JP6672789B2 - Photocurable composition - Google Patents

Description

  The present invention relates to a photocurable composition, and more particularly to a photocurable composition which has excellent workability before and after irradiation with active energy rays and can be cured in a short time.

  An organic polymer having a hydroxyl group or a 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”) at room temperature It is also known that they have the property of being crosslinked by the formation of a siloxane bond accompanied by a hydrolysis reaction of the crosslinkable silicon group due to moisture or the like, thereby obtaining a rubber-like cured product. Among these polymers having a crosslinkable silicon group, an organic polymer whose main chain skeleton is a polyoxyalkylene polymer or a (meth) acrylate polymer is used for sealing materials, adhesives, paints, and the like. Widely used for.

  Curable compositions used for sealing materials, adhesives, paints, and rubber-like cured products obtained by curing include various properties such as curability, adhesion, storage stability, and mechanical properties such as modulus, strength, and elongation. Properties are required, and many studies have been made on organic polymers containing a crosslinkable silicon group. In recent years, in various fields such as the field of assembling electronic components and electronic devices, quick curing has been required. However, in the case of a moisture-curable adhesive, there is a problem that the bonding time after application becomes short.

  On the other hand, as a photocrosslinkable composition using an organic polymer containing a crosslinkable silicon group, Patent Document 1 discloses a polymer having two or more hydrolyzable silyl groups in one molecule, and a polymer obtained by irradiation with light. A photo-crosslinkable composition comprising a compound that crosslinks a polymer, and a compound that generates an acid or a base when irradiated with light as a compound that crosslinks a polymer by light irradiation. It illustrates a crosslinkable composition (Patent Document 1, Claims 1 to 3).

  However, in the composition described in Patent Document 1, when a photoacid generator is used as a compound that crosslinks a polymer by light irradiation, there is a problem that rust is generated, and a photobase is used as a compound that crosslinks a polymer by light irradiation. When a generator was used, a long time was required for curing, and the curing reaction was sometimes insufficient.

  Various inventions such as Patent Literature 1 are disclosed for a photocurable composition using a photobase generator, but usually require a long time for curing and have not yet been put to practical use. In addition, the conventional photocurable composition has a small cured thickness of the cured product, and sometimes lacks the short-time thickness curability required for an application such as shortening of tact time or potting.

JP 2001-172514 A

  The present invention is a photocurable composition that can be cured by exposure to active energy rays because it does not cure even when exposed to air before irradiation with active energy rays, and thus can take a sufficient working time. It has a sufficient bonding time after irradiation, excellent thickness curability in a short time, no rust even when used for bonding electric and electronic parts, etc. An object of the present invention is to provide a photocurable composition that can be cured in a shorter time than a curable composition.

  In order to solve the above problems, the photocurable composition of the present invention comprises (A) a crosslinkable silicon group-containing organic polymer, (B) a photobase generator, and (C) silicon having a Si—F bond. And a compound.

  The curable composition of the present invention preferably further contains (D) an active energy ray-cleavable radical generator.

  The photobase generator (B) is preferably a photolatent tertiary amine. In the present invention, a substance that generates an amine compound by the action of an active energy ray is referred to as a photolatent amine compound. Further, a substance capable of generating an amine compound having a primary amino group by the action of an active energy ray is referred to as a photolatent primary amine and a substance capable of generating an amine compound having a secondary amino group is referred to as a photolatent primary amine. A substance that generates a secondary amine and an amine compound having a tertiary amino group is referred to as a photolatent tertiary amine, respectively.

  The above (A) the crosslinkable silicon group-containing organic polymer is a polyoxyalkylene polymer containing 0.8 or more crosslinkable silicon groups in one molecule on average, and 0.1% in one molecule. It is composed of a saturated hydrocarbon polymer containing at least 8 crosslinkable silicon groups and a (meth) acrylate polymer containing at least 0.8 crosslinkable silicon groups per molecule on average. It is preferable that at least one member is selected from the group.

  The curable composition of the present invention preferably further contains a base proliferating agent.

  The curable composition of the present invention preferably further contains a conductive filler.

The method for producing a cured product of the present invention is characterized by forming a cured product by irradiating the photocurable composition of the present invention with light.
The cured product of the present invention is a cured product formed by the method for producing a cured product of the present invention.

  The method for producing a product of the present invention is characterized by producing a product using the photocurable composition of the present invention.

  A first aspect of the product of the present invention is a product manufactured by the method for manufacturing a product of the present invention. A second aspect of the product of the present invention is a product produced by using the method for producing a cured product of the present invention. A third aspect of the product of the present invention is a product using the photocurable composition of the present invention as an adhesive. A fourth aspect of the product of the present invention is a product using the photocurable composition of the present invention as a coating agent.

  According to the present invention, the photocurable composition is not cured when not irradiated with active energy rays, and is cured by being irradiated with active energy rays. It is possible to provide a photocurable composition that is excellent in curability, has excellent thickness curability in a short time, and has excellent curability in a short time, while ensuring an appropriate bonding time. Further, the photocurable composition of the present invention does not cause rust even when used for bonding electric and electronic parts.

  Hereinafter, embodiments of the present invention will be described. However, these are exemplarily shown, and it goes without saying that various modifications can be made without departing from the technical idea of the present invention.

  The photocurable composition of the present invention comprises (A) a crosslinkable silicon-group-containing organic polymer, (B) a photobase generator, and (C) a compound having a Si—F bond. .

  The (A) crosslinkable silicon group-containing organic polymer is not particularly limited as long as it is an organic polymer having a crosslinkable silicon group. Those having the main chain skeleton are preferable because they do not contain or generate a low molecular cyclic siloxane that causes a contact obstacle.

  Specifically, polyoxyalkylene-based polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer Copolymer; ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymer of butadiene with acrylonitrile and / or styrene, polybutadiene, isoprene or butadiene Copolymers of acrylonitrile and styrene, etc., hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; dibasic acids such as adipic acid and glycol Polyester polymer obtained by condensation or ring-opening polymerization of lactones; (meth) acrylate polymer obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; (Meth) acrylic ester monomers, vinyl polymers obtained by radical polymerization of monomers such as vinyl acetate, acrylonitrile, and styrene; graft polymers obtained by polymerizing vinyl monomers in the organic polymer; polysulfide-based polymers Polymer: Nylon 6 by ring-opening polymerization of ε-caprolactam, Nylon 6.6 by condensation polymerization of hexamethylenediamine and adipic acid, Nylon 6.6 by condensation polymerization of hexamethylenediamine and sebacic acid, and ε-aminoundecanoic acid Nylon 11 by condensation polymerization, ε-amino laurolacta Polyamide polymers such as nylon 12 obtained by ring-opening polymerization of nylon and copolymerized nylon having two or more of the above-mentioned nylons; for example, polycarbonate polymers produced by condensation polymerization of bisphenol A and carbonyl chloride, diallyl Examples include phthalate-based polymers.

  Further, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene and hydrogenated polybutadiene, polyoxyalkylene polymers and (meth) acrylate polymers have relatively low glass transition temperatures and are obtained. Cured products are preferred because of their excellent cold resistance. Further, a polyoxyalkylene polymer and a (meth) acrylate polymer are particularly preferred because they have high moisture permeability and are excellent in deep curability when formed into a one-part composition.

  The crosslinkable silicon group of the (A) organic polymer used in the present invention 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. As the crosslinkable silicon group, for example, a group represented by the following general formula (1) is preferable.

In the formula (1), R ¹ represents 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, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to ^20, _R 1 3 SiO- ^{(R 1} is as defined above) triorganosiloxy group represented by, or 1-position of the 3-position of at least one hydrogen atom on the carbon atoms, halogen , -OR ⁴¹ , -NR ⁴² R ⁴³ , -N = R ⁴⁴ , -SR ⁴⁵ (R ⁴¹ , R ⁴² , R ⁴³ , and R ⁴⁵ each represent a hydrogen atom or a substituted or unsubstituted carbon atom having 1 to 20 carbon atoms. A hydrogen group, R ⁴⁴ is a divalent substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.), A perfluoroalkyl group having 1 to 20 carbon atoms, or 1 carbon atom substituted with a cyano group. ~ 20 hydrocarbons Are shown, when the R ¹ there are two or more, they may be the same or may be different. X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they may be the same or different. a represents 0, 1, 2 or 3, and b represents 0, 1 or 2. Also, b in the following p general formulas (2) need not be the same. p shows the integer of 0-19. However, it is assumed that a + (sum of b) ≧ 1 is satisfied.

  The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and a + (sum of b) is preferably in the range of 1 to 5. 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, the number may be about twenty.

  As the crosslinkable silicon group, a crosslinkable silicon group represented by the following general formula (3) is preferable because it is easily available.

In the formula (3), R ¹ and X are the same as described above, and a is an integer of 1, 2, or 3. In order to obtain a curable composition having a sufficient curing speed in consideration of curability, a in Formula (3) is preferably 2 or more, and more preferably 3.

Specific examples of the R ^1, shown, for example an alkyl group such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl, and aralkyl groups such as benzyl group, with R ¹ ₃ SiO- And the like. Of these, a methyl group is preferred.

  The hydrolyzable group represented by X is not particularly limited as long as it is other than an F atom, and may be any conventionally known hydrolyzable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxyl 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. Among these, a hydrogen atom, an alkoxyl group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group are preferred, and an alkoxyl group, an amide group and an aminooxy group are more preferred. Alkoxyl groups are particularly preferred from the viewpoint of gentle hydrolysis and easy handling. Among the alkoxyl groups, those having a smaller number of carbon atoms have higher reactivity, and the reactivity becomes lower 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, although it can be selected according to the purpose and use.

Specific structures of the crosslinkable silicon group include trialkoxysilyl groups [—Si (OR) ₃ ] such as trimethoxysilyl group and triethoxysilyl group, and dialkoxy groups such as methyldimethoxysilyl group and methyldiethoxysilyl group. A silyl group [—SiR ¹ (OR) ₂ ] is exemplified, and a trialkoxysilyl group [—Si (OR) ₃ ] is preferable because of high reactivity, and a trimethoxysilyl group is more preferable. Here, R is an alkyl group such as a methyl group or an ethyl group.

  The crosslinkable silicon groups may be used alone or in combination of two or more. The crosslinkable silicon group may be present in the main chain or the side chain or any of them.

  The number of silicon atoms forming a crosslinkable silicon group is one or more. In the case of silicon atoms linked by a siloxane bond or the like, the number is preferably 20 or less.

  The organic polymer having a crosslinkable silicon group may be linear or branched, and has a number average molecular weight of about 500 to 100,000, more preferably 1,000 to 50,000 in terms of polystyrene by GPC. And particularly preferably 3,000 to 30,000. If the number average molecular weight is less than 500, the cured product tends to be inferior in elongation properties, and if it exceeds 100,000, it tends to be disadvantageous in terms of workability due to high viscosity.

  In order to obtain a rubber-like cured product having a high strength, a high elongation and a low elastic modulus, the number of crosslinkable silicon groups contained in the organic polymer is 0.8 or more on average in one molecule of the polymer, preferably Is preferably 1.0 or more, more preferably 1.1 to 5. If the number of crosslinkable silicon groups contained in the molecule is less than 0.8 on average, the curability will be insufficient and it will be difficult to exhibit good rubber elasticity behavior. The crosslinkable silicon group may be at the terminal of the main chain or the terminal of the side chain of the organic polymer molecular chain, or may be at both terminals. In particular, when the crosslinkable silicon group is only at the terminal of the main chain of the molecular chain, the effective network length of the organic polymer component contained in the finally formed cured product becomes longer, so that high strength and high elongation are obtained. And 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 following general formula (4).
-R ² -O- ··· (4)
In the general formula (4), R ² is a linear or branched alkylene group having 1 to 14 carbon atoms, and preferably a linear or branched alkylene group having 1 to 14 carbon atoms, more preferably 2 to 4 carbon atoms. .

Specific examples of the repeating unit represented by the general formula (4) 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. 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.

  As a method for synthesizing a polyoxyalkylene polymer, for example, a polymerization method using an alkali catalyst such as KOH, for example, an organic aluminum as described in JP-A Nos. 61-197631, 61-215622, and 61-215623. A polymerization method using an organic aluminum-porphyrin complex catalyst obtained by reacting a compound with porphyrin, such as a double metal cyanide complex catalyst described in JP-B-46-27250 and JP-B-59-15336, etc. Although it is mentioned, it is not particularly limited. According to a polymerization method using an organic aluminum-porphyrin complex catalyst or a polymerization method using a double metal cyanide complex catalyst, a polyoxyalkylene-based polymer having a high molecular weight with a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less and a narrow molecular weight distribution. A polymer can be obtained.

  The main chain skeleton of the polyoxyalkylene polymer may contain other components such as a urethane bonding component. Examples of the urethane binding component include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate; Those obtained from the reaction with the coalescence can be given.

  The introduction of a crosslinkable silicon group into a polyoxyalkylene polymer is carried out in 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. The reaction can be performed by reacting a compound having a reactive functional group and a crosslinkable silicon group (hereinafter, referred to as a polymer reaction method).

  As a specific example of the polymer reaction method, an unsaturated group-containing polyoxyalkylene polymer is reacted with hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to hydrosilylate or mercapto to form a crosslinkable silicon group. A method for obtaining a polyoxyalkylene polymer having the following formula: The unsaturated group-containing polyoxyalkylene 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 having reactivity to the functional group, and Can be obtained.

  Other specific examples of the polymer reaction method 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, and a method of reacting a polyoxyalkylene compound having an isocyanate group at a terminal. Examples of the method include a method of reacting a polymer with a compound having an active hydrogen group such as a hydroxyl group or an amino group and a crosslinkable silicon group. When an isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group can be easily obtained.

  Specific examples of the polyoxyalkylene polymer having a crosslinkable silicon group include JP-B-45-36319, JP-B-46-12154, JP-A-50-156599, JP-A-54-6096, and JP-A-55-13767. Nos. 57-164123, JP-B-3-2450, JP-A-2005-213446, JP-A-2005-306891, WO2007-040143, U.S. Patent 3,632,557, U.S. Pat. Japanese Patent Publication Nos. 4,960,844 and the like can be cited.

  The above polyoxyalkylene polymers having a crosslinkable silicon group may be used alone or in combination of two or more.

  The saturated hydrocarbon polymer is a polymer substantially containing no carbon-carbon unsaturated bond other than an aromatic ring, and the polymer constituting the skeleton thereof includes (1) ethylene, propylene, 1-butene, isobutylene and the like. (2) a diene compound such as butadiene or isoprene is homopolymerized, or the olefin compound is copolymerized with the olefin compound. After that, it can be obtained by a method such as hydrogenation.However, the isobutylene-based polymer and the hydrogenated polybutadiene-based polymer can easily introduce a functional group into a terminal, easily control a molecular weight, and have a number of terminal functional groups. Is preferred, and an isobutylene-based polymer is particularly preferred.

  Those whose main chain skeleton is a saturated hydrocarbon-based polymer have characteristics that are excellent in heat resistance, weather resistance, durability, and moisture barrier properties.

  In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, or a copolymer with another monomer may be used. However, from the viewpoint of rubber properties, 50 units of the repeating units derived from isobutylene are used. Those containing not less than 80% by mass are preferable, those containing not less than 80% by mass are more preferable, and those containing 90 to 99% by mass are particularly preferable.

  As a method for synthesizing a saturated hydrocarbon-based polymer, various polymerization methods have been reported, and in recent years many so-called living polymerizations have been developed in particular. In the case of a saturated hydrocarbon polymer, particularly an isobutylene polymer, the inifer polymerization (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, 15, 2843) discovered by Kennedy et al. It is known that it can be easily produced by using the compound, can be polymerized to a molecular weight of about 500 to 100,000 with a molecular weight distribution of 1.5 or less, and can introduce various functional groups into molecular terminals.

  As a method for producing a saturated hydrocarbon polymer having a crosslinkable silicon group, for example, Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, JP-A-63-254149, JP-A-64-22904, These are described in, for example, Kaihei 1-197509, Japanese Patent No. 2539445, Japanese Patent No. 2873395, and Japanese Patent Application Laid-Open No. 7-53882, but are not particularly limited thereto.

  The above-mentioned saturated hydrocarbon polymers having a crosslinkable silicon group may be used alone or in combination of two or more.

  The (meth) acrylate-based monomer constituting the main chain of the (meth) acrylate-based polymer is not particularly limited, and various types can be used. For example, (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) Isobutyl acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, ( (Meth) alkyl acrylate monomers such as 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate; (meth) Cyclohexyl acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth ) Acrylate, dicyclopentanyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, etc. Alicyclic (meth) acrylate monomers; phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, parac Milphenoxyethylene glycol (meth) acrylate, hydroxyethylated o-phenylphenol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxydiethyl Aromatic (meth) acrylate monomers such as ethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, and phenylthioethyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylates such as 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, and 2-aminoethyl (meth) acrylate Monomers: γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxy Silyl group-containing (meth) acrylate monomers such as tildimethoxymethylsilane and methacryloyloxymethyldiethoxymethylsilane; derivatives of (meth) acrylic acid such as ethylene oxide adduct of (meth) acrylic acid; and (meth) acrylic Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, (meth) acrylate ) Perfluoroethyl acrylate, trifluoromethyl (meth) acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethylethyl (meth) acrylate, (meth) 2-perfluorohexylethyl acrylate And fluorine-containing (meth) acrylate monomers such as 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate.

  In the (meth) acrylate polymer, the following vinyl monomers can be copolymerized together with the (meth) acrylate monomer. Examples of the vinyl monomer include styrene monomers such as styrene, vinyl toluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; and fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride. Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; Methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexyl Maleimide monomers such as maleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and cinnamon Vinyl esters such as vinyl acid; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like.

