JP6520134B2 - Photocurable composition - Google Patents

Description

  The present invention relates to a photocurable composition, and more particularly to a photocurable composition having excellent 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. Further, further improvement in adhesion performance such as adhesion has been desired.

JP 2001-172514 A Japanese Patent Application Laid-Open No. 2004-099579

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

  The present inventors have found that use of the base-growing silicon compound described in Patent Document 2 causes no rust and cures in a short time, resulting in a photocurable composition having excellent adhesiveness. . That is, the present invention relates to the following photocurable composition.

(1) A photocurable composition comprising (A) an organic polymer having a crosslinkable silicon group, (B) a photobase generator, and (C) a base proliferating aminosilane
(2) Furthermore, silicon compounds having (D) (D1) Si-F bond, and / or (D2) boron trifluoride, complexes of boron trifluoride, alkali metal salts of fluorinating agents and polyvalent fluoro compounds A photocurable composition according to (1), which comprises one or more fluorine-based compounds selected from the group consisting of
(3) The photocurable composition as described in (1) or (2), wherein the (B) photobase generator is a photolatent tertiary amine.
(4) The organic polymer having the crosslinkable silicon group (A) is selected from the group consisting of the crosslinkable silicon group-containing polyoxyalkylene polymer and the crosslinkable silicon group-containing (meth) acrylic polymer 1 The photocurable composition according to any one of (1) to (3), which is a species or more.

  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 adhesiveness.

  The crosslinkable silicon group-containing organic polymer (A) is not particularly limited as long as it is an organic polymer having a crosslinkable silicon group, but it is an organic polymer whose main chain is not polysiloxane and various types other than polysiloxane are used. Those having a main chain skeleton of are preferred in that they do not contain or generate low molecular weight cyclic siloxanes which cause contact failure.

  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 of the organic polymer (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.

In the above formula (1), R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 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. shows the 20 hydrocarbon group, R ¹ there are two or more Come, they may be the same or may be 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.

  The organic polymer having a crosslinkable silicon group may be linear or branched, and the number average molecular weight thereof is about 500 to 100,000, more preferably 1,000 to 50,000 in terms of polystyrene in GPC. 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.

  In order to obtain a rubbery cured product exhibiting high strength, high elongation and low elastic modulus, the number of crosslinkable silicon groups contained in the organic polymer is preferably 0.8 or more in average per polymer molecule. 1.0 or more, more preferably 1.1 to 5 should be present. When the number of crosslinkable silicon groups contained in the molecule is less than 0.8 on average, the curability becomes insufficient and it becomes difficult to exhibit good rubber elastic behavior. The crosslinkable silicon group may be present at the end of the main chain or at the end of the side chain of the organic polymer molecular chain, or at both of them. In particular, when the crosslinkable silicon group is only at the end of the main chain of the molecular chain, the effective network length of the organic polymer component contained in the finally formed cured product becomes long, so high strength and high elongation can be obtained. And a rubber-like cured product having a low elastic modulus can be easily obtained.

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.

  The introduction of the crosslinkable silicon group into the polyoxyalkylene polymer is carried out in the polyoxyalkylene polymer having a functional group such as an unsaturated group, a hydroxyl group, an epoxy group or an isocyanate group in the molecule. The reaction can be performed by reacting a compound having a functional group having reactivity and a crosslinkable silicon 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 reacted with a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to hydrosilylate or mercapitize, and the crosslinkable silicon group The method of obtaining the polyoxyalkylene type polymer which has these 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 the end with a compound having an isocyanate group and a crosslinkable silicon group, or a polyoxyalkylene system having an isocyanate group at the end A method of reacting a polymer with a compound having an active hydrogen group such as a hydroxyl group or an amino group and a crosslinkable silicon group can be mentioned. When an isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group can be easily obtained.

  As specific examples of polyoxyalkylene polymers having a crosslinkable silicon group, JP-B Nos. 45-36319 and 46-12154, JP-A Nos. 50-156599, 54-6096, and 55-13767 can be mentioned. No. 57-164123, Japanese Examined Patent Application No. 3-2450, Japanese Patent Application Laid-Open Nos. 2005-213446, 2005-306891, International Publication Patent No. WO2007-040143, US Patents 3,632,557, 4,345,053, What is proposed by each gazette of the said 4,960,844 grade can be mentioned.

  The polyoxyalkylene polymer having the crosslinkable silicon 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.

  Examples of the method for producing a saturated hydrocarbon polymer having a crosslinkable silicon group include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, and the like. Although it describes in each specification etc. of the Hei 1-197509, patent gazette 2539445, patent gazette 2873395, Unexamined-Japanese-Patent No. 7-53882, etc., it is not limited in particular in these.

  The above-mentioned saturated hydrocarbon polymers having a crosslinkable silicon 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.

  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 Silicon-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, cyclohexene Maleimide-based monomers such as 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, cinnamon Vinyl esters such as vinyl acid; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; and 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 together with other (meth) acrylic acid monomers as needed. By using a group-containing (meth) acrylic acid ester-based monomer in combination, the number of silicon groups in the (meth) acrylic acid ester-based polymer (A) can be controlled. Particularly preferred is a methacrylic acid ester-based polymer comprising a methacrylic acid ester monomer because of good adhesion. In addition, in the case of lowering the viscosity, imparting flexibility, and imparting tackiness, it is preferable to appropriately use an acrylic acid ester monomer. 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 the radical polymerization method, radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator, or introducing a reactive silyl group at a controlled position such as an end Possible 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 and having a crosslinkable functional group at the molecular chain end at a high rate, It is preferred to use a controlled radical polymerization method.

