst and having improved adhesion to a substrate. It is providing the curable composition which gives.
- the curable composition of the present invention has (A) a polymer having a (meth) acryloyl group, (B) a silane coupling agent having a (meth) acryloyl group, and (C) (C1) having a Si—F bond.
- a silicon compound and / or (C2) one or more fluorine compounds selected from the group consisting of boron trifluoride, boron trifluoride complexes, fluorinating agents and alkali metal salts of polyvalent fluoro compounds, and ( D) A radical initiator is contained.
- the (A) is preferably a polyisobutylene polymer having a (meth) acryloyl group.
- the polyisobutylene polymer having the (meth) acryloyl group moisture proof performance can be improved.
- (D) is a photo radical initiator.
- the sealing material of the present invention is a sealing material made of the curable composition of the present invention.
- the electrical / electronic product of the present invention is an electrical / electronic product using the sealing material of the present invention.
- the moisture-proof material of the present invention is a moisture-proof material comprising the curable composition of the present invention.
- the product of the present invention is a product including a mirror or glass using the moisture-proof material of the present invention.
- the curable composition of the present invention has an effect of giving a cured product having excellent substrate adhesion by using a specific fluorine compound as a condensation reaction promoting catalyst.
- 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, or a (meth) acrylimide group.
- the polymer which has is mentioned. In this, it is preferable to use the compound which has a (meth) acryloyloxy group.
- the number of (meth) acryloyl groups in the polymer is preferably 1.0 or more, more preferably 1.1 or more, and particularly preferably 1.5 or more per molecule of the polymer. Moreover, two or more may be sufficient.
- a (meth) acryloyl group shows 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, and a polyester having a (meth) acryloyloxy group.
- Examples thereof include an epoxy polymer, 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.
- (meth) acryloyloxy groups into the polymer utilizes functional groups such as hydroxyl groups, epoxy groups and halogen atoms present at the ends of the polymer chain, such as (meth) acrylic acid and (meth) acrylic acid halides. This can be achieved by reacting a (meth) acrylic acid derivative.
- An 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 in which the main chain is a (meth) acrylic ester polymer.
- Such a polymer is preferably produced by anionic polymerization or radical polymerization, and radical polymerization is more preferable because of the versatility of the monomer or ease of control.
- radical polymerizations 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.
- living radical polymerization is used, a polymer having a (meth) acryloyloxy group at the end of the polymer chain can be produced.
- MMA polymethyl methacrylate
- HEMA (2-hydroxyethyl methacrylate
- BMA butyl methacrylate
- an acrylic polymer having a (meth) acryloyloxy group for example, poly (n-butyl acrylate) having an acryloyl group at both ends described in Production Example 1 of WO2012 / 008127 and the production of the same publication
- acrylic polymers having a (meth) acryloyloxy group examples include macromonomers AA-6 and AB-6 manufactured by Toa Gosei Co., Ltd., RC-100C and RC-200C manufactured by Kaneka Corporation. RC-300C and the like.
- hydrocarbon polymers examples include ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymers of butadiene and acrylonitrile and / or styrene.
- hydrocarbon polymers include polymers, polybutadiene, isoprene, copolymers of butadiene and acrylonitrile and styrene, and hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers. .
- saturated hydrocarbon polymers such as hydrogenated polyolefin polymers such as polyisobutylene, hydrogenated polyisoprene and hydrogenated polybutadiene have a large gas barrier property and are suitable for applications that require gas barrier properties.
- polyisobutylene is preferable because of its high gas barrier properties.
- Such a polymer can be suitably used for a moisture-proof coating of a mirror such as a mirror back surface coating or a mirror end surface coating.
- a hydrocarbon-based polymer having a (meth) acryloyloxy group can introduce a (meth) acryloyloxy group using a polymer having a hydroxyl group.
- a polyisobutylene polymer having a (meth) acryloyloxy group can be obtained by the methods described in JP2013-035901A and International Publication WO2013-047314A.
- a polyester polymer having a (meth) acryloyloxy group is also called a polyester acrylate.
- Such a polymer can be obtained by dehydrating and condensing a polyester polyol and (meth) acrylic acid.
- examples of the polyester polyol include a reaction product of a polyol and a carboxylic acid, or an anhydride thereof.
- Polyols include 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, neo Low molecular weight polyols such as pentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol and dipentaerythritol, and their alkylene oxide adducts Etc.
- Low molecular weight polyols such as pentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,6-hexanedio
- Carboxylic acid or anhydride thereof includes dibasic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and trimellitic acid or the like.
- dibasic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and trimellitic acid or the like.
- An anhydride etc. are mentioned.
- An epoxy resin having a (meth) acryloyloxy group is also referred to as an epoxy acrylate, and (meth) acrylic acid can be added to the epoxy resin.
- the epoxy resin include aromatic epoxy resins and aliphatic epoxy resins.
- aromatic epoxy resins examples include resorcinol diglycidyl ether; di- or polyglycidyl ethers of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or its alkylene oxide adducts; phenol novolac type epoxy resins and cresol novolac type epoxy resins Novolak type epoxy resin; glycidyl phthalimide; o-phthalic acid diglycidyl ester and the like.
- the document “Epoxy Resin-Recent Advances” (Shojodo, published in 1990), Chapter 2 and the document “Polymer Processing”, Vol. 9, Volume 22, Epoxy Resin [Polymer Press, Compounds published on pages 4 to 6 and 9 to 16 of "published in 1973” can be used as the aromatic epoxy resin.
- aliphatic epoxy resins include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; polyalkylenes such as diglycidyl ethers of polyethylene glycol and polypropylene glycol Diglycidyl ether of glycol; diglycidyl ether of neopentyl glycol, dibromoneopentyl glycol and its alkylene oxide adducts; di- or triglycidyl ether of trimethylolethane, trimethylolpropane, glycerin and its alkylene oxide adducts, and pentaerythritol And polyglycidyl ethers of polyhydric alcohols such as di, tri or tetraglycidyl ethers of the alkylene oxide adducts thereof Ether; hydrogenated bisphenol A and di- or polyglycid
- epoxy resin having a (meth) acryloyloxy group examples include bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, epichlorohydrin modified bisphenol A di (meth) acrylate, and ethylene oxide.
- examples thereof include modified bisphenol S di (meth) acrylate.
- a polyurethane-based polymer having a (meth) acryloyloxy group is also called a urethane (meth) acrylate, and further contains a hydroxyl group (meth) with respect to an isocyanate group-terminated polyurethane obtained by reacting a polyol with an excess of an organic polyisocyanate. It can be obtained by reacting acrylate.
- examples of the polyol include a low molecular weight polyol, a polyether polyol, a polyester polyol, and a polycarbonate polyol.
- examples of the low molecular weight polyol include ethylene glycol, propylene glycol, cyclohexanedimethanol and 3-methyl-1,5-pentanediol
- examples of the polyether polyol include polyethylene glycol and polypropylene glycol.
- organic polyisocyanate examples include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
- hydroxyl group-containing (meth) acrylate examples include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
- urethane (meth) acrylate polymers may be produced based on a known synthesis method. For example, in the presence of an addition catalyst such as dibutyltin dilaurate, an organic isocyanate and a polyol component to be used are heated and stirred to cause an addition reaction, and further, a hydroxyalkyl (meth) acrylate is added, followed by heating and stirring to cause an addition reaction.
- an addition catalyst such as dibutyltin dilaurate
- an organic isocyanate and a polyol component to be used are heated and stirred to cause an addition reaction, and further, a hydroxyalkyl (meth) acrylate is added, followed by heating and stirring to cause an addition reaction.
- Polyether (meth) acrylate polymers include polyalkylene glycol (meth) acrylate and polyalkylene glycol (meth) diacrylate. This polymer is polyalkylene glycol with (meth) acrylic acid and (meth) acrylic acid. It can obtain by making the derivative
- polyalkylene glycol (meth) acrylates examples include methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, 2-ethylhexyl polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate , Nonylphenyl polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate and the like.