  These may be used alone or a plurality of them may be copolymerized. Among them, a polymer composed of a (meth) acrylic acid-based monomer is preferable from the viewpoint of the physical properties of the product. More preferably, it is a (meth) acrylate polymer using one or more alkyl (meth) acrylate monomers and optionally using other (meth) acrylate monomers in combination, and is a silyl. The number of silicon groups in the (meth) acrylate polymer (A) can be controlled by using a group-containing (meth) acrylate monomer in combination. Particularly preferred is a methacrylic acid ester-based polymer comprising a methacrylic acid ester monomer because of its good adhesiveness. When lowering the viscosity and imparting flexibility, it is preferable to use an acrylate monomer as appropriate. In the present specification, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

  In the present invention, the method for obtaining the (meth) acrylate polymer is not particularly limited, and known polymerization methods (for example, JP-A-63-112624, JP-A-2007-230947, and JP-A-2001-40037). And a synthesis method described in JP-A-2003-313397), and a radical polymerization method using a radical polymerization reaction is preferable. As the radical polymerization method, a radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator, or a reactive silyl group is introduced at a controlled position such as a terminal. Possible controlled radical polymerization methods are mentioned. However, a polymer obtained by a normal free radical polymerization method using an azo compound, a peroxide, or the like as a polymerization initiator has a problem that the value of the molecular weight distribution is generally as large as 2 or more, and the viscosity is increased. I have. Therefore, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and a low viscosity and having a high proportion of a crosslinkable functional group at a molecular chain terminal, It is preferable to use a controlled radical polymerization method.

  Examples of the controlled radical polymerization method include a free radical polymerization method and a living radical polymerization method using a chain transfer agent having a specific functional group, and a reversible addition-fragmentation chain transfer (RAFT) polymerization method, A living radical polymerization method such as a radical polymerization method using a transition metal complex (Transition-Metal-Mediated Living Radical Polymerization) is more preferable. Further, a reaction using a thiol compound having a reactive silyl group or a reaction using a thiol compound having a reactive silyl group and a metallocene compound (JP-A-2001-40037) are also suitable.

  The above-mentioned (meth) acrylate polymers having a crosslinkable silicon group may be used alone or in combination of two or more.

  These organic polymers having a crosslinkable silicon group may be used alone or in combination of two or more. Specifically, it comprises a polyoxyalkylene polymer having a crosslinkable silicon group, a saturated hydrocarbon polymer having a crosslinkable silicon group, and a (meth) acrylate polymer having a crosslinkable silicon group. An organic polymer obtained by blending two or more selected from the group can also be used.

A method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylate polymer having a crosslinkable silicon group is disclosed in JP-A-59-122541. It has been proposed in, for example, Japanese Unexamined Patent Publication No. 63-112624, Japanese Patent Application Laid-Open No. 6-172631, and Japanese Patent Application Laid-Open No. 11-116763, but is not particularly limited thereto. A preferred specific example is a compound having a crosslinkable silicon group and a molecular chain substantially having the following general formula (5):
—CH ₂ —C (R ³ ) (COOR ⁴ ) — (5)
(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 (meth) acrylate monomer unit represented by the following general formula (6):
—CH ₂ —C (R ³ ) (COOR ⁵ ) — (6)
(Wherein R ³ is the same as above, and R ⁵ represents an alkyl group having 6 or more carbon atoms). A copolymer comprising a (meth) acrylate monomer unit represented by the following formula: This is a method of blending and producing a polyoxyalkylene-based polymer.

As R ^{4 in the} general formula (5), for example, a group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, preferably 1 to 4, more preferably 1 to 4 And 2 alkyl groups. The alkyl group of R ⁴ may be used alone or in combination of two or more.

Examples of ^{R 5} in the general formula (6), such as 2-ethylhexyl group, lauryl group, tridecyl group, cetyl group, stearyl group, carbon atoms, such as behenyl group 6 or more, usually 7-30, preferably 8-20 And a long-chain alkyl group. As in the case of R ⁴ , the alkyl group of R ⁵ may be used alone or as a mixture of two or more.

  The molecular chain of the (meth) acrylic acid ester-based copolymer substantially consists of the monomer units of the formulas (5) and (6), and “substantially” as used herein means the copolymer. It means that the total of the monomer units of the formulas (5) and (6) present therein exceeds 50% by mass. The total of the monomer units of the formulas (5) and (6) is preferably at least 70% by mass. The abundance ratio of the monomer unit of the formula (5) to the monomer unit of the formula (6) is preferably from 95: 5 to 40:60, more preferably from 90:10 to 60:40 by mass ratio.

  Examples of the monomer units (hereinafter, also referred to as other monomer units) other than formulas (5) and (6) which may be contained in the copolymer include, for example, α such as acrylic acid and methacrylic acid. , Β-unsaturated carboxylic acids; amide groups such as acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether and the like And a monomer unit derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

  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 and a (meth) acrylate polymer having a crosslinkable silicon group ) As an acrylate polymer, for example, a polymer having a crosslinkable silicon group described in JP-A-63-112842 and having a molecular chain substantially (1) having an alkyl group having 1 to 8 carbon atoms (meth) And (2) publicly known (meth) acrylic acid ester-based copolymers containing an acrylic acid alkyl ester monomer unit and (2) a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 10 or more carbon atoms. (Meth) acrylate-based copolymers can also be used.

  The number average molecular weight of the (meth) acrylate polymer is preferably from 600 to 10,000, more preferably from 600 to 5,000, even more preferably from 1,000 to 4,500. By setting the number average molecular weight in the above range, compatibility with the polyoxyalkylene polymer having a crosslinkable silicon group can be improved. The (meth) acrylate polymer may be used alone or in combination of two or more. The mixing ratio of the polyoxyalkylene polymer having a crosslinkable silicon group to the (meth) acrylate polymer having a crosslinkable silicon group is not particularly limited, but the (meth) acrylate ester is preferably It is preferable that the (meth) acrylate polymer is in the range of 10 to 60 parts by mass, more preferably 20 to 60 parts by mass, based on 100 parts by mass in total of the polymer and the polyoxyalkylene polymer. It is within the range of 50 parts by mass, and more preferably within the range of 25 to 45 parts by mass. If the amount of the (meth) acrylic acid ester-based polymer is more than 60 parts by mass, the viscosity becomes high and the workability deteriorates, which is not preferable.

  Organic polymers obtained by blending a saturated hydrocarbon polymer having a crosslinkable silicon group with a (meth) acrylate copolymer having a crosslinkable silicon group are described in JP-A-1-168774 and JP-A-2000-964. Although it is proposed in 186176 and the like, it is not particularly limited thereto.

  Furthermore, as a method for producing an organic polymer obtained by blending a (meth) acrylate copolymer having a crosslinkable silicon group, another method for producing an organic polymer in the presence of an organic polymer having a crosslinkable silicon group ( A method of polymerizing a (meth) acrylate monomer can be used. This production method is specifically disclosed in JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, etc. It is not limited to these.

  When two or more kinds of polymers are blended and used, a saturated hydrocarbon polymer having a crosslinkable silicon group and / or a crosslinkable polymer have been added to 100 parts by mass of a polyoxyalkylene polymer having a crosslinkable silicon group. It is preferable to use 10 to 200 parts by mass of the (meth) acrylate polymer having a functional silicon group, and it is more preferable to use 20 to 80 parts by mass.

  In the present invention, the photobase generator (B) acts as a curing catalyst for the crosslinkable silicon group-containing organic polymer (A) when irradiated with light. The photobase generator (B) is not particularly limited as long as it is a 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. Salts of organic acids and bases that decompose and decompose by irradiation with active energy rays such as light and infrared rays, (2) compounds that release amines by decomposing by intramolecular nucleophilic substitution reaction or rearrangement reaction, or ( 3) Known photobase generators such as those that cause a certain chemical reaction upon irradiation with energy rays such as ultraviolet rays, visible light, and infrared rays to release a base, and the like can be used.

The base generated from the photobase generator (B) is not particularly limited, but is preferably an organic base such as an amine compound, for example, a first base such as ethylamine, propylamine, octylamine, cyclohexylamine, and 1,5-diaminopentane. Primary alkylamines such as N-methylbenzylamine and 4,4'-methylenedianiline; Secondary alkylamines such as diethylamine; Secondary amino groups and tertiary amino such as imidazole Amines having a group; tertiary alkylamines such as trimethylamine, triethylamine, tributylamine and 1,8-diazabicyclo [2.2.2] octane (DABCO); tertiary heterocyclics such as 4-isopropylmorpholine Amine; 4-dimethylaminopyridine, N, N-dimethyl (3-phenoxy- Tertiary aromatic amines such as 2-hydroxypropyl) amine; 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 Amidines such as (DBN); phosphazene derivatives such as tris (dimethylamino) (methylimino) phosphorane described in JP-A-2011-80032, amine compounds having a tertiary amino group are preferable, and strong bases are used. Amidines and phosphazene derivatives are more preferred. As the amidines, both acyclic amidines and cyclic amidines can be used, but cyclic amidines are more preferable.
These bases may be used alone or in combination of two or more.

Examples of the acyclic amidines include a guanidine compound, a biguanide compound, and the like.
Examples of the guanidine-based compound include guanidine, 1,1,3,3-tetramethylguanidine, 1-butylguanidine, 1-phenylguanidine, 1-o-tolylguanidine, 1,3-diphenylguanidine and the like.
Examples of biguanide compounds include butyl biguanide, 1-o-tolyl biguanide and 1-phenyl biguanide.

  Further, among acyclic amidine compounds, when a photobase generator that generates an aryl-substituted guanidine-based compound such as phenylguanidine, 1-o-tolylbiguanide or 1-phenylbiguanide or an aryl-substituted biguanide-based compound is used, When used as a catalyst for coalescence (A), it is preferred because the curability of the surface tends to be good and the cured product obtained tends to have good adhesiveness.

  Examples of the cyclic amidines include a cyclic guanidine compound, an imidazoline compound, an imidazole compound, a tetrahydropyrimidine compound, a triazabicycloalkene compound, and a diazabicycloalkene compound.

  Examples of the cyclic guanidine-based compound include 1,5,7-triaza-bicyclo [4.4.0] dec-5-ene and 7-methyl-1,5, described in JP-A-2011-80032. 7-triaza-bicyclo [4.4.0] dec-5-ene, 7-ethyl-1,5,7-triaza-bicyclo [4.4.0] dec-5-ene, 7-isopropyl-1, 5,7-triaza-bicyclo [4.4.0] dec-5-ene and the like.

  Examples of the imidazoline-based compound include 1-methylimidazoline, 1,2-dimethylimidazoline, 1-methyl-2-ethylimidazoline, 1-methyl-2-octylimidazoline, and the like.

  Examples of the imidazole-based compound include imidazole, 2-ethyl-4-methylimidazole, and the like.

  Examples of the tetrahydropyrimidine compound include 1-methyl-1,4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1-methyl-2-ethyl- 1,4,5,6-tetrahydropyrimidine, 1-methyl-2-butyl-1,4,5,6-tetrahydropyrimidine, 1-ethyl-2-octyl-1,4,5,6-tetrahydropyrimidine and the like No.

  Examples of the triazabicycloalkene-based compound include, for example, 7-methyl-1,5,7-triazabicyclo [4.4.0] decene-5,7-ethyl-1,5,7-triazabicyclo [ 44.0] decene-5 and the like.

  Examples of the diazabicycloalkene-based compound include, for example, 1,5-diazabicyclo [4.2.0] octene-5,1,8-diazabicyclo [7.2.0] undecene-8,1,4-diazabicyclo [3 3.3.0] octene-4,3-methyl-1,4-diazabicyclo [3.3.0] octene-4,3,6,7,7-tetramethyl-1,4-diazabicyclo [3.3. 0] octene-4,7,8,8-trimethyl-1,5-diazabicyclo [4.3.0] nonene-5,1,8-diazabicyclo [7.3.0] dodecene-8,1,7- Diazabicyclo [4.3.0] nonene-6,8-phenyl-1,7-diazabicyclo [4.3.0] nonene-6,1,5-diazabicyclo [4.3.0] nonene-5,1, 5-diazabicyclo [4.4.0] decene- , 4-phenyl-1,5-diazabicyclo [4.4.0] decene-5,1,8-diazabicyclo [5.3.0] decene-7,1,8-diazabicyclo [7.4.0] tridecene -8,1,8-diazabicyclo [5.4.0] undecene-7,6-methylbutylamino-1,8-diazabicyclo [5.4.0] undecene-7,6-methyloctylamino-1,8 -Diazabicyclo [5.4.0] undecene-7,6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7,6-butylbenzylamino-1,8-diazabicyclo [5.4. 0] undecene-7,6-dihexylamino-1,8-diazabicyclo [5.4.0] undecene-7,9-methyl-1,8-diazabicyclo [5.4.0] undecene-7,9-me 1,8-diazabicyclo [5.3.0] decene-7,1,6-diazabicyclo [5.5.0] dodecene-6,1,7-diazabicyclo [6.5.0] tridecene-7, 1,8-diazabicyclo [7.5.0] tetradecene-8,1,10-diazabicyclo [7.3.0] dodecene-9,1,10-diazabicyclo [7.4.0] tridecene-9,1, 14-diazabicyclo [11.3.0] hexadecene-13, 1,14-diazabicyclo [11.4.0] heptadecene-13 and the like.

  Among the cyclic amidines, 1,8-diazabicyclo [5.4.] Is preferred from the viewpoint that it is industrially easy to obtain and that the conjugate acid exhibits a high catalytic activity due to its pKa value of 12 or more. 0] undecene-7 (DBU) and 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) are particularly preferred.

  As the photobase generator (B) used in the present invention, a known photobase generator can be used, but a photolatent amine compound which generates an amine compound by the action of active energy rays is preferable. Examples of the photolatent amine compound include a photolatent primary amine which generates an amine compound having a primary amino group by the action of an active energy ray, and an amine compound having a secondary amino group by the action of an active energy ray. Any of a photolatent secondary amine that generates an amine compound and a photolatent tertiary amine that generates an amine compound having a tertiary amino group by the action of an active energy ray can be used, but the generated base is high. Photolatent tertiary amines are more preferred in view of their catalytic activity.

Examples of the photolatent primary amine and the photolatent secondary amine include 1,3-bis [N- (2-nitrobenzyloxycarbonyl) -4-piperidyl] propane and N-{[(3 -Nitro-2-naphthalenemethyl) oxy] carbonyl} -2,6-dimethylpiperidine, N-{[(6,7-dimethoxy-3-nitro-2-naphthalenemethyl) oxy] carbonyl} -2,6-dimethyl Piperidine, N- (2-nitrobenzyloxycarbonyl) piperidine, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, N, N′-bis (2-nitrobenzyloxycarbonyl) hexyldiamine, o- Nitrobenzyl N-cyclohexylcarbamate, 2-nitrobenzylcyclohexylcarbamate, 1- (2-nitro Phenyl) ethylcyclohexylcarbamate, 2,6-dinitrobenzylcyclohexylcarbamate, 1- (2,6-dinitrophenyl) ethylcyclohexylcarbamate, 1- (3,5-dimethoxyphenyl) -1-methylethylcyclohexylcarbamate, bis [[ Ortho-nitrobenzyl urethane compounds such as (2-nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine and N- (2-nitrobenzyloxycarbonyl) pyrrolidine; α, α-dimethyl-3,5-dimethoxybenzylcyclohexyl Dimethoxybenzyl urethane compounds such as carbamate and 3,5-dimethoxybenzylcyclohexyl carbamate; 1- (3,5-dimethoxybenzoyl) -1- (3,5-dimethoxyphenyl) methylcyclohexyl Carbamate benzoins such as carbamate, 2-hydroxy-2-phenylacetophenone cyclohexyl carbamate, dibenzoin isophorone dicarbamate, 1-benzoyl-1-phenylmethylcyclohexyl carbamate, 2-benzoyl-2-hydroxy-2-phenylethylcyclohexyl carbamate O-acyloximes such as o-benzylcarbonyl-N- (1-phenylethylidene) hydroxylamine; [(pentane-1,5-diyl) biscarbamoyl] bis (diphenylmethylidenehydroxylamine), α- (cyclohexyl) O-carbamoyl oximes such as carbamoyloxyimino) -α- (4-methoxyphenyl) acetonitrile; N- (octylcarbamoyloxy) phthalimide; N-hydroxyimide carbamates such as (xylcarbamoyloxy) succinimide; formanilide derivatives such as 4,4'-methylenebis (formalinide); N-cyclohexyl-2-naphthalenesulfonamide; N-cyclohexyl-p-toluenesulfonamide aromatic _{sulfonamides; Co (NH 2 C 3 H} 7) Br + ClO 4 - cobalt amine complexes of the like.

  Examples of the photolatent tertiary amine include α-aminoketone derivatives, α-ammonium ketone derivatives, benzylamine derivatives, benzylammonium salt derivatives, α-aminoalkene derivatives, α-ammoniumalkene derivatives, amineimides, Examples include a benzyloxycarbonylamine derivative that generates amidine, and a salt of a carboxylic acid and a tertiary amine.

  Preferred examples of the α-aminoketone derivative include α-aminoketone compounds represented by the following formulas (I) to (IV).

