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WO2016063978A1 - Composition photodurcissable - Google Patents

Composition photodurcissable Download PDF

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Publication number
WO2016063978A1
WO2016063978A1 PCT/JP2015/079993 JP2015079993W WO2016063978A1 WO 2016063978 A1 WO2016063978 A1 WO 2016063978A1 JP 2015079993 W JP2015079993 W JP 2015079993W WO 2016063978 A1 WO2016063978 A1 WO 2016063978A1
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group
polymer
meth
compound
formula
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English (en)
Japanese (ja)
Inventor
翔馬 河野
智洋 緑川
岡村　直実
宏士 山家
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Cemedine Co Ltd
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Cemedine Co Ltd
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Priority to JP2016555407A priority Critical patent/JP6642834B2/ja
Priority to CN201580057428.2A priority patent/CN107148453B/zh
Publication of WO2016063978A1 publication Critical patent/WO2016063978A1/fr
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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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/10—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/10—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

  • the present invention relates to a photocurable composition excellent in adhesiveness, and particularly relates to a photocurable composition that can be cured in a short time and has excellent adhesiveness such as rising adhesiveness.
  • An organic polymer having a hydroxyl group or hydrolyzable group bonded to a silicon atom and having a silicon-containing group that can be crosslinked by forming a siloxane bond (hereinafter also referred to as “crosslinkable silicon group”) is obtained at room temperature. It is also known that the rubber has a property that a rubber-like cured product can be obtained by crosslinking by formation of a siloxane bond accompanied by hydrolysis reaction of a crosslinkable silicon group due to moisture or the like.
  • organic polymers whose main chain skeleton is a polyoxyalkylene polymer or a (meth) acrylic acid ester polymer are used for sealing materials, adhesives, paints, etc. Widely used.
  • the curable composition used for sealing materials, adhesives, paints, etc. and the rubber-like cured product obtained by curing have various properties such as curability, adhesiveness, storage stability, mechanical properties such as modulus, strength, and elongation. Properties are required, and many studies have been made on organic polymers containing crosslinkable silicon groups. In recent years, rapid curing is required in various fields such as an electronic component / electronic device assembling field, but in the case of a moisture-curing adhesive, there is a problem that a bonding time after application is shortened.
  • Patent Document 1 discloses a polymer having two or more hydrolyzable silyl groups in one molecule, and the polymer by light irradiation.
  • a photocrosslinkable composition comprising a compound that crosslinks a compound, and a compound containing a compound that generates an acid or a base upon irradiation with light as a compound that crosslinks a polymer by light irradiation.
  • the crosslinkable composition is exemplified (Patent Document 1, Claims 1 to 3).
  • An object of the present invention is to provide a fast-curing photocurable composition having excellent rising adhesiveness and workability.
  • the photocurable composition of the present invention comprises (A) a crosslinkable silicon group-containing organic polymer, (B) a photobase generator, and (C1) silicon having a Si—F bond.
  • the (A) crosslinkable silicon group-containing organic polymer is at least one selected from the group consisting of a crosslinkable silicon group-containing polyoxyalkylene polymer and a crosslinkable silicon group-containing (meth) acrylic polymer. It is preferable.
  • the (B) photobase generator is preferably a photolatent tertiary amine.
  • a substance that generates an amine compound by the action of active energy rays is referred to as a photolatent amine compound.
  • a substance that generates an amine compound having a primary amino group is a photolatent primary amine
  • a substance that generates an amine compound having a secondary amino group is a photolatent group.
  • Substances that generate secondary amines and amine compounds having tertiary amino groups are referred to as photolatent tertiary amines, respectively.
  • the cured product of the present invention is a cured product formed by irradiating the photocurable composition of the present invention with light.
  • the first aspect of the product of the present invention is a product configured using the photocurable composition of the present invention as an adhesive.
  • the 2nd aspect of the product of this invention is a product comprised using the photocurable composition of this invention as a coating agent.
  • the photocurable composition excellent in adhesiveness such as rising adhesiveness. Further, according to the present invention, the photocurable composition is not cured when not irradiated with active energy rays, but is cured by irradiation with active energy rays, and is excellent in rising adhesiveness after irradiation with active energy rays. It is possible to provide a photocurable composition having fast curability while ensuring a sufficient bonding time. In addition, since the photocurable composition of the present invention is in a liquid state after irradiation with active energy rays, it has excellent wettability and has a bonding time even after irradiation with active energy rays. Fast curability while having a long workable time.
  • the photocurable composition according to the present embodiment includes (A) a crosslinkable silicon group-containing organic polymer, (B) a photobase generator, (C1) a compound having a Si—F bond, and / or ( C2) one or more fluorine-based compounds selected from the group consisting of boron trifluoride, boron trifluoride complexes, fluorinating agents, and alkali metal salts of polyvalent fluoro compounds, and (D) photoradical polymerizability. And a monomer having a compound having one vinyl group.
  • the photocurable composition according to the present embodiment may further contain a monomer having a crosslinkable silicon group and a (meth) acryloyloxy group.
  • the crosslinkable silicon group-containing organic polymer is not particularly limited as long as it is an organic polymer having a crosslinkable silicon group.
  • the main chain is an organic polymer that is not polysiloxane, and the organic polymer having various main chain skeletons excluding polysiloxane does not contain or generate low-molecular cyclic siloxane that causes contact failure. It is suitable. Further, an organic polymer having a crosslinkable silicon group that is difficult to break the main chain, has good compatibility, and is easy to blend with an adhesion-imparting agent or the like is also preferable.
  • (A) Specific examples of the main chain skeleton of the crosslinkable silicon group-containing organic polymer include polyoxyalkylene polymers such as polyoxypropylene, polyoxytetramethylene, and polyoxyethylene-polyoxypropylene copolymers.
  • a hydrocarbon polymer such as an ethylene-propylene copolymer, polyisobutylene, polyisoprene, polybutadiene, hydrogenated polyolefin polymer obtained by hydrogenating these polyolefin polymers; two bases such as adipic acid; Polyester polymer obtained by condensation of acid and glycol or ring-opening polymerization of lactones; (meth) acrylic acid ester obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate Polymer: (meth) acrylic acid ester monomer, vinyl acetate, acrylic Vinyl polymer obtained by radical polymerization of monomers such as nitrile and styrene; Graft polymer obtained by polymerizing vinyl monomer in organic polymer; Polysulfide polymer; Polyamide polymer; Polycarbonate polymer A diallyl phthalate polymer and the like. These skeletons may be contained alone in (A) the crosslinkable silicon group-containing organic
  • saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers can be obtained with a relatively low glass transition temperature.
  • the cured product is preferable because it is excellent in cold resistance.
  • Polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferred because they have high moisture permeability and are excellent in deep part curability when made into a one-component composition.
  • the crosslinkable silicon group of the crosslinkable silicon group-containing organic polymer is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond.
  • a group represented by the general formula (1) is suitable.
  • R 1 is a hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms Group, an aralkyl group having 7 to 20 carbon atoms, a triorganosiloxy group represented by R 1 3 SiO— (R 1 is the same as above), or a —CH 2 OR 1 group (R 1 is the same as above) It is.
  • R 1 is a group in which at least one hydrogen atom on the 1st to 3rd carbon atoms is halogen, —OR 41 , —NR 42 R 43 , —N ⁇ R 44 , —SR 45 (R 41 , R 42 , R 43 and R 45 are each a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms or having no substituent, and R 44 is a divalent substitution having 1 to 20 carbon atoms.
  • R 1 is preferably a methyl group.
  • the plurality of R 1 may be the same or different.
  • X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, the plurality of X may be the same or different.
  • a is an integer of 0, 1, 2, or 3.
  • a is preferably 2 or more, more preferably 3.
  • Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different.
  • the number of silicon atoms forming the crosslinkable silicon group may be one or two or more. In the case of silicon atoms linked by a siloxane bond or the like, there may be about 20 silicon atoms.
  • the hydrolyzable group represented by X is not particularly limited as long as it is other than F atom.
  • Examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group.
  • 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, and an alkoxy group, an amide group, and an aminooxy group are more preferable.
  • An alkoxy group is particularly preferred from the viewpoint of mild hydrolysis and easy handling.
  • the alkoxy groups those having a smaller number of carbon atoms have higher reactivity, and the reactivity increases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group.
  • a methoxy group or an ethoxy group is usually used.
  • crosslinkable silicon group examples include trialkoxysilyl groups [—Si (OR) 3 ] such as trimethoxysilyl group and triethoxysilyl group, dialkoxy such as methyldimethoxysilyl group and methyldiethoxysilyl group.
  • examples thereof include a silyl group [—SiR 1 (OR) 2 ], a trialkoxysilyl group [—Si (OR) 3 ] is preferable in terms of high reactivity, and a trimethoxysilyl group is more preferable.
  • R is an alkyl group such as a methyl group or an ethyl group.
  • the crosslinkable silicon group may be used alone or in combination of two or more.
  • the crosslinkable silicon group can be present in the main chain, the side chain, or both.
  • the crosslinkable silicon group shown by several general formula (1) may mutually be connected.
  • the number of silicon atoms forming the crosslinkable silicon group is one or more, but in the case of silicon atoms linked by a siloxane bond or the like, the number of silicon atoms is preferably 20 or less.
  • the organic polymer having a crosslinkable silicon group may be linear or branched, and its number average molecular weight is about 500 to 100,000 in terms of polystyrene in GPC, more preferably 1,000 to 50,000. Particularly preferred is 3,000 to 30,000. If the number average molecular weight is less than 500, the cured product tends to be inconvenient in terms of elongation characteristics, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.
  • the average number of crosslinkable silicon groups contained in the organic polymer is 0.8 or more, preferably in one molecule of the polymer. Is 1.0 or more, more preferably 1.1 to 5. If the average number of crosslinkable silicon groups contained in the molecule is less than 0.8, the curability becomes insufficient and it becomes difficult to exhibit good rubber elastic behavior.
  • the crosslinkable silicon group may be present at the end of the main chain of the organic polymer molecular chain, at the end of the side chain, or both.
  • the crosslinkable silicon group is only at the end of the main chain of the molecular chain, the effective network length of the organic polymer component contained in the finally formed cured product is increased, so that the high strength, high elongation, A rubber-like cured product having a low elastic modulus is easily obtained.
  • the polyoxyalkylene polymer is essentially a polymer having a repeating unit represented by the general formula (2).
  • -R 2 -O- (2) In the general formula (2), R 2 is a linear or branched alkylene group having 1 to 14 carbon atoms, preferably a linear or branched alkylene group having 1 to 14 carbon atoms, and having 2 to 4 carbon atoms.
  • the linear or branched alkylene group is more preferable.