- polyalkylene glycol (meth) diacrylate examples include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di ( And (meth) acrylate, polypropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate.
- a polymer having a (meth) acrylamide group uses a polymer having an amino group instead of the hydroxyl group of a polymer having a hydroxyl group such as a polyol as a raw material of the polymer having a (meth) acryloyloxy group. ) It can be obtained by reacting acrylic acid chloride.
- the curable composition of the present invention uses a silane coupling agent having (B) (meth) acryloyl group.
- a 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 has a hydrolyzable group bonded to a silicon atom, and is a group that can be 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 which is a hydrolyzable group is bonded to a silicon atom.
- Specific examples of the crosslinkable silicon group include a trimethoxysilyl group and a methyldimethoxysilyl group.
- the silane coupling agent acts as an adhesion promoter.
- Examples of the (B) component silane coupling agent include compounds such as ⁇ -methacryloyloxypropyltrimethoxysilane and ⁇ -acryloyloxypropylmethyldimethoxysilane.
- the silane coupling agent having a (meth) acryloyl group as the component (B) is 1 to 20 parts by mass, more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the polymer having the (meth) acryloyl group as the component (A). Is preferred.
- the curable composition of the present invention includes (C) (C1) a silicon compound having a Si—F bond, and / or (C2) boron trifluoride, a complex of boron trifluoride, a fluorinating agent, and a polyvalent fluoro compound. Containing one or more fluorine-based compounds selected from the group consisting of alkali metal salts of In the curable composition of this invention, the hardened
- Component (C) acts as a condensation reaction promoting catalyst with which the crosslinkable silicon group of the silane coupling agent of component (B) reacts.
- the (C1) silicon compound having a Si—F bond known compounds having a group having a Si—F bond (hereinafter sometimes referred to as a fluorosilyl group) can be widely used.
- a fluorosilyl group organosilicon compounds having a fluorosilyl group are preferred, and organic polymers having a fluorosilyl group are more suitable because of high safety.
- the low molecular organosilicon compound which has a fluoro silyl group from the point from which a compound becomes low viscosity is preferable.
- Examples of the silicon compound having (C1) Si—F bond include an inorganic compound having a fluorosilyl group represented by the following formula (1), a low-molecular organic silicon compound having this fluorosilyl group, and an organic compound having this fluorosilyl group.
- a polymer etc. are mentioned as a suitable example.
- R 1 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R 2 3 SiO— (R 2 is independently substituted or unsubstituted having 1 to 20 carbon atoms. Or an organosiloxy group represented by a fluorine atom).
- a is any one of 1 to 3, and a is preferably 3.
- X is a hydroxyl group or a hydrolyzable group other than fluorine
- b is any of 0 to 2
- c is any of 0 to 2
- a + b + c is 3.
- a plurality of X are present, they may be the same or different.
- R 1 in the formula (1) is, for example, an alkyl group such as a methyl group or an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, or R 2
- R 2 3 SiO— a triorganosiloxy group represented by R 2 3 SiO— which is a methyl group, a phenyl group or the like. Of these, a methyl group is particularly preferred.
- the hydrolyzable group represented by X in the formula (1) includes a hydrogen atom, a halogen atom other than fluorine, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group. Group, mercapto group, alkenyloxy group and the like.
- a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable.
- fluorosilyl group represented by the formula (1) include silicon groups having no hydrolyzable group other than fluorine, such as fluorodimethylsilyl group, fluorodiethylsilyl group, fluorodipropylsilyl group, fluoro A silicon group in which one fluorine is substituted on a silicon group such as a diphenylsilyl group or a fluorodibenzylsilyl group; on a silicon group such as a difluoromethylsilyl group, a difluoroethylsilyl group, a difluorophenylsilyl group or a difluorobenzylsilyl group A silicon group in which two fluorine atoms are substituted; a silicon group in which three fluorine atoms are substituted on a silicon group which is a trifluorosilyl group.
- silicon groups having no hydrolyzable group other than fluorine such as fluorodimethylsilyl group, fluorodiethy
- silicon groups having both fluorine and other hydrolyzable groups fluoromethoxymethylsilyl group, fluoroethoxymethylsilyl group, fluoromethoxyethylsilyl group, fluoromethoxyphenylsilyl group, fluorodimethoxysilyl group, fluorodiethoxysilyl group , Fluorodipropoxysilyl group, fluorodiphenoxysilyl group, fluorobis (2-propenoxy) silyl group, difluoromethoxysilyl group, difluoroethoxysilyl group, difluorophenoxysilyl group, fluorodichlorosilyl group, difluorochlorosilyl group, etc. It is done. Among these, a silicon group having no hydrolyzable group other than fluorine and a fluorosilyl group in which R 1 is a methyl group are preferable, and a trifluorosilyl group is more preferable.
- a silicon group in which 2 to 3 fluorine atoms are substituted on a silicon group such as a difluoromethylsilyl group, a difluoromethoxysilyl group, a difluoroethoxysilyl group, or a trifluorosilyl group, is preferable.
- the group is most preferred.
- the compound having a fluorosilyl group represented by the formula (1) may be a commercially available reagent, or may be synthesized from a raw material compound.
- the synthesis method is not particularly limited, but a compound having a crosslinkable silicon group represented by the following formula (2) or a compound having a siloxane bond and a fluorinating agent are known methods (for example, Organometallics 1996, 15, 2478).
- a compound obtained by reacting using a page (Ishikawa et al., Etc.) is preferably used.
- -SiR 1 3-a X a (2) In Formula (2), R 1 and X are the same as in Formula (1), respectively, and a is any one of 1 to 3)
- crosslinkable silicon group represented by the above formula (2) examples include halosilyl groups such as alkoxysilyl groups and chlorosilyl groups, hydrosilyl groups, and the like.
- fluorinating agent used for fluorination of the alkoxysilyl group are not particularly limited.
- fluorinating agent used for fluorination of the halosilyl group are not particularly limited.
- the fluorinating agent used for fluorination of the hydrosilyl group are not particularly limited, and examples thereof include AgF, PF 5 , Ph 3 CBF 4 , SbF 3 , NOBF 4 , and NO 2 BF 4 .
- a compound having a siloxane bond is cleaved with BF 3 or the like to obtain a fluorosilyl group.
- BF 3 etherate, BF 3 alcohol complexes, BF 3 hydrate has high preferred reactive
- BF 3 ether complex is particularly preferred.
- silicon compound having a Si—F bond having no hydrolyzable group other than fluorine include, for example, fluorinated inorganic silicon compounds such as tetrafluorosilane and octafluorotrisilane; fluorotrimethylsilane, fluoro Triethylsilane, fluorotripropylsilane, fluorotributylsilane, fluorodimethylvinylsilane, fluorodimethylphenylsilane, fluorodimethylbenzylsilane, fluorodimethyl (3-methylphenyl) silane, fluorodimethyl (4-methylphenyl) silane, fluorodimethyl (4 -Chlorophenyl) silane, fluorotriphenylsilane, difluorodimethylsilane, difluorodiethylsilane, difluorodibutylsilane, difluoromethylphenylsilane, difluoro Pheny
- silicon compounds having Si-F bonds having hydrolyzable groups other than fluorine include fluorotrimethoxysilane, difluorodimethoxysilane, trifluoromethoxysilane, fluorotriethoxysilane, and difluorodiethoxysilane.
- fluorodimethylvinyl silane, fluorodimethylphenyl silane, fluorodimethylbenzyl silane, vinyl trifluorosilane, vinyl difluoromethyl silane, 3-mercaptopropyl trifluorosilane are available because of the availability of raw materials and the ease of synthesis.
- Fluorosilane, octadecylfluorodimethylsilane, octadecyldifluoromethylsilane, octadecyltrifluorosilane, 1,3-difluoro-1,1,3,3-tetramethyldisiloxane and the like are preferable.
- the organic polymer having a fluorosilyl group (also referred to herein as a fluorinated polymer) is not particularly limited as long as it is an organic polymer having a Si—F bond. Polymers can be widely used.
