JP6524669B2 - Photocurable composition - Google Patents

Description

  The present invention relates to a photocurable composition, and more particularly to a photocurable composition having excellent rising adhesion.

  An organic polymer having a silicon-containing group (hereinafter also referred to as “crosslinkable silicon group”) which has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond is It is also known to have the property of being crosslinked by the formation of a siloxane bond accompanied by the hydrolysis reaction of the crosslinkable silicon group with moisture or the like to obtain a rubber-like cured product. Among the polymers having these crosslinkable silicon groups, organic polymers whose main chain skeleton is a polyoxyalkylene polymer or a (meth) acrylate polymer are useful for applications such as sealing materials, adhesives and paints. It is widely used.

  The curable composition used for sealing materials, adhesives, paints and the like and rubber-like cured products obtained by curing have various properties such as curability, adhesion, storage stability, and mechanical properties such as modulus, strength and elongation. Many studies have been made so far on properties required and organic polymers containing a crosslinkable silicon group. In recent years, quick curing is required in various fields such as the electronic component / electronic device assembly field, but in the case of a moisture curing adhesive, there is a problem that the bonding possible time after application becomes short.

  On the other hand, as a photocrosslinkable composition using an organic polymer having a crosslinkable silicon group, Patent Document 1 discloses a polymer having two or more hydrolyzable silyl groups in one molecule, and the polymer by light irradiation. A photocrosslinkable composition comprising a compound to be crosslinked is disclosed, which is a compound to crosslink a polymer by light irradiation, and contains a compound to generate an acid or a base by being irradiated with light. The sex composition is illustrated (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 which crosslinks a polymer by light irradiation, there is a problem that rust occurs, and a photobase as a compound which crosslinks a polymer by light irradiation. In the case of using a generator, there is a problem that the efficiency is low and the curing takes a long time. In addition, further improvement is desired for adhesion performance such as rising adhesion.

JP 2001-172514 A

  The problem to be solved by the present invention is to provide a photocurable composition which cures in a short time after light irradiation without causing rust, and which is excellent in rising adhesion.

  The present inventors do not cause rust, cure in a short time, and as a photocurable composition having excellent rising adhesion, a crosslinkable silicon group-containing organic polymer, a photobase generator, silicon having a Si-F bond A photocurable composition containing a specific fluorine compound such as a compound and a compound having a photoradically polymerizable vinyl group is proposed, and a patent application is filed as patent application 2015-006460. The present inventors are photocurable containing a specific fluorine compound such as a polymer having a crosslinkable silicon group and a photoradical polymerizable vinyl group in the molecule, a photobase generator and a silicon compound having a Si-F bond. The composition was also found to cure in a short time without causing rust, and to be excellent in rising adhesion. That is, the present invention relates to the following photocurable composition.

(1) (A) An organic polymer having a crosslinkable silicon group and a photoradical polymerizable vinyl group in its molecule (excluding those having a Si-F bond), (B) a photobase generator, and C) a silicon compound having a (C1) Si-F bond, and / or selected from the group consisting of (C2) boron trifluoride, a complex of boron trifluoride, a fluorinating agent and an alkali metal salt of a polyvalent fluoro compound A photocurable composition comprising one or more fluorine-based compounds.
(2) The photocurable composition as described in (1), wherein the (B) photobase generator is a photolatable tertiary amine.
(3) (D) A crosslinkable silicon group-containing compound which further generates at least one amino group selected from the group consisting of a primary amino group and a secondary amino group by light. The photocurable composition according to claim 1 or 2.
(4) The photocurable composition according to (1) or (2), which further contains a silane coupling agent (excluding those having a Si-F bond).
(5) The photocurable composition according to any one of (1) to (3), which is a photocurable adhesive composition.
(6) A method for producing a cured product, comprising forming a cured product by irradiating light to the photocurable composition according to any one of (1) to (4).
(7) A cured product formed by the method described in (6).
(8) A method for producing a product characterized by using the photocurable composition according to any one of (1) to (4).
(9) A product produced by the method described in (6).
(10) A product produced by using the method according to (8).
(11) A product comprising the photocurable composition according to any one of (1) to (4) as an adhesive.
(12) A product comprising the photocurable composition according to any one of (1) to (4) as a coating agent.

  Since the photocurable composition of the present invention does not generate an acid upon light irradiation, it does not cause rust, and cures in a short time, and has an effect of being excellent in rising adhesion.

  The organic polymer in the polymer having a crosslinkable silicon group and a photoradical polymerizable vinyl group in the molecule used for the component (A) of the present invention (excluding those having a Si-F bond) has a main chain As long as it is an organic polymer that is not a polysiloxane, polymers having various main chain skeletons can be used.

  Specifically, polyoxyalkylene-based weights such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Combined: ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, copolymer of isoprene or butadiene with acrylonitrile and / or styrene, polybutadiene, isoprene or butadiene And copolymers of acrylonitrile, styrene, etc., hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; dibasic acids such as adipic acid and glycols Polyester polymers obtained by condensation or ring-opening polymerization of lactones; (meth) acrylate polymers obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; (Meth) acrylic acid 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 above organic polymers; polysulfide systems Polymers: nylon 6 by ring-opening polymerization of ε-caprolactam, nylon 6 · 6 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 6 · 10 by condensation polymerization of hexamethylenediamine and sebacic acid, ε-aminoundecanoic acid Nylon 11, ε-amino laurolacta by condensation polymerization 12, a polyamide-based polymer such as copolymerized nylon having two or more components of the above nylons by ring-opening polymerization of the above-mentioned nylon; for example, a polycarbonate-based polymer produced by condensation polymerization from bisphenol A and carbonyl chloride, diallyl Examples are phthalate polymers.

  Furthermore, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylate polymers can be obtained with a relatively low glass transition temperature. The cured product is preferable because it is excellent in cold resistance. In addition, polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferable because they have high moisture permeability and are excellent in deep-part curability when made into a one-pack composition.

  The crosslinkable silicon group in the component (A) used in the present invention is a group which has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and which can be crosslinked by forming a siloxane bond. As the crosslinkable silicon group, for example, a group represented by the following general formula (1) is preferable.

Formula (1), R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon 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 And R ⁴⁴ is a divalent substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), a C 1 to 20 perfluoroalkyl group, or a cyano group substituted by a cyano group. To 20 hydrocarbon groups, and when two or more R ¹ are present And they may be identical or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more X are present, they may be the same or different. a represents 0, 1, 2 or 3 and b represents 0, 1 or 2, respectively. Moreover, b in p following general formula (2) does not need to 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 a range of 1 to 3 and a + (sum of b) is preferably in a 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, but in the case of silicon atoms linked by a siloxane bond or the like, about 20 may be present.

  As the crosslinkable silicon group, a crosslinkable silicon group represented by the following general formula (3) is preferable from the viewpoint of easy availability.

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

  As a hydrolysable group shown by said X, if it is except F atom, it will not be specifically limited, What is necessary is just a conventionally well-known hydrolysable group. Specific examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amido group, an acid amide group, an aminooxy group, a mercapto group and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amido group, an aminooxy group, a mercapto group and an alkenyloxy group are preferable, and an alkoxy group, an amido group and an aminooxy group are more preferable. Alkoxy groups are particularly preferred in view of mild hydrolyzability and ease of handling. Among the alkoxy groups, those having a smaller number of carbon atoms are more reactive, and the reactivity becomes lower as the number of carbon atoms increases, as in the order of methoxy group> ethoxy group> propoxy group. Although it can be selected according to the purpose or application, usually a methoxy group or an ethoxy group is used.

Specific examples of the crosslinkable silicon group include trialkoxysilyl groups such as trimethoxysilyl group and triethoxysilyl group [-Si (OR) ₃ ], and dialkoxy such as methyldimethoxysilyl group and methyldiethoxysilyl group. A silyl group [-SiR < ¹ > (OR) ₂ ] is mentioned and a trialkoxy silyl group [-Si (OR) ₃ ] is suitable by the thing with high reactivity, and a trimethoxy silyl group is more preferable. Here, R is an alkyl group such as a methyl group or an ethyl group.

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

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

  Examples of the radically polymerizable vinyl group include groups containing a (meth) acryloyl group such as a (meth) acryloyloxy group.

  The organic polymer having a crosslinkable silicon group and a photoradical polymerizable vinyl group may have a linear or branched chain, and the number average molecular weight is preferably about 500 to 100,000 in terms of polystyrene in GPC, more preferably Is 1,000 to 50,000, and particularly preferably 3,000 to 30,000. If the number average molecular weight is less than 500, the elongation characteristic of the cured product tends to be inconvenient, and if it exceeds 100,000, the viscosity tends to be inconvenient in terms of workability because of high viscosity.

  The crosslinkable silicon group and the radically polymerizable vinyl group contained in the organic polymer are not particularly limited, but they are each not more than 2.0, preferably not more than 1.3, in one molecule of the polymer. More preferably, 0.8 or more and 1.3 or less may be present. When the number of the crosslinkable silicon group and the radically polymerizable vinyl group contained in the molecule is less than 0.8 on average, the curability tends to be insufficient. The crosslinkable silicon group and the radically polymerizable vinyl group may be present at the end of the main chain or at the end of the side chain of the organic polymer molecular chain, or may be present at both ends. In particular, when the crosslinkable silicon group is only at the end of the main chain of the molecular chain, it has excellent mechanical strength because the effective network length of the organic polymer component contained in the finally formed cured product becomes long. It becomes easy to obtain a cured product.

The polyoxyalkylene polymer is a polymer essentially having a repeating unit represented by the following general formula (4).
-R ² -O- (4)
In the above general formula (4), R ² is a linear or branched alkylene group having 1 to 14 carbon atoms, preferably a linear or branched alkylene group having 1 to 14 carbon atoms, and more preferably 2 to 4 carbon atoms. .

Specific examples of the repeating unit represented by the general formula (4) are
_{-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-
Etc. The main chain skeleton of the polyoxyalkylene polymer may consist of only one type of repeating unit, or may consist of two or more types of repeating units.

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

  The main chain skeleton of the polyoxyalkylene polymer may contain other components such as a urethane bond component. Examples of urethane bond components include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate, and polyoxyalkylene heavy chain having hydroxyl group It can be mentioned what is obtained from the reaction with coalescence.

  Introduction of a crosslinkable silicon group and a radically polymerizable vinyl group into a polyoxyalkylene polymer is 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 carried out by reacting a compound having a functional group having reactivity with this functional group and a crosslinkable silicon group or a radically polymerizable vinyl group (hereinafter referred to as a polymer reaction method).

  As a specific example of the polymer reaction method, the unsaturated group-containing polyoxyalkylene polymer is made to react with a hydrosilane or mercapto compound having a crosslinkable silicon group or a radically polymerizable vinyl group to hydrosilylate or mercapate, and crosslinkability A method of obtaining a polyoxyalkylene polymer having a silicon group can be mentioned. An unsaturated group-containing polyoxyalkylene polymer is prepared by reacting an organic polymer having a functional group such as a hydroxyl group with an organic compound having an active group and an unsaturated group that exhibit reactivity with the functional group, to obtain an unsaturated group. A polyoxyalkylene polymer containing can be obtained.

  Further, as another specific example of the polymer reaction method, a method of reacting a polyoxyalkylene polymer having a hydroxyl group at an end with a compound having an isocyanate group and a crosslinkable silicon group or a photoradical polymerizable vinyl group is used. There can be mentioned a method of reacting a polyoxyalkylene polymer having an isocyanate group with a compound having an active hydrogen group such as a hydroxyl group or an amino group, a crosslinkable silicon group or a vinyl group having photo radical polymerization. When an isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group and a photoradical polymerizable vinyl group can be easily obtained.

  The polyoxyalkylene polymer having the crosslinkable silicon group and the photoradical polymerizable vinyl group may be used alone or in combination of two or more.

  The saturated hydrocarbon polymer is a polymer substantially free of carbon-carbon unsaturated bonds other than aromatic rings, and the polymer forming the skeleton is (1) ethylene, propylene, 1-butene, isobutylene, etc. Or an olefin-based compound having 2 to 6 carbon atoms as the main monomer, (2) homopolymerization of a diene-based compound such as butadiene, isoprene or the like, or copolymerization with the above-mentioned olefin-based compound After that, it can be obtained by a method such as hydrogenation, but the isobutylene polymer and the hydrogenated polybutadiene polymer are easy to introduce a functional group at the terminal, easy to control the molecular weight, and the number of terminal functional groups. Is preferred, and isobutylene polymers are particularly preferred.

  Those having a main chain skeleton of a saturated hydrocarbon-based polymer have excellent heat resistance, weather resistance, durability, and moisture barrier properties.