In the formula (I), R ⁵¹ is an aromatic or heteroaromatic group, and R ⁵¹ is an aromatic group (which is unsubstituted or C ₁ -C ₁₈ alkyl, _3- C _{18 alkenyl, C} 3- _{C 18 alkinyl, C 1-C 18 ^{haloalkyl, NO 2, NR 58 R 59}} , N 3, OH, CN, OR 60, SR 60, C (O) R 61, C ( O) substituted one or more times by OR ⁶² or halogen, wherein R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ and R ⁶² are hydrogen or C ₁ -C ₁₈ alkyl), preferably phenyl, Naphthyl, phenanthryl, anthracyl, pyrenyl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo [b] thienyl, naphtho [2, 3-b] Thienyl, thiatrenyl, dibenzofuryl, chromenyl, xanthenyl, thioxanthyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, prinyl, quinolizinyl, isoquinolyl, quinolyl Phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, terphenylsyl, terphenylsyl, terphenylsyl, terphenylsyl More preferably, it is selected from the group consisting of phenoxazinyl.
R ⁵² and R ⁵³ are, independently of each other, hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₈ alkenyl, C ₃ -C ₁₈ alkynyl or phenyl, and if R ⁵² is hydrogen or C ₁ -C _{If 18} alkyl, R ⁵³ is further a group —CO—R ⁶⁴ , wherein R ⁶⁴ is C ₁ -C ₁₈ alkyl or phenyl; alternatively, R ⁵¹ and R ⁵³ are Together with the carbonyl group and the C atom to which ^R53 is attached, a benzocyclopentanone group is formed.
R ⁵⁴ and R ⁵⁶ together form a C ₂ -C ₁₂ alkylene bridge which is unsubstituted or substituted by one or more C ₁ -C ₄ alkyl groups. R ⁵⁵ and ^{R 57,} taken ^together, independently of ^{R 54} and ^{R 56,} _C 2 -C which is unsubstituted or substituted by one or more _C 1 -C ₄ alkyl group Form a ₁₂ alkylene bridge. Preferably R ⁵⁴ and R ⁵⁶ together form a C ₃ alkylene bridge, and R ⁵⁵ and R ⁵⁷ together are propylene or pentylene.

In the formula ^{(II) ~ (IV),} R 51 ~R 53 is the same as ^R 51 ^{to R 53} of each of the formula (I).
R ⁶⁶ is an alkyl group having 1 to 12 carbon atoms; -OH, -alkoxy having 1 to 4 carbon atoms, 2 to 2 carbon atoms substituted with -CN or -COO (alkyl having 1 to 4 carbon atoms). And 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 is an alkyl group having 1 to 12 carbon atoms; or —OH, an alkoxy group having 1 to 4 carbon atoms, or a carbon atom substituted with —CN or —COO (alkyl having 1 to 4 carbon atoms). R 2 represents an alkyl group having 2 to 4 carbon atoms, or 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 a phenyl group substituted by an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or —COO (alkyl having 1 to 4 carbon atoms), or R ⁶⁷ represents Together with RR ⁶⁶ , 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 an alkylene group having 2 or 3 carbon atoms. R ⁶⁶ and R ⁶⁷ together represent an alkylene group having 4 to 7 carbon atoms which can be interrupted by —O—, —S— or —CO—, or R ⁶⁶ and R ⁶⁶ and R ⁶⁷ represents OH, an alkoxy group having 1 to 4 carbon atoms or an alkylene group having 3 to 7 carbon atoms which can be substituted with -COO (alkyl having 1 to 4 carbon atoms). When a plurality of R ⁶⁶ and R ⁶⁷ are present, they may be the same or different.
Y ¹ represents a divalent group represented by the following 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 α-aminoketone compound represented by the formula (I) include 5- (4′-phenyl) phenacyl-1,5-diazabicyclo [4.3.0] nonane described in JP-A-2001-512421. 5-phenacyl-1,5-diazabicyclo [4.3.0] nonane, 5-naphthoylmethyl-1,5-diazabicyclo [4.3.0] nonane, 5- (1′-pyrenylcarbonylmethyl)- 1,5-diazabicyclo [4.3.0] nonane, 5- (4′-nitro) phenacyl-1,5-diazabicyclo [4.3.0] nonane, 5- (2 ′, 4′-dimethoxy) phenacyl -1,5-diazabicyclo [4.3.0] nonane, 5- (9'-anthroylmethyl) -1,5-diazabicyclo [4.3.0] nonane, 8- (4'-phenyl) phenacyl- (1 8- diazabicyclo [5.4.0] -7-undecene), and the like.

  Examples of the α-aminoketone compound represented by the formula (II) include 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane (Irgacure 907) and 2-benzyl- described in JP-A-11-71450. 2-dimethylamino-1- (4-morpholinophenyl) -butanone (Irgacure 369), 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone (Irgacure 379EG) and the like. No.

  Examples of the α-ammonium ketone derivative include an α-ammonium ketone compound represented by the following formula (VI).

In the formula (VI), k is 1 or 2, which corresponds to the number of positive charges of the cation. V ⁻ is a counter anion, a borate anion (such as tetraphenyl borate, methyl triphenyl borate, ethyl triphenyl borate, propyl triphenyl borate and butyl triphenyl borate), and a phenolate anion (phenolate, 4-tert-butyl phenolate) , 2,5-di-tert-butylphenolate, 4-nitrophenolate, 2,5-dinitrophenolate and 2,4,6-trinitrophenolate, etc.) and carboxylate anions (benzoic acid anion, toluic acid) Anions and phenylglyoxylate anions). Among these, from the viewpoint of photodegradability, borate anions and carboxylate anions are preferred, and butyltriphenylborate anion, tetraphenylborate anion, benzoate anion and phenylglyoxylate anion, photodegradability and thermal stability are more preferred. From the viewpoint of the above, a tetraphenylborate anion and a phenylglyoxylate anion are particularly preferred.

In the formula ^{(VI), R} 51 ~R ⁵³ is the same as ^R 51 ^{to R 53} of each of the formula (I).
R ⁷⁰ -R ⁷² are each, independently of one another, hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₈ alkenyl, C ₃ -C ₁₈ alkynyl or phenyl; or R ⁷⁰ and R ⁷¹ and / or R ⁷² And R ⁷¹ independently of one another form a C ₂ -C ₁₂ alkylene bridge; or R ⁷⁰ -R ⁷² together with the nitrogen atom to which they are attached, form P ₁ , P ₂ , P <t / 4> type Or a group of the following structural formulas (a), (b), (c), (d), (e), (f) or (g).

In the formula ^{(a) ~ (g),} R 51 and ^{R 52} are the same as ^{R 51} and ^{R 52} of said formula (I), l and q is a number from 2 to 12 each, independently of one another.

  Specific examples of the α-ammonium ketone derivative include, for example, phenacyltriethylammonium tetraphenylborate, (4-methoxyphenacyl) triethylammonium tetraphenylborate, described in JP-T-2001-513765 and WO2005 / 014696. -Phenacyl- (1-azonia-4-azabicyclo [2,2,2] -octane) tetraphenylborate, (1,4-phenacyl-1,4-diazoniabicyclo [2.2.2] octane) bis ( Tetraphenylborate), 1-naphthoylmethyl- (1-azonia-4-azabicyclo [2,2,2] -octane) tetraphenylborate, 1- (4′-phenyl) phenacyl- (1-azonia-4- Azabicyclo [2.2.2] octane) tetraphenylbo , 5- (4'-phenyl) phenacyl- (5-azonia-1-azabicyclo [4.3.0] -5-nonene) tetraphenylborate, 5- (4'-methoxy) phenacyl- (5- Azonia-1-azabicyclo [4.3.0] -5-nonene) tetraphenylborate, 5- (4′-nitro) phenacyl- (5-azonia-1-azabicyclo [4.3.0] -5-nonene ) Tetraphenylborate, 5- (4′-phenyl) phenacyl- (8-azonia-1-azabicyclo [5.4.0] -7-undecene) tetraphenylborate and the like.

  Examples of the benzylamine derivative include a benzylamine compound represented by the following formula (VII).

In the formula ^{(VII), R 51, R} 54 ~R 57 is the same as ^{R 51, R} 54 ^{~R 57} of each of the formula (I).
R ⁷³ and R ⁷⁴ each independently represent a hydrogen atom, an alkyl group or a halogen atom having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, 20 alkylthio groups, C1-20 alkylsilyl groups, C1-20 acyl groups, amino groups, cyano groups, C1-20 alkyl groups, phenyl groups, naphthyl groups, phenoxy groups and phenoxy groups Represents a phenyl group which may be substituted with a group selected from the group of a luthio group, and R ⁷³ and R ⁷⁴ may be bonded to each other to form a ring structure.

  Specific examples of the benzylamine derivative include, for example, 5-benzyl-1,5-diazabicyclo [4.3.0] nonane and 5- (anthracen-9-yl-methyl)-described in JP-A-2005-511536. 1,5-diazabicyclo [4.3.0] nonane, 5- (4′-cyanobenzyl) -1,5-diazabicyclo [4.3.0] nonane, 5- (3′-cyanobenzyl) -1, 5-diazabicyclo [4.3.0] nonane, 5- (2′-chlorobenzyl) -1,5-diazabicyclo [4.3.0] nonane, 5- (2 ′, 4 ′, 6′-trimethylbenzyl) ) -1,5-Diazabicyclo [4.3.0] nonane, 5- (4′-ethenylbenzyl) -1,5-diazabicyclo [4.3.0] nonane, 5- (3′-methoxybenzyl) -1,5-diazavik [4.3.0] nonane, 5- (naphth-2-yl-methyl) -1,5-diazabicyclo [4.3.0] nonane, 1,4-bis (1,5-diazabicyclo [4.3] .0] nonanylmethyl) benzene and benzylamine derivatives such as 8- (2 ', 6'-dichlorobenzyl) -1,8-diazabicyclo [5.4.0] undecane.

  Examples of the benzyl ammonium salt derivative include a benzyl ammonium salt represented by the following formula (VIII).

In the formula (VIII), V ^- and k V of the formula (VI) ^- which is similar to and k. R ⁵¹ is the same as ^{R 51} in the formula (I). R ⁷⁰ to R ⁷² are the same as ^R 70 ^{to R 72} of each of the formulas (VI). R ⁷³ and ^{R 74} are the same as ^{R 73} and ^{R 74} in the formula (VII).

  Specific examples of the benzyl ammonium salt derivative include, for example, photobase generators described in WO2010 / 095390 and WO2009 / 122664, for example, (9-anthryl) methyltriethylammonium tetraphenylborate, (9-oxo-9H) -Thioxanthen-2-yl) methyltriethylammonium tetraphenylborate, (9-anthryl) methyl 1-azabicyclo [2.2.2] octanium tetraphenylborate, (9-oxo-9H-thioxanthen-2-yl ) Methyl 1-azabicyclo [2.2.2] octanium tetraphenylborate, 9-anthrylmethyl-1-azabicyclo [2.2.2] octanium tetraphenylborate, 5- (9-anthrylmethyl)- 1,5-diazabicyclo 4.3.0] -5-nonenium tetraphenylborate, 8- (9-anthrylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium phenylglyoxylate, N- (9-anthrylmethyl) -N, N, N-trioctylammonium tetraphenylborate, 8- (9-oxo-9H-thioxanthen-2-yl) methyl-1,5-diazabicyclo [4.3.0] ] -5-nonenium tetraphenylborate, 8- (4-benzoylphenyl) methyl-1,8-diazabicyclo [5.4.0] -7-undecenium tetraphenylborate, {8- (t-butyl- 2-naphthalylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium tetraphenylborate, 8- (9-oxo-9H-thioxane Down 2-yl) methyl-1,8-diazabicyclo [5.4.0] -7-undecenium tetraphenylborate, N- benzophenone methyltrimethoxysilane -N- methyl ammonium tetraphenyl borate, and the like.

  Examples of the α-aminoalkene derivatives include, for example, 5- (2 ′-(4 ″ -biphenyl) allyl) -1,5-diazabicyclo [4.3.0] nonane and 5- (2 ′-(2 ″ -naphthyl) allyl) -1,5-diazabicyclo [4.3.0] nonane, 5- (2 ′-(4 ″ -diethylaminophenyl) allyl) -1,5-diazabicyclo [4 3.0.nonane, 5- (1′-methyl, 2 ′-(4 ″ -biphenyl) allyl) -1,5-diazabicyclo [4.3.0] nonane, 5- (1′-methyl, '-(2 "-thioxanthyl) allyl) -1,5-diazabicyclo [4.3.0] nonane, 5- (1'-methyl, 2'-(2" -fluorenyl) allyl) -1,5-diazabicyclo [4.3.0] nonane, 8- (2′- 4 "- biphenyl) allyl) - (1,8-diazabicyclo [5.4.0] -7-undecene), and the like.

  Examples of the α-ammonium alkene derivative include, for example, N- (2′-phenylallyl) -triethylammonium tetraphenylborate and 1- (2′-phenylallyl)-(1-azonia- described in JP-T-2002-523393. 4-azabicyclo [2,2,2] -octane) tetraphenyl borate, 1- (2′-phenylallyl)-(1-azonia-4-azabicyclo [2,2,2] -octane) tetraphenyl borate, 1 -(2'-phenylallyl)-(1-azonia-4-azabicyclo [2,2,2] -octane) tris (3-fluorophenyl) hexyl borate and the like.

  Examples of the amine imides include, for example, [(2-hydroxy-3-phenoxypropyl) dimethylaminio] (4-nitrobenzoyl) amine anion and [(2-hydroxy-3-phenoxypropyl) dimethyl described in WO2002 / 051905. [Aminio] (4-cyanobenzoyl) 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.

  Examples of the benzyloxycarbonylamine derivative that generates amidine by light include benzyloxycarbonylimidazoles, benzyloxycarbonylguanidines, and diamine derivatives.

  Examples of benzyloxycarbonylimidazoles include N- (2-nitrobenzyloxycarbonyl) imidazole, N- (3-nitrobenzyloxycarbonyl) imidazole, and N- (4-chloro-) described in JP-A-9-40750. 2-nitrobenzyloxycarbonyl) imidazole, N- (4-nitrobenzyloxycarbonyl) imidazole, N- (5-methyl-2-nitrobenzyloxycarbonyl) imidazole, N- (4,5-dimethyl-2-nitrobenzyl) (Oxycarbonyl) imidazole and the like.

  Examples of the benzyloxycarbonylguanidine include benzyloxycarbonyltetramethylguanidine described in WO 97/31033.

  Examples of the diamine derivative include N- (N ′-((1- (4,5-dimethoxy-2-nitrophenyl) ethoxy) carbonyl) aminopropyl) -N-methylacetamide described in JP-A-2011-116869. , N- (N '-(4,5-dimethoxy-2-nitrobenzyloxycarbonyl) aminopropyl) -6-heptane lactam and the like.

  Examples of the salt of the carboxylic acid and the tertiary amine include an α-ketocarboxylic acid ammonium salt and a carboxylic acid ammonium salt.

  Examples of the α-ketocarboxylic acid ammonium salt include dimethylglybenzyl ammonium salt of phenylglyoxylic acid and tri-n-butyl ammonium salt of phenylglyoxylic acid described in JP-A-55-22669.

  Examples of the ammonium carboxylate include a ketoprofen salt of diazabicycloundecene (DBU) described in JP-A-2009-280785, a ketoprofen salt of 2-methylimidazole, and a diazabicyclo described in JP-A-2011-80032. Undecene (DBU) xanthone acetate, diazabicycloundecene (DBU) thioxanthone acetate, 2- (carboxymethylthio) thioxanthone 3-quinuclidinol salt described in JP-A-2007-262276, 2- (carboxymethoxy) ) 3-quinuclidinol salts of thioxanthone, and 3-quinuclidinol salts of trans-o-coumaric acid described in JP 2010-254982 A and JP 2011-213783 A.

  Among the above-mentioned photobase generators (B), a photolatent tertiary amine is preferred from the viewpoint that the generated base exhibits high catalytic activity, and that the generation efficiency of the base is good and the storage stability as a composition is good. For example, a benzylammonium salt derivative, a benzyl-substituted amine derivative, an α-aminoketone derivative, and an α-ammonium ketone derivative are preferred.In particular, α-aminoketone derivatives and α-ammonium ketone derivatives are more preferred because of higher base generation efficiency. Preferably, the α-aminoketone derivative is more preferable than the solubility in the compound. Among the α-aminoketone derivatives, the α-aminoketone compound represented by the above formula (I) is better because of the basicity of the generated base, and the α-aminoketone compound represented by the above formula (II) is better because it is easily available.

These photobase generators (B) may be used alone or in combination of two or more.
The mixing ratio of the photobase generator (B) is not particularly limited, but is preferably 0.01 to 50 parts by mass, and more preferably 0.01 to 50 parts by mass with respect to (A) 100 parts by mass of the crosslinkable silicon group-containing organic polymer. 40 parts by mass is more preferable, and 0.1 to 30 parts by mass is further preferable.

  In the present invention, (C) a silicon compound having a Si-F bond acts as a curing catalyst for (A) a crosslinkable silicon group-containing organic polymer. As the silicon compound having a Si-F bond (C), a known compound containing a silicon group having a Si-F bond (hereinafter, sometimes referred to as a fluorosilyl group) can be widely used, and particularly, it is limited. However, any of a low molecular compound and a high molecular compound can be used, but an organosilicon compound having a fluorosilyl group is preferable, and an organic polymer having a fluorosilyl group has high safety and is more preferable. Further, a low molecular weight organosilicon compound having a fluorosilyl group is preferred from the viewpoint that the composition has a low viscosity.

  As the silicon compound (C) having a Si—F bond, specifically, a compound having a fluorosilyl group represented by the following formula (8) such as a fluorosilane represented by the following formula (7) (the specification of the present application) Preferred examples thereof include a fluorinated compound, an organic polymer having a fluorosilyl group (also referred to as a fluorinated polymer in the present specification), and the like.

R ¹¹ _4-d SiF _d (7)
(In the formula (7), 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. Which is a substituted or unsubstituted hydrocarbon group or a fluorine atom), wherein d is any of 1 to 3, and d is preferably 3. R ¹¹ And when a plurality of R ¹² are present, they may be the same or different.)

^{_{-SiF d R 11 e Z f ···}} (8)
(In the formula (8), R ¹¹ and d are the same as in the formula (7), Z is each independently a hydroxyl group or a hydrolyzable group other than fluorine, and e is any of 0 to 2. , F is any one of 0 to 2, and d + e + f is 3. When a plurality of R ¹¹ , R ¹² and Z are present, they may be the same or different.)