- the position of the SiF bond in the organic polymer is not particularly limited, and the effect is exhibited regardless of the position in the polymer molecule.
- Examples of the organic polymer having a Si—F bond include a polymer having a fluorosilyl group represented by the above formula (1), —Si (CH 3 ) F—, —Si (C 6 H 5 ) F—, — Examples thereof include polymers in which a fluorosilyl group such as SiF 2 — and ⁇ SiF is incorporated in the main chain of the polymer.
- the fluorinated polymer is a single polymer having the same fluorosilyl group and main chain skeleton, that is, the number of fluorosilyl groups per molecule, the bonding position thereof, and the number of Fs that the fluorosilyl group has,
- the polymer may be a single polymer having the same main chain skeleton, or may be a mixture of a plurality of polymers, any or all of which are different.
- the average number of fluorosilyl groups contained in the fluorinated polymer should be at least 1, preferably 1.1-5, more preferably 1.2-3, per molecule of polymer. When the number of fluorosilyl groups contained in one molecule is less than 1 on average, the effect of imparting adhesion becomes insufficient.
- the fluorinated polymer contains a substituent other than a fluorosilyl group such as a silicon group having only a hydrolyzable group other than fluorine as a hydrolyzable group (for example, a methyldimethoxysilyl group) together with a fluorosilyl group. It may be.
- a fluorinated polymer for example, a polymer in which one main chain end is a fluorosilyl group and the other main chain end is a silicon group having only a hydrolyzable group other than fluorine as a hydrolyzable group.
- fluorinated polymers are described in International Publication No. WO2008 / 032539.
- any method may be used for introducing the fluorosilyl group, but the introduction method (method (i)) by the reaction of a low molecular silicon compound having a fluorosilyl group with a polymer, and other than fluorine.
- a method (method (ii)) of modifying a silicon group of a polymer containing a crosslinkable silicon group having a hydrolyzable group (hereinafter sometimes referred to as “polymer (X)”) to a fluorosilyl group. can be mentioned.
- the method (i) include the following methods.
- a method in which a polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in a molecule is reacted with a compound having a functional group and a fluorosilyl group that are reactive with the functional group.
- a method of reacting a polymer having a hydroxyl group at the terminal with isocyanate propyldifluoromethylsilane or a method of reacting a polymer having a SiOH group at the terminal with difluorodiethoxysilane.
- (B) A method of hydrosilylating a polymer having an unsaturated group in the molecule with a hydrosilane having a fluorosilyl group. For example, a method in which a polymer having an allyl group at a terminal is reacted with difluoromethylhydrosilane can be mentioned.
- (C) A method of reacting a polymer containing an unsaturated group with a compound having a mercapto group and a fluorosilyl group. For example, a method in which a polymer having an allyl group at the terminal is reacted with mercaptopropyldifluoromethylsilane can be mentioned.
- the polymer having a crosslinkable silicon group having a hydrolyzable group other than fluorine (polymer (X)) used in the method (ii) contains a crosslinkable silicon group having a hydrolyzable group other than fluorine.
- Saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, (meth) acrylic acid ester polymers, and polysiloxane polymers are listed as preferred polymers. be able to.
- a known method can be used as a method for converting a crosslinkable silicon group having a hydrolyzable group other than fluorine into a fluorosilyl group.
- the method is represented by the above formula (2).
- the hydrolyzable silicon group is converted to a fluorosilyl group with a fluorinating agent.
- the fluorinating agent include the fluorinating agents described above.
- the BF 3 ether complex, the BF 3 alcohol complex, and the BF 3 dihydrate have high activity, and the fluorination proceeds efficiently.
- a salt or the like is not generated in the product, and post-treatment is easy, and thus a BF 3 ether complex is particularly preferable.
- the reaction proceeds without heating, but heating is preferable for more efficient fluorination.
- the heating temperature is preferably 50 ° C. or higher and 150 ° C. or lower, and more preferably 60 ° C. or higher and 130 ° C. If it is 50 ° C. or lower, the reaction does not proceed efficiently, and it may take time for fluorination. If the temperature is 150 ° C or higher, the fluorinated polymer may be decomposed.
- fluorination with BF 3 complex is used although depending on the type of polymer (X) which may coloration occurs, from the viewpoint of suppression of coloring, BF 3 alcohol complexes, it is preferable to use BF 3 dihydrate.
- the fluorinating agent used in the production of the fluorinated polymer may also act as a curing catalyst for the fluorinated polymer, and when water is present when producing the fluorinated polymer using the method (ii) above.
- the silanol condensation reaction proceeds and the viscosity of the resulting fluorinated polymer may increase. For this reason, it is desirable that the production of the fluorinated polymer be performed in an environment free from water as much as possible.
- the polymer (X) to be fluorinated is subjected to azeotropic dehydration using toluene, hexane or the like. It is preferable to perform a dehydration operation such as providing.
- fluorination hardly progresses after the dehydration operation, and the reactivity tends to be improved by adding a small amount of water. Is preferably added.
- BF 3 from components produced by BF 3 and reaction remaining fluorinated polymers produced is, 500 ppm than in B quantity It is preferable that it is less than 100 ppm, and it is especially preferable that it is less than 50 ppm.
- the fluorination method using a BF 3 ether complex or a BF 3 alcohol complex is preferable because the boron component can be removed relatively easily by vacuum devolatilization, and the method using a BF 3 ether complex is particularly preferable. .
- the polymer (X) has two or more hydrolyzable groups other than fluorine
- all hydrolyzable groups may be fluorinated, or the amount of the fluorinating agent is reduced. May be partially fluorinated by adjusting the fluorination conditions.
- the amount of the fluorinating agent is not particularly limited, and the moles of fluorine atoms in the fluorinating agent are not limited. The amount may be an amount that is at least equimolar with respect to the molar amount of the polymer (X).
- the molar amount of fluorine atoms in the fluorinating agent is contained in the polymer (X). It is preferable to use the fluorinating agent in such an amount that it is equimolar or more with respect to the total molar amount of the hydrolyzable group in the crosslinkable silicon group.
- the “fluorine atom in the fluorinating agent” means a fluorine atom effective for fluorination in the fluorinating agent, specifically, a hydrolyzable group in the crosslinkable silicon group of the polymer (X). A fluorine atom that can be substituted.
- the low molecular compound having a fluorosilyl group in the above method (i) can also be synthesized from a general-purpose crosslinkable silicon group-containing low molecular compound using the above fluorination method.
- the method (i) there is a reactive group for reacting the polymer and the silicon-containing low molecular weight compound together with the fluorosilyl group.
- a fluorinated polymer is obtained by the method (ii). It is preferable.
- the glass transition temperature of the fluorinated polymer is not particularly limited, but is preferably 20 ° C. or less, more preferably 0 ° C. or less, and particularly preferably ⁇ 20 ° C. or less. If the glass transition temperature exceeds 20 ° C., the viscosity in winter or in a cold region may increase, making it difficult to handle.
- the glass transition temperature can be determined by DSC measurement.
- the fluorinated polymer may be linear or branched.
- the number average molecular weight of the fluorinated polymer is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000 in terms of polystyrene in GPC.
- component (C) one or more fluorine compounds selected from the group consisting of boron trifluoride, boron trifluoride complexes, fluorinating agents and alkali metal salts of polyvalent fluoro compounds Can be used.
- boron trifluoride complex examples include boron trifluoride amine complex, alcohol complex, ether complex, thiol complex, sulfide complex, carboxylic acid complex, and water complex.
- boron trifluoride complexes an amine complex having both stability and catalytic activity is particularly preferable.
- Examples of the amine compound used for the boron trifluoride amine complex 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 , , 8,10-tetraoxaspiro [5.5] undecane), CTU
- octane pyridine, N-alkylpiperidine, 1,5,7-tri
- bicyclic tertiary amine compounds such as azabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, etc.