  In the isobutylene polymer, all of the monomer units may be formed of isobutylene units, or may be copolymers with other monomers, but from the viewpoint of rubber properties, 50 repeat units derived from isobutylene are used. Those containing at least mass% are preferable, those containing at least 80 mass% are more preferable, and those containing at from 90 to 99 mass% are particularly preferable.

  Conventionally, various polymerization methods have been reported as methods for synthesizing saturated hydrocarbon polymers, and in particular, a large number of so-called living polymerizations have been developed in recent years. In the case of saturated hydrocarbon polymers, especially isobutylene polymers, use the inifer polymerization (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, Vol. 15, p. 2843) found by Kennedy et al. It is known that they can be easily manufactured by the method described above, can be polymerized with a molecular weight distribution of about 500 to 100,000, with a molecular weight distribution of 1.5 or less, and can introduce various functional groups at molecular ends.

  A saturated hydrocarbon polymer having a crosslinkable silicon group and a photoradical polymerizable vinyl group can be produced in the same manner as the polyoxyalkylene polymer. The saturated hydrocarbon polymer having a crosslinkable silicon group and a photoradical polymerizable vinyl group may be used alone or in combination of two or more.

  It does not specifically limit as a (meth) acrylic-ester type monomer which comprises the principal chain of the said (meth) acrylic-ester type polymer, A various thing 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) acrylic acid alkyl ester monomers such as 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate; (meth) Cyclohexyl acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl ) Acrylate, dicyclopentanyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetramethyl piperidinyl (meth) acrylate, pentamethyl piperidinyl (meth) acrylate, etc. Alicyclic (meth) acrylic acid ester monomers; phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, paraquat Mil phenoxy ethylene glycol (meth) acrylate, hydroxyethylated o-phenyl phenol (meth) acrylate, 2-hydroxy 3- phenoxy propyl (meth) acrylate, phenoxy dye Aromatic (meth) acrylic acid ester monomers such as glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate and phenylthioethyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, (meth) acrylate (Meth) acrylic acid esters such as 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate Monomer; γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxy Silyl group-containing (meth) acrylic acid ester type monomers such as ethyl dimethoxymethylsilane and methacryloyloxymethyldiethoxymethylsilane; (meth) acrylic acid derivatives such as ethylene oxide adduct of (meth) acrylic acid; (meth) acrylic acid Acid trifluoromethyl methyl, (meth) acrylic acid 2-trifluoromethyl ethyl, (meth) acrylic acid 2-perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl 2-perfluorobutyl ethyl, (meth ) Perfluoroethyl acrylate, trifluoromethyl (meth) acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, (meth) Acrylic acid 2-perfluorohexylethyl And fluorine-containing (meth) acrylic acid ester-based monomers such as 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate. Also, poly (meth) acrylates such as (meth) acrylic acid ester monomers of (poly) ethylene glycol and diacrylates such as (meth) acrylic acid ester monomers of (poly) propylene glycol can also be used.

  In the (meth) acrylic acid ester-based polymer, the following vinyl-based monomers can be copolymerized together with the (meth) acrylic acid ester-based monomer. Examples of the vinyl-based monomer include styrene-based monomers such as styrene, vinyl toluene, α-methylstyrene, chlorostyrene, styrene sulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride Crosslinkable silicon group-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid Maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclic Maleimide-based monomers such as hexyl maleimide; nitrile-containing vinyl-based monomers such as acrylonitrile and methacrylonitrile; amide-containing vinyl-based monomers such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, Vinyl esters such as vinyl cinnamate; 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 in combination of two or more. Among them, a polymer composed of a (meth) acrylic acid-based monomer is preferable from the physical properties of the product and the like. More preferably, it is a (meth) acrylic acid ester-based polymer in which one or two or more kinds of (meth) acrylic acid alkyl ester monomers are used, and other (meth) acrylic acid monomers are optionally used in combination. A (meth) acrylic acid ester-based polymer having a crosslinkable silicon group and a photoradical polymerizable vinyl group is used in combination with a crosslinkable silicon-containing (meth) acrylic acid ester monomer and a monomer having a plurality of (meth) acrylate groups It can be obtained by In the present specification, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  In the present invention, the method for obtaining the (meth) acrylic acid ester-based polymer is not particularly limited, and known polymerization methods (for example, JP-A-63-112642, JP-A-2007-230947, JP-A-2001-40037). No., JP-A No. 2003-313397, etc. can be used, and a radical polymerization method using a radical polymerization reaction is preferred. As a 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 functional group can be introduced at a controlled position such as an end. Controlled radical polymerization methods are mentioned. However, a polymer obtained by a conventional free radical polymerization method using an azo compound, a peroxide or the like as a polymerization initiator has a problem that the value of molecular weight distribution is generally as large as 2 or more and the viscosity becomes high. There is. Therefore, in order to obtain a (meth) acrylic ester polymer having a narrow molecular weight distribution and a low viscosity (meth) acrylic ester polymer having a functional group at the molecular chain end at a high rate, It is preferred to use a radical polymerization method. A crosslinkable silicon group and a photoradical polymerizable vinyl group can be introduced by using this functional group.

  The controlled radical polymerization includes free radical polymerization using a chain transfer agent having a specific functional group and living radical polymerization, and addition-cleavage transfer reaction (RAFT) polymerization method, transition metal complex A living radical polymerization method such as a radical polymerization method (Transition-Metal-Mediated LivingRadical Polymerization) using is preferred. Further, reactions using a thiol compound having a functional group such as a crosslinkable silicon group, and reactions using a thiol compound having a functional group such as a crosslinkable silicon group and a metallocene compound (Japanese Patent Laid-Open No. 2001-40037) are also preferable. It is.

  These organic polymers having a crosslinkable silicon group and a photoradical polymerizable vinyl group may be used alone or in combination of two or more. Specifically, polyoxyalkylene polymers having a crosslinkable silicon group and a photoradical polymerizable vinyl group, saturated hydrocarbon polymers having a crosslinkable silicon group, and (meth) acrylic resins having a crosslinkable silicon group An acid polymer, and an organic polymer formed by blending two or more selected from the group consisting of these can also be used.

  In the present invention, the (B) photobase generator generates a base when irradiated with light, and the base cures the organic polymer having a crosslinkable silicon group and a photoradical polymerizable vinyl group in the (A) molecule. Act as a catalyst. The (B) photobase generator 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, and (1) ultraviolet rays / visible rays A salt of an organic acid and a base that decomposes by irradiation with active energy rays such as light and infrared rays to decompose, (2) a compound that decomposes by intramolecular nucleophilic substitution reaction or rearrangement reaction to release amines 3) A known photo base generator such as one that causes a chemical reaction to occur by irradiation of energy rays such as ultraviolet light, visible light and infrared light to release a base 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, the first such as ethylamine, propylamine, octylamine, cyclohexylamine or 1,5-diaminopentane is preferable. -Class alkylamines; primary aromatic amines such as N-methylbenzylamine and 4,4'-methylenedianiline; secondary alkylamines such as diethylamine; secondary amino groups such as imidazole and tertiary amino Amines having a hydroxyl group; tertiary alkyl amines such as trimethylamine, triethylamine, tributylamine, 1,8-diazabicyclo [2.2.2] octane (DABCO); tertiary heterocyclic rings 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 a strong base is preferred Amidines and phosphazene derivatives are more preferred. As the amidines, any of non-cyclic 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 non-cyclic amidines include guanidine compounds and biguanide compounds. Examples of guanidine compounds include guanidine, 1,1,3,3-tetramethylguanidine, 1-butyl guanidine, 1-phenyl guanidine, 1-o-tolyl guanidine, 1,3-diphenyl guanidine and the like. Examples of biguanide compounds include butyl biguanide, 1-o-tolylbiguanide and 1-phenyl biguanide.

  In addition, when a photobase generator that generates arylguanidine substituted compounds such as phenylguanidine, 1-o-tolylbiguanide and 1-phenylbiguanide or aryl substituted biguanide compounds among non-cyclic amidine compounds is used, When it is used as the catalyst of (A), it is preferable from the viewpoint that the curability of the surface tends to be good, the adhesiveness of the cured product to be obtained tends to be good, and the like.

  Examples of the cyclic amidines include cyclic guanidine compounds, imidazoline compounds, imidazole compounds, tetrahydropyrimidine compounds, triazabicycloalkene compounds, and diazabicycloalkene compounds.

  Examples of the cyclic guanidine compounds include 1,5,7-triaza-bicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,5 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 compound include 1-methylimidazoline, 1,2-dimethylimidazoline, 1-methyl-2-ethylimidazoline, 1-methyl-2-octylimidazoline and the like.

  Examples of the imidazole compounds include imidazole and 2-ethyl-4-methylimidazole.

  Examples of the tetrahydropyrimidine compounds 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, etc. It can be mentioned.

  Examples of the triazabicycloalkene compounds include 7-methyl-1,5,7-triazabicyclo [4.4.0] decene-5,7-ethyl-1,5,7-triazabicyclo [4]. 4.4.0] decene-5 etc. are mentioned.

  Examples of diazabicycloalkene compounds include 1,5-diazabicyclo [4.2.0] octene-5,1,8-diazabicyclo [7.2.0] undecene-8,1,4-diazabicyclo [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-5,1,1,7 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] Undecen-7, 6-dihexylamino-1,8-diazabicyclo [5.4.0] undecene-7, 9-methyl-1,8-diazabicyclo [5.4.0] undecene-7, 9-me Le-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-9,1,1,0 14-diazabicyclo [11.3.0] hexadecene-13, 1,14-diazabicyclo [11.4.0] heptadecene-13 and the like can be mentioned.

  Among the cyclic amidines, 1,8-diazabicyclo [5.4.2 from the viewpoint of industrial availability and high catalytic activity because the pKa value of the conjugate acid is 12 or more. 0) Undecen-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) is particularly preferred. In addition, a base having a reactive silicon group such as an amine having a reactive silicon group can also be used as a base.

  As the photobase generator (B) used in the present invention, known photobase generators can be used, but photolatent amine compounds that generate an amine compound by the action of active energy rays are preferable. As the photolatent amine compound, a photolatent primary amine which generates an amine compound having a primary amino group by the action of active energy rays, an amine compound having a secondary amino group by the action of active energy rays Although any of photolatable secondary amines that generate light and photolatent tertiary amines that generate amine compounds having a tertiary amino group by the action of active energy rays can be used, the generation base is high. A photolatable tertiary amine is more preferable in view of catalytic activity.

Examples of the photolatent primary amine and the photolatent secondary amine include 1,3-bis [N- (2-nitrobenzyloxycarbonyl) -4-piperidyl] propane, 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) hexyl diamine, o- Nitrobenzyl N-carbamic acid cyclohexyl, 2-nitrobenzyl cyclohexyl carbamate, 1- (2-nitro Phenyl) ethyl cyclohexylcarbamate, 2,6-dinitrobenzylcyclohexylcarbamate, 1- (2,6-dinitrophenyl) ethylcyclohexylcarbamate, 1- (3,5-dimethoxyphenyl) -1-methylethylcyclohexylcarbamate, bis [[ Orthonitrobenzylurethane compounds such as (2-nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, etc .; α, α-dimethyl-3,5-dimethoxybenzylcyclohexyl Dimethoxybenzyl urethane compounds such as carbamates 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-phenylmethyl cyclohexyl carbamate, 2-benzoyl-2-hydroxy-2-phenylethyl cyclohexyl 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- (cyclohexyl) N-hydroxyimido carbamates such as xylcarbamoyloxy) succinimide; formanilide derivatives such as 4,4'-methylene bis (formalinide); N-cyclohexyl-2-naphthalene sulfonamide, N-cyclohexyl-p-toluene sulfonamide, etc. Aromatic sulfonamides; cobalt amine complexes such as Co (NH ₂ C ₃ H ₇ ) Br + ClO ₄ ^{− and the} like.

  Examples of the photolatable tertiary amine include α-aminoketone derivatives, α-ammonium ketone derivatives, benzylamine derivatives, benzylammonium salt derivatives, α-aminoalkene derivatives, α-ammonium alkene derivatives, amine imides, and the like. Examples thereof include benzyloxycarbonylamine derivatives which generate amidine, and salts of carboxylic acids and tertiary amines.

  As an alpha-amino ketone derivative, the alpha-amino ketone compound shown by following formula (i)-(iv) is mentioned as a suitable example, for example.