  The fluorosilanes represented by the formula (7) include known fluorosilanes represented by the formula (7), and are not particularly limited. For example, fluorotrimethylsilane, fluorotriethylsilane, and fluorotripropylsilane , Fluorotributylsilane, fluorodimethylvinylsilane, fluorodimethylphenylsilane, fluorodimethylbenzylsilane, fluorodimethyl (3-methylphenyl) silane, fluorodimethyl (4-methylphenyl) silane, fluorodimethyl (4-chlorophenyl) silane, fluorotrifluorosilane Phenylsilane, difluorodimethylsilane, difluorodiethylsilane, difluorodibutylsilane, difluoromethylphenylsilane, difluorodiphenylsilane, trifluoroethylsilane, trifluoro Propylsilane, trifluorobutylsilane, trifluorophenylsilane, γ-glycidoxypropyltrifluorosilane, γ-glycidoxypropyldifluoromethylsilane, vinyltrifluorosilane, vinyldifluoromethylsilane, γ-methacryloxypropylfluorodimethyl Silane, γ-methacryloxypropyldifluoromethylsilane, γ-methacryloxypropyltrifluorosilane, 3-mercaptopropyltrifluorosilane, octadecylfluorodimethylsilane, octadecyldifluoromethylsilane, octadecyltrifluorosilane, 1,3-difluoro-1 , 1,3,3-tetramethyldisiloxane, 1,3,5,7-tetrafluoro-1,3,5,7-tetrasilatricyclo [3.3.1.1 (3,7)] Kang, 1,1-difluoro-1-silacycle 3-pentene, etc. fluoro tris (trimethylsiloxy) silane.

  Of these, fluorodimethylvinylsilane, fluorodimethylphenylsilane, fluorodimethylbenzylsilane, vinyltrifluorosilane, vinyldifluoromethylsilane, γ-methacryloxypropyl Fluorodimethylsilane, γ-methacryloxypropyldifluoromethylsilane, γ-methacryloxypropyltrifluorosilane, 3-mercaptopropyltrifluorosilane, octadecylfluorodimethylsilane, octadecyldifluoromethylsilane, octadecyltrifluorosilane, 1,3-difluoro -1,1,3,3-tetramethyldisiloxane and the like are preferred.

  In the compound having a fluorosilyl group represented by the formula (8), the hydrolyzable group represented by Z in the formula (8) is, for example, the same group as the hydrolyzable group represented by X in the formula (1). Specific examples include a hydrogen atom, a halogen atom other than fluorine, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. And the like. Of these, 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 is preferred from the viewpoint of gentle hydrolysis and easy handling. Particularly preferred.

R ¹¹ in the formula (8) includes, for example, an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and the like. ^{And a} triorganosiloxy group represented by R ¹² SiO— in which ¹² is a methyl group, a phenyl group, or the like. Of these, a methyl group is particularly preferred.

Specific examples of the fluorosilyl group represented by the formula (8) include, as a silicon group having no hydrolyzable group other than fluorine, a fluorodimethylsilyl group, a fluorodiethylsilyl group, a fluorodipropylsilyl group, and a fluorosilyl group. A silicon group in which one fluorine is substituted on a silicon group such as a diphenylsilyl group or a fluorodibenzylsilyl group; A silicon group in which two fluorines are substituted; a silicon group in which three fluorines are substituted on a silicon group which is a trifluorosilyl group; and a silicon group having both fluorine and other hydrolyzable groups is fluoro. Methoxymethylsilyl, fluoroethoxymethylsilyl, fluoromethoxy Lucilyl group, fluoromethoxyphenylsilyl group, fluorodimethoxysilyl group, fluorodiethoxysilyl group, fluorodipropoxysilyl group, fluorodiphenoxysilyl group, fluorobis (2-propenoxy) silyl group, difluoromethoxysilyl group, difluoroethoxysilyl Group, a difluorophenoxysilyl group, a fluorodichlorosilyl group, a difluorochlorosilyl group, and the like, and a silicon group having no hydrolyzable group other than fluorine or a fluorosilyl group in which R11 is a methyl group is preferable, and a trifluorosilyl group is preferable. Is more preferred.
Further, from the ease of synthesis, fluorodimethylsilyl group, difluoromethylsilyl group, trifluorosilyl group, fluoromethoxymethylsilyl group, fluoroethoxymethylsilyl group, fluoromethoxyethylsilyl group, fluorodimethoxysilyl group, fluorodiethoxysilyl group , A difluoromethoxysilyl group, a difluoroethoxysilyl group is more preferable, and a silicon group having no hydrolyzable group other than fluorine such as a fluorodimethylsilyl group, a difluoromethylsilyl group, and a trifluorosilyl group is more preferable from the viewpoint of stability. From the viewpoint of high curability, a silicon group in which two to three fluorines are substituted on a silicon group, such as a difluoromethylsilyl group, a difluoromethoxysilyl group, a difluoroethoxysilyl group, and a trifluorosilyl group, is preferred. Fluoro silyl group is most preferred.

  The compound having a fluorosilyl group represented by the formula (8) is not particularly limited, and any of a monomolecular compound and a polymer compound can be used. For example, inorganic compounds such as tetrafluorosilane and octafluorotrisilane can be used. Silicon compound: fluorosilanes represented by the above formula (7), fluorotrimethoxysilane, difluorodimethoxysilane, trifluoromethoxysilane, fluorotriethoxysilane, difluorodiethoxysilane, trifluoroethoxysilane, methylfluorodimethoxysilane, methyl Difluoromethoxysilane, methyltrifluorosilane, methylfluorodiethoxysilane, methyldifluoroethoxysilane, vinylfluorodimethoxysilane, vinyldifluoromethoxysilane, vinyltrifluorosilane, vinylflu Low molecular weight organic silicon compounds such as rhodiethoxysilane, vinyldifluoroethoxysilane, phenylfluorodimethoxysilane, phenyldifluoromethoxysilane, phenyltrifluorosilane, phenylfluorodiethoxysilane, phenyldifluoroethoxysilane, and fluorotrimethylsilane; And a high molecular compound such as a fluorinated polysiloxane having a fluorosilyl group represented by the formula (8), such as a fluorosilane represented by the formula (7) or a formula (8) at the terminal of the main chain or the side chain. Polymers having a fluorosilyl group are preferred.

The fluorosilanes represented by the formula (7) and the compound having a fluorosilyl group represented by the formula (8) may be a commercially available reagent or may be synthesized from a starting compound. Although there is no particular limitation on the synthesis method, a compound having a hydrolyzable silicon group represented by the following formula (9) and a fluorinating agent can be synthesized by a known method (for example, Organometallics 1996, 15, 2,478 (Ishikawa et al.) ) Etc.) are preferably used.
—SiR ¹¹ _3-p Z _p (9)
(In the formula (9), R ¹¹ and Z are the same as those in the formula (8), and p is any of 1 to 3.)

  Examples of the hydrolyzable silicon group represented by the above formula (9) include an alkoxysilyl group, a siloxane bond, a halosilyl group such as a chlorosilyl group, and a hydrosilyl group.

Specific examples of the fluorinating agent used for fluorination of the alkoxysilyl group are not particularly limited, and include, for example, NH ₄ F, Bu ₄ NF, HF, BF ₃ , Et ₂ NSF ₃ , HSO ₃ F, and SbF _5. , VOF ₃ , CF ₃ CHFCF ₂ NEt _{2 and the} like.
Specific examples of the fluorinating agent used for fluorination of the halosilyl group are not particularly limited. For example, AgBF ₄ , SbF ₃ , ZnF ₂ , NaF, KF, CsF, NH ₄ F, CuF ₂ , NaSiF ₆ , NaPF ₆ , NaSbF ₆ , NaBF ₄ , Me ₃ SnF, KF (HF) _{1.5 to 5, and the} like.
Specific examples of fluorinating agents used for the fluorination of hydrosilyl group is not particularly limited, for _{example, AgF, PF 5, Ph 3} CBF 4, SbF 3, NOBF 4, such as _NO 2 BF ₄ and the like.
The compound having a siloxane bond is cleaved by BF ₃ or the like to obtain a fluorosilyl group.

Among the methods for synthesizing a fluorosilyl group using these fluorinating agents, a method for fluorinating an alkoxysilane using BF ₃ is preferred because the reaction is simple, the reaction efficiency is high, and the safety is high. A fluorination method of chlorosilane using CuF ₂ or ZnF ₂ is preferable.

Examples of BF ₃ include BF ₃ gas, BF ₃ ether complex, BF ₃ thioether complex, BF ₃ amine complex, BF ₃ alcohol complex, BF ₃ carboxylic acid complex, BF ₃ phosphate complex, BF ₃ hydrate, and BF ₃ piperidine. Complexes, BF ₃ phenol complexes and the like can be used, but BF ₃ ether complexes, BF ₃ thioether complexes, BF ₃ amine complexes, BF ₃ alcohol complexes, BF ₃ carboxylic acid complexes, BF ₃ hydrates are easy to handle. Are preferred. Among them, BF ₃ ether complex, BF ₃ alcohol complex and BF ₃ hydrate have high reactivity and are preferable, and BF ₃ ether complex is particularly preferable.

The organic polymer having a fluorosilyl group (also referred to as a fluorinated polymer in the specification of the present application) is not particularly limited as long as it is an organic polymer having a Si—F bond. Polymers can be widely used.
The position of the SiF bond in the organic polymer is not particularly limited, and the effect is exhibited at any site in the polymer molecule. If the terminal of the main chain or the side chain is -SiR ′ ₂ F, the polymer Is represented in the form of -SiR'F- or ≡SiF (R 'is independently an arbitrary group).
As the organic polymer having a Si—F bond at the terminal of the main chain or the side chain, a polymer having a fluorosilyl group represented by the above formula (8) is preferable. Examples Although fluoro silyl group is incorporated in the main chain of the _{polymer, -Si (CH 3) F -} , - Si (C 6 H 5) F -, - SiF 2 -, and the like ≡SiF .

  The fluorinated polymer is a single polymer having the same type of fluorosilyl group and main chain skeleton, that is, the number of fluorosilyl groups per molecule, the bonding position thereof, and the number of F that the fluorosilyl group has, Further, the polymer may be a single polymer having the same main chain skeleton, or a mixture of a plurality of polymers in which any or all of them are different. In any case where the fluorinated polymer is a single polymer or a mixture of a plurality of polymers, the fluorinated polymer can be suitably used as a resin component of a curable composition showing rapid curability, In order to obtain a rubber-like cured product exhibiting curability, and having high strength and high elongation and exhibiting a low elastic modulus, the fluorosilyl group contained in the fluorinated polymer is at least on average per one molecule of the polymer. One, preferably 1.1 to 5, more preferably 1.2 to 3 is present. If the number of fluorosilyl groups contained in one molecule is less than one on average, curability may be insufficient, and good rubber elasticity may not be exhibited. When the number of fluorosilyl groups contained in one molecule is more than five on average, the rubbery cured product may have a small elongation. As described above, the fluorosilyl group may be present at the terminal of the main chain or the terminal of the side chain of the polymer molecular chain, or may be incorporated in the main chain. When present at the end of the polymer, the effective mesh length of the organic polymer component contained in the finally formed cured product becomes longer, so that a rubber-like cured product having high strength, high elongation, and low elastic modulus is obtained. It becomes easy to be. When two or more fluorosilyl groups are present in one molecule, the respective silicon groups may be the same or different.

  Further, the fluorinated polymer contains, together with the fluorosilyl group, a substituent other than a fluorosilyl group such as a silicon group having only a hydrolyzable group other than fluorine (for example, a methyldimethoxysilyl group). May be. As such a fluorinated polymer, for example, a polymer in which one main chain terminal is a fluorosilyl group and the other main chain terminal is a silicon group having only a hydrolyzable group other than fluorine as a hydrolyzable group Can be mentioned.

  In the fluorinated polymer, any method may be used to introduce the fluorosilyl group. The introduction method (method (i)) by reacting the fluorosilyl group-containing low-molecular silicon compound with the polymer may be used. A method (method (ii)) of modifying a silicon group of a polymer containing a reactive silicon group having a hydrolyzable group (hereinafter sometimes referred to as “polymer (X)”) into a fluorosilyl group is described. No.

The following method is a specific example of the method (i).
(A) A method in which a polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in a molecule is reacted with a compound having a functional group having a reactivity to the functional group and a fluorosilyl group. For example, a method of reacting a polymer having a hydroxyl group at a terminal with isocyanatopropyldifluoromethylsilane or a method of reacting a polymer having a SiOH group at a terminal with difluorodiethoxysilane are exemplified.
(B) A method in which a hydrosilane having a fluorosilyl group is allowed to act on a polymer containing an unsaturated group in a molecule to perform hydrosilylation. For example, there is a method in which difluoromethylhydrosilane is reacted with a polymer having an allyl group at a terminal.
(C) A method in which a polymer having an unsaturated group is reacted with a compound having a mercapto group and a fluorosilyl group. For example, there is a method in which a polymer having an allyl group at a terminal is reacted with mercaptopropyldifluoromethylsilane.

  As the polymer (polymer (X)) containing a reactive silicon group having a hydrolyzable group other than fluorine used in the above method (ii), the aforementioned crosslinkable silicon group-containing organic polymer (A) is used. It is preferably used.

In the method (ii), as a method for converting a reactive silicon group having a hydrolyzable group other than fluorine into a fluorosilyl group, a known method can be used. For example, the method is represented by the formula (9) described above. A hydrolyzable silicon group to be converted into a fluorosilyl group with a fluorinating agent.
Examples of the fluorinating agent include the above-mentioned fluorinating agents. Among them, BF ₃ ether complex, BF ₃ alcohol complex and BF ₃ dihydrate have high activity, fluorination proceeds efficiently, and BF ₃ It is more preferable because no salt or the like is generated in the product and the post-treatment is easy, and a BF ₃ ether complex is particularly preferable.
Further, in the fluorination by the BF ₃ ether complex, the reaction proceeds even without heating, but it is preferable to heat in order to perform the fluorination more efficiently. The heating temperature is preferably from 50 ° C to 150 ° C, more preferably from 60 ° C to 130 ° C. When the temperature is lower than 50 ° C., the reaction does not proceed efficiently and the fluorination may take time. If the temperature is higher than 150 ° C., the fluorinated polymer may be decomposed. In the fluorination with the BF ₃ complex, coloring may occur depending on the type of the polymer (X) used. However, from the viewpoint of suppressing coloring, it is preferable to use a BF ₃ alcohol complex or BF ₃ dihydrate.

The fluorinating agent used in the production of the fluorinated polymer may also act as a curing catalyst for the fluorinated polymer, and when water is present when producing the fluorinated polymer using the above method (ii). In addition, the silanol condensation reaction may proceed, and the viscosity of the obtained fluorinated polymer may increase. For this reason, the production of the fluorinated polymer is desirably carried out in an environment as free of water as possible. Before the fluorination, the fluorinated polymer (X) is subjected to azeotropic dehydration using toluene, hexane or the like. It is preferable to perform a dehydration operation such as providing. However, when the BF ₃ amine complex is used, fluorination hardly proceeds after the dehydration operation, and the reactivity tends to be improved by adding a small amount of water. Is preferably added. Further, from the viewpoint of the stability of the fluorinated polymer, it is preferable to remove components derived from the fluorinating agent and by-produced fluorinating agent after fluorination by filtration, decantation, liquid separation, devolatilization under reduced pressure, or the like. When a fluorinated polymer is produced using the above-mentioned BF ₃ -based fluorinating agent, BF ₃ remaining in the produced fluorinated polymer and BF ₃ derived components produced by the reaction are less than 500 ppm in B amount. Is more preferably, less than 100 ppm, particularly preferably less than 50 ppm. By removing BF ₃ and the components derived from BF ₃ , an increase in the viscosity of the obtained fluorinated polymer itself and a mixture of the fluorinated polymer and the polymer (X) can be suppressed. Considering this point, the fluorination method using a BF ₃ ether complex or a BF ₃ alcohol complex is preferable because the boron component can be relatively easily removed by vacuum devolatilization, and the method using the BF ₃ ether complex is particularly preferable. .

  Here, when the polymer (X) has two or more hydrolyzable groups other than fluorine, all the hydrolyzable groups may be fluorinated or a method such as reducing the amount of the fluorinating agent. May be partially fluorinated by adjusting fluorination conditions. For example, when the fluorinated polymer is produced using the polymer (X) in the method (ii), the amount of the fluorinating agent used is not particularly limited, and the molar amount of fluorine atoms in the fluorinating agent is not limited. It is sufficient that the amount is equal to or greater than the molar amount of the polymer (X). When all of the hydrolyzable groups contained in the polymer (X) are to be fluorinated by the method (ii), the molar amount of the fluorine atom in the fluorinating agent is limited by the amount of the polymer (X) contained in the polymer (X). It is preferable to use an amount of the fluorinating agent in such an amount that it becomes equimolar or more with respect to the total molar amount of the hydrolyzable group in the reactive silicon group. Here, the “fluorine atom in the fluorinating agent” refers to a fluorine atom effective for fluorination in the fluorinating agent, specifically, a hydrolyzable group in a reactive silicon group of the polymer (X). Refers to a fluorine atom that can be substituted.

  The low molecular compound having a fluorosilyl group in the above method (i) can also be synthesized from a general-purpose reactive silicon group-containing low molecular compound using the above fluorination method.

  In the method (i), there is a reactive group for reacting the polymer and the silicon-containing low molecular weight compound together with the fluorosilyl group. Therefore, when the reaction becomes complicated, the fluorinated polymer is obtained by the method (ii). Is preferred.

  The glass transition temperature of the fluorinated polymer is not particularly limited, but is preferably 20 ° C or lower, more preferably 0 ° C or lower, and particularly preferably -20 ° C or lower. When the glass transition temperature is higher than 20 ° C., the viscosity in winter or in a cold region becomes high, and it may be difficult to handle. In addition, the flexibility of a cured product obtained when used as a curable composition decreases, and May decrease. The glass transition temperature can be determined by DSC measurement.