- ⁇ -aminopropyltriethoxysilane ⁇ -aminopropylmethyldiethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane, N- ⁇ (aminoethyl) - ⁇ -aminopropyltriethoxysilane, N- ⁇ (Aminoethyl) - ⁇ -aminopropylmethyldiethoxysilane, N-3- [amino (dipropyleneoxy)] aminopropyltriethoxysilane, (aminoethylaminomethyl) phenethyltriethoxysilane, N- (6-aminohexyl) ) Aminopropyltriethoxysilane, N-phenyl- ⁇ -aminopropyltriethoxysilane, N- (2-aminoethyl) Aminosilane compounds such as 11-amino-undecyl triethoxy
- the fluorinating agent includes 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.
- nucleophilic fluorinating agent examples include 1,1,2,3,3,3-hexafluoro-1-such as 1,1,2,3,3,3-hexafluoro-1-diethylaminopropane.
- examples thereof include dialkylaminopropane compounds, trialkylamine trishydrofluoride compounds such as triethylamine trishydrofluoride, and dialkylaminosulfur trifluoride compounds such as diethylaminosulfur trifluoride.
- electrophilic fluorinating agent examples include N-fluoro such as bis (tetrafluoroboric acid) N, N′-difluoro-2,2′-bipyridinium salt compound and trifluoromethanesulfonic acid N-fluoropyridinium salt compound.
- N-fluoro such as bis (tetrafluoroboric acid) N, N′-difluoro-2,2′-bipyridinium salt compound and trifluoromethanesulfonic acid N-fluoropyridinium salt compound.
- 4-fluoro-1,4-diazoniabicyclo [2.2.pyridinium salt compounds such as bis (tetrafluoroboric acid) 4-fluoro-1,4-diazoniabicyclo [2.2.2] octane salts.
- N-fluorobis (sulfonyl) amine compounds such as octane compounds and N-fluorobis (phenylsulfonyl) amines.
- 1,1,2,3,3,3-hexafluoro-1-diethylaminopropane compounds are particularly preferable because they are liquid compounds and are easily available.
- alkali metal salt of the polyvalent fluoro compound examples include sodium hexafluoroantimonate, potassium hexafluoroantimonate, sodium hexafluoroarsenate, potassium hexafluoroarsenate, lithium hexafluorophosphate, sodium hexafluorophosphate, Potassium hexafluorophosphate, sodium pentafluorohydroxoantimonate, potassium pentafluorohydroxoantimonate, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, sodium tetrakis (trifluoromethylphenyl) borate, tri Sodium fluoro (pentafluorophenyl) borate, potassium trifluoro (pentafluorophenyl) borate, difluorobis (pentafluoro Eniru) sodium borate, difluoro (pentafluorophenyl)
- tetrafluoroboric acid or hexafluorophosphoric acid is preferable as the polyvalent fluoro compound component in the alkali metal salt of the polyvalent fluoro compound.
- the alkali metal in the alkali metal salt of the polyvalent fluoro compound is preferably at least one alkali metal selected from the group consisting of lithium, sodium and potassium.
- the mixing ratio of the component (C) is not particularly limited, but is preferably 0.001 to 80 parts by mass, and 0.001 to 30 parts by mass with respect to 100 parts by mass of the polymer (A) having a (meth) acryloyl group. Is more preferable, and 0.005 to 20 parts by mass is even more preferable. In addition, it exists in the tendency for a small amount to mix
- the curable composition of the present invention comprises one or more selected from the group consisting of the (C1) silicon compound having a Si—F bond and the (C2) fluorine-based compound, and (C1) and (C1) Either one of C2) or both may be used in combination.
- the curable composition of the present invention preferably contains the silicon compound having the (C1) Si—F bond.
- the curable composition of the present invention uses a radical polymerization initiator as the component (D).
- radical polymerization initiators include organic peroxides such as diacyl peroxides, ketone peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, and peroxycarbonates. be able to.
- radical polymerization initiator examples include benzoyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, dicumyl peroxide, cumene hydroperoxide and the like. Most commonly, benzoyl peroxide is used.
- photo radical initiator examples include benzoin ethers such as benzoin ethyl ether, benzoin butyl ether and benzoin isopropyl ether; benzophenones such as 4,4′-bisdimethylaminobenzophenone and 4,4′-bisdiethylaminobenzophenone; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl- Propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl-]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2- Til-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one, 2-methyl-1- [4- (methylthio)
- 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 And ⁇ -aminoacetophenones such as 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one; 2,4,6-trimethylbenzoyl Acylphosphine oxides such as diphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; and photoradicals having light absorption at long wavelengths (eg, wavelength 300 nm) such as amine synergists Initiators are preferred in terms of deep curability, acylphosphine oxides and amine synergists are more preferred. .
- -Hydroxyacetophenones are preferred because they can improve surface curability.
- Radical initiators are generally diluents such as inorganic substances such as calcium sulfate and calcium carbonate, dimethyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, aliphatic hydrocarbon, aromatic hydrocarbon, silicone oil, liquid paraffin, polymerizable monomer, water, etc. Diluted with inorganic substances such as calcium sulfate and calcium carbonate, dimethyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, aliphatic hydrocarbon, aromatic hydrocarbon, silicone oil, liquid paraffin, polymerizable monomer, water, etc. Diluted with inorganic substances such as calcium sulfate and calcium carbonate, dimethyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, aliphatic hydrocarbon, aromatic hydrocarbon, silicone oil, liquid paraffin, polymerizable monomer, water, etc. Diluted with inorganic substances such as calcium sulfate and calcium carbon
- the radical initiator of component (D) is 0.01 parts by mass or more and 20 parts by mass or less, preferably 0.1 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the polymer having (A) (meth) acryloyl group. Part or less, more preferably 1 to 10 parts by weight.
- a reactive diluent In the curable composition of the present invention, a reactive diluent, a co-catalyst, a silane coupling agent (adhesion imparting agent) other than the component (B), a photosensitizer, a bulking agent, and a diluent, if necessary.
- Various additives such as an ultraviolet absorber, a solvent, a fragrance, a pigment, and a dye may be added.
- a reactive diluent may be used.
- various monomers such as a low molecular weight monofunctional monomer and / or a polyfunctional monomer can be used.
- Specific examples of the monomer that can be used 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 examples thereof include monofunctional (meth) acrylates and polyfunctional (meth) acrylates. Can be used.
- Examples of monofunctional (meth) acrylates include (meth) acrylic acid, ethyl (meth) acrylate, 1-methoxyethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth) acrylate.
- polyfunctional acrylates examples include 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di ( (Meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, hydroxypivalate ester neopentyl glycol diacrylate, caprolactone modified hydroxypivalate ester neopentyl glycol diacrylate, neopentyl glycol modified trimethylol Propane di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, dicyclopentenyl diacrylate, ethylene oxide modified dicycle Pentenyl di (meth) acrylate, di (meth) acryloyl isocyanurate, trimethylolpropane tri
- (meth) acrylamide and N-vinyl compounds include N-methyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl (meth) acrylamide.
- the reactive diluent not only one kind of monomer but also a mixture of plural kinds of monomers can be used. Moreover, it is preferable that the addition amount of the reactive diluent with respect to the unit amount of the polymer which has (meth) acryloyl group of (A) component shall be below predetermined amount.
- the application property and printability of the curable composition can be controlled by making the addition amount of the reactive diluent with respect to the unit amount of the polymer having the (meth) acryloyl group of the component (A) not more than a predetermined amount.
- the reactive diluent is added in an amount of 0.1 to 50 parts by weight, preferably 0.5 parts by weight based on 100 parts by weight of the polymer having (meth) acryloyl group (A).
- Part to 40 parts by weight more preferably 1 part to 35 parts by weight.
- a base can be used.
- C It acts as a co-catalyst for improving the catalytic action of the component fluorine-based compound.
- Organic bases such as an amine compound, are preferable.
- amidines such as tertiary amines such as 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) are used. preferable.
- a photobase generator that generates a base when irradiated with light as a base can be used. Since the photobase generator does not act as a base before light irradiation, it is desirable to use a photobase generator when the base has an undesirable effect on the curable composition.