In the formula (i), in the formula, R ⁵¹ is an aromatic or heteroaromatic group, and R ⁵¹ is an aromatic group (which is unsubstituted or C ₁ -C ₁₈ alkyl, C _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) preferably substituted one or more times by OR ⁶² or halogen, preferably R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ and R ⁶² are hydrogen or C ₁ -C ₁₈ alkyl; 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, thiatrenil, dibenzofuryl, chromenyl, xanthenyl, thioxanthyl, phenoxatinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, isoquinolyl quinolinyl, Phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinolinyl, pteridinyl, carbazolyl, β-carbolinyl, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, fluorenyl More preferably, it is selected from the group consisting of phenoxazinyl.
R ⁵² and R ⁵³ are, independently of one another, 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 it is ₁₈ alkyl, then R ⁵³ is additionally a group -CO-R ⁶⁴ , wherein R ⁶⁴ is C ₁ -C ₁₈ alkyl or phenyl; or alternatively, R ⁵¹ and R ⁵³ are Together with the carbonyl atom and the C atom to which R ⁵³ is attached, form a benzocyclopentanone group.
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 , are C ₂ -C which is unsubstituted or substituted by one or more C ₁ -C ₄ alkyl groups ₁₂ form an alkylene bridge. It is preferred that 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 formulas (i).
R ⁶⁶ is an alkyl group having 1 to 12 carbon atoms; -OH, -alkoxy having 1 to 4 carbon atoms, -CN or -COO (alkyl having 1 to 4 carbon atoms) substituted with 2 to 2 carbon atoms Or R ⁶⁶ represents an alkenyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. R ⁶⁷ represents an alkyl group having 1 to 12 carbon atoms; or -OH,-an alkoxy group having 1 to 4 carbon atoms, -CN or -COO (alkyl having 1 to 4 carbon atoms) Or R ⁶⁷ represents an alkenyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenyl-C 1 to 3 alkyl group, or an unsubstituted group Or an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group substituted by -COO (alkyl having 1 to 4 carbon atoms), or R ⁶⁷ represents alkylene group having 1 to 7 carbon atoms together with the RR ^66, phenyl - alkylene group having 1 to 4 carbon atoms, o- xylylene group, 2-butenylene group, or o carbon atoms 2 or 3 Or R ⁶⁶ and R ⁶⁷ together represent an alkylene group of 4 to 7 carbon atoms which can be interrupted by -O-, -S- or -CO-, or R ⁶⁶ and R ⁶⁷ R ^{67 taken} together represents OH, an alkoxy group having 1 to 4 carbon atoms, or an alkylene group having 3 to 7 carbon atoms that may be substituted with —COO (alkyl having 1 to 4 carbon atoms). When there are a plurality of R ⁶⁶ and R ^67, they may be the same or different.
Y ¹ is a divalent group, -N ^{(R 68)} represented by the following formula (v) - represents a divalent group represented by - 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 having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms or a phenyl group , R ⁶⁹ represents one or more unbranched or branched C 2-16 alkylene groups which can be interrupted by -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-amino ketone 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) phenacil 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-amino ketone compound represented by the above formula (ii) include 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane (IRGACURE 907), 2-benzyl- described in JP-A-11-171450. 2-dimethylamino-1- (4-morpholinophenyl) -butanone (IRGACURE 369), 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone (IRGACURE 379), etc. It can be mentioned.

  As an alpha-ammonium ketone derivative, the alpha-ammonium ketone compound shown by following formula (vi) is mentioned, for example.

In the formula (vi), k is 1 or 2, which corresponds to the positive charge number of the cation. V ^- is a counter anion, and borate anion (tetraphenyl borate, methyl triphenyl borate, ethyl triphenyl borate, propyl triphenyl borate, butyl triphenyl borate and the like), 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 anion (benzoic acid anion, toluic acid) Anion and phenylglyoxylate anion etc. and the like. Among these, from the viewpoint of photodegradability, borate anions and carboxylate anions are preferable, and butyl triphenyl borate anion, tetraphenyl borate anion, benzoate anion and phenyl glyoxylate anion, photodegradability and thermal stability are more preferable. Particularly preferred are tetraphenyl borate anion and phenyl glyoxylate anion from the viewpoint of

In the formula ^{(vi), R} 51 ~R ⁵³ is the same as ^R 51 ^{to R 53} of each of the formulas (i).
R ^{70 to} R ⁷² are each, independently of one another, hydrogen, C _{1 to} C ₁₈ alkyl, C _{3 to} C ₁₈ alkenyl, C _{3 to} 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, together with the nitrogen atom to which R ⁷⁰ -R ⁷² is attached, P ₁ , P ₂ , P <t / 4> type Or a group of the following structural formula (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} in the formula (i), l and q is a number from 2 to 12 each, independently of one another.

  As specific examples of the α-ammonium ketone derivative, for example, phenacyltriethylammonium tetraphenylborate described in JP-A-2001-513765, WO 2005/014696, (4-methoxyphenacyl) triethylammonium tetraphenylborate, 1 -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-4-4) Azabicyclo [2.2.2] octane) tetraphenylbo And 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 And tetraphenylborate, 5- (4'-phenyl) phenacyl- (8-azonia-1-azabicyclo [5.4.0] -7-undecene) tetraphenylborate and the like.

  As a benzylamine derivative, the benzylamine compound shown by following formula (vii) is mentioned, for example.

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

  Specific examples of the benzylamine derivative include 5-benzyl-1,5-diazabicyclo [4.3.0] nonane, 5- (anthracene-9-yl-methyl)-described in, for example, 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-Diazabishiki [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 benzylamine derivatives such as 8- (2 ', 6'-dichlorobenzyl) -1,8-diazabicyclo [5.4.0] undecane, and the like.

  As a benzyl ammonium salt derivative, the benzyl ammonium salt shown by following formula (viii) is mentioned, for example.

In the formula (viii), V ^- and k V of the formula (vi) ^- is the same as, and k. R ⁵¹ is the same as ^{R 51} in 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, photo base generators described in WO 2010/095390 and WO 2009/122664, such as (9-anthryl) methyltriethylammonium tetraphenyl borate, (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 ] 8-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-thiooxane) 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 derivative include 5- (2 ′-(4 ′ ′-biphenyl) allyl) -1,5-diazabicyclo [4.3.0] nonane described in JP-A-2001-515500; (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 '-(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.

  As the α-ammonium alkene derivative, for example, N- (2′-phenylallyl) -triethylammonium tetraphenylborate described in JP-A-2002-523393, 1- (2′-phenylallyl)-(1-azonia-) 4-azabicyclo [2,2,2] -octane) tetraphenylborate, 1- (2'-phenylallyl)-(1-azonia-4-azabicyclo [2,2,2] -octane) tetraphenylborate, 1 And-(2'-phenylallyl)-(1-azonia-4-azabicyclo [2,2,2] -octane) tris (3-fluorophenyl) hexyl borate and the like.

  As the amine imides, for example, [(2-hydroxy-3-phenoxypropyl) dimethylaminio] (4-nitrobenzoyl) amine anion described in WO 2002/051905, [(2-hydroxy-3-phenoxypropyl) dimethyl] 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) dimethyl aminio] [4- (dimethylamino) benzoyl] amine anion, etc. are mentioned.

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

  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 And oxycarbonyl) imidazole and the like.

  Examples of benzyloxycarbonylguanidines include benzyloxycarbonyl tetramethylguanidine described in WO 97/31033 and the like.

  As a diamine derivative, for example, 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 salts of carboxylic acids and tertiary amines include α-ketocarboxylic acid ammonium salts and carboxylic acid ammonium salts.

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

  As the carboxylic acid ammonium salt, for example, ketoprofen salt of diazabicycloundecene (DBU) described in JP-A-2009-280785, ketoprofen salt of 2-methylimidazole, diazabicyclo described in JP-A-2011-80032. Xanthone acetate salt of undecene (DBU), thioxanthone acetate salt of diazabicyclo undecen (DBU), 3-quinuclidinol salt of 2- (carboxymethylthio) thioxanthone described in JP-A-2007-262276, 2- (carboxymethoxy) And 3-quinuclidinol salts of thioxanthone, and 3-quinuclidinol salts of trans-o-coumaric acid described in JP-A-2010-254982 and JP-A-2011-213783.

  Among the (B) photobase generators described above, photolatable tertiary amines are preferred from the viewpoint of high catalytic activity of the generated base, and the generation efficiency of the base is good and the storage stability as a composition is good. From the above, benzyl ammonium salt derivatives, benzyl substituted amine derivatives, α-amino ketone derivatives and α-ammonium ketone derivatives are preferable, and in particular, since the generation efficiency of the base is better, α-amino ketone derivatives and α-ammonium ketone derivatives are more preferable Preferably, the α-amino ketone derivative is more preferable than the solubility in the formulation. Among the α-amino ketone derivatives, the α-amino ketone compound represented by the above formula (i) is better than the basic strength of the generated base, and the α-amino ketone compound represented by the above formula (ii) is better than the availability.

  These (B) photobase generators may be used alone or in combination of two or more. The compounding ratio of the (B) photobase generator is not particularly limited, but it may be 0.1 parts by weight to 100 parts by weight of the organic polymer having a crosslinkable silicon group and a photoradical polymerizable vinyl group in the (A) molecule. 01-50 mass parts is preferable, 0.1-40 mass parts is more preferable, 0.5-30 mass parts is further more preferable.

  The photocurable composition of the present invention is a silicon compound having (C) (C1) Si-F bond, and / or (C2) boron trifluoride, a complex of boron trifluoride, a fluorinating agent and a polyvalent fluoro It includes one or more fluorine-based compounds selected from the group consisting of alkali metal salts of the compounds. In the photocurable composition of the present invention, curing is further promoted by including the component (C).

  In the present invention, the silicon compound having a (C1) Si-F bond acts as a curing catalyst for the compound having a crosslinkable silicon group (A). As the silicon compound having the (C1) Si-F bond, known compounds containing a silicon group having a Si-F bond (hereinafter sometimes referred to as a fluorosilyl group) can be used widely Although both low molecular weight compounds and high molecular weight compounds can be used, organic silicon compounds having a fluorosilyl group are preferable, and organic polymers having a fluorosilyl group are more preferable because of their high safety. In addition, a low molecular weight organosilicon compound having a fluorosilyl group is preferable in that the composition has a low viscosity.

  Specifically, the silicon compound having the (C1) Si-F bond is a compound having a fluorosilyl group represented by the following formula (6) such as fluorosilanes represented by the following formula (5) (this specification In the examples, fluorinated compounds are also referred to), organic polymers having a fluorosilyl group (herein also referred to as fluorinated polymers), etc. are mentioned as suitable examples.

R ⁸⁰ _4-d SiF _d (5)
(In the formula (5), each R ⁸⁰ independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ⁹⁰ SiO— (R ⁹⁰ each independently has 1 to 20 carbon atoms Or a substituted or unsubstituted hydrocarbon group, or an organosiloxy group represented by fluorine atom, d is any one of 1 to 3 and d is preferably 3. R ⁸⁰ And when two or more R ⁹⁰ are present, they may be the same or different)

-SiF _d R ⁸⁰ _e X ' _f (6)
(In formula (6), R ⁸⁰ and d are respectively the same as formula (5), X ′ is each independently a hydroxyl group or a hydrolyzable group other than fluorine, and e is any one of 0 to 2 And f is any of 0 to 2 and d + e + f is 3. When there are a plurality of R ⁸⁰ and X ′, they may be the same or different.)

  Examples of the fluorosilanes represented by the formula (5) include known fluorosilanes represented by the formula (5), which are not particularly limited. For example, fluorotrimethylsilane, fluorotriethylsilane, fluorotripropylsilane Fluorotributylsilane, fluorodimethylvinylsilane, fluorodimethylphenylsilane, fluorodimethylbenzylsilane, fluorodimethyl (3-methylphenyl) silane, fluorodimethyl (4-methylphenyl) silane, fluorodimethyl (4-chlorophenyl) silane, fluorotrimethylsilane Phenylsilane, difluorodimethylsilane, difluorodiethylsilane, difluorodibutylsilane, difluoromethylphenylsilane, difluorodiphenylsilane, trifluoroethylsilane, trifluoro Propylsilane, trifluorobutylsilane, trifluorophenylsilane, γ-glycidoxypropyltrifluorosilane, γ-glycidoxypropyl difluoromethylsilane, vinyl trifluorosilane, vinyldifluoromethylsilane, γ-methacryloxypropyl fluorodimethyl Silane, γ-methacryloxypropyl difluoromethylsilane, γ-methacryloxypropyl trifluorosilane, 3-mercaptopropyl trifluorosilane, octadecyl fluorodimethyl silane, octadecyl difluoromethyl silane, octadecyl trifluorosilane, 1,3-difluoro-1 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.