  The fluorinated polymer may be linear or branched. The number average molecular weight of the fluorinated polymer is preferably from 3,000 to 100,000, more preferably from 3,000 to 50,000, particularly preferably from 3,000 to 30,000 in terms of polystyrene by GPC. If the number average molecular weight is less than 3,000, the cured product tends to be inferior in elongation characteristics, and if it exceeds 100,000, the viscosity tends to be high, and the workability tends to be inconvenient.

  The blending ratio of the silicon compound (C) having the Si-F bond is not particularly limited, but when a polymer having a number average molecular weight of 3000 or more such as a fluorinated polymer is used as the component (C), (A) crosslinking The amount is preferably 0.01 to 80 parts by mass, more preferably 0.01 to 30 parts by mass, and still more preferably 0.05 to 20 parts by mass, based on 100 parts by mass of the organic polymer having a silicon group. Low molecular weight compounds having a fluorosilyl group having a number average molecular weight of less than 3000 as component (C) (for example, low molecular weight organosilicon having a fluorosilyl group represented by the formula (7) or a fluorosilyl group represented by the formula (8)) Compound, an inorganic silicon compound having a fluorosilyl group, or the like), 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of (A) the crosslinkable silicon group-containing organic polymer. Parts by mass are more preferred.

  The photocurable composition of the present invention preferably further contains (D) an active energy ray-cleavable radical generator. The active energy ray-cleavable radical generator (D) is an active energy ray-cleavable radical generator that cleaves upon irradiation with an active energy ray to generate radicals. The use of the energy ray-cleavable radical generator has a significantly higher curing rate than the use of photosensitizers such as benzophenones and thioxanthones which have been known as sensitizers for photobase initiators. And the photocurable composition of the present invention can be cured in a shorter time after irradiation with energy rays.

Examples of the active energy ray-cleavable radical generator include arylalkyl ketones such as benzoin ether derivatives and acetophenone derivatives, oxime ketones, acylphosphine oxides, S-phenyl thiobenzoates, titanocenes, and the like. Derivatives having a high molecular weight are exemplified. Commercially available cleavage-type radical generators include, for example, 1- (4-dodecylbenzoyl) -1-hydroxy-1-methylethane, 1- (4-isopropylbenzoyl) -1-hydroxy-1-methylethane, Benzoyl-1-hydroxy-1-methylethane, 1- [4- (2-hydroxyethoxy) -benzoyl] -1-hydroxy-1-methylethane, 1- [4- (acryloyloxyethoxy) -benzoyl] -1-hydroxy -1-methylethane, diphenyl ketone, phenyl-1-hydroxy-cyclohexyl ketone, benzyldimethyl ketal, bis (cyclopentadienyl) -bis (2,6-difluoro-3-pyryl-phenyl) titanium, (η ⁶ -isopropyl benzene) - (eta ⁵ - cyclopentadienyl) - iron (II Hexafluorophosphate, trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl) -phosphine oxide, bis (2,4,6-trimethylbenzoyl) -2, 4-dipentoxyphenylphosphine oxide or bis (2,4,6-trimethylbenzoyl) phenyl-phosphine oxide.
The mixing ratio of the (D) active energy ray-cleavable radical generator is not particularly limited, but is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the (A) crosslinkable silicon-containing organic polymer. 0.01 to 10 parts by mass is more preferable, and 0.1 to 5 parts by mass is further preferable. These active energy ray-cleavable radical generators may be used alone or in combination of two or more.

  The photocurable composition of the present invention preferably further contains a silane coupling agent. By blending the silane coupling agent, the overall adhesion to an adherend such as metal, plastic, and glass can be improved.

  Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, and N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane Amino-containing silanes such as N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane and 1,3-diaminoisopropyltrimethoxysilane N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propane Ketimine-type silanes such as amines; γ-glycidoxypropyltrimethoxysilane, γ-glycid Epoxy group-containing silanes such as xypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyl Mercapto group-containing silanes such as methyldimethoxysilane; vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-acryloyloxypropylmethyldimethoxysilane; γ Silanes containing chlorine atoms such as -chloropropyltrimethoxysilane; isocyanate-containing silanes such as γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropylmethyldimethoxysilane; hexyl Alkyl silanes such as rimethoxy silane, hexyl triethoxy silane and decyl trimethoxy silane; phenyl group-containing silanes such as phenyl trimethoxy silane, phenyl triethoxy silane, diphenyl dimethoxy silane and diphenyl diethoxy silane; It is not limited to these. Further, the amino group-containing silanes obtained by reacting the amino group-containing silanes with an epoxy group-containing compound containing the silanes, an isocyanate group-containing compound, and a (meth) acryloyl group-containing compound to modify the amino group are obtained. May be used.

  The mixing ratio of the silane coupling agent is not particularly limited, but is preferably 0.2 to 20 parts by mass, and more preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the crosslinkable silicon-containing organic polymer (A). Is more preferable, and 0.5 to 5 parts by mass is further preferable. These silane coupling agents may be used alone or in combination of two or more.

  In addition to the silane coupling agent described above, in the photocurable composition of the present invention, the adhesiveness-imparting agent is not particularly limited. Etc. can be used. The above-mentioned adhesiveness-imparting agent may be used alone or in combination of two or more.

  When the epoxy resin is contained, the toughness of the cured product can be increased by using a compound having an epoxy group. When an epoxy resin is added, it is natural that a curing agent for curing the epoxy resin can be used in combination with the photocurable composition of the present invention.

  In the present invention, (A) the curing catalyst for the crosslinkable silicon-containing organic polymer is selected from the group consisting of boron trifluoride, a complex of boron trifluoride, a fluorinating agent, and an alkali metal salt of a polyvalent fluoro compound. May contain one or more fluorine-based compounds.

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

Examples of the amine compound used in the boron trifluoride amine complex include, for example, ammonia, monoethylamine, triethylamine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, guanidine, 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine, N-methyl-3,3'-iminobis (propylamine), ethylenediamine, diethylenetriamine, triethylenediamine, pentaethylenediamine , 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,4-diaminobutane, 1,9-diaminononane, ATU (3,9-bis (3-aminopropyl) -2 , 4 8,10-tetraoxaspiro [5.5] undecane), CTU guanamine, dodecanoic acid dihydrazide, hexamethylenediamine, m-xylylenediamine, dianisidine, 4,4'-diamino-3,3'-diethyldiphenylmethane, diamino Diphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, m-toluylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, melamine, 1,3-diphenylguanidine, Di-o-tolylguanidine, 1,1,3,3-tetramethylguanidine, bis (aminopropyl) piperazine, N- (3-aminopropyl) -1,3-propanediamine, bis (3-aminopropyl) ether , San Techno Chemical Co., Ltd. Compounds having a plurality of primary amino groups such as amines, piperazine, cis-2,6-dimethylpiperazine, cis-2,5-dimethylpiperazine, 2-methylpiperazine, N, N'-di-t-butylethylenediamine , 2-aminomethylpiperidine, 4-aminomethylpiperidine, 1,3-di- (4-piperidyl) -propane, 4-aminopropylaniline, homopiperazine, N, N'-diphenylthiourea, N, N'- Compounds having a plurality of secondary amino groups such as diethylthiourea and N-methyl-1,3-propanediamine; furthermore, methylaminopropylamine, ethylaminopropylamine, ethylaminoethylamine, laurylaminopropylamine, 2-hydroxy Ethylaminopropylamine, 1- (2-aminoethyl) piperazine, N -Aminopropylpiperazine, 3-aminopyrrolidine, 1-o-tolylbiguanide, 2-aminomethylpiperazine, N-aminopropylaniline, ethylamineethylamine, 2-hydroxyethylaminopropylamine, laurylaminopropylamine, 2-aminomethylpiperidine , 4-aminomethylpiperidine, a compound represented by the formula H ₂ N (C ₂ H ₄ NH) _n H (n ≒ 5) (trade name: Polyate, manufactured by Tosoh Corporation), N-alkylmorpholine, 1,8-diazabicyclo [5.4.0] undecene-7,6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7,1,5-diazabicyclo [4.3.0] nonene-5,1,1. 4-diazabicyclo [2.2.2] octane, pyridine, N-alkylpiperidine, 1,5 Bicyclic tertiary such as 7-triazabicyclo [4.4.0] dec-5-ene and 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene Other than amine compounds, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-3- [amino (dipropyleneoxy)] aminopropyltriethoxysilane, (aminoethylaminomethyl) phenethyltriethoxysilane, N- ( 6-aminohexyl) aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N- (2-amido) Ethyl) aminosilane compounds such as 11-amino-undecyl triethoxy silane.
Examples of commercially available products of the amine complex of boron trifluoride include Anchor 1040, Anchor 1115, Anchor 1170, Anchor 1222, and BAK1171 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.

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

  Examples of the electrophilic fluorinating agent include N-fluoro such as bis (tetrafluoroboric acid) N, N′-difluoro-2,2′-bipyridinium salt compound and trifluoromethanesulfonic acid N-fluoropyridinium salt compound. Pyridinium salt compounds, 4-fluoro-1,4-diazoniabicyclo [2.2.] Such as bis (tetrafluoroboric acid) 4-fluoro-1,4-diazoniabicyclo [2.2.2] octane salt and the like. 2] N-fluorobis (sulfonyl) amine-based compounds such as octane-based compounds and N-fluorobis (phenylsulfonyl) amine. Among these, the 1,1,2,3,3,3-hexafluoro-1-diethylaminopropane compound is a liquid compound and is particularly preferable because it is easily available.

Examples of the alkali metal salt of the polyvalent fluoro compound include sodium hexafluoroantimonate, potassium hexafluoroantimonate, sodium hexafluoroarsenate, potassium hexafluoroarsenate, lithium hexafluorophosphate, sodium hexafluorophosphate, Potassium hexafluorophosphate, sodium pentafluorohydroxoantimonate, potassium pentafluorohydroxoantimonate, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, sodium tetrakis (trifluoromethylphenyl) borate, tri Sodium fluoro (pentafluorophenyl) borate, potassium trifluoro (pentafluorophenyl) borate, difluorobis (pentafluorophenyl) Sulfonyl) sodium borate, difluoro (pentafluorophenyl) potassium borate, and the like.
Among these, tetrafluoroboric acid or hexafluorophosphoric acid is preferable as the polyvalent fluoro compound component in the alkali metal salt of the polyvalent fluoro compound. The alkali metal in the alkali metal salt of the polyvalent fluoro compound is preferably at least one alkali metal selected from the group consisting of lithium, sodium and potassium.

  The mixing ratio of the fluorine-based compound is not particularly limited, but is preferably 0.001 to 10 parts by mass, and more preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the crosslinkable silicon-containing organic polymer (A). More preferably, the amount is 0.001 to 2 parts by mass. These fluorine compounds may be used alone or in combination of two or more.

  The photocurable composition of the present invention may further contain a base proliferating agent. The base proliferating agent is not particularly limited as long as it is a substance that generates a base by the action of a base, and a conventionally known base proliferating agent can be used.

  As the base proliferating agent, a fluorenyl base proliferating agent, a sulfone base proliferating agent, or a 3-nitropentan-2-yl base proliferating agent can be suitably used.

  Specific examples of the fluorenyl base proliferating agent include, for example,

And the like.

  Specific examples of the sulfone base proliferating agent include, for example,

And the like.

  As the 3-nitropentan-2-yl base proliferating agent, for example,

And the like.

Moreover, when improving the adhesiveness of the photocurable composition of the present invention, it is preferable to contain a base-proliferating aminosilane as a base-proliferating agent. Examples of the base-proliferating aminosilane include a base-proliferating amine compound having a crosslinkable silicon group at an amine residue (a compound that generates an amine compound having a crosslinkable silicon group when decomposed). As such a compound, 9-fluorenylmethyl ester of carbamic acid having a crosslinkable silicon group (C ₁₃ H ₉ CH ₂ OCONR ¹⁰ R ¹¹ , wherein R ¹⁰ and R ¹¹ are a hydrogen atom or a hydrocarbon group, etc. An organic group, and at least one of R ¹⁰ and R ¹¹ is an organic group such as a hydrocarbon group having a crosslinkable silicon group), a 2-arylsulfonylethyl ester of carbamic acid having a crosslinkable silicon group (ArSO ₂ CH ₂ CH ₂ OCONR ¹⁰ R ¹¹ , wherein Ar is an aromatic group which may have a substituent, R ¹⁰ and R ¹¹ are the same as described above), 3-nitropentane-carbamic acid having a crosslinkable silicon group And 2-yl esters (CH ₃ CH ₂ CH (NO ₂ ) CH (CH ₃ ) OCONR ¹⁰ R ¹¹ , wherein R ¹⁰ and R ¹¹ are the same as above).

The crosslinkable silicon group in the carbamic acid having a crosslinkable silicon group is the same as the crosslinkable silicon group in (A). Specific examples of the carbamic acid having a crosslinkable silicon group 3-trimethoxysilylpropyl carbamate _{((CH 3 O) 3 SiCH} 2 CH 2 CH 2 NHCOOH) and 3-triethoxysilylpropyl carbamate ((C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOOH).

  The mixing ratio of the base proliferating agent is not particularly limited, but is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, based on 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer. Preferably, 0.1 to 30 parts by mass is more preferable. These base proliferating agents may be used alone or in combination of two or more.

  The photocurable composition of the present invention may contain a compound having a photoradical polymerizable vinyl group. As the compound having a photo-radical polymerizable vinyl group, a known compound having a photo-radical polymerizable vinyl group can be used, and is not particularly limited. For example, a compound having a (meth) acryloyl group; Examples include N-vinyl compounds in which a vinyl group is directly bonded to a nitrogen atom.

  Examples of the compound having a (meth) acryloyl group include a compound having a (meth) acryloyloxy group and a compound having a (meth) acrylamide group, and a compound having a (meth) acryloyloxy group in terms of storage stability. preferable. Further, a compound having a (meth) acrylamide group is preferable from the viewpoint of reactivity.

  As the compound having a (meth) acryloyloxy group, any of a monomer and an oligomer can be used, and from the viewpoint of viscosity, a monomer having a (meth) acryloyloxy group is preferable. Further, an oligomer having a (meth) acryloyloxy group is preferable from the viewpoint of the physical properties of the cured product.

  The monomer having the (meth) acryloyloxy group is not particularly limited as long as it is a compound having at least one (meth) acryloyloxy group. For example, monofunctional (meth) acrylates, polyfunctional (meth) Acrylates and the like.

  As monofunctional (meth) acrylates, for example, (meth) acrylic acid, ethyl (meth) acrylate, 1-methoxyethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate , Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate , Dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acyl Relate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) ) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate, nonylphenoxytetraethylene glycol (meth) acrylate, dimethyl (meth) acrylamide, Dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, methoxydiethylene glyco (Meth) acrylate, ethoxydiethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, 2-ethylhexyl polyethylene glycol (meth) acrylate, nonylphenyl polypropylene glycol (meth) acrylate, methoxydi Propylene glycol (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, polyethylene glycol (meth) ) Acrylate, polypropylene glycol (meth) acrylate, epichlorohydrin-modified butyl (meth) acryle Epichlorohydrin-modified phenoxy (meth) acrylate, ethylene oxide-modified phthalic acid (meth) acrylate, ethylene oxide-modified succinic acid (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, N, N-dimethylamino Examples include ethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, and ethylene oxide-modified phosphoric acid (meth) acrylate. When flexibility is required, it is preferable to use monofunctional (meth) acrylates.

  Examples of the polyfunctional acrylates include 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexane glycol di ( (Meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethylene oxide-modified neopentyl glycol di (meth) acrylate Propylene oxide-modified neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, epichlorophenol Phosphorus-modified bisphenol A di (meth) acrylate, ethylene oxide-modified bisphenol S di (meth) acrylate, hydroxypivalic acid ester neopentyl glycol diacrylate, caprolactone-modified hydroxypivalic acid ester neopentyl glycol diacrylate, neopentyl glycol-modified trimethylolpropane Di (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, dicyclopentenyl diacrylate, ethylene oxide-modified dicyclopentenyl di (meth) acrylate, di (meth) acryloyl isocyanurate, trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropanetetra (meth) a Relate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxy penta (meth) acrylate. Polyfunctional acrylates are preferred because oxygen inhibition is less likely to occur.

  Examples of the oligomer having a (meth) acryloyloxy group include an acrylic oligomer, a polyester (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, a urethane (meth) acrylate oligomer, and a polyether (meth) acrylate oligomer.

  As the acrylic oligomer, an oligomer whose main chain is a (meth) acrylic ester polymer and has a (meth) acryloyloxy group can be used. Such a polymer is preferably produced by anionic polymerization or radical polymerization, and radical polymerization is more preferable because of versatility of the monomer and ease of control. Among radical polymerizations, it is preferably produced by living radical polymerization or radical polymerization using a chain transfer agent, more preferably a living radical polymerization method, and particularly preferably an atom transfer radical polymerization method. When a living radical polymerization method is used, a polymer having a (meth) acryloyloxy group at a polymer chain terminal can be obtained.

  Examples of the acrylic oligomer include n-butyl polyacrylate having an acryloyl group at both ends described in Production Example 1 of WO2012 / 008127 and one end described in Production Example 2 of the same publication. Polyacrylic acid n-butyl having an acryloyl group, poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) having an acryloyl group at both terminals described in Production Example 1 of WO2005 / 000927 Poly (n-butyl acrylate / 2-ethylhexyl acrylate) having acryloyl groups at both ends described in Production Example 2 of WO 2006/112420, both ends described in Production Example 3 of the same publication Poly (2-ethylhexyl acrylate) having an acryloyl group Can.

  As the skeletal components of the acrylic oligomer, polymethyl methacrylate (MMA), polystyrene (St), poly (acrylonitrile (AN) / St), poly (2-hydroxyethyl methacrylate (HEMA) / MMA), poly (HEMA) / Butyl methacrylate (BMA)) and many other oligomers are commercially available.