  • repeating unit represented by the general formula (2) examples include -CH 2 O -, - CH 2 CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H 5) O -, - CH 2 C (CH 3) 2 O-, —CH 2 CH 2 CH 2 CH 2 O— and the like can be mentioned.
  • the main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units.
  • Examples of the method for synthesizing the polyoxyalkylene polymer include, but are not limited to, a polymerization method using an alkali catalyst such as KOH, a polymerization method using a double metal cyanide complex catalyst, and the like. According to the polymerization method using a double metal cyanide complex catalyst, a polyoxyalkylene polymer having a number average molecular weight of 6,000 or more and a high molecular weight of Mw / Mn of 1.6 or less and a narrow molecular weight distribution can be obtained.
  • the main chain skeleton of the polyoxyalkylene polymer may contain other components such as a urethane bond component.
  • a urethane bond component is obtained from a reaction between an aromatic polyisocyanate such as toluene (tolylene) diisocyanate and diphenylmethane diisocyanate; an aliphatic polyisocyanate such as isophorone diisocyanate and a polyoxyalkylene polymer having a hydroxyl group. Ingredients can be mentioned.
  • a polyoxyalkylene polymer having a functional group such as an unsaturated group, a hydroxyl group, an epoxy group, or an isocyanate group in the molecule is added with a compound having a functional group reactive to this functional group and a crosslinkable silicon group.
  • a crosslinkable silicon group can be introduced into the polyoxyalkylene polymer (hereinafter referred to as polymer reaction method).
  • a hydrosilane or mercapto compound obtained by allowing a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to act on an unsaturated group-containing polyoxyalkylene polymer to form a crosslinkable silicon group
  • the method of obtaining the polyoxyalkylene type polymer which has can be mentioned.
  • An unsaturated group-containing polyoxyalkylene-based polymer is obtained by reacting an organic polymer having a functional group such as a hydroxyl group with an organic compound having an active group and an unsaturated group that are reactive with the functional group.
  • a polyoxyalkylene polymer containing can be obtained.
  • polymer reaction method examples include a method of reacting a polyoxyalkylene polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a crosslinkable silicon group, or a polyoxyalkylene having an isocyanate group at a terminal.
  • examples thereof include a method of reacting an alkylene polymer with a compound having an active hydrogen group such as a hydroxyl group or an amino group and a crosslinkable silicon group.
  • an isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group can be easily obtained.
  • the polyoxyalkylene polymer having a crosslinkable silicon group may be used alone or in combination of two or more.
  • the saturated hydrocarbon polymer is a polymer that does not substantially contain other carbon-carbon unsaturated bonds other than aromatic rings.
  • the polymer forming the skeleton is either (1) polymerizing an olefinic compound having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene or isobutylene as a main monomer, or (2) a diene such as butadiene or isoprene. It can be obtained by homopolymerizing the system compound or by hydrogenating the diene compound and the olefin compound after copolymerization.
  • the isobutylene polymer and the hydrogenated polybutadiene polymer are preferable because it is easy to introduce a functional group at the terminal, easily control the molecular weight, and can increase the number of terminal functional groups, and the isobutylene polymer is particularly preferable. preferable.
  • the main chain skeleton is a saturated hydrocarbon polymer
  • the main chain skeleton has characteristics of excellent heat resistance, weather resistance, durability, and moisture barrier properties.
  • all of the monomer units may be formed from isobutylene units, or may be a copolymer with other monomers. From the viewpoint of rubber properties, a polymer containing 50% by mass or more of repeating units derived from isobutylene is preferred, a polymer containing 80% by mass or more is more preferred, and a polymer containing 90 to 99% by mass is particularly preferred.
  • a polymerization method As a method for synthesizing a saturated hydrocarbon polymer, various polymerization methods may be mentioned. In particular, various living polymerizations have been developed. In the case of saturated hydrocarbon polymers, particularly isobutylene polymers, the inifer polymerization found by Kennedy et al. (J. P. Kennedy et al., J. Polymer Sci., Polymer Chem. Page). According to this polymerization method, a polymer having a molecular weight of about 500 to 100,000 can be polymerized with a molecular weight distribution of 1.5 or less, and various functional groups can be introduced at the molecular ends.
  • saturated hydrocarbon polymers particularly isobutylene polymers
  • the inifer polymerization found by Kennedy et al. J. P. Kennedy et al., J. Polymer Sci., Polymer Chem. Page.
  • a polymer having a molecular weight of about 500 to 100,000 can be polymerized with a molecular weight distribution of 1.5 or less,
  • a method for producing a saturated hydrocarbon polymer having a crosslinkable silicon group for example, a cationic polymerization method using a combination of an organic halogen compound that generates a stable carbon cation and a Friedel-Crafts acid catalyst as a copolymerization initiator is used.
  • a cationic polymerization method using a combination of an organic halogen compound that generates a stable carbon cation and a Friedel-Crafts acid catalyst as a copolymerization initiator is used.
  • An example is the inifer method disclosed in Japanese Patent Publication No. 4-69659.
  • the saturated hydrocarbon polymer having a crosslinkable silicon group may be used alone or in combination of two or more.
  • (meth) acrylic acid ester monomer constituting the main chain of the (meth) acrylic acid ester polymer.
  • (meth) acrylic acid monomers such as acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid alkyl ester monomers such as stearyl acid; alicyclic (meth) acrylic acid ester monomers; aromatic (meth) acrylic acid ester monomers; (meth) acrylic acid 2-methoxyethyl (meth) ) Acrylic acid ester monomers; silyl group-containing (meth) acrylic acid ester monomers such as ⁇ - (methacryloyloxypropyl) trimethoxysilane, ⁇ - (methacryloyloxypropyl) dimethoxymethylsilane; (meth) acrylic acid alkyl ester mono
  • the following vinyl monomers can be copolymerized with the (meth) acrylate monomer.
  • vinyl monomers include styrene, maleic anhydride, vinyl acetate and the like.
  • acrylic acid and glycidyl acrylate may be contained as monomer units (hereinafter also referred to as other monomer units).
  • a polymer composed of a (meth) acrylic acid monomer is preferred.
  • the (meth) acrylic acid ester type polymer which used the 1 type (s) or 2 or more types (meth) acrylic-acid alkylester monomer and used together with the other (meth) acrylic acid monomer as needed is more preferable.
  • the number of silicon groups in the (meth) acrylic acid ester polymer (A) can be controlled by using a silyl group-containing (meth) acrylic acid ester monomer in combination.
  • a methacrylic acid ester polymer comprising a methacrylic acid ester monomer is particularly preferred because of its good adhesion.
  • (meth) acrylic acid represents acrylic acid and / or methacrylic acid.
  • the method for producing the (meth) acrylate polymer is not particularly limited, and for example, a radical polymerization method using a radical polymerization reaction can be used.
  • the radical polymerization method includes a radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator, or a controlled radical capable of introducing a reactive silyl group at a controlled position such as a terminal.
  • a polymerization method is mentioned.
  • a polymer obtained by a free radical polymerization method using an azo compound, a peroxide or the like as a polymerization initiator generally has a large molecular weight distribution value of 2 or more and a high viscosity.
  • Examples of the controlled radical polymerization method include free radical polymerization method and living radical polymerization method using a chain transfer agent having a specific functional group, such as an addition-cleavage transfer reaction (RAFT) polymerization method, Living radical polymerization methods such as a radical polymerization method using a transition metal complex (Transition-Metal-Mediated Living Radical Polymerization) are more preferable. Further, a reaction using a thiol compound having a reactive silyl group and a reaction using a thiol compound having a reactive silyl group and a metallocene compound are also suitable.
  • RAFT addition-cleavage transfer reaction
  • Living radical polymerization methods such as a radical polymerization method using a transition metal complex (Transition-Metal-Mediated Living Radical Polymerization) are more preferable.
  • the (meth) acrylic acid ester-based polymer having a crosslinkable silicon group may be used alone or in combination of two or more.
  • organic polymers having a crosslinkable silicon group may be used alone or in combination of two or more. Specifically, a group consisting of a polyoxyalkylene polymer having a crosslinkable silicon group, a saturated hydrocarbon polymer having a crosslinkable silicon group, and a (meth) acrylic acid ester polymer having a crosslinkable silicon group. An organic polymer obtained by blending two or more selected from the above can also be used.
  • an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group For example, it has a crosslinkable silicon group and the molecular chain is substantially the general formula (3): —CH 2 —C (R 3 ) (COOR 4 ) — (3) (Wherein R 3 represents a hydrogen atom or a methyl group, and R 4 represents an alkyl group having 1 to 5 carbon atoms) and a general formula (4): —CH 2 —C (R 3 ) (COOR 5 ) — (4) (Wherein R 3 is the same as described above, and R 5 represents an alkyl group having 6 or more carbon atoms) A copolymer composed of a (meth) acrylic acid ester monomer unit is represented by a crosslinkable silicon group And a method of blending and producing a polyoxyalkylene-based polymer having.
  • R 4 in the general formula (3) for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group and the like have 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms, An alkyl group having 1 to 2 carbon atoms is preferable.
  • the alkyl group of R 4 may alone, or may be a mixture of two or more.
  • R 5 in the general formula (4) is, for example, a long group having 6 or more carbon atoms such as 2-ethylhexyl group, lauryl group or stearyl group, usually 7 to 30 carbon atoms, preferably 8 to 20 carbon atoms. Chain alkyl groups.
  • the alkyl group of R 5 is as in the case of R 4, may be alone or in admixture.
  • the molecular chain of the (meth) acrylic acid ester copolymer is substantially composed of monomer units of the formulas (3) and (4).
  • “substantially” means that the total of the monomer units of the formula (3) and the formula (4) present in the copolymer exceeds 50% by mass.
  • the total of the monomer units of the formula (3) and the formula (4) is preferably 70% by mass or more.
  • the abundance ratio of the monomer unit of the formula (3) and the monomer unit of the formula (4) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40 by mass ratio.
  • (Meth) having a crosslinkable silicon group used in a method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group with a (meth) acrylic acid ester polymer having a crosslinkable silicon group
  • the acrylate polymer include, for example, a (meth) acrylic acid alkyl ester monomer unit having a crosslinkable silicon group and a molecular chain substantially having (1) an alkyl group having 1 to 8 carbon atoms.
  • (meth) acrylic acid ester-based copolymers such as (meth) acrylic acid ester-based copolymers containing (meth) acrylic acid alkyl ester monomer units having an alkyl group having 10 or more carbon atoms Coalescence can also be used.
  • the number average molecular weight of the (meth) acrylic acid ester polymer is preferably 600 to 10,000, more preferably 600 to 5,000, and still more preferably 1,000 to 4,500. By setting the number average molecular weight within this range, compatibility with the polyoxyalkylene polymer having a crosslinkable silicon group is improved.