  Among these, fluorodimethylvinylsilane, fluorodimethylphenylsilane, fluorodimethylbenzylsilane, vinyltrifluorosilane, vinyldifluoromethylsilane, γ-methacryloxypropyl from the viewpoint of easy availability of raw materials and easy synthesis. Fluorodimethylsilane, γ-methacryloxypropyl difluoromethylsilane, γ-methacryloxypropyl trifluorosilane, 3-mercaptopropyl trifluorosilane, octadecyl fluorodimethyl silane, octadecyl difluoromethyl silane, octadecyl trifluorosilane, 1,3-difluoro -1,1,3,3-Tetramethyldisiloxane and the like are preferable.

  In the compound having a fluorosilyl group represented by the formula (6), as the hydrolyzable group represented by X ′ in the formula (6), for example, the same hydrolyzable group as X in the formula (1) Specific examples thereof include a hydrogen atom, a halogen atom other than fluorine, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amido group, an acid amide group, an aminooxy group, a mercapto group and an alkenyloxy group. And the like. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amido group, an aminooxy group, a mercapto group and an alkenyloxy group are preferable, and an alkoxy group is preferable from the viewpoint of mild hydrolyzability. Particularly preferred.

Further, R ⁸⁰ in the above formula (6) is, for example, an alkyl group such as methyl group and ethyl group, a cycloalkyl group such as cyclohexyl group, an aryl group such as phenyl group, an aralkyl group such as benzyl group, R ⁹⁰ is a methyl group, triorganosiloxy group represented by ^R 90 SiO- can be mentioned a phenyl group. Of these, methyl is particularly preferred.

Specific examples of the fluorosilyl group represented by the formula (6) include a fluorodimethylsilyl group, a fluorodiethylsilyl group, a fluorodipropylsilyl group, and a fluorodiethylsilyl group as a silicon group having no hydrolyzable group other than fluorine. Silicon group in which one fluorine is substituted on silicon group such as diphenylsilyl group and fluorodibenzylsilyl group; on silicon group such as difluoromethyl silyl group, difluoroethyl silyl group, difluorophenyl silyl group, difluorobenzyl silyl group Silicon group substituted by two fluorines; silicon group substituted by three fluorines on a silicon group which is a trifluorosilyl group; and as a silicon group having both fluorine and another hydrolysable group, fluoro Methoxymethylsilyl, fluoroethoxymethylsilyl, fluoromethoxyethylsilyl, fluoro Oromethoxyphenylsilyl group, fluorodimethoxysilyl group, fluorodiethoxysilyl group, fluorodipropoxysilyl group, fluorodiphenoxysilyl group, fluorobis (2-propenoxy) silyl group, difluoromethoxysilyl group, difluoroethoxysilyl group, difluoro Phenoxysilyl group, fluoro dichloro silyl group, difluoro chloro silyl group, etc. are mentioned, silicon group which does not have hydrolysable group other than fluorine, fluoro silyl group where R ⁸⁰ is methyl group is preferable, trifluoro silyl group is more preferable preferable.
In addition, from the ease of synthesis, fluorodimethylsilyl group, difluoromethylsilyl group, trifluorosilyl group, fluoromethoxymethylsilyl group, fluoroethoxymethylsilyl group, fluoromethoxyethylsilyl group, fluorodimethoxysilyl group, fluorodiethoxysilyl group And difluoromethoxysilyl group and difluoroethoxysilyl group are more preferable, and from the viewpoint of stability, a silicon group having no hydrolyzable group other than fluorine such as fluorodimethylsilyl group, difluoromethylsilyl group and trifluorosilyl group is more preferable From the viewpoint of curability, preferred are silicon groups in which 2 to 3 fluorines are substituted on the silicon group, such as difluoromethylsilyl group, difluoromethoxysilyl group, difluoroethoxysilyl group, trifluorosilyl group, etc. Roshiriru group is most preferred.

  It does not specifically limit as a compound which has a fluoro silyl group shown by said Formula (6), Both a monomolecular compound and a high molecular compound can be used, For example, Inorganics, such as tetrafluorosilane and octafluoro trisilane Silicon compounds; fluorosilanes represented by the above formula (5), fluorotrimethoxysilane, difluorodimethoxysilane, trifluoromethoxysilane, fluorotriethoxysilane, difluorodiethoxysilane, trifluoroethoxysilane, methylfluorodimethoxysilane, methyl Difluoromethoxysilane, Methyltrifluorosilane, Methylfluorodiethoxysilane, Methyldifluoroethoxysilane, Vinylfluorodimethoxysilane, Vinyldifluoromethoxysilane, Vinyltrifluorosilane, Vinylfulfol Low-molecular-weight organosilicon compounds such as lodiethoxysilane, vinyldifluoroethoxysilane, phenylfluorodimethoxysilane, phenyldifluoromethoxysilane, phenyltrifluorosilane, phenylfluorodiethoxysilane, phenyldifluoroethoxysilane, fluorotrimethylsilane, etc .; 6) a high-molecular compound such as a fluorinated polysiloxane having a fluorosilyl group shown by 6), and fluorosilanes shown by the above-mentioned formula (5), or a compound represented by the formula (6) at the end of the main chain or side chain Preferred are polymers having a fluorosilyl group.

A commercially available reagent may be used for the fluorosilanes shown by said Formula (5), and the compound which has a fluoro silyl group shown by said Formula (6), You may synthesize | combine from a raw material compound. The synthesis method is not particularly limited, but a compound having a crosslinkable silicon group represented by the following formula (7) and a fluorinating agent are known methods (for example, Organometallics 1996, pages 15, 2478 (Ishikawa et al.), Etc. The compound obtained by making it react using (iii) is used suitably.
-SiR ⁸⁰ _3-q X ' _q (7)
(In the formula (7), R ⁸⁰ and X ′ are respectively the same as the formula (6), and q is any of 1 to 3.)

  As a crosslinkable silicon group shown by the said Formula (7), halo silyl groups, such as an alkoxy silyl group, a siloxane bond, a chloro silyl group, hydrosilyl group, etc. are mentioned, for example.

Alkoxy Specific examples of fluorinating agents used for the fluorination of a silyl group is not particularly limited, for _{example, NH 4 F, Bu 4 NF} , HF, BF 3, Et 2 NSF 3, HSO 3 F, SbF 5 , VOF ₃ , CF ₃ CHFCF ₂ NEt _{2 and the} like.
Specific examples of fluorinating agents used for the fluorination of halosilyl group is 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, like _{KF (HF) 1.5~5.}
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 synthesis methods of fluorosilyl group using these fluorinating agents, the reaction is simple, the reaction efficiency is high, the safety is high, etc., and thus the fluorination method of alkoxysilane using BF ₃ Preferred is the fluorination method of chlorosilane using CuF ₂ or ZnF ₂ .

As BF ₃ , 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, BF ₃ piperidine A complex, BF ₃ phenol complex, etc. can be used, but BF ₃ ether complex, BF ₃ thioether complex, BF ₃ amine complex, BF ₃ alcohol complex, BF ₃ carboxylic acid complex, BF ₃ hydration because of easy handling etc. Are preferred. Among them, the BF ₃ ether complex, the BF ₃ alcohol complex, and the BF ₃ hydrate are preferably highly reactive, and the BF ₃ ether complex is particularly preferable.

The organic polymer having a fluorosilyl group (also referred to as a fluorinated polymer in the present specification) is not particularly limited as long as it is an organic polymer having a Si-F bond, and known organics having a Si-F bond Polymers are widely available.
The position of the SiF bond in the organic polymer is also not particularly limited, and the effect is exhibited at any site in the polymer molecule, and the end of the main chain or side chain is -SiR ⁿ ₂ F, the polymer When it is incorporated into the main chain of the formula, it is represented in the form of -SiR ⁿ F- or ≡SiF (R ⁿ is each independently an arbitrary group).
As the organic polymer having a Si-F bond at the end of the main chain or side chain, a polymer having a fluorosilyl group represented by the above-mentioned formula (6) 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 in which the fluorosilyl group and the main chain skeleton are the same, that is, the number of fluorosilyl group per molecule, the bonding position thereof, and the number of F which the fluorosilyl group has, And a single polymer in which the main chain skeleton is the same, or a mixture of multiple 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 exhibiting fast curing, but it is expensive. In order to obtain a rubbery cured product exhibiting curability, high strength, high elongation and low elastic modulus, the fluorosilyl group contained in the fluorinated polymer is at least on average per molecule of polymer. One, preferably 1.1 to 5, and more preferably 1.2 to 3 may be present. When the number of fluorosilyl groups contained in one molecule is less than one on average, the curability may be insufficient and it may be difficult to exhibit good rubber elastic behavior.

Further, the fluorinated polymer contains, together with the fluorosilyl group, a substituent other than the fluorosilyl group such as a silicon group having only a hydrolyzable group other than fluorine as a hydrolyzable group (for example, a methyldimethoxysilyl group etc.) It may be As such a fluorinated polymer, for example, a polymer in which one main chain end is a fluorosilyl group, and the other main chain end is a silicon group having only a hydrolyzable group other than fluorine as a hydrolysable group. Can be mentioned. An example of a fluorinated polymer is described in WO 2008/032539.

  In the fluorinated polymer, the introduction of the fluorosilyl group may be carried out by any method, but the introduction method by the reaction of the low molecular weight silicon compound having the fluorosilyl group with the polymer (method (i)) and fluorine A method (method (ii)) of modifying a silicon group of a crosslinkable silicon group-containing polymer having a hydrolyzable group (hereinafter sometimes referred to as "polymer (X)") to a fluorosilyl group It can be mentioned.

The following method is mentioned as a specific example of method (i).
(I) A method of reacting a polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in a molecule with a compound having a functional group having reactivity with the functional group and a fluorosilyl group. For example, a method of reacting a polymer having a hydroxyl group at an end with isocyanate propyl difluoromethylsilane, or a method of reacting a polymer having an SiOH group at an end and difluorodiethoxysilane may be mentioned.
(Ii) A method of hydrosilylation by causing a hydrosilane having a fluorosilyl group to act on a polymer containing an unsaturated group in the molecule. For example, there is a method of reacting difluoromethyl hydrosilane with a polymer having an allyl group at the end.
(Iii) A method of reacting a compound having a mercapto group and a fluorosilyl group with a polymer containing an unsaturated group. For example, there is a method of reacting mercaptopropyl difluoromethylsilane with a polymer having an allyl group at the end.

  As a polymer (polymer (X)) containing a crosslinkable silicon group having a hydrolyzable group other than fluorine, which is used in the above method (ii), a crosslinkable silicon group having a hydrolyzable group other than fluorine is used. Preferred polymers include saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene and hydrogenated polybutadiene, polyoxyalkylene polymers, (meth) acrylate polymers, and polysiloxane polymers. It can be mentioned.

Further, in the method (ii), as a method for converting a crosslinkable silicon group having a hydrolyzable group other than fluorine into a fluorosilyl group, a known method can be used, and for example, it is shown by the above-mentioned formula (7) And a method of converting the hydrolyzable silicon group to be 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, and fluorination proceeds efficiently, and further secondary Salts and the like are not generated in the product, and post treatment is easy, which is more preferable, and BF ₃ ether complex is particularly preferable.
Furthermore, although fluorination with BF ₃ ether complex proceeds without heating, the reaction proceeds, but in order to conduct fluorination more efficiently, heating is preferable. As heating temperature, 50 degreeC or more and 150 degrees C or less are preferable, and 60 degreeC or more and 130 degreeC are more preferable. Reaction may not advance efficiently that it is 50 degrees C or less, and fluorination may take time. If the temperature is 150 ° C. or higher, the fluorinated polymer may be decomposed. In the fluorination with a BF ₃ complex, coloration may occur depending on the type of the polymer (X) to be used, but from the viewpoint of suppression of coloration, 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 if moisture is present when producing the fluorinated polymer using the method of (ii) above The silanol condensation reaction may proceed to increase the viscosity of the resulting fluorinated polymer. For this reason, it is desirable that the production of the fluorinated polymer is carried out in an environment in which the water does not exist as much as possible, and before fluorination, the polymer (X) to be fluorinated is subjected to azeotropic dehydration using toluene, hexane or the like. It is preferable to perform a dewatering operation such as feeding. However, in the case of using a BF ₃ amine complex, fluorination does not easily proceed after dehydration operation, and there is a tendency for the reactivity to be improved by adding a small amount of water, so that the increase in water viscosity is acceptable. Is preferably added. Further, from the viewpoint of the stability of the fluorinated polymer, it is preferable to remove the fluorinating agent and the by-produced fluorinating agent-derived component after fluorination by filtration, decantation, liquid separation, vacuum evaporation or the like. When producing a fluorinated polymer 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 preferred, less than 100 ppm is more preferred, and less than 50 ppm is particularly preferred. By removing BF ₃ and BF ₃ -derived components, it is possible to suppress the increase in viscosity and the like of the obtained fluorinated polymer itself and the mixture of the fluorinated polymer and the polymer (X). Taking this point into consideration, the fluorination method using BF ₃ ether complex and BF ₃ alcohol complex is preferable because the boron component can be relatively easily removed by vacuum degassing, and the method using BF ₃ ether complex is particularly preferable. .