  Commercially available acrylic oligomers include, for example, macro monomers AA-6, AA-714, AB-6, AJ-7, AN-6, AS-6, AW-6, AZ manufactured by Toagosei Co., Ltd. -8, HA-6, HN-6, HS-6 and RC-300, RC-100, RC-200 manufactured by Kaneka Corporation.

  Examples of the polyester (meth) acrylate oligomer include a dehydration condensate of a polyester polyol and (meth) acrylic acid. Here, examples of the polyester polyol include a reaction product of the polyol with a carboxylic acid or an anhydride thereof.

  Polyols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, tetramethylene glycol, hexamethylene glycol, Low molecular weight polyols such as pentyl glycol, cyclohexane dimethanol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol and dipentaerythritol, and alkylene oxide adducts thereof And the like.

  As the carboxylic acid or its anhydride, orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, dibasic acid such as tetrahydrophthalic acid and trimellitic acid or its anhydride Objects and the like.

  Examples of the epoxy (meth) acrylate oligomer include compounds obtained by adding (meth) acrylic acid to an epoxy resin. Examples of the epoxy resin include an aromatic epoxy resin and an aliphatic epoxy resin.

  Specific examples of the aromatic epoxy resin include resorcinol diglycidyl ether; bisphenol A, bisphenol F, bisphenol S, di or polyglycidyl ether of bisphenolfluorene or an alkylene oxide adduct thereof; phenol novolak epoxy resin and cresol novolac type Novolak type epoxy resins such as epoxy resins; glycidyl phthalimide; diglycidyl o-phthalate; In addition to these, Chapter 2 of the document “Epoxy Resins-Recent Advances” (issued by Shokodo, 1990), and Epoxy Resins [Vol. Published in 1973], pages 4 to 6 and 9 to 16 can be mentioned.

  Specific examples of the aliphatic epoxy resin include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; and diglycidyl ethers of polyethylene glycol and polypropylene glycol. Diglycidyl ether of polyalkylene glycol; neopentyl glycol, dibromoneopentyl glycol and its diglycidyl ether of alkylene oxide adduct; trimethylolethane, trimethylolpropane, di or triglycidyl ether of glycerin and its alkylene oxide adduct, And polyglycyls of polyhydric alcohols such as di, tri or tetraglycidyl ether of pentaerythritol and its alkylene oxide adduct Ether; hydrogenated bisphenol A and di- or polyglycidyl ethers of alkylene oxide adducts; tetrahydrophthalic acid diglycidyl ether; hydroquinone diglycidyl ether, and the like.

  In addition to these, there may be mentioned the compounds described on pages 3 to 6 of the above-mentioned document "Polymer processing", separate volume epoxy resin. In addition to these aromatic epoxy resins and aliphatic epoxy resins, epoxy compounds having a triazine nucleus as a skeleton, such as TEPIC (Nissan Chemical Co., Ltd.) and Denacol EX-310 (Nagase Kasei Co., Ltd.), and the like, And compounds described in the above-mentioned document "Polymer processing", separate volume epoxy resin, pp. 289-296. In the above, as the alkylene oxide of the alkylene oxide adduct, ethylene oxide and propylene oxide are preferable.

  Examples of the urethane (meth) acrylate oligomer include a reaction product obtained by further reacting a hydroxyl group-containing (meth) acrylate with a polyol and an organic polyisocyanate reaction product. Here, examples of the polyol include a low molecular weight polyol, polyethylene glycol, polyester polyol, and polycarbonate polyol. Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, cyclohexane dimethanol, and 3-methyl-1,5-pentanediol. Examples of the polyether polyol include polyethylene glycol and polypropylene glycol. Is a reaction product of these low molecular weight polyols and / or polyether polyols with an acid component such as dibasic acid such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid or anhydride thereof. . Examples of the organic polyisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. These urethane (meth) acrylate oligomers may be those produced according to a conventionally known synthesis method. For example, in the presence of an addition catalyst such as dibutyltin dilaurate, a method of heating and stirring an organic isocyanate and a polyol component to cause an addition reaction, further adding a hydroxyalkyl (meth) acrylate, heating and stirring to cause an addition reaction, and the like.

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

  Examples of the compound having a (meth) acrylamide group include a compound represented by the following formula (10) and a compound represented by the following formula (11).

In the formula ^{(10), R 80} represents a hydrogen atom or a methyl ^{group, R 81} and ^{R 82} represents a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 20, ^{R 81} and ^{R 82} in one molecule Or the same group or different groups.
The hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group, more preferably an alkyl group having 1 to 3 carbon atoms, and may be linear or branched. The alkyl group may be an alkyl group further having a hydroxyl group, an aromatic group and a diaminoalkyl group.
Specific examples of the alkyl group include a methyl group, a propyl group, a butyl group, a butyl group, and a hexyl group.
Examples of the alkyl group having a hydroxyl group include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
Examples of the alkyl group having an aromatic group include a benzyl group.
Examples of the dialkylaminoalkyl group include an N, N-dimethylaminoethyl group and N, N-dimethylaminopropyl.

In the formula ^{(11), R 80} is the same as ^{R 80} in the formula (10).

  Specific examples of (meth) acrylamide represented by the formula (10) include N-methyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl ( (Meth) acrylamide, N-sec-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, Nn-hexyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide , N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di -N-propyl (meth) acrylamide, N, N-diisoprop Pill (meth) acrylamide, N, N-di -n- butyl (meth) acrylamide, N, N-dihexyl (meth) acrylamide, N, N-dibenzyl (meth) include (meth) acrylamide derivatives such as acrylamide.

  Specific examples of the (meth) acrylamide represented by the formula (11) include acryloylmorpholine and methacrylolylmorpholine, and acryloylmorpholine is preferable from the viewpoint of good curability.

  Examples of the N-vinyl compound include N-vinylpyrrolidone and N-vinylcaprolactam. In the present invention, the N-vinyl compound is preferable from the viewpoint of reactivity and the point that oxygen inhibition hardly occurs.

  The compounding ratio of the photo-radical polymerizable compound having a vinyl group is not particularly limited, but is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the (A) crosslinkable silicon-containing organic polymer. 0.1 to 50 parts by mass, more preferably 0.1 to 30 parts by mass. These compounds having a photoradical polymerizable vinyl group may be used alone or in combination of two or more.

  The photocurable composition of the present invention produces, in addition to the photobase generator (B), one or more amino groups selected from the group consisting of primary amino groups and secondary amino groups by light. May be further contained. The crosslinkable silicon group-containing compound that produces one or more amino groups selected from the group consisting of a primary amino group and a secondary amino group by the light can improve the adhesive performance.

  As the crosslinkable silicon group-containing compound that produces one or more amino groups selected from the group consisting of primary amino groups and secondary amino groups by the light, primary amino groups and 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. In the present specification, 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 is also referred to as a photoaminosilane-generating compound.

  As the aminosilane compound generated by the light irradiation, a compound having a crosslinkable silicon group and a substituted or unsubstituted amino group is used. The substituent of the substituted amino group is not particularly limited, and includes, for example, an alkyl group, an aralkyl group, and an aryl group. The crosslinkable silicon group is not particularly limited, and includes the crosslinkable silicon group described in the section of (A) the organic polymer. A silicon-containing group to which a hydrolyzable group is bonded is preferable. Among these, an alkoxy group such as a methoxy group and an ethoxy group is preferred because of its mild hydrolyzability and easy handling. In the aminosilane compound, a hydrolyzable group or a hydroxyl group can be bonded to one silicon atom in a range of 1 to 3, and preferably 2 or more, and particularly preferably 3 or more.

The aminosilane compound generated by the light irradiation is not particularly limited, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyl Dimethoxysilane, γ-aminopropylmethyldiethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltri Monoamines such as methoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane Γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl ) Aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (6-aminohexyl) aminopropyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N , N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine and the like; and triamines such as γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane and the like.

Among the aminosilane compounds generated by the light irradiation, an aminosilane compound having a primary amino group (—NH ₂ ) is preferable from the viewpoint of adhesiveness, and γ-aminopropyltrimethoxysilane and γ are preferable from the viewpoint of availability. -Aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane are preferable, and γ-aminopropyltrimethoxysilane and γ-aminopropyltrimethoxysilane are preferred in view of adhesiveness and curability. Ethoxysilane is more preferred.

  Examples of the photoaminosilane-generating compound include a silicon compound having a photofunctional group represented by the following formulas (12) to (13), an aromatic sulfonamide derivative represented by the following formula (14), and a compound represented by the following formula (15). O-acyl oxime derivatives represented by the following, and trans-O-coumaric acid derivatives represented by the following formula (16).

In the formula (12), n is an integer of 1 to 3, Y represents a hydroxyl group or a hydrolyzable group, and an alkoxy group is preferable. When a plurality of Y are present, they may be the same or different. R ¹⁰¹ represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a substituent, and is preferably a vinyl group, an allyl group, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group. . When a plurality of R ¹⁰¹ are present, they may be the same or different. 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, and j is 1 to 6 integers. R ¹⁰³ is a substituted or unsubstituted hydrocarbon group bonded to silicon and nitrogen atoms 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 combine with each other to form a cyclic structure, and may include a heteroatom bond. Z is an oxygen atom or a sulfur atom, preferably an oxygen atom. Q represents a photofunctional group.

In the formula (13), n, Y, R ¹⁰¹ , Z, and Q are the same as those in the formula (12). 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 preferably 1 or 2. when t is 2 or more, t pieces of groups bonded to R ¹⁰⁴ may be different even in the same. 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 combine with each other to form a cyclic structure, and may include a heteroatom bond.

In the formula (14), n, Y, R ^{101 to} R ¹⁰³ , h and j are the same as those in the formula (12). R ^{106 to} R ¹¹⁰ each independently represent a hydrogen 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, substituted or unsubstituted alkyl group (preferably alkyl group having 1 to 5 carbon atoms), substituted or unsubstituted alkoxy group (preferably alkoxy group having 1 to 5 carbon atoms), unsubstituted or substituted Examples include an aryl group, an unsubstituted or substituted aryloxy group, a heterocyclic structure-containing group, a group having a plurality of rings, and combinations thereof. Any of R ^{106 to} R ¹¹⁰ may be bonded to each other to form a cyclic structure. 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 functional group such as a heterocyclic or non-aromatic ring, or a carbonyl group are bonded. Or a condensed ring or the like may be formed.

In the formula (15), n, Y, R ¹⁰¹ , R ¹⁰³ , h and j are the same as in the formula (12), and R ^{106 to} R ¹¹⁰ are the same as in the formula (14). R ¹¹¹ is the same as R ^{106 to} R ^{110 in the} formula (14).

In the formula (16), n, Y, R ¹⁰¹ , R ¹⁰³ , h and j are the same as in the formula (12), and R ^{106 to} R ¹⁰⁹ are the same as in the formula (14). 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 combine with each other to form a cyclic structure, and may include a heteroatom bond. R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, and a phosphino group. A phosphinyl group, a phosphono group, a phosphonate group, or an organic group, 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, carbon The alkoxy group, the unsubstituted or substituted aryl group, and the aryloxy group of Formulas 1 to 5 are preferable. 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 is preferably a hydrogen atom, a silyl group, a silanol group, a phosphino group, a phosphinyl group, or a phosphono group. Or an organic group is more preferred.

  In the formulas (12) to (16), examples of the unsubstituted or substituted alkyl group having 1 to 10 carbon atoms (or 1 to 5 carbon atoms) include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. 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 and the like.

  The photofunctional group Q includes a known photosensitive group and is not particularly limited. Examples thereof include a group having a cyclic structure represented by the following formula (17), an oxime residue represented by the following formula (18), These substituted groups are exemplified, and a group having a cyclic structure represented by the following formula (17) is preferable.

−AQ ′ (17)
[In the above formula (17), A is a direct bond or a divalent linking group, and Q ′ is a cyclic structure-containing group. The direct bond means that Q ′ is directly bonded to Z without going through a linking group. Examples of the divalent linking group in A include, for example, a divalent linking that includes 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. And an alkylene group and a carbonyl group which may contain a substituent, and a combination thereof. Further, the substituent of A may have a cyclic structure, or the substituents may be bonded to each other to form a cyclic structure. As the cyclic structure, for example, those similar to Q ′ can be mentioned.
The cyclic structure in Q ′ may be any of a single ring and a plurality of rings, and may be any of a monocyclic and a heterocyclic, and includes a functional group such as a vinyl group, a carbonyl group, and an imino group. It is more preferable that the compound has a cyclic structure showing aromaticity. Examples of Q ′ include, for example, an aryl group, an aryloxy group, a heterocyclic group containing at least one heteroatom such as nitrogen, oxygen, and sulfur, and a cyclic group to which a carbonyl group is bonded, each of which may have a substituent. Examples include groups having a structure, combinations thereof, and condensed rings thereof. Further, the substituent may further have a cyclic structure. Further, the substituent of A and Q ′ may be bonded. ]

(In the formula (18), R ¹¹⁶ and R ¹¹⁷ each independently represent 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, R ¹¹⁶ 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. And R ¹¹⁷ may be bonded to each other to form a double bond or an aromatic or non-aromatic ring, wherein R ¹¹⁶ , R ¹¹⁷ , or R ¹¹⁶ and R ¹¹⁷ are bonded to each other. The double bond or the aromatic or non-aromatic ring may further have one or two oxime groups shown in the above formula.)

  Examples of the group having a cyclic structure represented by the formula (17) include, for example, an aromatic group represented by the following formula (19), a group having a heterocyclic structure, and these substituted groups. Groups are preferred. Further, the groups in the photofunctional group may be bonded to each other to form a cyclic structure.

(In the formula (19), A is the same as A in the formula (17), and is preferably a substituted or unsubstituted alkylene group, a carbonyl group, and a combination thereof. R ^{118 to} R ¹²² are each independently Represents a hydrogen 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 group. An alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), a substituted or unsubstituted alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group , either .R ¹¹⁸ to R ¹²² which heterocyclic structure-containing group, group and the like these combinations having a plurality of rings include bonded to each other, forming a cyclic structure Attached either to each other also good .R ¹¹⁸ to R ^122, if they form a cyclic structure, the structure a plurality of benzene rings are condensed, the benzene ring and the heterocyclic or non-aromatic ring, such as a carbonyl group A structure or the like in which a ring or the like to which a functional group is bonded may be formed, or the substituent of A may be bonded to any of R ^{118 to} R ^122. )

  Examples of the aromatic group represented by the formula (19) include an o-nitrobenzyl group represented by the following formula (20-1), an m-nitrobenzyl group represented by the following formula (20-2), and a compound represented by the following formula: A nitrobenzyl group such as a p-nitrobenzyl group represented by (20-3); a benzyl group represented by the following formula (21); a benzoyl group represented by the following formula (22); , A nitrobenzyl group is preferable, an o-nitrobenzyl group and a p-nitrobenzyl group are more preferable, and an o-nitrobenzyl group is particularly preferable. Further, the groups in the photofunctional group may be bonded to each other to form a cyclic structure.

(In the formulas (20-1) to (20-3), R ^{118 to} R ¹²¹ are the same as those in the formula (19). R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a carbon atom. Represents 10 to 10 unsubstituted or substituted alkyl groups, phenyl groups and substituted phenyl groups, and k is 1 or 2. When k is 2, a plurality of R ¹²³ and R ¹²⁴ may be the same or different. May be.)

(In the formula (21), R ^{118 to} R ¹²² are the same as those in the formula (19). R ¹²⁵ and R ¹²⁶ each independently represent a hydrogen atom, an unsubstituted or substituted alkyl having 1 to 10 carbon atoms. Group, phenyl group, and substituted phenyl group.)

(In the formula (XI), R ^{118 to} R ¹²² are the same as those in the formula (19). R ¹²⁷ and R ¹²⁸ each independently represent a hydrogen atom, an unsubstituted or substituted alkyl having 1 to 10 carbon atoms. Group, phenyl group, and substituted phenyl group.)

  As the benzoyl group represented by the formula (22), for example, a benzoylphenylmethyl group represented by the following formula (23) is preferable.

(In the formula (23), R ^{118 to} R ¹²² are the same as those in the formula (19). 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, 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.)

  Examples of the group having a heterocyclic structure include a coumarin derivative residue represented by the following formula (24), an imide group represented by the following formula (25), and these substituted groups.

(Wherein ^{(24), R 136} and ^{R 137} each independently represent a hydrogen atom or a ^substituent, R 138 ^{to R 142} each independently represent a hydrogen atom or a ^{substituent, R 138} ~ Examples of R ¹⁴² include the same ones as R ^{118 to} R ^{122 in the} formula (19), and two or more of R ^{138 to} R ¹⁴² may combine to form a cyclic structure. ¹³⁸ to R ¹⁴² either 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, a functional group such as a carbonyl group bound A structure in which rings and the like are condensed may be formed.)

(In the formula (25), R ¹⁴³ and R ¹⁴⁴ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, group, a carboxyl group, an alkoxycarbonyl group, an acyl group, R ¹⁴³ and R ¹⁴⁴ are bonded to double bond or may form an aromatic or non-aromatic ring. the R ^143, R ¹⁴⁴ , or a double bond formed by bonding R ¹⁴³ and R ¹⁴⁴ to each other or an aromatic or non-aromatic ring, further has one or two imide groups represented by the above formula. May be.)