  • the (meth) acrylic acid ester polymer may be used alone or in combination of two or more.
  • the compounding ratio of the polyoxyalkylene polymer having a crosslinkable silicon group and the (meth) acrylic acid ester polymer having a crosslinkable silicon group is not particularly limited, but the (meth) acrylic acid ester polymer and The (meth) acrylic acid ester polymer is preferably in the range of 10 to 60 parts by mass, more preferably in the range of 20 to 50 parts by mass with respect to 100 parts by mass in total with the polyoxyalkylene polymer. More preferably, it is in the range of 25 to 45 parts by mass.
  • the amount of the (meth) acrylic acid ester polymer is more than 60 parts by mass, the viscosity becomes high and workability deteriorates, which is not preferable.
  • a method for producing an organic polymer obtained by blending a (meth) acrylic acid ester-based copolymer having a crosslinkable silicon group, in addition, in the presence of an organic polymer having a crosslinkable silicon group A method of polymerizing a (meth) acrylic acid ester monomer can be used.
  • the saturated hydrocarbon polymer having a crosslinkable silicon group and / or the crosslinkability with respect to 100 parts by mass of the polyoxyalkylene polymer having a crosslinkable silicon group It is preferable to use 10 to 200 parts by mass, and more preferably 20 to 80 parts by mass of the (meth) acrylic acid ester-based polymer having a silicon group.
  • the photobase generator (B) acts as a curing catalyst for the (A) crosslinkable silicon group-containing organic polymer when irradiated with light.
  • the photobase generator (B) may be any substance that generates a base by the action of active energy rays such as ultraviolet rays, electron beams, X-rays, infrared rays, and visible rays.
  • active energy rays such as ultraviolet rays, electron beams, X-rays, infrared rays, and visible rays.
  • a photobase generator As a photobase generator (B), a known photobase generator such as a compound to be released, or (3) a compound that causes a predetermined chemical reaction upon irradiation with energy rays such as ultraviolet rays, visible light, and infrared rays to release a base. Can be used.
  • an organic base such as an amine compound is preferable.
  • examples thereof include primary alkylamines such as octylamine and primary fragrances such as N-methylbenzylamine.
  • DBU 1,8-diazabicyclo [5.4.0] undecene-7
  • Amidines such as nonene-5 (DBN) and phosphazene derivatives.
  • amine compounds having a tertiary amino group are preferred, and amidines and phosphazene derivatives which are strong bases are more preferred.
  • amidines both acyclic amidines and cyclic amidines can be used, and cyclic amidines are more preferable. These bases may be used alone or in combination of two or more.
  • non-cyclic amidines examples include guanidine compounds and biguanide compounds.
  • examples of guanidine compounds include 1,1,3,3-tetramethylguanidine and 1-phenylguanidine.
  • biguanide compounds examples include 1-o-tolyl biguanide and 1-phenyl biguanide.
  • photobase generators that generate aryl-substituted guanidine compounds such as phenylguanidine, 1-o-tolylbiguanide, 1-phenylbiguanide, or aryl-substituted biguanide compounds are polymers ( When it is used as the catalyst of A), it is preferable because it shows a tendency that the curability of the surface is good and a tendency that the adhesiveness of the resulting cured product becomes good.
  • cyclic amidines include cyclic guanidine compounds, imidazoline compounds, imidazole compounds, tetrahydropyrimidine compounds, triazabicycloalkene compounds, and diazabicycloalkene compounds.
  • Examples of the cyclic guanidine compound include 1,5,7-triaza-bicyclo [4.4.0] dec-5-ene.
  • Examples of the imidazoline compounds include 1-methylimidazoline.
  • Examples of the imidazole compound include imidazole.
  • Examples of the tetrahydropyrimidine compound include 1-methyl-1,4,5,6-tetrahydropyrimidine.
  • Examples of the triazabicycloalkene compound include 7-methyl-1,5,7-triazabicyclo [4.4.0] decene-5.
  • Examples of the diazabicycloalkene compound include 1,5-diazabicyclo [4.3.0] nonene-5, 1,8-diazabicyclo [5.4.0] undecene-7, and the like.
  • 1,8-diazabicyclo [5.4.0] undecene is known because it is easily available industrially, and has a pKa value of 12 or more for the conjugate acid and exhibits high catalytic activity.
  • -7 (DBU) and 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) are particularly preferred.
  • photobase generator (B) various photobase generators can be used. Photolatent amine compounds that generate amine compounds by the action of active energy rays are preferred.
  • the photolatent amine compound includes a photolatent primary amine that generates an amine compound having a primary amino group by the action of active energy rays, and an amine compound having a secondary amino group by the action of active energy rays. Any of the photolatent secondary amine that is generated and the photolatent tertiary amine that generates an amine compound having a tertiary amino group by the action of active energy rays can be used. In view of the high catalytic activity of the generated base, a photolatent tertiary amine is more preferable.
  • photolatent primary amines and photolatent secondary amines include orthonitrobenzylurethane compounds described in WO2015 / 088021, dimethoxybenzylurethane compounds, benzoins carbamates, o-acyloximes O-carbamoyl oximes; N-hydroxyimide carbamates; formanilide derivatives; aromatic sulfonamides; cobalt amine complexes and the like.
  • photolatent tertiary amines examples include ⁇ -aminoketone derivatives, ⁇ -ammonium ketone derivatives, benzylamine derivatives, benzylammonium salt derivatives, ⁇ -aminoalkene derivatives, ⁇ -ammonium alkene derivatives, amine imides, and amidines by light. And benzyloxycarbonylamine derivatives that generate a carboxylic acid and a tertiary amine salt.
  • ⁇ -aminoketone derivative for example, ⁇ -aminoketone compounds represented by the formulas (I) to (IV) are preferable.
  • R 51 is an aromatic or heteroaromatic group, and R 51 is an aromatic group (which is unsubstituted or an alkyl group having 1 to 18 carbon atoms (hereinafter referred to as R x , An alkenyl group having 3 to 18 carbon atoms (hereinafter sometimes referred to as R y ), an alkynyl group having 3 to 18 carbon atoms (hereinafter sometimes referred to as R z ), carbon One or more times with a haloalkyl group having a number of 1 to 18, NO 2 , NR 58 R 59 , N 3 , OH, CN, OR 60 , SR 60 , C (O) R 61 , C (O) OR 62 , or halogen R 58 , R 59 , R 60 , R 61 and R 62 are preferably hydrogen or R x ) and are selected from the group consisting of phenyl, naphthyl, phenanthryl, anthr
  • R 52 and R 53 are each independently hydrogen, R x , R y , R z , or a phenyl group. If R 52 is hydrogen or R x , then R 53 is —CO—R 64 (wherein R 64 is R x or a phenyl group); or R 51 and R 53 are Together with the C atom to which the carbonyl group and R 53 are bonded form a benzocyclopentanone group.
  • R 54 and R 56 may be the same group and are unsubstituted or form an alkylene bridge having 2 to 12 carbon atoms which is substituted by one or more alkyl groups having 1 to 4 carbon atoms.
  • R 55 and R 57 may be the same group, independently of R 54 and R 56 , or have one or more carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms. 2 to 12 alkylene bridges are formed. R 54 and R 56 together form an alkylene bridge having 3 carbon atoms, and R 55 and R 57 may be the same group, and are preferably a propylene group or a pentylene group.
  • R 51 ⁇ R 53 are the same as R 51 ⁇ R 53 each formula (I).
  • R 66 is an alkyl group having 1 to 12 carbon atoms; —OH, —an alkoxy group having 1 to 4 carbon atoms, —CN or —COOR q (R q is an alkyl group having 1 to 4 carbon atoms; the same applies hereinafter. )) Represents an alkyl group having 2 to 4 carbon atoms.
  • R 66 represents an alkenyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or a phenyl-alkyl group having 1 to 3 carbon atoms.
  • R 67 represents an alkyl group having 1 to 12 carbon atoms, or an —OH group, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 2 to 4 carbon atoms substituted with —CN or —COOR q. .
  • R 67 is an alkenyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenyl-alkyl group having 1 to 3 carbon atoms, or unsubstituted or having a carbon number. It represents a 1 to 12 alkyl group, an alkoxy group having 1 to 4 carbon atoms or a phenyl group substituted by —COOR q .
  • R 67 may be the same group as R 66, and is an alkylene group having 1 to 7 carbon atoms, a phenyl-alkylene group having 1 to 4 carbon atoms, an o-xylylene group, a 2-butenylene group, or a carbon number. 2 or 3 oxaalkylene groups are represented.
  • R 66 and R 67 may be the same group, and represent an alkylene group having 4 to 7 carbon atoms that can be interrupted by —O—, —S—, or —CO—.
  • R 66 and R 67 may be the same group, and represent an OH group, an alkoxy group having 1 to 4 carbon atoms, or an alkylene group having 3 to 7 carbon atoms that can be substituted with —COOR q .
  • R 66 and R 67 may be the same or different.
  • Y 1 represents a divalent group represented by the formula (V), a divalent group represented by —N (R 68 ) —, or —N (R 68 ) —R 69 —N (R 68 ) —.
  • R 68 represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, a phenyl-alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or a phenyl group.
  • R 69 represents an unbranched or branched alkylene group having 2 to 16 carbon atoms which can be interrupted by one or more —O— or —S—.
  • Y 2 represents an alkylene group having 1 to 6 carbon atoms, a cyclohexylene group, or a direct bond.
  • Examples of the ⁇ -aminoketone compound represented by the formula (I) include 5-naphthoylmethyl-1,5-diazabicyclo [4.3.0] nonane, 5- (4′-nitro) phenacyl-1,5- And diazabicyclo [4.3.0] nonane.
  • Examples of the ⁇ -aminoketone compound represented by the formula (II) include 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane (Irgacure 907), 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone (Irgacure 369), 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone (Irgacure 379), and the like.
  • Examples of ⁇ -ammonium ketone derivatives include ⁇ -ammonium ketone compounds represented by the formula (VI).
  • V ⁇ is a counter anion, such as a borate anion (tetraphenyl borate, methyl triphenyl borate, ethyl triphenyl borate, propyl triphenyl borate, butyl triphenyl borate, etc.), a phenolate anion (phenolate, 4-tert-butylphenol) And 2,5-di-tert-butylphenolate, 4-nitrophenolate, 2,5-dinitrophenolate, and 2,4,6-trinitrophenolate), and carboxylate anion (benzoate anion) , Toluic acid anion, phenylglyoxylic acid anion, etc.).