  Here, when the polymer (X) has two or more hydrolyzable groups other than fluorine, all hydrolyzable groups may be fluorinated, or a method such as reducing the amount of fluorinating agent , And may be partially fluorinated by adjusting the conditions of fluorination. For example, in the case of producing a fluorinated polymer using the polymer (X) in the method (ii) above, the amount of the fluorinating agent used is not particularly limited, and the molar amount of fluorine atoms in the fluorinating agent The amount may be such that it is equimolar or more with respect to the molar amount of the polymer (X). When it is going to fluorinate all the hydrolysable groups which a polymer (X) contains by the method of (ii), the molar amount of the fluorine atom in a fluorinating agent contains a polymer (X) It is preferable to use an amount of fluorinating agent that is equal to or greater than the total molar amount of hydrolyzable groups in the crosslinkable silicon group. Here, "a fluorine atom in the fluorinating agent" means a fluorine atom effective for fluorination in the fluorinating agent, specifically, a hydrolyzable group in the crosslinkable silicon group of the polymer (X) Refers to a fluorine atom that can be substituted.

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

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

  The glass transition temperature of the fluorinated polymer is not particularly limited, but is preferably 20 ° C. or less, more preferably 0 ° C. or less, and particularly preferably −20 ° C. or less. When the glass transition temperature exceeds 20 ° C., the viscosity in winter or cold region may become high and handling may be difficult, and the flexibility of the cured product obtained when used as a curable composition is reduced, and the elongation May decrease. The glass transition temperature can be determined by DSC measurement.

  The fluorinated polymer may be linear or may have branches. The number average molecular weight of the fluorinated polymer is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000 in terms of polystyrene in GPC.

  The compounding ratio of the silicon compound having the (C1) Si-F bond is not particularly limited, but when using a polymer compound having a number average molecular weight of 3,000 or more such as a fluorinated polymer, (A) crosslinkable silicon group and light 0.01 to 80 parts by mass is preferable, 0.01 to 30 parts by mass is more preferable, and 0.05 to 20 parts by mass is more preferable with respect to 100 parts by mass of the radical polymerizable vinyl group-containing organic polymer. Low molecular weight compounds having a fluorosilyl group having a number average molecular weight of less than 3,000 (for example, fluorosilanes represented by the formula (5), low molecular weight organosilicon compounds having a fluorosilyl group represented by the formula (6), fluorosilyl group 0.01 to 50 parts by mass relative to 100 parts by mass of the organic polymer having a crosslinkable silicon group and a radically polymerizable vinyl group in the (A) molecule Preferably, 0.05 to 20 parts by mass is more preferable, and 0.1 to 15 parts by mass is particularly preferable.

  In the present invention, at least one fluorine compound selected from the group consisting of (C2) boron trifluoride, a complex of boron trifluoride, a fluorinating agent and an alkali metal salt of a polyvalent fluoro compound is a crosslinkable silicon group (A) acts as a curing catalyst for the organic polymer having a crosslinkable silicon group and a radically polymerizable vinyl group in the molecule (A).

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

Examples of the amine compound used for the amine complex of boron trifluoride include ammonia, monoethylamine, triethylamine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, guanidine, and the like. 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-toluylene diamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, melamine, 1,3-diphenylguanidine, Di-o-tolyl guanidine, 1,1,3,3-tetramethyl guanidine, bis (aminopropyl) piperazine, N- (3-aminopropyl) -1,3-propanediamine, bis (3-aminopropyl) ether , Made by Sun Techno Chemical Co. Compounds having a plurality of primary amino groups such as hamamine, piperazine, cis-2,6-dimethyl piperazine, cis-2,5-dimethyl piperazine, 2-methyl piperazine, N, N'-di-t-butyl ethylene diamine , 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, and further 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] Undecen-7,6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7,1,5-diazabicyclo [4.3.0] nonene-5,1,4-diazabicyclo [2.2 .2] Octane, pyridine, N-alkylpiperidine, 1,5,7-tria Polycyclic tertiary amine compounds such as xavicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, etc. Other, 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-aminoethyl) Aminosilane compounds such as 11-amino-undecyl triethoxy silane.
Examples of commercially available products of the boron trifluoride amine complex include anchor 1040, anchor 1115, anchor 1170, anchor 1222, BAK 1171 and the like manufactured by Air Products Japan Co., Ltd.

  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-, such as 1,1,2,3,3,3-hexafluoro-1-diethylaminopropane and the like. Dialkylaminopropane compounds, trialkylamine trishydrofluoride compounds such as triethylamine trishydrofluoride, dialkylaminosulfur trifluoride compounds such as diethylaminosulfur trifluoride, etc. may be mentioned.

  Examples of the electrophilic fluorinating agent include N-fluoro such as bis (tetrafluoroboric acid) N, N'-difluoro-2,2'-bipyridinium salt compound, trifluoromethanesulfonic acid N-fluoropyridinium salt compound, etc. 4-fluoro-1,4-diazoniabicyclo [2.2.4] such as pyridinium salt compounds, bis (tetrafluoroboric acid) 4-fluoro-1,4-diazoniabicyclo [2.2.2] octane salt and the like. 2] Octane compounds, N-fluorobis (sulfonyl) amine compounds such as N-fluorobis (phenylsulfonyl) amine, etc. may be mentioned. Among these, 1,1,2,3,3,3-hexafluoro-1-diethylaminopropane type compounds are particularly preferable because they are liquid compounds and easy to obtain.

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, triborate Sodium fluoro (pentafluorophenyl) borate, potassium trifluoro (pentafluorophenyl) borate, difluorobis (pentafluorophenyl) Sulfonyl) sodium borate, difluoro (pentafluorophenyl) potassium borate, and the like.
Among these, as a polyvalent fluoro compound component in the alkali metal salt of a polyvalent fluoro compound, tetrafluoroboric acid or hexafluorophosphoric acid is preferable. 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 compounding ratio of the (C2) fluorine-based compound is not particularly limited, but it is 0.001 with respect to 100 parts by mass of the organic polymer having a crosslinkable silicon group and a photoradical polymerizable vinyl group in the (A) molecule. 10 parts by mass is preferable, 0.001 to 5 parts by mass is more preferable, and 0.001 to 2 parts by mass is more preferable. These fluorine compounds may be used alone or in combination of two or more.

  The photocurable composition of the present invention comprises one or more selected from the group consisting of the silicon compound having the (C1) Si-F bond and the above (C2) fluorine-based compound, and the (C1) and Either (C2) may be used alone, or both may be used in combination. In particular, the photocurable composition of the present invention preferably contains a silicon compound having the (C1) Si-F bond.

  The photocurable composition of the present invention is, if necessary, an organic polymer having a crosslinkable silicon group and an organic polymer other than the component (A) (except for those having a Si-F bond). Silane coupling agent (adhesion imparting agent), photosensitizer, extender, diluent, plasticizer, water absorbent, curing catalyst, physical property modifier for improving tensile properties, etc., reinforcing agent, coloring agent, difficult Various additives such as flame retardants, anti-sagging agents, antioxidants, anti-aging agents, UV absorbers, solvents, perfumes, pigments, dyes and the like may be added.

When an organic polymer having the crosslinkable silicon group other than the component (A) (except that having a Si-F bond) is used for the curable composition of the present invention, the cured product When the mechanical strength is improved or used as an adhesive, the adhesion strength to the adherend can be improved. The crosslinkable silicon group in this polymer is the same as the crosslinkable silicon group in component (A). Although the number of crosslinkable silicon groups in this polymer is not particularly limited, it is preferable that the number is 1.1 or more, preferably 1.4 or more in average in one molecule of the polymer. The polymer main chain is also the same as the main chain in the component (A). When this polymer is used, it is preferably 1 to 80% by mass, and more preferably 1 to 60% by mass in the photocurable composition.

  The photocurable composition of the present invention comprises, in addition to the (B) photobase generator, (D) at least one amino selected from the group consisting of a primary amino group and a secondary amino group by light. It is preferable to further include a crosslinkable silicon group-containing compound that generates a group. The crosslinkable silicon group-containing compound capable of generating at least one amino group selected from the group consisting of a primary amino group and a secondary amino group by the light can improve adhesion performance.

  Examples of the crosslinkable silicon group-containing compound which forms one or more amino groups selected from the group consisting of a primary amino group and a secondary amino group by the light include a primary amino group and a primary amino group by light irradiation. Any compound can be used as long as it generates an aminosilane compound having at least one amino group selected from the group consisting of secondary amino groups and a crosslinkable silicon group. In the present specification, the crosslinkable silicon group-containing compound that generates one or more amino groups selected from the group consisting of a primary amino group and a secondary amino group by the 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 examples thereof include an alkyl group, an aralkyl group and an aryl group. Moreover, it does not specifically limit as a crosslinkable silicon group, The crosslinkable silicon group described by the term of the said (A) organic polymer can be mentioned, The silicon-containing group which the hydrolysable group couple | bonded is preferable. Among these, an alkoxy group such as a methoxy group and an ethoxy group is preferable because of its mild hydrolyzability and easy handling. In the aminosilane compound, the hydrolyzable group and the hydroxyl group can be bonded to one silicon atom in a range of 1 to 3, preferably 2 or more, and particularly preferably 3 or more.

  The aminosilane compound generated by the light irradiation is not particularly limited, and examples thereof include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, and γ-aminopropylmethyl. Dimethoxysilane, γ-aminopropylmethyldiethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltriol Monoamines such as methoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane and the like , 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 And diamines such as N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine; triamines such as γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane; and the like.

Among the aminosilane compounds generated by the light irradiation, aminosilane compounds having a primary amino group (-NH ₂ ) are preferable from the viewpoint of adhesiveness, and from the viewpoint of availability γ-aminopropyltrimethoxysilane, γ -Aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ- (2-aminoethyl) aminopropyltrimethoxysilane are preferable, and from the viewpoint of adhesion and curing, γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane More preferred is ethoxysilane.

  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 following formula (15) The O-acyl oxime derivative shown, the trans-O-coumaric acid derivative shown by following formula (16), etc. are mentioned.

In said Formula (12), n is an integer of 1-3, Y shows a hydroxyl group or a hydrolysable group, and an alkoxy group is preferable. When two or more Y exist, 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 exist, 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, more preferably a hydrogen atom. h is an integer of 1 to 5 and j is an integer of 1 to 6. R ¹⁰³ is a substituted or unsubstituted hydrocarbon group which is bonded to a silicon atom and a nitrogen atom at h + j different carbon atoms, and a plurality of substituted or unsubstituted hydrocarbon groups which are 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 the molecular weight is 1,000 or less. R ¹⁰² and R ¹⁰³ may combine to form a cyclic structure, and may contain a hetero atom bond. Z is an oxygen atom or a sulfur atom, preferably an oxygen atom. Q represents a photofunctional group.

In said Formula (13), n, Y, R < ¹⁰¹ >, Z, and Q are the same as that of said 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, preferably 1 or 2. When t is 2 or more, t groups attached to R ¹⁰⁴ may be the same or different. R ¹⁰⁴ is a hydrogen atom or an organic group, preferably a hydrogen atom or a substituted or unsubstituted t-valent hydrocarbon group, and more preferably a hydrogen atom or a substituted or unsubstituted t-valent alkyl group. R ¹⁰⁴ and R ¹⁰⁵ may combine to form a cyclic structure, and may contain a hetero atom bond.

In the formula ^{(14), n, Y,} R 101 ~R 103, h and j are the same as the equation (12). Each of R ^{106 to} R ¹¹⁰ 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 substituted group 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 And aryl groups, unsubstituted or substituted aryloxy groups, heterocyclic structure-containing groups, groups having a plurality of rings, combinations thereof and the like. Any one 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 heterocyclic ring, a nonaromatic ring, or a functional group such as a carbonyl group is bonded You may form the structure etc. which the fused ring etc. condensed.