- photobase generator photolatent tertiary amines such as benzylammonium salt derivatives, benzyl-substituted amine derivatives, ⁇ -aminoketone derivatives, ⁇ -ammonium ketone derivatives and the like are preferable.
- the blending ratio thereof is not particularly limited, but is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the polymer having (A) (meth) acryloyl group.
- the amount is more preferably 1 to 40 parts by mass, and further preferably 0.5 to 30 parts by mass.
- the curable composition of the present invention can further contain a silane coupling agent other than the component (B), and epoxy group-containing silanes are particularly preferable.
- the silane coupling agent acts as an adhesion promoter.
- Examples of the silane coupling agent include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ - (3,4-epoxycyclohexyl).
- Epoxy group-containing silanes such as ethyltrimethoxysilane; ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltri Amino groups such as methoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltriethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane Containing silanes; N- (1,3-dimethyl) Ketimine type silanes such as butylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3-di
- modified amino group-containing silanes modified by reacting the amino group-containing silanes with an epoxy group-containing compound, an isocyanate group-containing compound, and a (meth) acryloyl group-containing compound containing the silanes. It may be used.
- 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 in combination of two or more.
- a carbonyl compound having a triplet energy of 225 to 310 kJ / mol is preferable.
- the blending 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 independently and may use 2 or more types together.
- extender examples include talc, clay, calcium carbonate, magnesium carbonate, anhydrous silicon, hydrated 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 can further contain a diluent.
- a diluent By blending a diluent, physical properties such as viscosity can be adjusted.
- known diluents can be widely used, and are not particularly limited.
- ⁇ such as saturated hydrocarbon solvents such as normal paraffin and isoparaffin, linearlen dimer (trade name of Idemitsu Kosan Co., Ltd.), etc.
- aromatic hydrocarbon solvents such as toluene and xylene
- alcohol solvents such as ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, diacetone alcohol, ethyl acetate, butyl acetate, amyl acetate, acetic acid
- solvents such as ester solvents such as cellosolve, citrate solvents such as acetyltriethyl citrate, 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.
- plasticizer examples include phosphoric esters such as tributyl phosphate and tricresyl phosphate, phthalic esters such as dioctyl phthalate, aliphatic monobasic esters such as glycerol monooleate, dioctyl adipate, and the like. And aliphatic dibasic acid esters, polypropylene glycols, liquid polybutene, liquid polyisobutylene, low molecular weight polybutadiene and other hydrocarbon plasticizers. These may be used alone or in combination of two or more.
- the silane coupling agent and silicate described above are suitable.
- the silicate is not particularly limited, and examples thereof include tetraalkoxysilane or a partial hydrolysis condensate thereof. More specifically, tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, Tetraalkoxysilanes (tetraalkyl silicates) such as methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, And those partial hydrolysis-condensation products are mentioned.
- condensation reaction accelerating catalyst other than the component (C) known condensation reaction accelerating catalysts can be widely used and are not particularly limited, and examples thereof include organic metal compounds, bases such as acids and amines.
- organometallic compounds include stannous octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate, Organic tin compounds such as dioctyltin dilaurate, dioctyltin diversate, tin octylate and tin naphthenate; dialkyltin oxides such as dimethyltin oxide, dibutyltin oxide and dioctyltin oxide; reactants of dibutyltin oxide and phthalate,
- the method for producing the curable composition of the present invention is not particularly limited.
- the components (A), (B), (C) and (D) are blended in a predetermined amount, and if necessary, other blends. It can be manufactured by blending substances and degassing and stirring. There is no particular limitation on the order of blending each component and other compounding substances, and it may be determined as appropriate.
- the curable composition of the present invention can be a one-component type or a two-component type as required, but can be suitably used particularly as a one-component type.
- the curable composition of the present invention is cured by active energy rays or heat. Therefore, it can be used as a photocurable composition that is cured by light irradiation and can be cured at room temperature (for example, 23 ° C.), but curing may be accelerated by heating as necessary.
- the active energy rays include ultraviolet rays, visible
- electromagnetic waves such as light rays, infrared rays
- electromagnetic waves such as X-rays and ⁇ rays, electron rays, proton rays, neutron rays, etc.
- curing by ultraviolet ray or electron beam irradiation is preferable, and curing by ultraviolet ray irradiation is more preferable.
- the ultraviolet rays include g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), and the like.
- the active energy ray source is not particularly limited, but may be, for example, 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, or a metal halide depending on the nature of the photobase generator used. It is done.
- the irradiation energy of ultraviolet rays for example, preferably 10 ⁇ 20,000mJ / cm 2, more preferably 50 ⁇ 10,000mJ / cm 2. If it is less than 10 mJ / cm 2 , the curability may be insufficient, and if it is greater than 20,000 mJ / cm 2 , it will not only waste time and cost, but also damage the substrate. May end up.
- the curing temperature is preferably 30 to 200 ° C, more preferably 80 to 180 ° C.
- the curable composition of the present invention is excellent in adhesion to a substrate and moisture resistance of a cured product, and is suitably used as a moisture proof material.
- a polyisobutylene polymer having a (meth) acryloyl group as the polymer having a (A) (meth) acryloyl group, the moisture-proof performance of the coating film can be remarkably improved.
- the moisture-proof material of the present invention consists of the curable composition of the present invention.
- coating thickness to a to-be-adhered body is preferable 100 micrometers or more, and 200 micrometers or more are more preferable.
- the moisture-proof material of the present invention is excellent in adhesion to substrates such as glass and metal in addition to moisture-proof performance, and is suitable for mirror or glass sealing, particularly sealing of the end and outer periphery of mirrors and laminated glass Is preferably used.
- the laminated glass is a laminate of a plurality of glasses.
- the laminated glass is sufficient if a plurality of transparent materials are laminated, but are usually laminated in the order of glass, resin layer, and glass.
- the material constituting the resin layer is not particularly limited as long as it has adhesiveness with glass and the resin layer is transparent.
- the laminated glass can be obtained as follows. First, using a moisture-proof material made of the curable composition of the present invention, the moisture-proof material is applied around a laminated glass whose outer periphery is unsealed.
- the application method is not particularly limited, and examples thereof include methods known in the art using brush coating, extrusion, spraying, gravure, kiss roll, dispenser, and air knife. Subsequently, the moisture-proof material is cured.
- the moisture-proof material of the present invention is cured by active energy rays or heat, and can be cured by the same method as 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 paint, a putty material, a primer, and the like.
- the curable composition of the present invention includes, for example, a sealing material used for electrical / electronic products, for example, a sealing material used as an organic EL element protective agent for products including organic EL elements; Coating agent used for coating for insulation, mirror and solar power generation panel and outer peripheral part of panel; Sealing agent for multi-layer glass, sealing agent for vehicles, such as architectural and industrial sealing agent; Electrical and electronic component materials such as battery back surface sealing agents; electrical insulating materials such as insulation coating materials for electric wires and cables; pressure-sensitive adhesives; adhesives; elastic adhesives; contact adhesives and the like.
- the curable composition of the present invention is used as a sealing material
- examples include known methods such as brush coating, extrusion, spraying, gravure, kiss roll, dispenser, and air knife.
- the coating method can be used.
- the coating thickness is preferably 100 ⁇ m or more, and more preferably 200 ⁇ m or more.
- the curable composition of the present invention is used as an adhesive, there are no particular restrictions on the method of application to the adherend, but application methods such as screen printing, stencil printing, roll printing, and spin coating are preferably used.
- application methods such as screen printing, stencil printing, roll printing, and spin coating are preferably used.
- the curable composition of the present invention is used as a coating agent, there are no particular restrictions on the method of application to the adherend, but brush coating, extrusion, spraying, gravure, kiss roll, dispenser, air knife application, and disc A coating method such as a coating method (for example, International Publication No. 2010/137418) is preferably used.
- the coating thickness is preferably 100 ⁇ m or more, and more preferably 200 ⁇ m or more.
- the number average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions unless otherwise specified.