  • a borate anion tetraphenyl borate, methyl triphenyl borate, ethyl triphenyl borate, propyl triphenyl borate, butyl triphenyl borate, etc.
  • a phenolate anion phenolate, 4-tert-butylphenol
  • borate anion and carboxylate anion are preferable from the viewpoint of photodegradability, more preferably butyltriphenylborate anion, tetraphenylborate anion, benzoate anion, and phenylglyoxylate anion, photodegradability and heat. From the viewpoint of stability, a tetraphenylborate anion and a phenylglyoxylate anion are particularly preferable.
  • R 51 ⁇ R 53 are the same as R 51 ⁇ R 53 each formula (I).
  • R 70 to R 72 are each independently hydrogen, R x , R y , R z , or a phenyl group.
  • R 70 and R 71 and / or R 72 and R 71 independently form an alkylene bridge having 2 to 12 carbon atoms.
  • R 70 to R 72 together with the bonded nitrogen atom form a P 1 , P 2 , P ⁇ t / 4> type phosphazene base.
  • R 70 to R 72 form a group of the structural formula (a), (b), (c), (d), (e), (f), or (g).
  • R ' is an alkyl group having 1 to 10 carbon atoms
  • R 51 and R 52 are the same as R 51 and R 52 of formula (I)
  • l and q Each is independently a number from 2 to 12.
  • Examples of ⁇ -ammonium ketone derivatives include 1-naphthoylmethyl- (1-azonia-4-azabicyclo [2,2,2] -octane) tetraphenylborate, 5- (4′-nitro) phenacyl- (5 -Azonia-1-azabicyclo [4.3.0] -5-nonene) tetraphenylborate and the like.
  • benzylamine derivative examples include a benzylamine compound represented by the formula (VII).
  • R 51, R 54 ⁇ R 57 are the same as R 51, R 54 ⁇ R 57 each formula (I).
  • R 73 and R 74 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a halogen atom, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, Is an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, an amino group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a naphthyl group Represents a phenyl group which may be substituted with a group selected from the group of phenoxy group and phenylthio group, and R 73 and R 74 may be bonded to
  • benzylamine derivatives examples include 5-benzyl-1,5-diazabicyclo [4.3.0] nonane, 5- (anthracen-9-yl-methyl) -1,5-diazabicyclo [4.3.0].
  • Nonane, benzylamine derivatives such as 5- (naphth-2-yl-methyl) -1,5-diazabicyclo [4.3.0] nonane, and the like.
  • benzylammonium salt derivative examples include a benzylammonium salt represented by the formula (VIII).
  • VIII V - and k V of the formula (VI) - which is similar to and k.
  • R 51 is the same as R 51 in formula (I).
  • R 70 ⁇ R 72 are the same as R 70 ⁇ R 72 each formula (VI).
  • R 73 and R 74 are the same as R 73 and R 74 of formula (VII).
  • benzylammonium salt derivative examples include (9-anthryl) methyl 1-azabicyclo [2.2.2] octanium tetraphenylborate, 5- (9-anthrylmethyl) -1,5-diazabicyclo [4.3. .0] -5-nonenium tetraphenylborate and the like.
  • Examples of the ⁇ -aminoalkene derivative include 5- (2 ′-(2 ′′ -naphthyl) allyl) -1,5-diazabicyclo [4.3.0] nonane.
  • Examples of the ⁇ -ammonium alkene derivative include 1- (2′-phenylallyl)-(1-azonia-4-azabicyclo [2,2,2] -octane) tetraphenylborate.
  • amine imides include [(2-hydroxy-3-phenoxypropyl) dimethylaminio] (4-nitrobenzoyl) amine anion, [(2-hydroxy-3-phenoxypropyl) dimethylaminio] (4-cyano Benzoyl) amine anion, [(2-hydroxy-3-phenoxypropyl) dimethylaminio] (4-methoxybenzoyl) amine anion, [(2-hydroxy-3-phenoxypropyl) dimethylaminio] benzoylamine anion, [( 2-hydroxy-3-phenoxypropyl) dimethylaminio] [4- (dimethylamino) benzoyl] amine anion and the like.
  • benzyloxycarbonylamine derivatives that generate amidine by light include benzyloxycarbonylimidazoles, benzyloxycarbonylguanidines, and diamine derivatives.
  • Examples of benzyloxycarbonylimidazoles include N- (2-nitrobenzyloxycarbonyl) imidazole.
  • Examples of benzyloxycarbonylguanidines include benzyloxycarbonyltetramethylguanidine.
  • Examples of the diamine derivative include N- (N ′-((1- (4,5-dimethoxy-2-nitrophenyl) ethoxy) carbonyl) aminopropyl) -N-methylacetamide.
  • Examples of the salt of carboxylic acid and tertiary amine include ammonium ⁇ -ketocarboxylate and ammonium carboxylate.
  • Examples of the ⁇ -ketocarboxylic acid ammonium salt include dimethyl benzyl ammonium salt of phenylglyoxylic acid.
  • carboxylic acid ammonium salt examples include diazabicycloundecene (DBU) ketoprofen salt, diazabicycloundecene (DBU) xanthone acetate, 2- (carboxymethylthio) thioxanthone 3-quinuclidinol salt, and trans- and 3-quinuclidinol salt of o-coumaric acid.
  • DBU diazabicycloundecene
  • DBU diazabicycloundecene
  • DBU diazabicycloundecene
  • DBU diazabicycloundecene
  • xanthone acetate 2- (carboxymethylthio) thioxanthone 3-quinuclidinol salt
  • trans- and 3-quinuclidinol salt of o-coumaric acid examples include diazabicycloundecene (DBU) ketoprofen salt, diazabicycloundecene (DBU) xanth
  • a photolatent tertiary amine is preferable from the viewpoint that the generated base exhibits a high catalytic activity, and the base generation efficiency is high and the storage stability as a composition is good.
  • Benzylammonium salt derivatives, benzyl-substituted amine derivatives, ⁇ -aminoketone derivatives, ⁇ -ammonium ketone derivatives are preferred.
  • ⁇ -aminoketone derivatives and ⁇ -ammonium ketone derivatives are more preferable due to better base generation efficiency, and ⁇ -aminoketone derivatives are more preferable than the solubility in the blend.
  • the ⁇ -aminoketone compound represented by the formula (I) is preferable from the basic strength of the generated base, and the ⁇ -aminoketone compound represented by the formula (II) is preferable from the viewpoint of availability.
  • photobase generators (B) may be used alone or in combination of two or more.
  • the blending ratio of the photobase generator (B) is not particularly limited, but is preferably 0.01 to 50 parts by weight, and preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of the (A) crosslinkable silicon group-containing organic polymer. Part by mass is more preferable, and 0.5 to 30 parts by mass is even more preferable.
  • the silicon compound having a Si—F bond acts as a curing catalyst for the (A) crosslinkable silicon group-containing organic polymer.
  • various compounds containing a silicon group having a Si—F bond (hereinafter sometimes referred to as a fluorosilyl group) can be used, and there is no particular limitation. Either a low molecular compound or a high molecular compound can be used. An organosilicon compound having a fluorosilyl group is preferable, and an organic polymer having a fluorosilyl group is more preferable 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.
  • silicon compounds having a Si—F bond include compounds having a fluorosilyl group represented by formula (6) such as fluorosilanes represented by formula (5) (hereinafter referred to as fluorinated compounds).
  • fluorinated compounds include organic polymers having a fluorosilyl group (hereinafter also referred to as fluorinated polymers).
  • R 11 4-d SiF d (5)
  • R 11 is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R 12 SiO— (R 12 is each independently having 1 to 20 carbon atoms) Or a substituted or unsubstituted hydrocarbon group, or a fluorine atom), d is any one of 1 to 3, and d is preferably 3.
  • R 11 when there are a plurality of R 12 s , they may be the same or different.
  • R 11 e Z f (In Formula (6), R 11 and d are the same as those in Formula (5), Z is each independently a hydroxyl group or another hydrolyzable group excluding fluorine, and e is any one of 0 to 2) F is any one of 0 to 2, and d + e + f is 3.
  • R 11 , R 12 and Z When a plurality of R 11 , R 12 and Z are present, they may be the same or different.
  • fluorosilanes represented by the formula (5) include fluorosilanes represented by the formula (5).
  • fluorosilanes represented by the formula (5) examples include fluorodimethylphenylsilane, vinyl trifluorosilane, ⁇ -methacryloxypropyl trifluorosilane, octadecyl trifluorosilane, and the like.
  • the hydrolyzable group represented by Z in the formula (6) is, for example, the same group as the hydrolyzable group represented by X in the formula (1).
  • a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, or an alkenyloxy group is preferable. Particularly preferred.
  • R 11 in the formula (6) for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a triorganosiloxy represented by R 12 SiO— in which R 12 is a methyl group, a phenyl group, or the like. Groups and the like. Of these, a methyl group is particularly preferred.
  • Examples of the fluorosilyl group represented by the formula (6) include silicon groups having no hydrolyzable groups other than fluorine, such as fluorodimethylsilyl group, difluoromethylsilyl group, fluoromethoxymethylsilyl group, fluoroethoxymethylsilyl group.
  • a fluoromethoxyphenylsilyl group, a silicon group having no hydrolyzable group other than fluorine, and a fluorosilyl group in which R 11 is a methyl group are preferred, and a trifluorosilyl group is more preferred.
  • a silicon group having no hydrolyzable group other than fluorine such as a fluorodimethylsilyl group, a difluoromethylsilyl group, and a trifluorosilyl group
  • difluoromethyl A silicon group in which 2 to 3 fluorine atoms are substituted on a silicon group, such as a silyl group, a difluoromethoxysilyl group, a difluoroethoxysilyl group, or a trifluorosilyl group, is preferable, and a trifluorosilyl group is most preferable.
  • the compound having a fluorosilyl group represented by the formula (6) is not particularly limited, and either a monomolecular compound or a polymer compound can be used.
  • inorganic silicon compounds low molecular organic silicon compounds such as vinyl difluoromethoxysilane, vinyl trifluorosilane, phenyldifluoromethoxysilane, and phenyltrifluorosilane; fluorinated poly having a fluorosilyl group represented by formula (6) at the terminal
  • examples thereof include polymer compounds such as siloxane, and preferred are fluorosilanes represented by the formula (5) and polymers having a fluorosilyl group represented by the formula (6) at the terminal of the main chain or side chain.
  • organic polymer having a fluorosilyl group (hereinafter also referred to as a fluorinated polymer), various organic polymers having a Si—F bond can be used.
  • the SiF bond in the organic polymer exhibits an effect at any site in the polymer molecule.