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

In said Formula (16), n, Y, R < ¹⁰¹ >, R < ¹⁰³ >, h and j are the same as said Formula (12), R < ¹⁰⁶ > -R < ¹⁰⁹ > is the same as said 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, more preferably a hydrogen atom. R ¹⁰³ and R ¹¹² may combine to form a cyclic structure, and may contain a hetero atom 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, a phosphino group , Phosphinyl group, phosphono group, phosphonato group, or organic group, hydrogen atom, nitro group, cyano group, hydroxy group, mercapto group, halogen atom, acetyl group, allyl group, alkyl group having 1 to 5 carbon atoms, carbon The alkoxy group of the number 1-5, an unsubstituted or substituted aryl group, and an aryloxy group are preferable. R ¹¹⁵ represents a hydrogen atom or a substituent, and is preferably a hydrogen atom or a protecting group which can be deprotected by heating and / or irradiation with light; hydrogen atom, silyl group, silanol group, phosphino group, phosphinyl group, phosphono group Or an organic group is more preferred.

  In the above 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. Groups, tert-butyl group, n-pentyl group, chloromethyl group, chloroethyl group, fluoromethyl group, cyanomethyl group and the like. As a C1-C5 alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, n-butoxy group etc. are mentioned, for example. As a non-substituted or substituted aryl group, a phenyl group, p-methoxyphenyl group, p-chlorophenyl group, p-trifluoromethylphenyl group etc. are mentioned, for example. As an aryloxy group, a phenoxy group etc. are mentioned, for example.

  Examples of the photofunctional group Q include known photosensitive groups and are not particularly limited. For example, a group having a cyclic structure represented by the following formula (17), an oxime residue represented by the following formula (18), These groups etc. which were substituted are mentioned and the group which has a cyclic structure shown by following formula (17) is preferable.

-A-Q '(17)
[In the above-mentioned formula (17), A is a direct bond or a divalent linking group, and Q ′ is a cyclic structure-containing group. Direct bonding means that Q ′ is directly bonded to Z without a linking group. Examples of the divalent linking group for A include, for example, a divalent linkage containing an alkylene group, a carbonyl group, an ether bond, an ester bond, a -CONH- group, or a combination thereof which may have a substituent. A group etc. are mentioned and the alkylene group which may contain a substituent, a carbonyl group, and those combinations are preferable. In addition, the substituent of A may have a cyclic structure, and the substituents may be bonded to each other to form a cyclic structure. Examples of the cyclic structure include those similar to Q ′.
The cyclic structure in Q ′ is preferably either a single ring or a plurality of rings, and may be any of single ring cyclic ring and heterocyclic ring, but includes functional groups such as vinyl group, carbonyl group, imino group, etc. It is preferable to have a cyclic structure exhibiting aromaticity. Examples of Q ′ include an aryl group, an aryloxy group, a heterocyclic group containing one or more kinds of hetero atoms such as nitrogen, oxygen, and sulfur, and a cyclic group having a carbonyl group which may have a substituent, for example. And groups including structures, combinations thereof, condensed rings thereof and the like. In addition, the substituent may further have a cyclic structure. Also, the substituent of A and Q ′ may be bonded. ]

(In the above formula (18), each of R ¹¹⁶ and R ¹¹⁷ independently represents 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, and the R ¹¹⁶ , R ¹¹⁷ , or R ¹¹⁶ and R ¹¹⁷ are formed by bonding to each other Further, one or two oxime groups shown in the above formula may be formed on the double bond or the aromatic or non-aromatic ring.

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

In (Formula (19), A is the same as A in the formula (17), a substituted or unsubstituted alkylene group, a carbonyl group, and combinations thereof are preferred ^.R 118 ^{to R 122} are each independently And 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, a substituted or unsubstituted group Alkyl group (preferably an alkyl group of 1 to 5 carbon atoms), substituted or unsubstituted alkoxy group (preferably an alkoxy group of 1 to 5 carbon atoms), unsubstituted or substituted aryl group, 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 ring to which a functional group is bonded may form a condensed structure, etc. Also, the substituent of A may be bonded to any of R ^{118 to} R ¹²² .

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

(In the above formulas (20-1) to (20-3), R ^{118 to} R ¹²¹ are the same as the above formula (19). R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or 1 carbon atom To 10 unsubstituted or substituted alkyl group, phenyl group or substituted phenyl group, k is 1 or 2, and when k is 2, a plurality of R ¹²³ and R ¹²⁴ are identical or different from each other Also good.)

(In the above formula (21), R ^{118 to} R ¹²² are the same as the above 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, a phenyl group and a substituted phenyl group are shown)

(In the above-mentioned formula (XI), R ^{118 to} R ¹²² are the same as the above-mentioned formula (19). R ¹²⁷ and R ¹²⁸ each independently represent a hydrogen atom or a C 1-10 unsubstituted or substituted alkyl Group, a phenyl group and a substituted phenyl group are shown)

  As a benzoyl group shown by said Formula (22), the benzoyl phenylmethyl group shown, for example by following formula (23) is suitable.

(In the above formula (23), R ^{118 to} R ¹²² are the same as the above formula (19). R ¹³⁰ is a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, a phenyl group or a substituted phenyl group R ^{131 to} R ¹³⁵ each independently represent a hydrogen atom, a nitro group, a cyano group, a hydroxy group, a mercapto group, a halogen atom, an acetyl group, an allyl group, an alkyl group having 1 to 5 carbon atoms, or 1 carbon atom. 5 alkoxy group, an unsubstituted or substituted aryl group, .R ¹³¹ to R ¹³⁵ showing the aryloxy group is bonded to double bond or may form an aromatic or non-aromatic ring R ^{131 to} R ¹³⁵ and R ^{118 to} R ¹²² may combine to form a cyclic structure, and may include a hetero atom bond. May be.)

  As group which has the said heterocyclic structure, the coumarin derivative residue shown by following formula (24), the imide group shown by following formula (25), these substituted groups, etc. are mentioned.

(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 those similar to R ^{118 to} R ^{122 in} formula (19) above, and two or more of R ^{138 to} R ¹⁴² may combine to form a cyclic structure. ^When any of ^{138 to} R ¹⁴² is bonded to each other to form a cyclic structure, a structure in which a plurality of benzene rings are condensed, a benzene ring and a heterocyclic ring, a nonaromatic ring, or a functional group such as a carbonyl group is bonded A ring or the like may form a condensed structure or the like.)

(In the above 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, 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 the double bond or aromatic or non-aromatic ring which R ¹⁴³ and R ¹⁴⁴ are bonded to each other to form an imide group shown in the above formula is one or two forms May be

  Examples of the —OQ group wherein the photofunctional group Q is an o-nitrobenzyl group represented by the above formula (20-1) include, for example, (2,6-dinitrobenzyl) oxy group, (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 nitrobenzyloxy groups such as groups.

  Examples of the —OQ group wherein the photofunctional group Q is a p-nitrobenzyl group represented by the above formula (20-3) include, for example, (2,4-dinitrobenzyl) oxy group, (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) 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 And nitrobenzyloxy groups such as oxy group.

  As the -OQ group in which the photofunctional group Q is a benzyl group represented by the above formula (21), for example, 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- Mention may be made of benzyloxy groups such as an pyroxy group.

  As the -OQ group in which the photofunctional group Q is a benzoylphenylmethyl group represented by the above formula (23), for example, 1- (3,5-dimethoxybenzoyl) -1- (3,5-dimethoxyphenyl) methyloxy And benzoin oxy groups such as 1-hydroxy-1-phenylacetophenonoxy group, 1-benzoyl-1-phenylmethyloxy group, 1-benzoyl-1-hydroxy-1-phenylethyloxy group and the like.

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

  The —OQ group in which the photofunctional group Q is an imide group represented by the above formula (25) is, for example, a phthalimido oxy group, a succinimido oxy group, a succinimide imidooxy group, a maleic acid imidooxy group, a hexahydrophthalic acid imidooxy group Cyclohexanetetracarboxylic acid imide dioxy group, tetrabromo phthalic acid imide oxy group, tetrachloro phthalic acid imide oxy group, hetic acid imide oxy group, hemic acid imide oxy group, trimellitic acid imide oxy group, pyromellitic imide dioxy group, naphthalene tetracarboxylic acid imide dioxy group etc And an imidooxy group of

  Examples of the —OQ group in which the photofunctional group Q is an oxime residue represented by the above formula (18) include, for example, N- (1-phenylethylidene) aminooxy group, diphenylmethylideneaminooxy group, di (4-methoxy) group Phenyl) methylidene aminooxy group, N- (dimethyl methylidene) amino oxy group, N-(acetophenone methylidene) amino oxy group, N-[1-(2- naphthyl) ethylidene] amino oxy group, N-(cyclohexene Sylidene) aminooxy group, N- (fluorenylidene) aminooxy group, N- [di (nitrophenyl) methylidene] aminooxy group, N- (nitrofluorenylidene) aminooxy group, N- (dinitrofluorenylidene) And oxime oxy groups such as aminooxy group, N- (trinitrofluorenylidene) aminooxy group and the like. .

  In the above formulas (12) and (13), examples of the residue excluding the ZQ group include 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 and N-trimethoxysilylmethyl-N-phenylaminocarbonyl 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 group ] -1, 6-hex Diaminocarbonyl groups such as N-aminocarbonylcarbonyl group, N- (trimethoxysilylmethyl) ethylenediaminocarbonyl group, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediaminocarbonyl group; N- [3- ( And aminocarbonyl groups such as triaminocarbonyl groups such as trimethoxysilyl) propyl] diethylene triaminocarbonyl group.

Among the above-mentioned aminocarbonyl groups, an aminocarbonyl group having an amino group (-NH ₂ ) is preferable from the viewpoint of adhesiveness, and 3- (trimethoxysilyl) propylaminocarbonyl group, 3- (triethoxysilyl) propylaminocarbonyl Group, 3- (methyldimethoxysilyl) propylaminocarbonyl group, N- [3- (trimethoxysilyl) propyl] ethylenediaminocarbonyl group is more preferable, and from the adhesive property and curing property, 3- (trimethoxysilyl) propylaminocarbonyl The group 3- (triethoxysilyl) propylaminocarbonyl is most preferred.

  In said Formula (14), as an arylsulfonyl group, aromatic sulfonyl groups, such as 2-naphthalene sulfonyl group and p-toluene sulfonyl group, are mentioned, for example.

  In the above formula (14), examples of the residue other than the arylsulfonyl group include 3- (trimethoxysilyl) propylamino group, 3- (triethoxysilyl) propylamino group, 3- (triisopropoxysilyl) Propylamino, 3- (methyldimethoxysilyl) propylamino, 3- (methyldiethoxysilyl) propylamino, N- [3- (trimethoxysilyl) -2-methylpropyl] -N-ethylamino, 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) A monoamino group such as methyl-N-cyclohexylamino group, N-trimethoxysilylmethyl-N-phenylamino group, etc .; N- [3- (trimethoxysilyl) propyl] ethylenediamino group, N- [3- (methyldimethoxyne) 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 -(Trimethoxysilyl) propyl] diamino group such as ethylene diamino group; N- [3- (trimethoxy) Silyl) propyl] include triamino groups such as diethylene triamino group.

  In the above formula (15), examples of the residue other than the aryl oxime group include 3- (trimethoxysilyl) propylcarbonyl group, 3- (triethoxysilyl) propylcarbonyl group, 3- (triisopropoxysilyl) Examples thereof include carbonyl group such as propylcarbonyl group, 3- (methyldimethoxysilyl) propylcarbonyl group and 3- (methyldiethoxysilyl) propylcarbonyl group.

  In the above formula (16), as the trans-o-coumaric acid derivative residue, 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-) Trans-O-coumaric acid residues such as hydroxy-5-nitrophenyl) -1-propenyl group and (E) -2- (1-hydroxy-2-anthryl) -1-propenyl group can be mentioned.

  Although the compounding ratio of the said crosslinkable silicon group containing compound does not have a restriction | limiting in particular, 0.01-50.00 mass parts is preferable with respect to 100 mass parts of (A) crosslinkable silicon group containing organic polymers, and 1.00 -20.00 mass parts is more preferable, and 3.00-10.00 mass parts are further more 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 further contain a silane coupling agent, and in particular, epoxy group-containing silanes are preferred. The silane coupling agent acts as an adhesion promoter. Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) Epoxy group-containing silanes such as ethyltrimethoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltri Amino groups such as methoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane Containing silanes; N- (1,3-dimeth Ketimine-type silanes such as butylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine; γ-mercapto Mercapto-containing silanes such as propyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane; vinyls such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane and γ-acryloyloxypropylmethyldimethoxysilane -Type unsaturated group-containing silanes; chlorine-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanates-containing silanes such as γ-isocyanate propyltriethoxysilane and γ-isocyanate propylmethyldimethoxysilane; hexyl Examples of the alkylsilanes such as dimethoxysilane, hexyltriethoxysilane and decyltrimethoxysilane; phenyl group-containing silanes such as phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane; It is not limited to these. In addition, modified amino group-containing silanes in which the amino group is modified by reacting the amino group-containing silane with the epoxy group-containing compound, the isocyanate group-containing compound, and the (meth) acryloyl group-containing compound containing the silanes You may use.