- GPC gel permeation chromatography
- the maximum frequency molecular weight measured by GPC under the measurement conditions and converted with standard polyethylene glycol is referred to as the number average molecular weight.
- the product is dissolved in 650 ml of n-hexane, washed with 500 ml of pure water three times, reprecipitated from methanol, and then the solvent is reduced in pressure. By distilling down, the obtained polymer was vacuum-dried at 80 degrees for 24 hours to obtain the desired acryloyl-terminated polyisobutylene polymer.
- SEC size exclusion chromatography
- a methanol solution of sodium methoxide was added to the obtained polyoxypropylene diol, methanol was distilled off under reduced pressure by heating, and the terminal hydroxyl group of the polyoxypropylene diol was converted to sodium alkoxide to obtain a polyoxyalkylene polymer. .
- the polyoxyalkylene polymer was reacted with allyl chloride to remove unreacted allyl chloride and purified to obtain a polyoxyalkylene polymer having an allyl group at the terminal.
- This polyoxyalkylene polymer having an allyl group at the terminal is reacted with methyldimethoxysilane, which is a silicon hydride compound, by adding 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt%, and methyldimethoxysilyl at the terminal.
- a polyoxyalkylene polymer having a group was obtained.
- the peak top molecular weight was 15000 and the molecular weight distribution was 1.3.
- the number of terminal methyldimethoxysilyl groups was 1.7 per molecule.
- a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser is degassed under reduced pressure and then purged with nitrogen gas. Under a nitrogen stream, 2.4 g of BF 3 diethyl ether complex is added and heated to 50 ° C. Warm up. Subsequently, a mixture of 1.6 g of dehydrated methanol was slowly added dropwise and mixed. In a new flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 100 g of the obtained polymer and 5 g of toluene were placed. After stirring at 23 ° C. for 30 minutes, the mixture was heated to 110 ° C.
- a polyoxyalkylene polymer having a fluorosilyl group at the terminal (hereinafter referred to as a fluorinated polymer) was obtained.
- a 1H NMR spectrum of the obtained fluorinated polymer (measured in a CDCl 3 solvent using NMR 400 manufactured by Shimazu Co., Ltd.) was measured, and a peak corresponding to the polymer silylmethylene (—CH 2 —Si) as a raw material was measured. (M, 0.63 ppm) disappeared, and a broad peak appeared on the low magnetic field side (0.7 ppm-).
- Examples 1 to 10 A polymer having a (meth) acryloyl group as the component (A) in a flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser at the blending ratio shown in Table 1, component (B) Other components such as silane coupling agent having (meth) acryloyl group, (C) component fluorine compound, (D) component radical initiator and reactive diluent are added, stirred, dissolved and curable composition I got a thing. The adhesion and moisture permeability to the adherend of the obtained curable composition were evaluated by the following methods.
- IRGACURE 184 manufactured by BASF * 14: manufactured by IRGACURE 1173, manufactured by BASF * 15: 2- (dimethylamino) -2-[(4 -Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, IRGACURE 379EG, manufactured by BASF
- Example 2 Evaluation of moisture permeability
- the curable composition obtained in Example 1 was applied to a thickness of 220 ⁇ m, and UV irradiation (irradiation conditions: UV-LED 365 nm, illuminance: 1000 mW / cm 2, integrated light quantity: 3000mJ / cm 2) to cure the curable composition performed. After irradiation, it was cured at 23 ° C. and 50% RH for 2 days. After the curing, the cured film was used, and the moisture permeability of 50 ° C. and 85% RH was measured in accordance with the moisture permeability test method of JIS Z0208 moisture-proof packaging material. As a result, the moisture permeability was 10.5 g / m 2 24 h.
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Abstract
Description
式(1)中、R1は置換あるいは非置換の炭素原子数1~20の炭化水素基、またはR2 3SiO-(R2はそれぞれ独立に、炭素原子数1~20の置換あるいは非置換の炭化水素基、又はフッ素原子である)で示されるオルガノシロキシ基のいずれかを示す。aは1~3のいずれかであり、aが3であることが好ましい。R1及びR2が複数存在する場合、それらは同じであっても異なっていてもよい。Xは水酸基又はフッ素以外の加水分解性基であり、bは0~2のいずれかであり、cは0~2のいずれかであり、a+b+cは3である。Xが複数存在する場合、それらは同じであっても異なっていてもよい。 -SiF a R 1 b X c (1)
In the formula (1), R 1 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R 2 3 SiO— (R 2 is independently substituted or unsubstituted having 1 to 20 carbon atoms. Or an organosiloxy group represented by a fluorine atom). a is any one of 1 to 3, and a is preferably 3. When a plurality of R 1 and R 2 are present, they may be the same or different. X is a hydroxyl group or a hydrolyzable group other than fluorine, b is any of 0 to 2, c is any of 0 to 2, and a + b + c is 3. When a plurality of X are present, they may be the same or different.
-SiR1 3-aXa・・・(2)
(式(2)中、R1及びXはそれぞれ式(1)と同じであり、aは1~3のいずれかである。) The compound having a fluorosilyl group represented by the formula (1) may be a commercially available reagent, or may be synthesized from a raw material compound. The synthesis method is not particularly limited, but a compound having a crosslinkable silicon group represented by the following formula (2) or a compound having a siloxane bond and a fluorinating agent are known methods (for example, Organometallics 1996, 15, 2478). A compound obtained by reacting using a page (Ishikawa et al., Etc.) is preferably used.
-SiR 1 3-a X a (2)
(In Formula (2), R 1 and X are the same as in Formula (1), respectively, and a is any one of 1 to 3)
(イ)分子中に水酸基、エポキシ基やイソシアネート基等の官能基を有する重合体に、この官能基に対して反応性を示す官能基およびフルオロシリル基を有する化合物を反応させる方法。たとえば、末端に水酸基を有する重合体とイソシアネートプロピルジフルオロメチルシランを反応させる方法や、末端にSiOH基を有する重合体とジフルオロジエトキシシランを反応させる方法が挙げられる。
(ロ)分子中に不飽和基を有する重合体に、フルオロシリル基を有するヒドロシランを作用させてヒドロシリル化する方法。たとえば、末端にアリル基を有する重合体に、ジフルオロメチルヒドロシランを反応させる方法が挙げられる。
(ハ)不飽和基を含有する重合体に、メルカプト基およびフルオロシリル基を有する化合物を反応させる方法。たとえば、末端にアリル基を有する重合体に、メルカプトプロピルジフルオロメチルシランを反応させる方法が挙げられる。 Specific examples of the method (i) include the following methods.
(A) A method in which a polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in a molecule is reacted with a compound having a functional group and a fluorosilyl group that are reactive with the functional group. For example, a method of reacting a polymer having a hydroxyl group at the terminal with isocyanate propyldifluoromethylsilane, or a method of reacting a polymer having a SiOH group at the terminal with difluorodiethoxysilane.
(B) A method of hydrosilylating a polymer having an unsaturated group in the molecule with a hydrosilane having a fluorosilyl group. For example, a method in which a polymer having an allyl group at a terminal is reacted with difluoromethylhydrosilane can be mentioned.
(C) A method of reacting a polymer containing an unsaturated group with a compound having a mercapto group and a fluorosilyl group. For example, a method in which a polymer having an allyl group at the terminal is reacted with mercaptopropyldifluoromethylsilane can be mentioned.
本発明の硬化性組成物は活性エネルギー線又は熱によって硬化される。よって、光照射により硬化する光硬化性組成物として用いることができ、常温(例えば、23℃)で硬化することが可能であるが、必要に応じて加熱により硬化を促進してもよい。 The curable composition of the present invention can be a one-component type or a two-component type as required, but can be suitably used particularly as a one-component type.
The curable composition of the present invention is cured by active energy rays or heat. Therefore, it can be used as a photocurable composition that is cured by light irradiation and can be cured at room temperature (for example, 23 ° C.), but curing may be accelerated by heating as necessary.