  • -SiR ' 2 F when the SiF bond is located at the end of the main chain or side chain and -SiR'F- or ⁇ SiF when incorporated in the main chain of the polymer (R' is independently An arbitrary group such as a methyl group, or an arbitrary atom such as F).
  • a polymer having a fluorosilyl group represented by the formula (6) is preferable.
  • the fluorinated polymer is a single polymer in which the main chain skeleton is the same as a fluorosilyl group, that is, the number of fluorosilyl groups per molecule, the bonding position thereof, and the number of Fs that the fluorosilyl group has, and
  • 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. Any of these fluorinated polymers can be suitably used as a resin component of a curable composition exhibiting rapid curability.
  • the fluorosilyl group contained in the fluorinated polymer is at least on average per molecule of the polymer.
  • each silicon group may be the same or different.
  • the fluorinated polymer has a fluorosilyl group and other substituents excluding fluorosilyl groups such as silicon groups having only other hydrolyzable groups excluding fluorine as hydrolyzable groups (for example, methyldimethoxysilyl group). It may contain a group.
  • fluorinated polymer in which one main chain end is a fluorosilyl group and the other main chain end is a silicon group having only other hydrolyzable groups excluding fluorine as hydrolyzable groups. .
  • Various methods can be used to introduce the fluorosilyl group into the fluorinated polymer.
  • an introduction method by a reaction between a low molecular silicon compound having a fluorosilyl group and a polymer, and a polymer containing a reactive silicon group having other hydrolyzable groups other than fluorine (hereinafter referred to as “polymer”)
  • a method in which the silicon group of “polymer (X)” is modified to a fluorosilyl group.
  • the polymer (X) a crosslinkable silicon group-containing organic polymer (A) is preferably used.
  • a hydrolyzable silicon group represented by the formula (7) is fluorinated. And a method of converting to a fluorosilyl group with an agent.
  • -SiR 11 3-p Z p (7) (In Formula (7), R 11 and Z are the same as in Formula (6), respectively, and p is any one of 1 to 3)
  • the fluorinating agent include BF 3 ether complex, BF 3 alcohol complex, and BF 3 dihydrate. These are preferable because they have high activity, efficiently undergo fluorination, and no salt or the like is generated in the by-product, and post-treatment is easy, and BF 3 ether complexes are particularly 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.
  • the glass transition temperature can be measured 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. If the number average molecular weight is less than 3,000, the cured product tends to be disadvantageous in terms of elongation characteristics, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.
  • the mixing ratio of the silicon compound (C1) having a Si—F bond is not particularly limited, but when a polymer compound having a number average molecular weight of 3,000 or more such as a fluorinated polymer is used as the component (C1), (A)
  • the amount is preferably 0.01 to 80 parts by weight, more preferably 0.01 to 30 parts by weight, and still more preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the crosslinkable silicon group-containing organic polymer.
  • a low molecular compound having a fluorosilyl group having a number average molecular weight of less than 3,000 as the component (C1) for example, a low molecular organic compound having a fluorosilane group represented by the formula (5) or a fluorosilyl group represented by the formula (6)
  • the amount is preferably 0.01 to 10 parts by weight, preferably 0.05 to 100 parts by weight with respect to 100 parts by weight of the (A) crosslinkable silicon group-containing organic polymer. 5 parts by mass is more preferable.
  • the blending ratio of the photobase generator (B) used as the curing catalyst and the silicon compound (C1) having a Si—F bond is (B): (C1).
  • the mass ratio is preferably 1: 0.008 to 1: 300, more preferably 1: 0.016 to 1:40.
  • (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 are hydrolytic condensation of crosslinkable silicon groups It becomes a compound that promotes the reaction and acts as a curing catalyst for the (A) crosslinkable silicon group-containing organic polymer.
  • boron trifluoride complexes examples include boron trifluoride amine complexes, alcohol complexes, ether complexes, thiol complexes, sulfide complexes, carboxylic acid complexes, and water complexes.
  • amine complexes having both stability and catalytic activity are particularly preferred.
  • Examples of the amine compound used in the amine complex of boron trifluoride include a compound having a plurality of primary amino groups, such as monoethylamine, piperidine, aniline, a compound having a plurality of secondary amino groups, and the formula H 2
  • a compound having a plurality of primary amino groups such as monoethylamine, piperidine, aniline
  • a compound having a plurality of secondary amino groups and the formula H 2
  • bicyclic tertiary amine compounds such as N (C 2 H 4 NH) n H (n ⁇ 5) (trade name: Polyate, manufactured by Tosoh Corporation)
  • ⁇ -aminopropyltriethoxysilane And aminosilane compounds such as Examples of commercially available amine complexes of boron trifluoride include Anchor 1040, Anchor 1115, Anchor 1170, Anchor 1222, and BAK 1171 manufactured by Air Products Japan.
  • 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-diethylaminopropane and the like.
  • electrophilic fluorinating agent examples include bis (tetrafluoroboric acid) N, N′-difluoro-2,2′-bipyridinium salt compounds.
  • alkali metal salt of the polyvalent fluoro compound examples include potassium hexafluorophosphate.
  • the blending ratio of the (C2) fluorine-based compound is not particularly limited, but is preferably 0.001 to 10 parts by mass, and 0.001 to 5 parts by mass with respect to 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer. Part is more preferable, and 0.001 to 2 parts by mass is still more preferable.
  • These fluorine compounds may be used alone or in combination of two or more.
  • the photocurable composition contains at least one selected from the group consisting of (C1) a silicon compound having a Si—F bond and (C2) a fluorine-based compound, and only one of (C1) and (C2) Well, you may use both together.
  • the photocurable composition according to this embodiment preferably contains a silicon compound having a (C1) Si—F bond.
  • (D) As a compound having one vinyl group capable of photoradical polymerization various compounds having one vinyl group capable of photoradical polymerization can be used.
  • a compound having one (meth) acryloyl group and an N-vinyl compound in which one vinyl group is directly bonded to a nitrogen atom can be used.
  • Examples of the compound having a (meth) acryloyl group include a compound having one (meth) acryloyloxy group and a compound having one (meth) acrylamide group, and one (meth) acryloyloxy from the viewpoint of storage stability. Compounds having a group are preferred. Moreover, the compound which has one (meth) acrylamide group from a reactive point is preferable.
  • the compound having one (meth) acryloyloxy group either a monomer (hereinafter also referred to as a monomer) or a polymer can be used, and a monomer having a (meth) acryloyloxy group is preferable from the viewpoint of viscosity. .
  • cured material is suitable.
  • the oligomer and the polymer are collectively referred to as a polymer.
  • the monomer having one (meth) acryloyloxy group is not particularly limited as long as it is a compound having one (meth) acryloyloxy group.
  • monofunctional (meth) acrylates can be mentioned.
  • the (meth) acrylate group is preferably an acrylate group from the viewpoint of reactivity.
  • Examples of monofunctional (meth) acrylates include long chains having 8 to 18 carbon atoms such as 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, and isostearyl (meth) acrylate.
  • Hydrocarbon (meth) acrylates such as cyclohexyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate Acrylate; alkoxy groups such as 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, etc.
  • cycloaliphatic (meth) such as cyclohexyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate Acrylate
  • (Meth) acrylate having; phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylates of phenol derivatives modified with alkylene oxide, ethoxylated o-phenylphenol acrylate, etc.
  • examples of polyfunctional acrylates that may be used within a range that does not impair the effect of the photocurable composition according to the present embodiment include 1,6-hexane glycol di (meth) acrylate, polyethylene glycol di (meth) ) Acrylate, bisphenol A di (meth) acrylate, dicyclopentenyl diacrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, and the like.
  • Examples of the polymer having a (meth) acryloyloxy group include an acrylic polymer, a polyester (meth) acrylate polymer, and an epoxy (meth) acrylate polymer having a monomer having one (meth) acryloyloxy group as a skeleton. , Urethane (meth) acrylate polymers, polyether (meth) acrylate polymers, and the like.
  • the polymer include an epoxy (meth) acrylate polymer, a urethane (meth) acrylate polymer, and a polyether (meth) acrylate polymer.
  • Examples of the compound having a (meth) acrylamide group having one vinyl group include N-alkyl (meth) acrylamides such as N-methyl (meth) acrylamide and N-ethyl (meth) acrylamide, N, N-dimethyl ( N, N-dialkyl (meth) acrylamides such as (meth) acrylamide and N, N-diethyl (meth) acrylamide, and (meth) acryloylmorpholine.
  • N-vinyl compound having one vinyl group examples include N-vinylpyrrolidone and N-vinylcaprolactam.
  • the N-vinyl compound is preferable from the viewpoint of reactivity and resistance to oxygen inhibition.
  • (D) Although there is no restriction
  • These radically polymerizable compounds having one vinyl group may be used alone or in combination of two or more.
  • the compound having one photoradically polymerizable vinyl group is 30 parts by mass with respect to 100 parts by mass of (A) the crosslinkable silicon group-containing organic polymer. It is preferable that it is less than. If it is 30 parts by mass or more, the photocurable composition may become sticky after irradiation with active energy rays, which is not preferable because of poor wettability to the adherend. It is preferable that the photocurable composition is in a liquid state after irradiation with an active energy ray because the wettability to the adherend is excellent and sufficient adhesive strength can be exhibited. In addition, even when the adherend is not smooth or when attaching adherends with complicated shapes, it is possible to demonstrate sufficient adhesive strength by being excellent in wettability, so that after irradiation with active energy rays The state is preferably liquid.
  • adherends can be bonded together while the liquid state is maintained after UV irradiation, the adherends can be bonded together after UV irradiation. Can also be used.
  • the photocurable composition according to this embodiment includes a crosslinkable silicon group-containing compound that generates one or more amino groups selected from the group consisting of a primary amino group and a secondary amino group by light. It is preferable.
  • the crosslinkable silicon group-containing compound that generates one or more amino groups selected from the group consisting of primary amino groups and secondary amino groups by light can improve adhesion performance.
  • the primary amino group and the primary amino group can be obtained by light irradiation. Any compound that generates an aminosilane compound having at least one amino group selected from the group consisting of secondary amino groups and a crosslinkable silicon group can be used.
  • the crosslinkable silicon group-containing compound that generates one or more amino groups selected from the group consisting of a primary amino group and a secondary amino group by light is also referred to as a photoaminosilane generating compound.
  • the aminosilane compound generated by light irradiation a compound having a crosslinkable silicon group and a substituted or unsubstituted amino group is used.
  • substituent of the substituted amino group include an alkyl group, an aralkyl group, and an aryl group.
  • a crosslinkable silicon group the crosslinkable silicon group described in the section of (A) crosslinkable silicon group-containing organic polymer can be mentioned, and a silicon-containing group to which a hydrolyzable group is bonded is preferable.