  The amino group-containing silane acts as a silanol condensation catalyst, and the ketimine-type silanes form an amino group-containing silane in the presence of water, which acts as a silanol condensation catalyst. Therefore, it is preferable to use a silane coupling agent other than amino group-containing silanes and ketimine-type silanes. When amino group-containing silanes or ketimine-type silanes are used, they should be used with careful attention to the type and amount used as long as the purpose and effect of the present invention are achieved.

  As described above, the use of amino group-containing silanes and ketimine-type silanes may be limited in the present invention. However, when it is desirable to use amino group-containing silanes or ketimine-type silanes as an adhesion imparting agent, no compound having an amino group is generated before light irradiation, and amino group-containing silanes by light irradiation Can be used. As a compound which generate | occur | produces amino group containing silanes by light irradiation, the compound described in the synthesis example 1 of Unexamined-Japanese-Patent No. 2007-231235 can be mentioned. Moreover, the compound which generate | occur | produces amino group containing silanes by various light irradiation can be obtained by using the compound which has a crosslinkable silicon group as a raw material in the synthesis | combination of the compound which generate | occur | produces amines by light irradiation.

  Although the compounding ratio of the said silane coupling agent does not have a restriction | limiting in particular, 0.01-20 mass% is preferable in a composition, and 0.025-10 mass% is more preferable. These silane coupling agents may be used alone or in combination of two or more.

  The photosensitizer is preferably a carbonyl compound having a triplet energy of 225-310 kJ / mol, for example, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2 , 4-Diisopropylthioxanthone, isopropylthioxanthone, phthalimide, anthraquinone, 9, 10-dibutoxyanthracene, acetophenone, propiophenone, benzophenone, acyl naphthalene, 2 (acyl methylene) thiazoline, 3-acyl coumarin and 3,3'-carbonyl Examples include biscoumarin, perylene, coronene, tetracene, benzanthracene, phenothiazine, flavin, acridine, ketocoumarin, etc. Thioxanthone, 3-acyl coumarin, Beauty 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.

  Further, as a photosensitizer, an active energy ray cleaving type radical generator of a type which is cleaved by irradiation with an active energy ray to generate a radical is more preferable. The use of the active energy ray-cleavable radical generator cures much faster than the use of photosensitizers such as benzophenones and thioxanthones known as sensitizers for photobase initiators. It is possible to show the speed and to cure the photocurable composition of the present invention in a further short time after energy beam irradiation.

  Examples of the energy ray cleavable radical generator include arylalkyl ketones such as benzoin ether derivatives and acetophenone derivatives, oxime ketones, acyl phosphine oxides, S-phenyl thiobenzoate, titanocenes, and the like. Molecular weight derivatives are mentioned. Examples of commercially available cleavage type radical generators include 1- (4-dodecylbenzoyl) -1-hydroxy-1-methylethane, 1- (4-isopropylbenzoyl) -1-hydroxy-1-methylethane, 1- 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, benzyl dimethyl ketal, bis (cyclopentadienyl) -bis (2,6-difluoro-3-pyryl-phenyl) titanium, (η6-isopropylbenzene) )-(Η5-cyclopentadienyl) -iron (II) Xafluorophosphate, trimethylbenzoyldiphenyl phosphine oxide, bis (2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl) -phosphine oxide, bis (2,4,6-trimethylbenzoyl) -2, Examples include 4-dipentoxyphenyl phosphine oxide or bis (2,4,6-trimethyl benzoyl) phenyl-phosphine oxide and the like.

  Although the compounding ratio of a photosensitizer does not have a restriction | limiting in particular, 0.01-5 mass% is preferable in a composition, and 0.025-2 mass% is more preferable. These photosensitizers may be used alone or in combination of two or more.

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

  The photocurable composition of the present invention can further contain a diluent. By blending a diluent, physical properties such as viscosity can be adjusted. As the diluent, known diluents can be widely used, and there is no particular limitation. For example, saturated hydrocarbon solvents such as normal paraffin and isoparaffin, α such as Linearene dimer (trade name of Idemitsu Kosan Co., Ltd.) -Olefin derivatives, aromatic hydrocarbon solvents such as toluene and xylene, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, alcohol solvents such as diacetone alcohol, ethyl acetate, butyl acetate, amyl acetate, acetic acid Examples include various solvents such as ester solvents such as cellosolve, citric acid ester solvents such as acetyl triethyl citrate, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Reactive diluents having unsaturated groups may be used. By using a reactive diluent, not only the viscosity of the composition can be adjusted, but also the volatilization of the diluent from the cured product can be prevented, and the physical properties of the cured product can be adjusted. Specific examples of the reactive diluent include (meth) acrylic acid esters such as methyl (meth) acrylate and (poly) propylene glycol mono (meth) acrylic acid ester, 1-octene, 4-vinylcyclohexene, allyl acetate, 1,1-diacetoxy-2-propene, methyl 1-undecenoate, 8-acetoxy-1,6-octadiene and the like, but it is not limited thereto. Although the compounding ratio of a diluent does not have a restriction | limiting in particular, 0.01-20 mass% is preferable in a composition, and 0.025-10 mass% is more preferable. These diluents may be used alone or in combination of two or more.

  Examples of the plasticizer include phosphate esters such as tributyl phosphate and tricresyl phosphate, phthalate esters such as dioctyl phthalate, aliphatic monobasic acid esters such as glyce 57 phosphorus monooleyl ester, and adipine. Aliphatic dibasic acid esters such as dioctyl acid, polypropylene glycols, etc. may be mentioned. 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 preferable. The silicate is not particularly limited, and examples thereof include tetraalkoxysilanes and partial hydrolytic condensates thereof, and more specifically, tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, Tetraalkoxysilane (tetraalkyl silicate) such as methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, etc. And their partial hydrolytic condensates.

  A known curing catalyst can be widely used as the curing catalyst, and there is no particular limitation. Examples thereof include organic metal compounds and amines, and in particular, it is preferable to use a silanol condensation catalyst. Examples of the silanol condensation catalyst include stannas octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dibutyltin bistriethoxy silicate, dibutyltin distearate Organotin compounds such as dioctyltin dilaurate, dioctyltin diversatate, tin octylate and tin naphthenate; dialkyltin oxides such as dimethyltin oxide, dibutyltin oxide and dioctyltin oxide; reaction products of dibutyltin oxide and phthalate ester Titanates such as tetrabutyl titanate, tetrapropyl titanate, etc .; aluminum tris acetylacetonate, aluminum tris ethoxide Organoaluminum compounds such as acetoacetate and diisopropoxyaluminum ethylacetoacetate; Chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; organic acid lead such as lead octylate and lead naphthenate; bismuth octylate And bismuth of an organic acid such as bismuth neodecanoate and bismuth rosin acid; and other acidic catalysts and basic catalysts which are known as silanol condensation catalysts. However, depending on the amount of the organotin compound added, the toxicity of the resulting photocurable composition may be increased. In the present invention, the photobase of the component (B) and the fluorine compound of the component (C) act as a curing catalyst. Therefore, when using a curing catalyst other than the components (B) and (C), the purpose and effect of the present invention It is preferable to use in the range which can achieve.

  The method for producing the photocurable composition of the present invention is not particularly limited. For example, the components (A), (B), and (C) are compounded in predetermined amounts, and if necessary, other compounded substances It can be produced by blending and degassing and stirring. There is no particular limitation on the blending order of each component and other compounded substances, and it may be determined as appropriate.

  The photocurable composition of the present invention can be made into a one-component type or a two-component type, if necessary, but it can be suitably used particularly as a one-component type. The photocurable composition of the present invention is a photocurable composition which is cured by light irradiation, and can be cured at normal temperature (for example, 23 ° C.), and suitably used as a normal temperature photocurable composition. Although it is used, if necessary, curing may be promoted by heating as appropriate.

  The method for producing a cured product of the present invention can form a cured product by irradiating light to the photocurable composition of the present invention. The cured product of the present invention is a cured product formed by the method. Further, the method for producing the product of the present invention is characterized by producing using the photocurable composition of the present invention. The product of the present invention is a product produced by using the method, and can be suitably used for an electronic circuit, an electronic component, a building material, an automobile and the like.

  There are no particular restrictions on the conditions under which the photocurable composition of the present invention is irradiated with light, but when active energy rays are applied during curing, light rays such as ultraviolet rays, visible light, infrared rays, etc. may be used as active energy rays. Other than electromagnetic waves such as X-ray and γ-ray, electron beam, proton beam, neutron beam etc. can be used, but curing speed, availability and price of irradiation equipment, easy handling under sunlight or general lighting Curing by ultraviolet light or electron beam irradiation is preferable in view of properties and the like, and curing by ultraviolet light irradiation is more preferable. The ultraviolet light also includes g-ray (wavelength 436 nm), h-ray (wavelength 405 nm), i-ray (wavelength 365 nm), and the like. The active energy ray source is not particularly limited, but depending on the nature of the photobase generator to be used, for example, high pressure mercury lamp, low pressure mercury lamp, electron beam irradiation device, halogen lamp, light emitting diode, semiconductor laser, metal halide etc. Be

As irradiation energy, in the case of an ultraviolet-ray, for example, 10 to 20,000 mJ / cm ² is preferable, and 50 to 10,000 mJ / 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 , it will not only waste time and cost even if it is exposed to light more than necessary, it will damage the substrate There are times when

  When the photocurable composition of the present invention is used as an adhesive, the method of applying to the adherend is not particularly limited, but application methods such as screen printing, stencil printing, roll printing, spin coating, and dispenser It is preferably used. The thinner the coating thickness of the photocurable composition on the adherend, the more easily the effects of the present invention can be obtained, and it is 500 μm or less, preferably 200 μm or less, more preferably 100 μm or less, particularly preferably 50 μm or less.

  Further, in the present invention, there is no limitation on the timing of application and light irradiation of the photocurable composition on the adherend, and after the photocurable composition is irradiated with light, it is joined to the adherend to form a product. The product may be manufactured by applying the photocurable composition to an adherend and curing the composition by light irradiation.

  The photocurable composition of the present invention is a quick-curing type photocurable composition excellent in workability, and is particularly useful as a tacky / adhesive composition, and an adhesive, sealing material, adhesive, coating It can be suitably used as a material, potting material, paint, putty material, primer and the like. The photocurable composition of the present invention is, for example, a coating for moisture proofing or insulation of a mounted circuit board or the like, a coating agent used for coating a solar power generation panel or a peripheral portion of the panel, etc .; , Sealants for construction and industry, etc .; Sealants for construction and industry, etc .; Materials for electrical and electronic parts such as solar cell back surface sealants; Electrical insulation materials such as insulation covering materials for electric wires and cables; Adhesive materials; adhesives; elastic adhesives; contact adhesives etc. can be suitably used.

  EXAMPLES The present invention will be more specifically described below with reference to examples, but it is needless to say that these examples are exemplarily shown 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, unless otherwise specified. In the present invention, the molecular weight of the maximum frequency measured by GPC under the measurement conditions and converted to standard polyethylene glycol is referred to as number average molecular weight.
・ Analyzer: Alliance (made by Waters), type 2410 differential refraction detector (made by Waters), type 996 multi-wavelength detector (made by Waters), Milleniam data processor (made by Waters)
Column: Plgel GUARD + 5 μm Mixed-C x 3 (50 x 7.5 mm, 300 x 7.5 mm: manufactured by PolymerLab)
Flow rate: 1 mL / min Converted polymer: polyethylene glycol Measuring temperature: 40 ° C.
-Solvent at GPC measurement: THF

2) Measurement of NMR Measurement of NMR was performed using the following measuring device.
FT-NMR measuring apparatus: JNM-ECA 500 (500 MHz) manufactured by JEOL Ltd.