続いて、前記防湿材を硬化させる。本発明の防湿材は活性エネルギー線又は熱によって硬化され、前述した本発明の硬化性組成物と同様の方法により硬化させることができる。 In the present invention, the laminated glass can be obtained as follows. First, using a moisture-proof material made of the curable composition of the present invention, the moisture-proof material is applied around a laminated glass whose outer periphery is unsealed. The application method is not particularly limited, and examples thereof include methods known in the art using brush coating, extrusion, spraying, gravure, kiss roll, dispenser, and air knife.
Subsequently, the moisture-proof material is cured. The moisture-proof material of the present invention is cured by active energy rays or heat, and can be cured by the same method as the curable composition of the present invention described above.
数平均分子量は、特に指定がない限りゲルパーミエーションクロマトグラフィー(GPC)により下記条件で測定した。本発明において、該測定条件でGPCにより測定し、標準ポリエチレングリコールで換算した最大頻度の分子量を数平均分子量と称する。
・分析装置:Alliance(Waters社製)、2410型示差屈折検出器(Waters社製)、996型多波長検出器(Waters社製)、Milleniamデータ処理装置(Waters社製)
・カラム:PlgelGUARD+5μmMixed-C×3本(50×7.5mm,300×7.5mm:PolymerLab社製)
・流速:1mL/分
・換算したポリマー:ポリエチレングリコール
・測定温度:40℃
・GPC測定時の溶媒:THF 1) Measurement 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 maximum frequency molecular weight measured by GPC under the measurement conditions and converted with standard polyethylene glycol is referred to as the number average molecular weight.
・ Analyzer: Alliance (manufactured by Waters), 2410 type differential refraction detector (manufactured by Waters), 996 type multi-wavelength detector (manufactured by Waters), Millenium data processor (manufactured by Waters)
Column: PlgelGUARD + 5 μmMixed-C × 3 (50 × 7.5 mm, 300 × 7.5 mm: manufactured by PolymerLab)
・ Flow rate: 1 mL / min ・ Converted polymer: Polyethylene glycol ・ Measurement temperature: 40 ° C.
・ Solvent for GPC measurement: THF
NMRの測定は、下記測定装置を用いて行った。
FT-NMR測定装置:日本電子(株)製JNM-ECA500(500MHz) 2) Measurement of NMR Measurement of NMR was performed using the following measuring apparatus.
FT-NMR measuring device: JNM-ECA500 (500 MHz) manufactured by JEOL Ltd.
5Lのセパラブルフラスコの容器内を窒素置換した後、n-ヘキサン(モレキュラーシーブスで乾燥したもの)280mL及び塩化ブチル(モレキュラーシーブスで乾燥したもの)2500mLを加え、窒素雰囲気下で攪拌しながら-70℃まで冷却した。次いで、イソブチレン1008mL(10.7mol))、p-ジクミルクロライド27.4g(0.119mol)及びα-ピコリン1.33g(0.014mol)を加えた。反応混合物が-70度まで冷却された後で、四塩化チタン5.2mL(0.047mol)を加えて重合を開始した。重合開始後、ガスクロマトグラフィーで残存イソブチレン濃度を測定して、イソブチレン残存量が0.5%を下回った段階で、約200gのメタノールを加えた。反応溶液から溶剤等を留去した後、生成物をn-ヘキサン2Lに溶解させ、1Lの純水で3回水洗を行った。溶媒を減圧下に留去して、得られた重合体を80度で24時間真空乾燥することにより塩素末端ポリイソブチレン系重合体A-1を得た。サイズ排除クロマトグラフィー(SEC)法により得られた重合体A-1の分子量をポリスチレン換算で測定したところ、Mw:5,800、Mn:5,200、Mw/Mn:1.12であった。 (Synthesis Example 1) Synthesis of polyisobutylene polymer having an acryloyl group at the end After replacing the inside of a 5 L separable flask with nitrogen, 280 mL of n-hexane (dried with molecular sieves) and butyl chloride (with molecular sieves) 2500 mL) was added and the mixture was cooled to −70 ° C. with stirring under a nitrogen atmosphere. Subsequently, 1008 mL (10.7 mol) of isobutylene), 27.4 g (0.119 mol) of p-dicumyl chloride and 1.33 g (0.014 mol) of α-picoline were added. After the reaction mixture was cooled to −70 ° C., 5.2 mL (0.047 mol) of titanium tetrachloride was added to initiate polymerization. After the initiation of polymerization, the residual isobutylene concentration was measured by gas chromatography. When the residual amount of isobutylene was less than 0.5%, about 200 g of methanol was added. After the solvent and the like were distilled off from the reaction solution, the product was dissolved in 2 L of n-hexane and washed with 1 L of pure water three times. The solvent was distilled off under reduced pressure, and the resulting polymer was vacuum dried at 80 ° C. for 24 hours to obtain a chlorine-terminated polyisobutylene polymer A-1. When the molecular weight of the polymer A-1 obtained by size exclusion chromatography (SEC) was measured in terms of polystyrene, it was Mw: 5,800, Mn: 5,200, and Mw / Mn: 1.12.
攪拌装置、窒素ガス導入管、温度計および環流冷却器を備えた新しいフラスコに、分子量約2,000のポリオキシプロピレンジオールを開始剤とし、亜鉛ヘキサシアノコバルテート-グライム錯体触媒の存在下、プロピレンオキシドを反応させて得られた水酸基価換算分子量14500、かつ分子量分布1.3のポリオキシプロピレンジオールを得た。得られたポリオキシプロピレンジオールにナトリウムメトキシドのメタノール溶液を添加し、加熱減圧下メタノールを留去してポリオキシプロピレンジオールの末端水酸基をナトリウムアルコキシドに変換し、ポリオキシアルキレン系重合体を得た。 (Synthesis Example 2) Synthesis of fluorinated polymer A new flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was charged with zinc hexacyanocobaltate using polyoxypropylene diol having a molecular weight of about 2,000 as an initiator. -A polyoxypropylene diol having a hydroxyl value-converted molecular weight of 14500 and a molecular weight distribution of 1.3 obtained by reacting propylene oxide in the presence of a glyme complex catalyst was obtained. A methanol solution of sodium methoxide was added to the obtained polyoxypropylene diol, methanol was distilled off under reduced pressure by heating, and the terminal hydroxyl group of the polyoxypropylene diol was converted to sodium alkoxide to obtain a polyoxyalkylene polymer. .
得られた末端にメチルジメトキシシリル基を有するポリオキシアルキレン系重合体の分子量をGPCにより測定した結果、ピークトップ分子量は15000、分子量分布1.3であった。H1-NMR測定により末端のメチルジメトキシシリル基は1分子あたり1.7個であった。 Next, the polyoxyalkylene polymer was reacted with allyl chloride to remove unreacted allyl chloride and purified to obtain a polyoxyalkylene polymer having an allyl group at the terminal. This polyoxyalkylene polymer having an allyl group at the terminal is reacted with methyldimethoxysilane, which is a silicon hydride compound, by adding 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt%, and methyldimethoxysilyl at the terminal. A polyoxyalkylene polymer having a group was obtained.
As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer having a methyldimethoxysilyl group at the terminal by GPC, the peak top molecular weight was 15000 and the molecular weight distribution was 1.3. As a result of H1-NMR measurement, the number of terminal methyldimethoxysilyl groups was 1.7 per molecule.
表1に示す配合割合にて、攪拌機、温度計、窒素導入口、モノマー装入管および水冷コンデンサーを装着したフラスコに、(A)成分の(メタ)アクリロイル基を有する重合体、(B)成分の(メタ)アクリロイル基を有するシランカップリング剤、(C)成分のフッ素系化合物、(D)成分のラジカル開始剤及び反応性希釈剤等その他の成分を添加し撹拌し、溶解させ硬化性組成物を得た。得られた硬化性組成物の被着体への接着性及び透湿度を下記の方法で評価した。 (Examples 1 to 10)
A polymer having a (meth) acryloyl group as the component (A) in a flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser at the blending ratio shown in Table 1, component (B) Other components such as silane coupling agent having (meth) acryloyl group, (C) component fluorine compound, (D) component radical initiator and reactive diluent are added, stirred, dissolved and curable composition I got a thing. The adhesion and moisture permeability to the adherend of the obtained curable composition were evaluated by the following methods.