  • alkoxy groups such as a methoxy group and an ethoxy group are preferable because they are mildly hydrolyzable and easy to handle.
  • the hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, preferably 2 or more, particularly preferably 3.
  • the aminosilane compound generated by light irradiation is not particularly limited.
  • ⁇ -aminopropyltrimethoxysilane ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane
  • Monoamines such as N-phenyl- ⁇ -aminopropyltrimethoxysilane
  • diamines such as ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane, ⁇ - (2-aminoethyl) aminopropylmethyldimethoxysilane, ⁇ - (2 And triamines such as-(2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane.
  • aminosilane compounds generated by light irradiation aminosilane compounds having a primary amino group (—NH 2 ) are preferable from the viewpoint of adhesion, and ⁇ -aminopropyltrimethoxysilane and ⁇ -aminopropyl are preferable from the viewpoint of availability.
  • Triethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, and ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane are preferable, and ⁇ -aminopropyltrimethoxysilane and ⁇ -aminopropyltriethoxysilane are preferable in terms of adhesiveness and curability. More preferred.
  • Examples of the photoaminosilane generating compound include a silicon compound having a photofunctional group represented by formulas (8) to (9), an aromatic sulfonamide derivative represented by formula (10), and an O— represented by formula (11). And acyl oxime derivatives, trans-O-coumaric acid derivatives represented by the formula (12), and the like.
  • n is an integer of 1 to 3
  • Y represents a hydroxyl group or a hydrolyzable group, and an alkoxy group is preferable.
  • R 101 represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a substituent, vinyl group, allyl group, unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, unsubstituted or substituted aryl group Is preferred.
  • R 101 represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a substituent, vinyl group, allyl group, unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, unsubstituted or substituted aryl group Is preferred.
  • R 101 represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a substituent, vinyl group, allyl group, unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, un
  • R 102 is a hydrogen atom or an organic group, preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a substituent, and more preferably a hydrogen atom.
  • h is an integer of 1 to 5
  • j is an integer of 1 to 6.
  • R 103 is a substituted or unsubstituted hydrocarbon group bonded to a silicon atom and a nitrogen atom at h + j different carbon atoms, and a plurality of substituted or unsubstituted groups bonded to each other via one or more ether oxygen atoms. It is an h + j-valent group selected from the group consisting of hydrocarbon groups and has a molecular weight of 1,000 or less.
  • R 102 and R 103 may be bonded to each other to form a cyclic structure, and may include a hetero atom bond.
  • Z is an oxygen atom or a sulfur atom, preferably an oxygen atom.
  • Q represents a
  • R 105 is a divalent group selected from the group consisting of a substituted or unsubstituted hydrocarbon group and a plurality of substituted or unsubstituted hydrocarbon groups bonded to each other via one or more ether oxygen atoms.
  • t is an integer of 1 or more, and 1 or 2 is preferable. When t is 2 or more, t groups bonded to R 104 may be the same or different.
  • R 104 is a hydrogen atom or an organic group, preferably a hydrogen atom or a substituted or unsubstituted t-valent hydrocarbon group, more preferably a hydrogen atom or a substituted or unsubstituted t-valent alkyl group.
  • R 104 and R 105 may be bonded to each other to form a cyclic structure, and may include a hetero atom bond.
  • R 106 to R 110 each independently represents a hydrogen atom or a substituent.
  • substituents include a nitro group, a cyano group, a hydroxy group, a mercapto group, a halogen atom, an acetyl group, a carbonyl group, a substituted or non-substituted group.
  • R 106 to R 110 When any of R 106 to R 110 is bonded to each other to form a cyclic structure, a structure in which a plurality of benzene rings are condensed, a benzene ring and a heterocyclic ring, a non-aromatic ring, or a functional group such as a carbonyl group is bonded.
  • a structure such as a condensed ring may be formed.
  • n, Y, R 101 , R 103 , h and j are the same as in formula (8), and R 106 to R 110 are the same as in formula (10).
  • R 111 is the same as R 106 to R 110 in the formula (10).
  • R 112 is a hydrogen atom or an organic group, preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a substituent, and more preferably a hydrogen atom.
  • R 103 and R 112 may be bonded to each other to form a cyclic structure, and may include a hetero atom bond.
  • R 113 and R 114 are each independently a hydrogen atom, halogen atom, hydroxy group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group.
  • R 115 is a hydrogen atom or a substituent, and is preferably a hydrogen atom or a protective group that can be deprotected by heating and / or irradiation with light, and includes a hydrogen atom, a silyl group, a silanol group, a phosphino group, a phosphinyl group, a phosphono group, Or an organic group is more preferable.
  • examples of the unsubstituted or substituted alkyl group having 1 to 10 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, n- Examples include butyl group, tert-butyl group, n-pentyl group, chloromethyl group, chloroethyl group, fluoromethyl group, cyanomethyl group and the like.
  • examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group.
  • Examples of the unsubstituted or substituted aryl group include a phenyl group, a p-methoxyphenyl group, a p-chlorophenyl group, and a p-trifluoromethylphenyl group.
  • Examples of the aryloxy group include a phenoxy group.
  • the photofunctional group Q includes a known photosensitive group and is not particularly limited.
  • a group having a cyclic structure represented by the formula (13), an oxime residue represented by the formula (14), or a substituted group are exemplified, and a group having a cyclic structure represented by the formula (13) is preferable.
  • A is a direct bond or a bivalent coupling group, and Q 'is a cyclic structure containing group.
  • a direct bond means that Q ′ is directly bonded to Z without a linking group.
  • the divalent linking group in A for example, a divalent linking group containing an alkylene group, a carbonyl group, an ether bond, an ester bond, a —CONH— group, or a combination thereof, each of which may have a substituent. Group, etc. are mentioned, The alkylene group and carbonyl group which may contain the substituent, and those combinations are preferable.
  • the substituent of A may have a cyclic structure.
  • substituents may couple
  • Examples of the cyclic structure include the same structure as Q ′.
  • the cyclic structure in Q ′ may be either a single ring or a plurality of rings, and may be either a monocyclic ring or a heterocyclic ring, but includes a functional group such as a vinyl group, a carbonyl group, or an imino group. It is preferable to have a cyclic structure exhibiting aromaticity.
  • Q ′ for example, an aryl group, an aryloxy group, a heterocyclic group containing one or more heteroatoms such as nitrogen, oxygen, sulfur and the like, each having a substituent, and a cyclic structure in which a carbonyl group is bonded And a combination thereof and a condensed ring thereof. Further, the substituent may further have a cyclic structure. Moreover, the substituent of A and Q ′ may be bonded. ]
  • R 116 and R 117 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, an amino group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, an alkyl group. It is at least one selected from the group consisting of an oxy group, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, an alkenyloxy group, a substituted or unsubstituted aryl group having 4 to 50 carbon atoms, and an aryloxy group.
  • R 116 and R 117 may be bonded to each other to form a double bond or an aromatic or non-aromatic ring, and R 116 and R 117 , or R 116 and R 117 may be bonded to each other.
  • the double bond or aromatic or non-aromatic ring formed may further have one or two oxime groups represented by the above formula.
  • Examples of the group having a cyclic structure represented by the formula (13) include an aromatic group represented by the formula (15), a group having a heterocyclic structure, and these substituted groups. preferable. Further, groups in the photofunctional group may be bonded to each other to form a cyclic structure.
  • A is the same as A in Formula (13), and is preferably a substituted or unsubstituted alkylene group, a carbonyl group, or a combination thereof.
  • R 118 to R 122 are each independently hydrogen. Represents an atom or a substituent, and examples of the substituent include a nitro group, a cyano group, a hydroxy group, a mercapto group, a halogen atom, an acetyl group, a carbonyl group, a substituted or unsubstituted allyl group, and a substituted or unsubstituted alkyl group.
  • .R 118 either ⁇ R 122 are bonded to each other, if they form a cyclic structure, the structure a plurality of benzene rings are condensed, a benzene ring and a heterocyclic ring or non-aromatic ring, functional group such as a carbonyl group And a ring or the like in which a ring is bonded may be formed, or a substituent of A and any of R 118 to R 122 may
  • Examples of the aromatic group represented by the formula (15) include an o-nitrobenzyl group represented by the formula (16-1), an m-nitrobenzyl group represented by the formula (16-2), and a formula (16-3).
  • a nitrobenzyl group such as p-nitrobenzyl group represented by formula (18), a benzyl group represented by formula (17), a benzoyl group represented by formula (18) or a substituted group thereof, and a nitrobenzyl group is preferred.
  • O-nitrobenzyl group and p-nitrobenzyl group are more preferable, and o-nitrobenzyl group is particularly preferable.
  • groups in the photofunctional group may be bonded to each other to form a cyclic structure.
  • R 118 to R 121 are the same as those in the formula (15).
  • R 123 and R 124 each independently represents a hydrogen atom, a carbon number of 1 to 10 represents an unsubstituted or substituted alkyl group, a phenyl group, a substituted phenyl group, k is 1 or 2, and when k is 2, a plurality of R 123 and R 124 may be the same or different. Good.
  • R 118 to R 122 are the same as in formula (15).
  • R 125 and R 126 are each independently a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms. Represents a phenyl group or a substituted phenyl group.
  • R 118 to R 122 are the same as in the formula (15).
  • R 127 and R 128 each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms. Represents a phenyl group or a substituted phenyl group.
  • benzoyl group represented by the formula (18) for example, a benzoylphenylmethyl group represented by the formula (19) is preferable.
  • R 118 to R 122 are the same as in the formula (15).
  • R 130 represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or a substituted phenyl group.
  • R 131 to R 135 each independently represent a hydrogen atom, a nitro group, a cyano group, a hydroxy group, a mercapto group, a halogen atom, an acetyl group, an allyl group, an alkyl group having 1 to 5 carbon atoms, or a carbon number.
  • R 131 to R 135 may be bonded to each other to form a double bond or an aromatic or non-aromatic ring.
  • R 131 to R 135 and R 118 to R 122 may be bonded to each other to form a cyclic structure, and include a hetero atom bond. May be good.
  • Examples of the group having a heterocyclic structure include a coumarin derivative residue represented by the formula (20), an imide group represented by the formula (21), and these substituted groups.
  • R 136 and R 137 each independently represent a hydrogen atom or a substituent
  • R 138 ⁇ R 142 each independently represent a hydrogen atom or a substituent
  • R 138 ⁇ R the 142 is the same as R 118 ⁇ R 122 of formula (15)
  • R 138 of 142 ⁇ R 142 When one of them is bonded to each other to form a cyclic structure, a structure in which a plurality of benzene rings are condensed, a benzene ring and a heterocyclic ring, a non-aromatic ring, a ring in which a functional group such as a carbonyl group is bonded, or the like is condensed.