  Examples of the —OQ group in which the photofunctional group Q is an o-nitrobenzyl group represented by the formula (20-1) include, for example, a (2,6-dinitrobenzyl) oxy group, a (2-nitrobenzyl) oxy group, (3-nitro-2-naphthalene) methyloxy group, (6,7-dimethoxy-3-nitro-2-naphthalenemethyl) oxy group, [1- (2,6-dinitrophenyl) ethyl] oxy group, [1 -(2-nitrophenyl) ethyl] oxy group, [1- (3,5-dimethoxyphenyl-2-nitrobenzyl) -1-methylethyl] oxy group, (2,4-dinitrobenzyl) oxy group, (3 , 4,5-trimethoxy-2-nitrobenzyl) oxy group, (3,4-dimethoxy-2-nitrobenzyl) oxy group, (3-methyl-2-nitrobenzyl) oxy group, (3-methoxy- -Nitrobenzyl) oxy group, (4,5,6-trimethoxy-2-nitrobenzyl) oxy group, (4,5-dichloro-2-nitrobenzyl) oxy group, (4,5-dimethyl-2-nitrobenzyl) ) Oxy group, (5-methyl-4-methoxy-2-nitrobenzyl) oxy group, (α-ethyl-2-nitrobenzyl) oxy group, [α- (2-nitrophenyl) -2-nitrobenzyl] oxy And a nitrobenzyloxy group such as a group.

  Examples of the —OQ group in which the photofunctional group Q is the p-nitrobenzyl group represented by the formula (20-3) include, for example, a (2,4-dinitrobenzyl) oxy group and a (3,4-dinitrobenzyl) oxy Group, (4-nitrobenzyl) oxy group, [1- (4-nitronaphthalene) methyl] oxy group, [1- (6,7-dimethoxy-4-nitronaphthalene) methyl] oxy group, [1- (2 , 4-Dinitrophenyl) ethyl] oxy group, [1- (4-nitrophenyl) ethyl] oxy group, [1- (3,5-dimethoxyphenyl-4-nitrobenzyl) -1-methylethyl] oxy group, (2,3,5-trimethoxy-4-nitrobenzyl) oxy group, (2,3-dimethoxy-4-nitrobenzyl) oxy group, (3-methyl-4-nitrobenzyl) oxy group, (3-methoxy -4-nitrobenzyl) oxy group, (2,5,6-trimethoxy-4-nitrobenzyl) oxy group, (2,5-dichloro-4-nitrobenzyl) oxy group, (2,5-dimethyl-4- (Nitrobenzyl) oxy group, (5-methyl-2-methoxy-4-nitrobenzyl) oxy group, (α-ethyl-4-nitrobenzyl) oxy group, [α- (4-nitrophenyl) -4-nitrobenzyl A nitrobenzyloxy group such as an oxy group;

  Examples of the —OQ group in which the photofunctional group Q is a benzyl group represented by the formula (21) include, for example, a 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-phenylxanthene-9- And a benzyloxy group such as an yloxy group.

  Examples of the —OQ group in which the photofunctional group Q is the benzoylphenylmethyl group represented by the formula (23) include 1- (3,5-dimethoxybenzoyl) -1- (3,5-dimethoxyphenyl) methyloxy And a benzoinoxy group such as a 1-hydroxy-1-phenylacetophenoneoxy group, a 1-benzoyl-1-phenylmethyloxy group, and a 1-benzoyl-1-hydroxy-1-phenylethyloxy group.

  Examples of the —OQ group in which the photofunctional group Q is a coumarin derivative residue represented by the formula (24) include a 7-methoxycoumarin-4-ylmethoxy group and a 6-bromo-7-methoxycoumarin-4-ylmethoxy group. And a coumarin-4-ylmethoxy group.

  Examples of the —OQ group in which the photofunctional group Q is an imide group represented by the formula (25) include, for example, a phthalimidooxy group, a succinimidooxy group, a succinimideoxy group, a maleic imideoxy group, a hexahydrophthalic imideoxy group, Cyclohexanetetracarboxylic imide dioxy group, tetrabromophthalic imide oxy group, tetrachloro phthalic imide oxy group, het imide oxy group, hymic imide oxy group, trimellitic imide oxy group, pyromellitic imide dioxy group, naphthalene tetra carboxylic imide dioxy group, etc. Imidooxy group.

  Examples of the —OQ group in which the photofunctional group Q is the oxime residue represented by the formula (18) include, for example, an N- (1-phenylethylidene) aminooxy group, a diphenylmethylideneaminooxy group, a di (4-methoxy) group. Phenyl) methylideneaminooxy group, N- (dimethylmethylidene) aminooxy group, N- (acetophenonemethylidene) aminooxy group, N- [1- (2-naphthyl) ethylidene] aminooxy group, N- (cyclohexyl) (Siliden) aminooxy group, N- (fluorenylidene) aminooxy group, N- [di (nitrophenyl) methylidene] aminooxy group, N- (nitrofluorenylidene) aminooxy group, N- (dinitrofluorenylidene) Oximeoxy groups such as aminooxy group and N- (trinitrofluorenylidene) aminooxy group; .

  In the formulas (12) and (13), as the residue excluding the ZQ group, for example, 3- (trimethoxysilyl) propylaminocarbonyl group, 3- (triethoxysilyl) propylaminocarbonyl group, 3- ( Triisopropoxysilyl) propylaminocarbonyl group, 3- (methyldimethoxysilyl) propylaminocarbonyl group, 3- (methyldiethoxysilyl) propylaminocarbonyl group, N- [3- (trimethoxysilyl) -2-methylpropyl ] -N-ethylaminocarbonyl group, N- [3- (trimethoxysilyl) propyl] -N-phenylaminocarbonyl group, N- [3- (trimethoxysilyl) propyl] -N-benzylaminocarbonyl group, N -[3- (Triethoxysilyl) propyl] -N-vinylbenzylaminocarbonyl Monoaminocarbonyl such as N-triethoxysilylmethyl-N-cyclohexylaminocarbonyl group, N- (methyldiethoxysilyl) methyl-N-cyclohexylaminocarbonyl group, N-trimethoxysilylmethyl-N-phenylaminocarbonyl group Group: N- [3- (trimethoxysilyl) propyl] ethylenediaminocarbonyl group, N- [3- (methyldimethoxysilyl) propyl] ethylenediaminocarbonyl group, N- [3- (triethoxysilyl) propyl] ethylenediamino Carbonyl group, N- [3- (methyldiethoxysilyl) propyl] ethylenediaminocarbonyl group, N- [3- (triisopropoxysilyl) propyl] ethylenediaminocarbonyl group, N- [3- (trimethoxysilyl) propyl ] -1,6-hex A diaminocarbonyl group such as a rangeaminocarbonyl group, an N- (trimethoxysilylmethyl) ethylenediaminocarbonyl group, an N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediaminocarbonyl group; N- [3- ( Trimethoxysilyl) propyl] and an aminocarbonyl group such as a triaminocarbonyl group such as a diethylenetriaminocarbonyl group.

Among the aminocarbonyl groups, an aminocarbonyl group having an amino group (—NH ₂ ) is preferable from the viewpoint of adhesiveness, and 3- (trimethoxysilyl) propylaminocarbonyl group and 3- (triethoxysilyl) propylaminocarbonyl Group, 3- (methyldimethoxysilyl) propylaminocarbonyl group, and N- [3- (trimethoxysilyl) propyl] ethylenediaminocarbonyl group are more preferable, and 3- (trimethoxysilyl) propylaminocarbonyl is more preferable in terms of adhesiveness and curability. The group, 3- (triethoxysilyl) propylaminocarbonyl, is most preferred.

  In the formula (14), examples of the arylsulfonyl group include an aromatic sulfonyl group such as a 2-naphthalenesulfonyl group and a p-toluenesulfonyl group.

  In the formula (14), examples of the residue excluding the arylsulfonyl group include a 3- (trimethoxysilyl) propylamino group, a 3- (triethoxysilyl) propylamino group, and a 3- (triisopropoxysilyl) Propylamino group, 3- (methyldimethoxysilyl) propylamino group, 3- (methyldiethoxysilyl) propylamino group, N- [3- (trimethoxysilyl) -2-methylpropyl] -N-ethylamino group, N- [3- (trimethoxysilyl) propyl] -N-phenylamino group, N- [3- (trimethoxysilyl) propyl] -N-benzylamino group, N- [3- (triethoxysilyl) propyl] -N-vinylbenzylamino group, N-triethoxysilylmethyl-N-cyclohexylamino group, N- (methyldiethoxysilyl ) Monoamino groups such as methyl-N-cyclohexylamino group, N-trimethoxysilylmethyl-N-phenylamino group; N- [3- (trimethoxysilyl) propyl] ethylenediamino group, N- [3- (methyldimethoxy Silyl) propyl] ethylenediamino group, N- [3- (triethoxysilyl) propyl] ethylenediamino group, N- [3- (methyldiethoxysilyl) propyl] ethylenediamino group, N- [3- (triisopropoxy) Silyl) propyl] ethylenediamino group, N- [3- (trimethoxysilyl) propyl] -1,6-hexylenediamino group, N- (trimethoxysilylmethyl) ethylenediamino group, N, N′-bis [3 A diamino group such as-(trimethoxysilyl) propyl] ethylenediamino group; N- [3- (trimethoxy) Silyl) propyl] include triamino groups such as diethylene triamino group.

  In the formula (15), examples of the residue excluding the aryl oxime group include a 3- (trimethoxysilyl) propylcarbonyl group, a 3- (triethoxysilyl) propylcarbonyl group, and a 3- (triisopropoxysilyl) And carbonyl groups such as a propylcarbonyl group, a 3- (methyldimethoxysilyl) propylcarbonyl group, and a 3- (methyldiethoxysilyl) propylcarbonyl group.

  In the formula (16), the trans-o-coumaric acid derivative residue includes, for example, (E) -2- (2-hydroxyphenyl) ethenyl group, (E) -2- (2-hydroxyphenyl) -1 -Propenyl group, (E) -2- (2-hydroxyphenyl) -1-propenyl group, (E) -2- (2-hydroxyphenyl) -2-phenylethenyl group, (E) -2- (2 -Hydroxy-4,5-methylenedioxyphenyl) ethenyl group, (E) -2- (2-hydroxy-4,5-dimethoxyphenyl) -1-propenyl group, (E) -2- (2- And trans-O-coumaric acid residues such as a hydroxy-5-nitrophenyl) -1-propenyl group and an (E) -2- (1-hydroxy-2-anthryl) -1-propenyl group.

  The mixing ratio of the crosslinkable silicon group-containing compound is not particularly limited, but is preferably 0.01 to 50.00 parts by mass, and more preferably 1.00 to 100 parts by mass of the crosslinkable silicon group-containing organic polymer (A). To 20.00 parts by mass is more preferable, and 3.00 to 10.00 parts by mass is further preferable. These crosslinkable silicon group-containing compounds may be used alone or in combination of two or more.

  The photocurable composition of the present invention may contain a chlorinated polyolefin. The chlorinated polyolefin is not particularly limited as long as it is a chlorinated polyolefin, but preferably has a chlorine content in the range of 20 to 60% by mass, more preferably 30 to 50% by mass, and more preferably 35 to 45% by mass. Is more preferable.

  As the raw material of the chlorinated polyolefin, for example, crystalline polypropylene, amorphous polypropylene, polybutene, low-density polyethylene, high-density polyethylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-vinyl acetate Copolymers and the like, and modified polyolefin resins into which a carboxyl group, a hydroxyl group, an acid anhydride group, or the like is introduced, and the like. As the chlorinated polyolefin, a chlorinated polypropylene containing 50 mol% or more of propylene-based units is preferable because of excellent adhesion to the olefin.

  The photocurable composition of the present invention may contain, if necessary, a photosensitizer other than (D) the active energy ray-cleavable radical generator, a bulking agent, a plasticizer, a moisture absorber, a curing catalyst, and a tensile property. Physical property modifiers, reinforcing agents, coloring agents, flame retardants, anti-sagging agents, antioxidants, ultraviolet absorbers, anti-aging agents, solvents, organic fillers, conductive fillers, thermally conductive fillers, fragrances, pigments, etc. And various additives such as dyes.

  As the photosensitizer other than (D) the active energy ray-cleavable radical generator, a carbonyl compound having a triplet energy of 225 to 310 kJ / mol is preferable. For example, xanthone, thioxanthone, 2-chlorothioxanthone, 2,2 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, phthalimide, anthraquinone, 9,10-dibutoxyanthracene, acetophenone, propiophenone, benzophenone, acylnaphthalene, 2 (acylmethylene) Thiazoline, 3-acylcoumarin and 3,3'-carbonylbiscoumarin, perylene, coronene, tetracene, benzanthracene, phenothiazine, flavin, acridine, ketocoumarin, etc. The recited, thioxanthone, 3-acylcoumarin and 2 (aroylmethylene) - thiazoline, and more preferably a thioxanthone Obi 3 acylcoumarin. These sensitizers enhance the reactivity of the generated amine base without shortening the shelf life of the composition.

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

  Examples of the plasticizer include phosphates such as tributyl phosphate and tricresyl phosphate, phthalates such as dioctyl phthalate, aliphatic monobasic esters such as glycerin monooleate, and 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.

  As the water absorbent, the above-mentioned silane coupling agent and silicate are suitable. The silicate is not particularly limited and includes, for example, tetraalkoxysilane or a partially hydrolyzed condensate thereof, and more specifically, tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, Tetraalkoxysilanes (tetraalkylsilicate) such as methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane and tetra-t-butoxysilane; And partially hydrolyzed condensates thereof.

  As the curing catalyst, known curing catalysts can be widely used, and there is no particular limitation. Examples thereof include organometallic compounds and amines, and it is particularly preferable to use a silanol condensation catalyst. As the silanol condensation catalyst, for example, stannas octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate Organic tin compounds such as dioctyltin dilaurate, dioctyltin diversate, tin octylate and tin naphthenate; dialkyltin oxides such as dimethyltin oxide, dibutyltin oxide and dioctyltin oxide; reactants of dibutyltin oxide with phthalic acid esters ; Titanates such as tetrabutyl titanate and tetrapropyl titanate; aluminum trisacetylacetonate, aluminum trisethyl Organoaluminum compounds such as acetoacetate and diisopropoxyaluminum ethyl acetoacetate; Chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; Organic lead such as lead octylate and naphthenate; bismuth octylate And bismuth organic acids such as bismuth neodecanoate and bismuth rosinate; and other acidic and basic catalysts known as silanol condensation catalysts. However, depending on the amount of the organotin compound added, the resulting photocurable composition may become more toxic.

  The physical property modifier is added for the purpose of improving the physical properties of the curable composition such as the tensile properties. As an example of the physical property modifier, for example, a silicon compound having one silanol group in one molecule and having a primary amino group is preferably used. Examples of the silicon compound include triphenylsilanol, trialkylsilanol, dialkylphenylsilanol, diphenylalkylsilanol and the like.

  Examples of the flame retardant include phosphorus-based flame retardants such as red phosphorus and ammonium polyphosphate; metal oxide-based flame retardants such as antimony trioxide; brominated flame retardants; and chlorine-based flame retardants.

  As the anti-sagging agent, known anti-sagging agents can be widely used, and there is no particular limitation. Examples thereof include polyamide waxes; hydrogenated castor oil derivatives; calcium stearate, aluminum stearate, and barium stearate. Examples include metal soaps, organic bentonites, colloidal silica, modified polyester polyols, inorganic thixotropic agents such as asbestos powder, and organic thixotropic agents such as fatty acid amides. Further, when a rubber powder having a particle size of 10 to 500 μm as described in JP-A-11-349916 or an organic fiber as described in JP-A-2003-155389 is used, the thixotropic property is high. A composition having good workability is obtained. These anti-sagging agents may be used alone or in combination of two or more.

  The antioxidant is used to prevent oxidation of the curable composition and to improve weather resistance and heat resistance. Examples thereof include hindered amine-based and hindered phenol-based antioxidants. Can be Examples of the hindered amine antioxidant include, for example, N, N ', N ", N" "-tetrakis- (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine- 4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-triazine.N, N'-bis- (2,2,6 Polycondensate of 2,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine.N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{6- (1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl {(2,2,6,6-tetramethyl-4-piperidyl) imino {hexamethylene} (2 , 2,6,6-tetramethyl-4- Peridyl) imino}], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, [bis (2,2,6,6-tetramethyl-decanedioate) 1 (octyloxy) -4-piperidyl) ester, reaction product of octane with 1,1-dimethylethyl hydroperoxide (70%)]-polypropylene (30%), bis (1,2,2,6,6- Pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl seba Kate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl ) Propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9- Examples include, but are not limited to, tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione. Eristol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene-bis [3- (3,5-di-ter t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester of benzenepropanoic acid, 2,4 -Dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ′, 3 ″, 5 5 ', 5 "-hexane-tert-butyl-4-a, a', a"-(mesitylene-2,4,6-tolyl) tri-p-cresol, calcium M-diethylbis [[[3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) Bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3 , 5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, N-phenylbenzeneamine The reaction product of 2,4,4-trimethylpentene with 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5 Triazin-2-ylamino) phenol and the like, but not limited thereto. The antioxidants may be used alone or in combination of two or more.

  The ultraviolet absorber is used for preventing the photo-deterioration of the curable composition and improving the weather resistance. For example, benzotriazole-based, triazine-based, benzophenone-based, and benzoate-based ultraviolet absorbers Agents and the like. Examples of the ultraviolet absorber include 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol and 2- (2H-benzotriazol-2-yl) -4,6- Di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3- (2H-benzotriazole-2) -Yl) -5-tert-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product, 2- (2H-benzotriazol-2-yl) -6- (linear and branched dodecyl) -4 A benzotriazole-based ultraviolet absorber such as -methylphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(f Triazine-based ultraviolet absorbers such as (sil) oxy] -phenol, benzophenone-based ultraviolet absorbers such as octabenzone, and 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; Examples include, but are not limited to, benzoate UV absorbers. The ultraviolet absorbers may be used alone or in combination of two or more.

  Anti-aging agents are used to prevent heat deterioration of the curable composition and improve heat resistance. For example, anti-aging agents such as amine-ketones, aromatic secondary amines Antioxidants, benzimidazole antioxidants, thiourea antioxidants, phosphorous acid antioxidants, and the like.