Synthesis Example 1
In a stirrer equipped with a thermometer, 589.4 parts by weight of polypropylene glycol (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., trade name: Diol-2000) is dehydrated, and then 4,4-diphenylmethane diisocyanate (MDI) 110. Six parts by weight were added, and reaction was performed at 70 to 90 ° C. for 3 hours under a nitrogen stream to obtain a urethane prepolymer A having an NCO / OH equivalent ratio of 1.5. 0.5 equivalent of 3-mercaptopropyltrimethoxysilane is reacted with urethane prepolymer A with respect to the NCO group of this urethane prepolymer A, and on average, one end has a trimethoxysilyl group at one end and an NCO group at the other end. A polymer was obtained. An equivalent amount of 4-hydroxybutyl acrylate is reacted with this polymer with respect to the NCO group of the obtained polymer to obtain a polymer having an average of trimethoxysilyl groups at one end and an acryloyloxy group at the other end. The

(Composition example 2)
An equivalent amount of 3-mercaptopropyltrimethoxysilane is reacted with urethane prepolymer A with respect to the NCO group of urethane prepolymer A obtained in Synthesis Example 1 to obtain a polymer having trimethoxysilyl groups at both ends on average. The

(Composition example 3)
An equivalent amount of 4-hydroxybutyl acrylate was reacted with the urethane prepolymer A with respect to the NCO group of the urethane prepolymer A obtained in Synthesis Example 1 to obtain a polymer having acryloyloxy groups at both ends on average.

Synthesis Example 4 Synthesis of Fluorinated Polymer In a new flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, a polyoxypropylene diol having a molecular weight of about 2,000 as an initiator and zinc hexacyanocobaltate -A polyoxypropylene diol having a hydroxyl value reduced molecular weight of 14500 and a molecular weight distribution of 1.3 obtained by reacting propylene oxide in the presence of a glyme complex catalyst was obtained. A methanol solution of sodium methoxide was added to the obtained polyoxypropylene diol, and methanol was distilled off under heating and reduced pressure to convert the terminal hydroxyl group of the polyoxypropylene diol to a sodium alkoxide to obtain a polyoxyalkylene polymer. .

Next, allyl chloride is reacted with the polyoxyalkylene polymer to remove unreacted allyl chloride, and purification is performed to obtain a polyoxyalkylene polymer having an allyl group at the end. Methyldimethoxysilane, which is a silicon hydride compound, is reacted with 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3% by weight with a polyoxyalkylene polymer having an allyl group at the end to cause methyldimethoxysilyl terminal A polyoxyalkylene polymer having a group was obtained.
As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer having a methyldimethoxysilyl group at an end by GPC, the peak top molecular weight was 15,000, and the molecular weight distribution was 1.3. According to the 1 H-NMR measurement, the number of terminal methyldimethoxysilyl groups was 1.7 per molecule.

In a flask equipped with a stirrer, nitrogen gas inlet tube, thermometer and reflux condenser, after degassing under reduced pressure, replace with nitrogen gas, charge 2.4 g of BF ₃ diethyl ether complex under nitrogen flow, add to 50 ° C. It 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 A4 and 5 g of toluene were placed. After stirring for 30 minutes at 23 ° C., the temperature was raised to 110 ° C. and stirring under reduced pressure was performed for 2 hours to remove toluene. In this container, 4.0 g of the mixture obtained earlier was slowly dropped under a nitrogen stream, and after completion of dropping, the reaction temperature was raised to 120 ° C., and the reaction was allowed to react for 30 minutes. After completion of the reaction, vacuum degassing was performed to remove the unreacted material. A polyoxyalkylene polymer having a fluorosilyl group at its end (hereinafter referred to as a fluorinated polymer) was obtained. The 1 H NMR spectrum of the obtained fluorinated polymer (measured in CDCl ₃ solvent using NMR 400 manufactured by Shimazu) was measured, and it was found that a peak corresponding to silylmethylene (-CH ₂ -Si) of the polymer as the raw material (M, 0.63 ppm) disappeared, and a broad peak appeared on the lower magnetic field side (0.7 ppm ̃).

Synthesis Example 5 Synthesis of Polyoxyalkylene-Based Polymer P1 Having Trimethoxysilyl Group at End Terminal In a flask equipped with a stirrer, nitrogen gas inlet tube, thermometer and reflux condenser, ethylene glycol is used as an initiator and zinc Propylene oxide was reacted in the presence of a hexacyanocobaltate-glyme complex catalyst to obtain polyoxypropylene triol. A methanol solution of sodium methoxide is added to the obtained polyoxypropylene triol, and the methanol is distilled off under heating and reduced pressure to convert the terminal hydroxyl group of polyoxypropylene triol into a sodium alkoxide to obtain a polyoxyalkylene polymer M1. The

  Next, allyl chloride is reacted with polyoxyalkylene polymer M1 to remove unreacted allyl chloride, and purification is performed to obtain a polyoxyalkylene polymer having an allyl group at an end. A trimethoxysilane that is a silicon hydride compound is reacted with a polyoxyalkylene polymer having an allyl group at this end by adding 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt%, and trimethoxysilyl at the end. A polyoxyalkylene polymer P1 having a group was obtained.

As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer P1 having a trimethoxysilyl group at an end by GPC, the peak top molecular weight was 25,000, and the molecular weight distribution was 1.3. The terminal trimethoxysilyl group was 1.7 per molecule according to 1 H-NMR measurement.

Synthesis Example 6 Synthesis of Polyoxyalkylene Polymer P2 Having Trimethoxysilyl Group at End Terminal In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, ethylene glycol is used as an initiator and zinc Propylene oxide was reacted in the presence of a hexacyanocobaltate-glyme complex catalyst to obtain polyoxypropylene triol. A methanol solution of sodium methoxide is added to the obtained polyoxypropylene triol, and methanol is distilled off under heating and reduced pressure to convert the terminal hydroxyl group of the polyoxypropylene triol into a sodium alkoxide to obtain a polyoxyalkylene polymer M2. The

  Next, allyl chloride is reacted with polyoxyalkylene polymer M2 to remove unreacted allyl chloride, and purification is performed to obtain a polyoxyalkylene polymer having an allyl group at an end. A trimethoxysilane that is a silicon hydride compound is reacted with a polyoxyalkylene polymer having an allyl group at this end by adding 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt%, and trimethoxysilyl at the end. A polyoxyalkylene polymer P2 having a group was obtained.

  As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer P2 having a trimethoxysilyl group at the end by GPC, the peak top molecular weight was 12000, and the molecular weight distribution was 1.3. The terminal trimethoxysilyl group was 1.7 per molecule according to 1 H-NMR measurement.

Synthesis Example 7 Synthesis of (Meth) acrylic Polymer P3 Having Trimethoxysilyl Group In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 40.00 g of ethyl acetate, methyl methacrylate 70.00 g, 30.00 g of 2-ethylhexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 12.00 g of 3-methacryloxypropyltrimethoxysilane (trade name: KBM 503, manufactured by Shin-Etsu Chemical Co., Ltd.), and a metal catalyst The contents of the flask were heated to 80 ° C. while introducing nitrogen gas into the flask. Then, 4.30 g of 3-mercaptopropyltrimethoxysilane fully purged with nitrogen gas was added at once in the flask under stirring. After 4.30 g of 3-mercaptopropyltrimethoxysilane was added, heating and cooling were performed for 4 hours so that the temperature of the contents in the flask under stirring could be maintained at 80 ° C. Furthermore, 4.30 g of 3-mercaptopropyltrimethoxysilane fully purged with nitrogen gas was additionally added to the flask under stirring for 5 minutes. The reaction was carried out for 4 hours while further cooling and heating so that the temperature of the contents in the flask under stirring could be maintained at 90 ° C. after the addition of 4.30 g of the total amount of 3-mercaptopropyltrimethoxysilane. . After a total of 8 hours and 5 minutes of reaction, the temperature of the reaction product is returned to room temperature, and 20.00 g of a benzoquinone solution (95% THF solution) is added to the reaction product to terminate the polymerization, thereby having a trimethoxysilyl group (meta ) An acrylic polymer P3 was obtained. The peak top molecular weight was 4000, and the molecular weight distribution was 2.4. The trimethoxysilyl group contained by H1-NMR measurement was 2.00 per molecule.

Synthesis Example 8
The flask was charged with 15.3 g of 2-nitrobenzyl alcohol and 344 parts of toluene, and refluxed at about 113 ° C. for 60 minutes. Then, it was added dropwise 20.5 parts of 3-isocyanate propyl trimethoxysilane, and stirred for 5 hours, aminosilane by light represented by _{o-NO 2 C 6 H 4} CH 2 OCONHCH 2 CH 2 CH 2 Si (OCH 3) 3 To give a compound that generates.

Example 1
In a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser at the compounding ratio shown in Table 1, (A) a crosslinkable silicon group and a photoradical polymerizable vinyl in the molecule The fluorinated polymer obtained in Synthesis Example 4 was added as an organic polymer having a group, and a silicon compound having a (C) Si-F bond, and the mixture was stirred and dissolved. Also. (B) The photobase generator and propylene carbonate are placed in another 100 mL eggplant flask at the mixing ratio shown in Table 1, stirred and dissolved, and the entire solution is poured into the previously taken 300 mL flask, The mixture was stirred under reduced pressure to obtain a photocurable composition.

In Table 1, the compounding quantity of each compounding substance is shown by g, and the details of other compounding substances are as follows.
* 1) 2- (Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, manufactured by BASF, trade name “IRGACURE379EG”.
* 2) Kyoeisha Chemical Co., Ltd. product name, "light acrylate DPM-A".

1) Adhesiveness evaluation A photocurable composition is apply | coated so that it may become width 5 mm * length 25 mm * thickness 200micrometer using a glass rod to adherends (acrylic resin board), UV irradiation (irradiation conditions: UV) -LED365nm, intensity: 1000mW / cm ^2, the accumulated amount of light: 3000mJ / cm ²⁾ was carried out. Immediately after the irradiation, an adherend (acrylic resin plate) was laminated, pressed with a small eyeball clip, and aged for 15 minutes at 23 ° C. and 50% RH. After the curing, the measurement was performed at a test speed of 50 mm / min according to the tensile shear adhesive strength test method of JIS K 6850 rigid adherend.

(Comparative example 1)
(A) 30 g of an organic polymer having a crosslinkable silicon group and 30 g of an organic polymer having a photopolymerizable vinyl group, instead of the organic polymer 60 g having a crosslinkable silicon group and a photoradical polymerizable vinyl group in the molecule A photocurable composition was obtained in the same manner as in Example 1 except for the use, and the adhesion strength was measured. The results are shown in Table 1.

Claims (12)

(A) An organic polymer having a crosslinkable silicon group represented by the following general formula (3) and a photoradical polymerizable vinyl group in the molecule (with the exception of those having a Si-F bond),
(B) Photobase generator, and (C) Silicon compound having (C1) Si-F bond, and / or (C2) boron trifluoride, complex of boron trifluoride, fluorinating agent and polyvalent fluoro compound At least one fluorine-containing compound selected from the group consisting of alkali metal salts of
The photocurable composition characterized by including.
However, in the general formula (3), R ¹ is a triorganosiloxy group represented by a hydrocarbon group having 1 to 20 carbon atoms , R ₃ SiO— ( R is a hydrocarbon group having 1 to 20 carbon atoms ), Or at least one hydrogen atom on the 1- to 3-position carbon atom is a halogen, -OR ⁴¹ , -NR ⁴² R ⁴³ , -N = R ⁴⁴ , -SR ⁴⁵ , a perfluoroalkyl having 1 to 20 carbon atoms Group or a hydrocarbon group having 1 to 20 carbon atoms substituted with a cyano group is shown, and when two or more R ¹ are present, they may be the same or different. R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁵ each represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms , R ⁴⁴ represents a divalent substituted or unsubstituted C 1 to 20 carbon atom It is a hydrocarbon group. X represents a hydroxyl group or a hydrolyzable group, and when two or more X are present, they may be the same or different. a is an integer of 1, 2 or 3;   The photocurable composition according to claim 1, wherein the photobase generator (B) is a photolatable tertiary amine.   (D) Further containing a compound capable of generating an aminosilane compound having one or more amino groups selected from the group consisting of a primary amino group and a secondary amino group and a crosslinkable silicon group by light. The photocurable composition according to claim 1 or 2, characterized in that   The photocurable composition according to any one of claims 1 to 3, further comprising a silane coupling agent (excluding one having a Si-F bond).   The photocurable composition according to any one of claims 1 to 4, which is a photocurable adhesive composition.   A method for producing a cured product, comprising forming a cured product by irradiating light to the photocurable composition according to any one of claims 1 to 4.   A cured product formed by the method according to claim 6.   The manufacturing method of the product characterized by manufacturing using the photocurable composition of any one of Claims 1-4.   A product manufactured by the method according to claim 6.   A product manufactured using the method of claim 8.   An article comprising the photocurable composition according to any one of claims 1 to 4 as an adhesive. The product which uses the photocurable composition of any one of Claims 1-4 as a coating agent.