  • a structure or the like may be formed.
  • R 143 and R 144 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a cycloalkyl group, a hydroxyl group, or an alkoxy group.
  • R 143 and R 144 are bonded to the double bond to one another, or optionally form an aromatic or non-aromatic ring .
  • Examples of the —OQ group in which the photofunctional group Q is an o-nitrobenzyl group represented by the formula (16-1) include (2,6-dinitrobenzyl) oxy group, (2-nitrobenzyl) oxy group, ( And nitrobenzyloxy groups such as 3,4-dimethoxy-2-nitrobenzyl) oxy group.
  • Examples of the —OQ group in which the photofunctional group Q is a p-nitrobenzyl group represented by the formula (16-3) include (2,4-dinitrobenzyl) oxy group, (4-nitrobenzyl) oxy group, [ And nitrobenzyloxy groups such as 1- (4-nitronaphthalene) methyl] oxy group.
  • Examples of the —OQ group in which the photofunctional group Q is a benzyl group represented by the formula (17) include 3,5-dimethoxybenzyloxy group, [1- (3,5-dimethoxyphenyl) -1-methylethyl] Oxy group, 9-anthrylmethyloxy group, 9-phananthrylmethyloxy group, 1-pyrenylmethyloxy group, [1- (anthraquinone-2-yl) ethyl] oxy group, 9-phenylxanthen-9-yloxy And benzyloxy groups such as groups.
  • Examples of the —OQ group in which the photofunctional group Q is a benzoylphenylmethyl group represented by the formula (19) include 1- (3,5-dimethoxybenzoyl) -1- (3,5-dimethoxyphenyl) methyloxy group And benzoinoxy groups such as 1-hydroxy-1-phenylacetophenoneoxy group.
  • Examples of the —OQ group in which the photofunctional group Q is a coumarin derivative residue represented by the formula (20) include a coumarin-4-ylmethoxy group such as a 7-methoxycoumarin-4-ylmethoxy group.
  • Examples of the —OQ group in which the photofunctional group Q is an imide group represented by the formula (21) include imideoxy groups such as a phthalimidooxy group and a hexahydrophthalic acid imideoxy group.
  • Examples of the —OQ group in which the photofunctional group Q is an oxime residue represented by the formula (14) include N- (1-phenylethylidene) aminooxy group, diphenylmethylideneaminooxy group, N- (cyclohexylidene) ) Oximeoxy groups such as aminooxy groups.
  • examples of the residue excluding the ZQ group include 3- (trimethoxysilyl) propylaminocarbonyl group, 3- (triethoxysilyl) propylaminocarbonyl group, 3- (methyl Monoaminocarbonyl groups such as dimethoxysilyl) propylaminocarbonyl group, 3- (methyldiethoxysilyl) propylaminocarbonyl group; N- [3- (trimethoxysilyl) propyl] ethylenediaminocarbonyl group, N, N′-bis And diaminocarbonyl groups such as [3- (trimethoxysilyl) propyl] ethylenediaminocarbonyl group; and aminocarbonyl groups such as triaminocarbonyl group such as N- [3- (trimethoxysilyl) propyl] diethylenetriaminocarbonyl group.
  • aminocarbonyl groups an aminocarbonyl group having an amino group (—NH 2 ) is preferable from the viewpoint of adhesion, and 3- (trimethoxysilyl) propylaminocarbonyl group, 3- (triethoxysilyl) propylaminocarbonyl group , 3- (methyldimethoxysilyl) propylaminocarbonyl group and N- [3- (trimethoxysilyl) propyl] ethylenediaminocarbonyl group are more preferable, and 3- (trimethoxysilyl) propylaminocarbonyl group is preferred in view of adhesiveness and curability. 3- (triethoxysilyl) propylaminocarbonyl group is most preferred.
  • examples of the arylsulfonyl group include aromatic sulfonyl groups such as 2-naphthalenesulfonyl group and p-toluenesulfonyl group.
  • examples of the residue excluding the arylsulfonyl group include 3- (trimethoxysilyl) propylamino group, 3- (triethoxysilyl) propylamino group, 3- (methyldimethoxysilyl) propylamino And a monoamino group such as a 3- (methyldiethoxysilyl) propylamino group; a diamino group; and a triamino group.
  • examples of the residue excluding the aryloxime group include 3- (trimethoxysilyl) propylcarbonyl group, 3- (triethoxysilyl) propylcarbonyl group, and 3- (triisopropoxysilyl) propyl.
  • Examples include carbonyl groups such as carbonyl group, 3- (methyldimethoxysilyl) propylcarbonyl group, and 3- (methyldiethoxysilyl) propylcarbonyl group.
  • the blending ratio of the crosslinkable silicon group-containing compound is not particularly limited, but is preferably 0.01 to 50.00 parts by mass, preferably 1.00 to 100 parts by mass with respect to 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer. 20.00 parts by mass is more preferable, and 3.00 to 10.00 parts by mass is more preferable.
  • These crosslinkable silicon group-containing compounds may be used alone or in combination of two or more.
  • a silane coupling agent if necessary, a photosensitizer, a bulking agent, a plasticizer, a moisture absorbent, a curing catalyst, a physical property modifier that improves tensile properties, and the like.
  • Various additives such as reinforcing agents, colorants, flame retardants, anti-sagging agents, antioxidants, anti-aging agents, ultraviolet absorbers, solvents, fragrances, pigments, dyes, resin fillers, and the like may be added.
  • the photocurable composition according to the present embodiment can improve adhesion to general adherends such as metals, plastics, and glass by blending a silane coupling agent.
  • silane coupling agents include amino group-containing silanes; ketimine type silanes; epoxy group-containing silanes; mercapto group-containing silanes; vinyl type unsaturated group-containing silanes; chlorine atom-containing silanes; Alkyl silanes; phenyl group-containing silanes; isocyanurate group-containing silanes, and the like, but are not limited thereto.
  • modified amino group-containing silanes in which amino groups are modified by reacting amino group-containing silanes with epoxy group-containing compounds, isocyanate group-containing compounds, and (meth) acryloyl group-containing compounds containing the above silanes are used. May be.
  • the blending ratio of the silane coupling agent is not particularly limited, but is preferably 0.2 to 20 parts by weight, and 0.3 to 15 parts by weight with respect to 100 parts by weight of the (A) crosslinkable silicon group-containing organic polymer. More preferred is 0.5 to 10 parts by mass.
  • 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, and examples thereof include anthraquinone, thioxanthone, 3-acylcoumarin, and 2 (aroylmethylene) -thiazoline. And 3-acyl coumarins are preferred. These sensitizers enhance the reactivity of the generated amine base without shortening the shelf life of the composition.
  • an active energy ray-cleaving radical generator that is cleaved by irradiation with active energy rays to generate radicals is more preferable.
  • an active energy ray-cleaving radical generator is used, the curing rate is much faster than when photosensitizers such as benzophenones and thioxanthones, which are sensitizers for photobase initiators, are used. Therefore, the photocurable composition which concerns on this embodiment can be hardened further in a short time after energy beam irradiation.
  • Examples of the energy ray-cleaving radical generator include arylalkyl ketones such as benzoin ether derivatives and acetophenone derivatives, oxime ketones, acylphosphine oxides, thiobenzoic acid S-phenyls, titanocenes, and high molecular weights thereof. Derivatized derivatives.
  • 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, hydrous silicon, calcium silicate, titanium dioxide, carbon black and the like. These may be used alone or in combination of two or more.
  • plasticizer examples include phosphate esters such as tributyl phosphate and tricresyl phosphate, phthalate esters such as dioctyl phthalate, aliphatic monobasic esters such as glycerin monooleate, dioctyl adipate, and the like. Aliphatic dibasic acid esters, polypropylene glycols and the like. These may be used alone or in combination of two or more.
  • the above-described silane coupling agent and silicate are suitable. It does not specifically limit as a silicate, For example, tetraalkoxysilane or its partial hydrolysis-condensation product is mentioned.
  • known curing catalysts can be widely used, and are not particularly limited. Examples thereof include organometallic compounds and amines, and it is particularly preferable to use a silanol condensation catalyst.
  • the silanol condensation catalyst include organic tin compounds; dialkyl tin oxides; reaction products of dibutyl tin oxide and phthalic acid esters; titanic acid esters; organoaluminum compounds; chelate compounds such as titanium tetraacetylacetonate; Organic acid bismuth etc. are mentioned.
  • the toxicity of the resulting photocurable composition may increase depending on the amount of the organotin compound added.
  • the resin filler is a particulate filler made of an organic resin or the like, and known organic fine particles such as polyethyl acrylate, polyurethane, polyethylene, and polypropylene can be used.
  • urea resin-based filler “PERGOPAK series” manufactured by ALBEMARLE may be used.
  • melamine resin filler examples include “Eposter M30” manufactured by Nippon Shokubai Co., Ltd.
  • the urethane resin filler include cross-linked urethane resin fillers such as “Art Pearl C-200, C-300, C-400, C-800” manufactured by Negami Kogyo Co., Ltd.
  • Examples of the benzoguanamine resin filler include “Eposter M05, MS” manufactured by Nippon Shokubai Co., Ltd.
  • Examples of the phenol resin filler include “PR-RES-5” manufactured by Sumitomo Bakelite Co., Ltd., “Shonol PMB-1010” manufactured by Showa Polymer Co., Ltd., and the like.
  • Acrylic resin fillers include “Techpolymer MBX Series” manufactured by Sekisui Plastics Co., Ltd., Art Pearl G-400, G-800, GR-400, GR-800, J-4P, J manufactured by Negami Kogyo Co., Ltd. -4PY, J-5P, J-7P, J7PY, S-5P and the like.
  • Examples of the styrene resin filler include “Techpolymer SBX series” manufactured by Sekisui Plastics Co., Ltd.
  • the resin filler (resin fine powder) is preferably a true spherical material that can be easily obtained by suspension polymerization of a monomer (for example, methyl methacrylate). Moreover, since a resin filler is suitably contained as a filler in the solution composition, a spherical crosslinked resin filler is preferable.
  • a urethane resin filler and an acrylic resin filler are preferable, and a urethane resin filler is more preferable in terms of good compatibility with the component (A).
  • the average particle size of the resin filler is preferably 1 to 150 ⁇ m, more preferably 5 to 30 ⁇ m.
  • the average particle diameter is a 50% cumulative particle diameter measured by a laser diffraction scattering method. If the average particle size is smaller than 1 ⁇ m, it may be difficult to disperse in the conductive adhesive system. On the other hand, if it is larger than 150 ⁇ m, it tends to be clogged with an application nozzle.