  Examples of the amine-ketone type anti-aging agents include, for example, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline And amine-ketones such as a reaction product of diphenylamine and acetone, but are not limited thereto.

  Examples of the aromatic secondary amine antioxidant include N-phenyl-1-naphthylamine, alkylated diphenylamine, octylated diphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, p- (P-toluenesulfonylamide) diphenylamine, N, N'-di-2-naphthyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine , N-phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine, N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine Examples include, but are not limited to, secondary amines.

  Examples of the benzimidazole antioxidants include, for example, benzimidazoles such as 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, and zinc salts of 2-mercaptobenzimidazole, but are not limited thereto. is not.

  Examples of the thiourea-based antioxidant include, but are not limited to, thiourea-based agents such as 1,3-bis (dimethylaminopropyl) -2-thiourea and tributylthiourea.

  Examples of the phosphorous acid antioxidant include, but are not limited to, phosphorous acid such as tris (nonylphenyl) phosphite.

  The amount of the antioxidant used is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, based on 100 parts by mass of the organic polymer (A). More preferably, it is used in the range of 0.2 to 5 parts by mass.

  As the conductive filler, carbon particles, or metal particles such as silver, copper, nickel, gold, tin, zinc, platinum, palladium, iron, tungsten, morphene, solder, or the like, or a conductive material such as metal It may be a conductive particle such as a particle prepared by covering with a coating. Similarly, polymer particles such as polyethylene, polystyrene, phenolic resins, epoxy resins, acrylic resins or benzoguanamine resins, or glass beads, silica, graphite, or ceramic, coated on the surface with a conductive coating such as a metal. It is also possible to use non-conductive particles.

  The conductive filler has various shapes (spherical shape, elliptical shape, cylindrical shape, flake, needle shape, resin shape, whisker, flat plate, granular mass, crystal, and acicular shape). The particles may have a slightly rough or jagged surface. The shape of the electrically conductive particles is not particularly limited. Combinations of particle shape, size and hardness may be used in the compositions of the present invention. As the conductive filler, in the case where the photocurable composition of the present invention contains a conductive filler, from the viewpoint of light transmission, a spherical shape, a dendritic shape, and a needle shape are preferably used. Can be.

  The method for producing the photocurable composition of the present invention is not particularly limited. For example, the components (A), (B), and (C) are blended in predetermined amounts, and if necessary, other compounding substances are blended. It can be manufactured by mixing and degassing and stirring. The order of blending each component and other blending substances is not particularly limited, and may be determined as appropriate.

  The photocurable composition of the present invention can be of a one-pack type or a two-pack type, if necessary, but can be suitably used particularly as a one-pack type. The photocurable composition of the present invention is a photocurable composition that is cured by irradiation with light, and can be cured at room temperature (for example, 23 ° C.), and is suitable as a room temperature photocurable curable composition. Although used, curing may be promoted by heating as appropriate.

The method for producing a cured product of the present invention is characterized by forming a cured product by irradiating the photocurable composition of the present invention with light. The cured product of the present invention is a cured product formed by the method.
Further, a method for producing a product of the present invention is characterized in that the product is produced using the photocurable composition of the present invention. The product of the present invention is a product manufactured by using the method, and can be suitably used for electronic circuits, electronic components, building materials, automobiles, and the like.

  The conditions for irradiating the photocurable composition of the present invention with light are not particularly limited, but when irradiating active energy rays during curing, the active energy rays include ultraviolet rays, visible rays, rays such as infrared rays, Electron beams, proton beams, neutron beams, etc. can be used in addition to electromagnetic waves such as X-rays and γ-rays. Curing speed, availability and price of irradiation equipment, easy handling under sunlight or general lighting Curing by irradiation of ultraviolet rays or electron beams is preferable from the viewpoint of properties and the like, and curing by irradiation of ultraviolet rays is more preferable. The ultraviolet rays include g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), and the like. The active energy ray source is not particularly limited, but 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, a metal halide, and the like, depending on the properties of the photobase generator used. Can be

For The irradiation energy such as ultraviolet, preferably ^{10~20,000mJ / cm 2, 50~10,000mJ / cm} 2 is more preferable. If it is less than 10 mJ / cm ² , the curability may be insufficient, and if it is more than 20,000 mJ / cm ² , not only is it necessary to waste time and cost even if the light is applied unnecessarily, but the substrate may be damaged. In some cases.

  The method of applying the photocurable composition of the present invention to an adherend is not particularly limited, but an application method such as screen printing, stencil printing, roll printing, spin coating, or application using a dispenser is preferably used.

  Further, in the present invention, there is no limitation on the timing of application of the photocurable composition to the adherend and light irradiation, and after irradiating the photocurable composition with light, the photocurable composition is bonded to the adherend, and the product is bonded. It may be manufactured, or a photocurable composition may be applied to an adherend, and the composition may be cured by irradiating light to manufacture a product.

  The photo-curable composition of the present invention is a fast-curing type photo-curable composition having excellent workability, and is particularly useful as a viscous / adhesive composition, and includes an adhesive, a sealing material, a coating material, and potting. It can be suitably used as a material, a paint, a putty material, a primer and the like. The photocurable composition of the present invention is, for example, a coating agent used for coating a circuit board or the like for the purpose of moisture proofing or insulation, a solar power generation panel or a coating for an outer peripheral portion of the panel; , Sealing agents for vehicles, architectural and industrial sealants; electric and electronic parts materials such as sealants for backsides of solar cells; electric insulating materials such as insulating coatings for electric wires and cables; three-dimensional objects by stereolithography It can be suitably used for applications such as a material for forming; an adhesive; an elastic adhesive; and a contact adhesive.

  Hereinafter, the present invention will be described in more detail with reference to Examples. However, it is needless to say that these Examples are illustrative and should not be construed as limiting.

1) Measurement of number average molecular weight The number average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions. In the present invention, the molecular weight of the highest frequency measured by GPC under the above measurement conditions and converted with standard polyethylene glycol is referred to as a number average molecular weight.
-Analyzer: Alliance (manufactured by Waters), 2410 type differential refraction detector (manufactured by Waters), 996 type multi-wavelength detector (manufactured by Waters), Millennium data processor (manufactured by Waters)
・ Column: Plgel GUARD + 5 μm Mixed-C × 3 (50 × 7.5 mm, 300 × 7.5 mm: manufactured by PolymerLab)
-Flow rate: 1 mL / min-Converted polymer: polyethylene glycol-Measurement temperature: 40 ° C
-Solvent for GPC measurement: THF

2) Measurement of NMR and IR The measurement of NMR and IR was performed using the following measuring apparatus.
FT-NMR measurement device: JNM-ECA500 (500 MHz) manufactured by JEOL Ltd.
FT-IR measuring device: FT-IR460Plus manufactured by JASCO Corporation

(Synthesis Example 1) Synthesis of polyoxyalkylene-based polymer A having a trimethoxysilyl group at a terminal In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, ethylene glycol was used as an initiator, and zinc was added. Propylene oxide was reacted in the presence of a hexacyanocobaltate-glyme complex catalyst to obtain polyoxypropylene triol. A methanol solution of sodium methoxide was added to the obtained polyoxypropylene triol, and methanol was distilled off under reduced pressure under heating to convert the terminal hydroxyl group of polyoxypropylene triol into sodium alkoxide, thereby obtaining a polyoxyalkylene polymer M1. Was.

  Next, 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. The polyoxyalkylene polymer having an allyl group at the terminal is reacted with trimethoxysilane, a silicon hydride compound, by adding 150 ppm of a platinum vinyl siloxane complex isopropanol solution containing 3 wt% of platinum, and reacting with trimethoxysilyl at the terminal. A polyoxyalkylene polymer A1 having a group was obtained.

As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A1 having a trimethoxysilyl group at the terminal by GPC, the peak top molecular weight was 12,000 and the molecular weight distribution was 1.3. According to H ¹ -NMR measurement, the number of terminal trimethoxysilyl groups was 1.7 per molecule.

(Synthesis Example 2) Synthesis of polyoxyalkylene polymer C having a fluorosilyl group (fluorinated polymer C) In a new flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, a molecular weight of about 2, 000 polyoxypropylene diol as an initiator and a polyoxypropylene diol having a hydroxyl value-converted molecular weight of 14500 and a molecular weight distribution of 1.3 obtained by reacting propylene oxide in the presence of a zinc hexacyanocobaltate-glyme complex catalyst. Obtained. A methanol solution of sodium methoxide was added to the obtained polyoxypropylene diol, and methanol was distilled off under heating and reduced pressure to convert the terminal hydroxyl group of polyoxypropylene diol to sodium alkoxide, thereby obtaining a polyoxyalkylene polymer M2. Was.

Next, 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. The polyoxyalkylene polymer having an allyl group at the terminal is reacted with methyldimethoxysilane, which is a silicon hydride compound, and 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt%, and reacted with methyldimethoxysilyl at the terminal. A polyoxyalkylene polymer A2 having a group was obtained.
As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A2 having a methyldimethoxysilyl group at the terminal by GPC, the peak top molecular weight was 15,000 and the molecular weight distribution was 1.3. As a result of H1-NMR measurement, the number of terminal methyldimethoxysilyl groups was 1.7 per molecule.

A flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was degassed under reduced pressure, replaced with nitrogen gas, and charged with 2.4 g of a BF ₃ diethyl ether complex under a nitrogen gas stream. Warmed. Subsequently, a mixture of 1.6 g of dehydrated methanol was slowly dropped and mixed. In a new flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 100 g of the obtained polymer A2 and 5 g of toluene were placed. After stirring at 23 ° C for 30 minutes, the mixture was heated to 110 ° C and stirred under reduced pressure for 2 hours to remove toluene. 4.0 g of the mixture obtained above was slowly added dropwise to the container under a nitrogen stream, and after the completion of the addition, the reaction temperature was raised to 120 ° C., and the mixture was reacted for 30 minutes. After completion of the reaction, degassing was performed under reduced pressure to remove unreacted substances. A polyoxyalkylene polymer C having a fluorosilyl group at a terminal (hereinafter, referred to as a fluorinated polymer C) was obtained. When the 1H NMR spectrum of the obtained fluorinated polymer C (measured in a CDCl3 solvent using NMR400 manufactured by Shimazu) was measured, a peak corresponding to silylmethylene (—CH2-Si) of the polymer A2 as a raw material was obtained. (M, 0.63 ppm) disappeared, and a broad peak appeared on the low magnetic field side (from 0.7 ppm).

(Examples 1 to 6, Comparative Examples 1 to 5)
At a mixing ratio shown in Table 1, a polyoxyalkylene polymer A obtained in Synthesis Example 1 was added to a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube, and a water-cooled condenser, Dehydration was performed by heating (100 ° C.), degassing, and stirring for 2 hours. After cooling, each of the fluorinated polymer C obtained in Synthesis Example 2, a photobase generator, an active energy ray-cleavable radical generator, and a strong base catalyst is added, and the mixture is stirred and mixed to form a photocurable composition and a curable composition. A composition was prepared.

In Table 1, the amount of each compounding substance is shown in parts by mass, the polyoxyalkylene-based polymer A is the polyoxyalkylene-based polymer A obtained in Synthesis Example 1, and the fluorinated polymer C is in Synthesis Example 2. The obtained fluorinated polymer C, and details of other compounding substances are as follows.
* 1 PBG-SA2 (manufactured by San Apro Co., Ltd., a photobase generator that generates 1,8-diazabicyclo (5.4.0) undecene-7 upon irradiation with active energy rays, diluted to 20% by mass with a propylene carbonate solution (In Table 1, parts by mass of the solid content are shown.)
* 2 Irgacure (registered trademark) 379EG (manufactured by BASF, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone), Used diluted to 50% by mass with a propylene carbonate solution. In Table 1, parts by mass of the solid content are described. )
* 3 Irgacure (registered trademark) 907 (manufactured by BASF, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one), diluted to 50% by mass with a propylene carbonate solution. In Table 1, parts by mass of the solid content are described. )
* 4 NBC-101 (manufactured by Midori Kagaku Co., Ltd., N- (2-methyl-2-phenylpropionyloxy) -N-cyclohexylamine, diluted with propylene carbonate solution to 50% by mass. Used in Table 1. Parts by mass are shown.)
* 5 Irgacure (registered trademark) 1173 (manufactured by BASF, active energy ray-cleavable radical generator, 2-hydroxy-2-methyl-1-phenyl-propan-1-one.
* 6 DBU (1,8-diazabicyclo (5.4.0) undecene-7).

  The obtained photocurable composition and curable composition were tested by the following method. The results are shown in Table 1.

Workability test without UV irradiation Examples 1 to 6 and Comparative Examples 1 to 3 using a screen printer under an environment of 23 ° C. and 50% RH under a fluorescent lamp to which a film for cutting a wavelength of 500 nm or less is attached. A workability test was carried out for the composition prepared in the above, without UV irradiation.
Continuous application to a PET film is performed at a screen speed of 50 mm / sec, and the liquid can be worked by touch with the finger, and the hardened case is disabled, and the time during which screen printing is possible is measured.
A case where work was possible for 8 hours or more was rated as ◎, a case where work was possible for 4 hours to less than 8 hours was rated as ○, and a case where work was disabled for less than 4 hours was rated as ×.

State after UV irradiation The photocurable compositions of Examples 1 to 6 and Comparative Examples 1 to 3 are applied to an acrylic plate (25 mm x 75 mm x 3 mm) to a thickness of about 100 m, and after UV irradiation [irradiation conditions: metal halide lamp illuminance 330mW / cm ^2, integrated light quantity: 3000mJ ^/ cm 2], in an environment of 23 ° C. 50% RH, to confirm the cure degree of the photocurable composition surface by finger touch. The case of a liquid state was evaluated as ○, the case of gelation (between liquid and solid) was evaluated as Δ, and the case of hardening was evaluated as ×.

Bonding test after UV irradiation The photocurable compositions of Examples 1 to 6 and Comparative Examples 1 to 3 were applied on an acrylic plate (25 mm x 75 mm x 3 mm) in an area of 25 mm x 25 mm to a thickness of about 100 m, and UV was applied. Irradiation [irradiation conditions: metal halide lamp, illuminance: 330 mW / cm ² , integrated light amount: 3000 mJ / cm ² ].
After UV irradiation, in an environment of 23 ° C. and 50% RH, an acrylic plate of the same size is bonded and pressed with a small eye clip to perform a bonding test. The case where bonding was possible without any bubbles was visually observed even after 30 seconds or more of UV irradiation, and the case where bonding was impossible in less than 30 seconds, or the case where bubbles were generated were rated as x. did.

Curability test The photocurable compositions that require UV irradiation (Examples 1 to 6 and Comparative Examples 1 to 3) have a thickness of 7 mm in a cylindrical container having a diameter of 20 mm and a height of 7 mm. Immediately after pouring the object and UV irradiation [irradiation condition: metal halide lamp, illuminance: 330 mW / cm ² , integrated light amount: 3000 mJ / cm ² ], touch with a finger every 30 seconds in an environment of 23 ° C and 50% RH in a dark room. The time until the surface became non-sticky and hardened was measured.
For the curable composition that does not require UV irradiation (Comparative Examples 4 and 5), the curable composition is poured into a cylindrical container having a diameter of 20 mm and a height of 7 mm so that the thickness becomes 7 mm. Below, the time until the surface became non-sticky by finger touch and hardened every 30 seconds was measured.

Thickness curability The photocurable compositions requiring UV irradiation (Examples 1 to 6 and Comparative Examples 1 to 3) are illuminated in a cylindrical container (polypropylene) having a diameter of 20 mm and a height of 7 mm so that the thickness becomes 7 mm. After the curable composition is poured, after UV irradiation [irradiation conditions: metal halide lamp, illuminance: 330 mW / cm ² , accumulated light amount: 3000 mJ / cm ² ], after curing in a dark room at 23 ° C. and 50% RH for 24 hours, The cured product was taken out, and the cured thickness of the cured product was measured.
The curable composition that does not require UV irradiation (Comparative Examples 4 and 5) is poured into a cylindrical container (polypropylene) having a diameter of 20 mm and a height of 7 mm so that the thickness becomes 7 mm, and the composition is heated at 23 ° C. 50% After curing for 24 hours in an environment of RH, the cured product was taken out, and the cured thickness of the cured product was measured.

  As shown in Table 1, the photocurable composition of the present invention is a photocurable composition that is not cured when active energy rays are not irradiated, but is cured by active energy rays irradiation, and is liquid immediately after active energy rays irradiation. It has excellent thickness curability and rapid curability while securing an appropriate bonding time.

Claims (7)

(A) a crosslinkable silicon group-containing organic polymer,
(B) a photobase generator;
(C) a silicon compound having a Si-F bond,
(D) A photocurable adhesive, comprising: an active energy ray-cleavable radical generator . The photocurable adhesive according to claim 1 , wherein the photobase generator (B) is a photolatent tertiary amine . The above (A) the crosslinkable silicon group-containing organic polymer is a polyoxyalkylene polymer containing 0.8 or more crosslinkable silicon groups in one molecule on average, and 0.1% in one molecule. It is composed of a saturated hydrocarbon polymer containing at least 8 crosslinkable silicon groups and a (meth) acrylate polymer containing at least 0.8 crosslinkable silicon groups per molecule on average. the photocurable adhesive according to claim 1 or 2, characterized in that at least one selected from the group. The process according to claim 1 for light-curing adhesive according to any one of 3, cured product, and forming a cured product by irradiation with light. A method for producing a product, characterized by producing using the photocurable adhesive according to any one of claims 1 to 3 . (A) a crosslinkable silicon group-containing organic polymer,
(B) a photobase generator;
(C) a silicon compound having a Si-F bond,
(D) A photocurable sealing material comprising: an active energy ray-cleavable radical generator . (A) a crosslinkable silicon group-containing organic polymer,
(B) a photobase generator;
(C) a silicon compound having a Si-F bond,
(D) A photocurable potting material comprising: an active energy ray-cleavable radical generator .