*1:合成例1で得られた重合体
*2:紫光UV3700B、日本合成化学工業(株)製、ウレタンアクリレート系重合体
*3:IBXA、共栄社化学(株)製
*4:KAYARAD R-684、日本化薬社製
*5:3-アクリロイルプロピルトリメトキシシラン、KBM5103、信越化学社製
*6:3-メタクリロイルプロピルトリメトキシシラン、KBM503、信越化学社製
*7:3-グリシドキシプロピルトリエトキシシラン、KBM403、信越化学社製
*8:トリス-(トリメトキシシリルプロピル)イソシアヌレート、KBM9659、信越化学社製
*9:合成例2で得られたSiF結合を有する有機重合体
*10:BF3エーテル錯体
*11:ジオクチル錫、ネオスタンU830、日東化成社製
*12:アルミニウムビスエチルアセトアセテート・モノアセチルアセトネート、アルミキレートD、川研ファインケミカル社製
*13:IRGACURE 184、BASF社製
*14:IRGACURE 1173、BASF社製
*15:2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノン、IRGACURE379EG、BASF社製 In Table 1, the compounding quantity of each compounding substance is shown by g, and the details of the compounding substance are as follows.
* 1: Polymer obtained in Synthesis Example 1 * 2: Purple light UV3700B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., urethane acrylate polymer * 3: IBXA, manufactured by Kyoeisha Chemical Co., Ltd. * 4: KAYARAD R-684 * 5: 3-acryloylpropyltrimethoxysilane, KBM5103, Shin-Etsu Chemical * 6: 3-methacryloylpropyltrimethoxysilane, KBM503, Shin-Etsu Chemical * 7: 3-glycidoxypropyltri Ethoxysilane, KBM403, manufactured by Shin-Etsu Chemical Co., Ltd. * 8: Tris- (trimethoxysilylpropyl) isocyanurate, KBM9659, manufactured by Shin-Etsu Chemical Co., Ltd. * 9: Organic polymer having SiF bond obtained in Synthesis Example 2 * 10: BF 3 ether complex * 11: dioctyltin, NEOSTANN U830, Nitto Kasei Co., Ltd. * 12: aluminum bis ethyl Acetoacetate monoacetylacetonate, aluminum chelate D, manufactured by Kawaken Fine Chemical Co., Ltd. * 13: IRGACURE 184, manufactured by BASF * 14: manufactured by IRGACURE 1173, manufactured by BASF * 15: 2- (dimethylamino) -2-[(4 -Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, IRGACURE 379EG, manufactured by BASF
被着材(15cm角ガラス板)に、ガラス棒を用いて硬化性組成物を厚さ100μmになるように塗布し、UV照射(照射条件:UV-LED365nm、照度:1000mW/cm2、積算光量:3000mJ/cm2)を行い硬化性組成物を硬化させた。照射後23℃、50%RH下で2日間養生した。前記養生後、JISK5600塗料一般試験方法に準拠し、2mm角の100マス碁盤目試験を行った。結果を表1に示す。 1) Evaluation of substrate adhesion (adhesiveness) A curable composition was applied to an adherend (15 cm square glass plate) to a thickness of 100 μm using a glass rod, and UV irradiation (irradiation conditions: UV- LED365nm, illuminance: 1000mW / cm 2, integrated light quantity: 3000mJ / cm 2) to cure the curable composition performed. After irradiation, it was cured at 23 ° C. and 50% RH for 2 days. After the curing, a 2 mm square 100 square grid test was performed in accordance with the JISK5600 paint general test method. The results are shown in Table 1.
15cm角テフロン(登録商標)シート上に、実施例1で得られた硬化性組成物を厚さ220μmになるように塗布し、UV照射(照射条件:UV-LED365nm、照度:1000mW/cm2、積算光量:3000mJ/cm2)を行い硬化性組成物を硬化させた。照射後23℃、50%RH下で2日間養生した。前記養生後、硬化皮膜を用い、JIS Z0208防湿包装材料の透湿度試験方法に準拠し、50℃85%RHの透湿度を測定した結果、10.5g/m2 24hの透湿度となった。 2) Evaluation of moisture permeability On a 15 cm square Teflon (registered trademark) sheet, the curable composition obtained in Example 1 was applied to a thickness of 220 μm, and UV irradiation (irradiation conditions: UV-LED 365 nm, illuminance: 1000 mW / cm 2, integrated light quantity: 3000mJ / cm 2) to cure the curable composition performed. After irradiation, it was cured at 23 ° C. and 50% RH for 2 days. After the curing, the cured film was used, and the moisture permeability of 50 ° C. and 85% RH was measured in accordance with the moisture permeability test method of JIS Z0208 moisture-proof packaging material. As a result, the moisture permeability was 10.5 g / m 2 24 h.
表1に示す配合割合にて、実施例1~10と同様に硬化性組成物を調製し接着性を評価した。評価結果を表1に示す。 (Comparative Examples 1 to 8)
A curable composition was prepared in the same manner as in Examples 1 to 10 at the blending ratio shown in Table 1, and the adhesion was evaluated. The evaluation results are shown in Table 1.
Claims (7)
- (A)(メタ)アクリロイル基を有する重合体、
(B)(メタ)アクリロイル基を有するシランカップリング剤、
(C)(C1)Si-F結合を有する珪素化合物、及び/又は(C2)三フッ化ホウ素、三フッ化ホウ素の錯体、フッ素化剤及び多価フルオロ化合物のアルカリ金属塩からなる群から選択される1種以上のフッ素系化合物、及び、
(D)ラジカル開始剤
を含有することを特徴とする硬化性組成物。 (A) a polymer having a (meth) acryloyl group,
(B) a silane coupling agent having a (meth) acryloyl group,
(C) (C1) selected from the group consisting of a silicon compound having a Si—F bond, and / or (C2) boron trifluoride, a complex of boron trifluoride, a fluorinating agent and an alkali metal salt of a polyvalent fluoro compound. One or more fluorine-based compounds, and
(D) A curable composition containing a radical initiator. - 前記(A)が(メタ)アクリロイル基を有するポリイソブチレン系重合体であることを特徴とする請求項1に記載の硬化性組成物。 The curable composition according to claim 1, wherein (A) is a polyisobutylene polymer having a (meth) acryloyl group.
- 前記(D)が光ラジカル開始剤であることを特徴とする請求項1又は2に記載の硬化性組成物。 The curable composition according to claim 1 or 2, wherein (D) is a photo radical initiator.
- 請求項1~3のいずれか1項記載の硬化性組成物からなる封止材。 A sealing material comprising the curable composition according to any one of claims 1 to 3.
- 請求項4記載の封止材を用いてなる電気・電子製品。 An electrical / electronic product using the sealing material according to claim 4.
- 請求項1~3のいずれか1項記載の硬化性組成物からなる防湿材。 A moisture-proof material comprising the curable composition according to any one of claims 1 to 3.
- 請求項6記載の防湿材を用いてなる鏡又はガラスを含む製品。 A product containing a mirror or glass using the moisture-proof material according to claim 6.
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JPWO2020080309A1 (en) * | 2018-10-18 | 2021-09-16 | 株式会社スリーボンド | Photocurable composition |
JP7368738B2 (en) | 2018-10-18 | 2023-10-25 | 株式会社スリーボンド | photocurable composition |
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JP7393705B2 (en) | 2022-03-01 | 2023-12-07 | ダイキン工業株式会社 | Articles and their manufacturing methods, and surface treatment agents |
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JP6979153B2 (en) | 2021-12-08 |
JPWO2016152392A1 (en) | 2018-01-18 |
KR102503389B1 (en) | 2023-02-24 |
KR20170129725A (en) | 2017-11-27 |
CN107428891A (en) | 2017-12-01 |
JP2021143338A (en) | 2021-09-24 |
CN107428891B (en) | 2021-04-20 |
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