  • the Tg of the resin filler is preferably 20 ° C. to ⁇ 60 ° C., more preferably 0 ° C. to ⁇ 50 ° C. Tg is measured by differential scanning calorimetry (DSC method).
  • the blending ratio of the resin filler is not particularly limited, but is preferably 0.5 to 200 parts by mass and more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the component (A).
  • a resin filler may be used independently and may use 2 or more types together.
  • the method for producing the photocurable composition according to this embodiment is not particularly limited, and for example, a predetermined amount of components (A), (B), (C1) and / or (C2), and (D) is blended. Moreover, it can manufacture by mix
  • the photocurable composition according to the present embodiment 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 photocurable composition according to this embodiment is a photocurable composition that is cured by light irradiation, can be cured at room temperature (for example, 23 ° C.), and is preferably used as a room temperature photocurable curable composition. However, if necessary, curing may be accelerated by heating.
  • cured material which concerns on this embodiment is a method of forming hardened
  • the cured product according to the present embodiment is a cured product obtained by this method.
  • the manufacturing method of the product which concerns on this embodiment is a method of manufacturing using the photocurable composition which concerns on this embodiment.
  • the product according to the present embodiment is a product obtained by using this method, and can be suitably used for electronic circuits, electronic parts, building materials, automobiles, and the like.
  • an active energy ray As an active energy ray, ultraviolet rays, visible rays, infrared rays, etc.
  • electromagnetic waves such as light rays, X-rays, and ⁇ rays, electron beams, proton beams, neutron beams, and the like can be used.
  • the ultraviolet ray includes 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, and includes, 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, and a metal halide depending on the properties of the photobase generator used.
  • a light emitting diode is preferred.
  • the irradiation energy is preferably 10 to 20,000 mJ / cm 2, more preferably 20 to 10,000 mJ / cm 2, and still more preferably 50 to 5,000 mJ / 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 , even if light is irradiated more than necessary, time and cost are wasted and the substrate is damaged. There is.
  • the method of applying the photocurable composition according to the present embodiment to the adherend is not particularly limited, but screen printing, stencil printing, roll printing, dispenser coating, spin coating and the like are preferably used.
  • a photocurable composition is apply
  • the photocurable composition according to the present embodiment is a fast-curing photocurable composition excellent in workability, and is particularly useful as an adhesive / adhesive composition, and is an adhesive, a sealing material, and an adhesive. , Coating materials, potting materials, paints, putty materials, primers and the like.
  • the photocurable composition according to the present embodiment includes, for example, a coating agent used for moisture-proofing and insulation of a mounted circuit board and the like, a coating for solar power generation panels and a peripheral portion of the panel, and the like; Sealing agents, sealing agents for vehicles, etc .; architectural and industrial sealing agents; electrical and electronic component materials such as solar cell back surface sealing agents; electrical insulating materials such as insulation coating materials for electric wires and cables; It can be suitably used for applications such as a material for forming a molded article; an adhesive; an adhesive; an elastic adhesive; a contact adhesive.
  • the photocurable composition according to the present embodiment can solve problems such as a light-shielding portion, and is a display device for mobile phones including a smartphone, a tablet, a notebook PC, a PDA, a car navigation system, and an outdoor installation instrument. It can be particularly suitably used as an adhesive for a constituent member of an image display device such as a liquid crystal panel. Moreover, when using as a structural member use of an image display apparatus, it has sufficient performance even if it does not contain (D) component.
  • D contain
  • a methanol solution of sodium methoxide is added to the obtained polyoxypropylene diol, methanol is distilled off under heating and reduced pressure, and the terminal hydroxyl group of the polyoxypropylene diol is converted to sodium alkoxide to obtain a polyoxyalkylene polymer M1. It was.
  • the polyoxyalkylene polymer M1 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 end is reacted with trimethoxysilane, which is a silicon hydride compound, by adding a platinum vinyl siloxane complex isopropanol solution to react with the polyoxyalkylene having a trimethoxysilyl group at the end.
  • trimethoxysilane which is a silicon hydride compound
  • the peak top molecular weight was 25,000 and the molecular weight distribution was 1.3.
  • the number of terminal trimethoxysilyl groups was 1.7 per molecule.
  • a methanol solution of sodium methoxide is added to the obtained polyoxypropylene diol, methanol is distilled off under reduced pressure by heating, and the terminal hydroxyl group of the polyoxypropylene diol is converted to sodium alkoxide to obtain a polyoxyalkylene polymer M2. It was.
  • the polyoxyalkylene polymer M2 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 end is reacted with trimethoxysilane, which is a silicon hydride compound, by adding a platinum vinyl siloxane complex isopropanol solution to react with the polyoxyalkylene having a trimethoxysilyl group at the end.
  • trimethoxysilane which is a silicon hydride compound
  • the peak top molecular weight was 12,000 and the molecular weight distribution was 1.3.
  • the number of terminal trimethoxysilyl groups was 1.7 per molecule.
  • the temperature of the reaction product was returned to room temperature, 20.00 g of a benzoquinone solution (95% THF solution) was added to the reaction product to terminate the polymerization, and a trimethoxysilyl group (meta ) Acrylic polymer A3 was obtained.
  • the (meth) acrylic polymer A3 had a peak top molecular weight of 4,000 and a molecular weight distribution of 2.4.
  • the number of trimethoxysilyl groups contained by 1 H-NMR measurement was 2.00 per molecule.
  • a methanol solution of sodium methoxide is added to the obtained polyoxypropylene diol, methanol is distilled off under reduced pressure by heating, and the terminal hydroxyl group of the polyoxypropylene diol is converted to sodium alkoxide to obtain a polyoxyalkylene polymer M3. It was.
  • the polyoxyalkylene polymer M3 was reacted with allyl chloride to remove unreacted allyl chloride and purified to obtain a polyoxyalkylene polymer having an allyl group at the terminal.
  • the polyoxyalkylene polymer having an allyl group at the terminal is reacted with methyldimethoxysilane, which is a silicon hydride compound, by adding a platinum vinylsiloxane complex isopropanol solution, and the polyoxyalkylene having a methyldimethoxysilyl group at the terminal is reacted.
  • a polymer A4 was obtained.
  • the peak top molecular weight was 15,000 and the molecular weight distribution was 1.3.
  • the number of terminal methyldimethoxysilyl groups was 1.7 per molecule.
  • fluorinated polymer C1 a polyoxyalkylene polymer C1 having a fluorosilyl group at the terminal (hereinafter referred to as fluorinated polymer C1) was obtained.
  • Example 1 A photocurable composition was prepared by adding each compounded substance to a flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube, and a water-cooled condenser, and mixing and stirring them at the mixing ratio shown in Table 1. Was prepared.
  • the compounding amount of each compounding substance is indicated by g
  • the polymers A1 to A3 are the polymers A1 to A3 obtained in Synthesis Examples 2 to 4, respectively
  • the photoaminosilane generating compound X is the compound of Synthesis Example 1. It is the obtained photoaminosilane generating compound X
  • the fluorinated polymer C1 is the fluorinated polymer C1 obtained in Synthesis Example 5
  • the details of other compounding substances are as follows.
  • N-vinyl-2-pyrrolidone Product name N-vinylpyrrolidone manufactured by Nippon Shokubai Co., Ltd. Isobonyl acrylate: Osaka Organic Chemical Industry Co., Ltd., trade name IBXA. 2-Hydroxy-2-methyl-1-phenyl-propan-1-one: Product name IRGACURE 1173 manufactured by BASF Corporation. Lauryl acrylate: trade name Light acrylate LA, manufactured by Kyoeisha Chemical Co., Ltd. Lauryl methacrylate: Product name SR313, manufactured by Sartomer. 3-acryloxypropyltrimethoxysilane: Shin-Etsu Chemical Co., Ltd., trade name KBM5103. Ethoxylated o-phenylphenol acrylate: manufactured by Toagosei Co., Ltd., trade name Aronix M-106.
  • a photocurable composition is poured into a cylindrical container having a diameter of 20 mm and a height of 7 mm so as to have a thickness of 7 mm, and irradiated with UV [irradiation conditions: UV-LED lamp (wavelength 365 nm, illuminance: 1000 mW / cm 2 ), integrated. Light amount: 1000 mJ / cm 2 ], Immediately after UV irradiation and after a predetermined time elapsed, the surface of the photocurable composition was checked by finger touch. The liquid case was defined as liquid, the case where the surface was cured was defined as cured, and the case where the surface was adhesive was defined as adhesive.
  • Examples 2 to 14 and Comparative Examples 1 to 6 As shown in Tables 1 and 2, after obtaining a photocurable composition by the same method as in Example 1 except that the compounding substances were changed, the characteristics of the obtained photocurable composition were evaluated. The results are shown in Tables 1-2.
  • the photocurable compositions according to the examples of the present invention were curable in a short time and exhibited excellent rising adhesiveness. Furthermore, the photocurable compositions according to the examples of the present invention are in a liquid state after UV irradiation and have a time for bonding even after UV irradiation, and therefore have an appropriate workable time. However, it had fast curability. In addition, when (D) a compound having one photoradically polymerizable vinyl group was contained, even when the surface curability was equal, the rising adhesiveness was excellent.

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Abstract

La présente invention concerne une composition photodurcissable contenant : (A) un polymère organique réticulable contenant un groupe silicium ; (B) un générateur de photobase ; (C1) un composé silicium ayant une liaison Si-F, et/ou (C2) un ou plusieurs composés à base de fluor sélectionnés parmi le groupe constitué du trifluorure de bore, un complexe de trifluorure de bore, un agent de fluoration, et un sel de métal alcalin d'un composé fluoré polyvalent ; et (D) un composé ayant un groupe vinyle photopolymérisable de manière radicalaire.
PCT/JP2015/079993 2014-10-24 2015-10-23 Composition photodurcissable Ceased WO2016063978A1 (fr)

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WO2019064385A1 (fr) * 2017-09-27 2019-04-04 日立化成株式会社 Composition de résine durcissable, dispositif d'affichage d'image, et procédé de production d'un dispositif d'affichage d'image
JPWO2019156163A1 (ja) * 2018-02-07 2021-01-28 三菱ケミカル株式会社 光硬化性組成物、造形物及びハイドロゲル
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WO2019064385A1 (fr) * 2017-09-27 2019-04-04 日立化成株式会社 Composition de résine durcissable, dispositif d'affichage d'image, et procédé de production d'un dispositif d'affichage d'image
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WO2024219323A1 (fr) * 2023-04-20 2024-10-24 日油株式会社 Composé polyoxyalkylène contenant un groupe alcényle, modificateur de silicone, silicone modifiée par polyoxyalkylène et composition d'émulsion

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