  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, a reaction using a thiol compound having a reactive silyl group, and a reaction using a thiol compound having a reactive silyl group and a metallocene compound (JP-A-2001-40037) are also suitable.

  The (meth) acrylic acid ester-based polymer having the crosslinkable silicon group may be used alone or in combination of two or more.

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

JP-A-59-122541 discloses a method of producing an organic polymer formed by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylate polymer having a crosslinkable silicon group. Japanese Patent Application Laid-Open No. 63-112642, Japanese Patent Application Laid-Open No. 6-172631, Japanese Patent Application Laid-Open No. 11-116763 and the like, but the present invention is not particularly limited thereto. A preferred embodiment has a crosslinkable silicon group and a molecular chain substantially having the following general formula (5):
^{_{-CH 2 -C (R 3) (}} COOR 4) - ··· (5)
Wherein R ³ is a hydrogen atom or a methyl group, and R ⁴ is an alkyl group having 1 to 5 carbon atoms. A (meth) acrylic acid ester monomer unit and a compound represented by the following general formula (6):
^{_{-CH 2 -C (R 3) (}} COOR 5) - ··· (6)
(In the formula, R ³ is the same as above, R ⁵ is an alkyl group having 6 or more carbon atoms), and a crosslinkable silicon group is formed of a copolymer composed of (meth) acrylic acid ester monomer units It is the method of blending and manufacturing the polyoxyalkylene type polymer which it has.

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

The R ^{5 in the} general formula (6) has, for example, 6 or more carbon atoms such as 2-ethylhexyl group, lauryl group, tridecyl group, cetyl group, stearyl group and behenyl group, usually 7 to 30, preferably 8 to 20 And long-chain alkyl groups of In addition, the alkyl group of R ⁵ may be independent or may be a mixture of two or more, as in the case of R ⁴ .

  The molecular chain of the (meth) acrylic acid ester copolymer substantially consists of monomer units of the formulas (5) and (6), and "substantially" as used herein means the copolymer It means that the sum total of the monomer unit of Formula (5) and Formula (6) which exists in more than 50 mass%. The total of the monomer units of the formulas (5) and (6) is preferably 70% by mass or more. The mass ratio of the monomer unit of the formula (5) to the monomer unit of the formula (6) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40.

  Examples of monomer units other than the formula (5) and the formula (6) which may be contained in the copolymer (hereinafter also referred to as other monomer units) include α such as acrylic acid and methacrylic acid. Amides such as acrylamide, methacrylamide, N-methylol acrylamide and N-methylol methacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether and the like Monomers containing an amino group of the following; and other monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

  A crosslinkable silicon group used in a method of producing an organic polymer formed by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylate polymer having a crosslinkable silicon group (meth ) As the acrylic ester polymer, for example, having a crosslinkable silicon group described in JP-A-63-112642, and having a molecular chain substantially having (1) an alkyl group having 1 to 8 carbon atoms (Meta) ) A known (meth) acrylic acid ester copolymer containing an acrylic acid alkyl ester monomer unit and a (meth) acrylic acid alkyl ester monomer unit having (2) an alkyl group having 10 or more carbon atoms (Meth) acrylic acid ester type copolymers of the following can also be used.

  600-10,000 are preferable, as for the number average molecular weight of the said (meth) acrylic acid ester type polymer, 600-5,000 are more preferable, and 1,000-4,500 are more preferable. By setting the number average molecular weight to the above range, the compatibility with the polyoxyalkylene polymer having a crosslinkable silicon group can be improved. The (meth) acrylate polymers may be used alone or in combination of two or more. The compounding ratio of the crosslinkable silicon group-containing polyoxyalkylene polymer to the crosslinkable silicon group-containing (meth) acrylic acid ester polymer is not particularly limited, but the (meth) acrylic acid ester-based polymer It is preferable that the said (meth) acrylic-ester type polymer is in the range of 10-60 mass parts with respect to a total of 100 mass parts of a polymer and the said polyoxyalkylene type polymer, More preferably, it is 20- It is in the range of 50 parts by mass, more preferably in the range of 25 to 45 parts by mass. When the amount of the (meth) acrylic acid ester-based polymer is more than 60 parts by mass, the viscosity becomes high and the workability is deteriorated.

  Organic polymers formed by blending a crosslinkable silicon group-containing saturated hydrocarbon polymer and a crosslinkable silicon group-containing (meth) acrylic acid ester copolymer are disclosed in JP-A-1-168764 and JP-A-2000- Although it is proposed by the 186176 gazette etc., it is not limited in particular in these.

  Furthermore, as a method for producing an organic polymer obtained by blending a (meth) acrylic acid ester copolymer having a crosslinkable silicon group, another method may be used in the presence of an organic polymer having a crosslinkable silicon group ( A method of polymerizing the (meth) acrylic acid ester type monomer can be used. This manufacturing method is specifically disclosed in JP-A-59-78223, JP-A-59-168, 14, JP-A-60-228516, JP-A-60-228517, etc. It is not limited to these.

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

  In the present invention, the (B) photobase generator generates a base upon irradiation with light, and the base acts as a curing catalyst for the (A) organic polymer having a crosslinkable silicon group. 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. In addition, although a photo-acid generator is known as a compound which generate | occur | produces the curing catalyst of the organic polymer which has a crosslinkable silicon group by the effect | action of light, it replaces with (B) photo-base generator of this invention. Even if the agent is used, the adhesion of the cured product becomes inferior because the growth reaction of the (D) base proliferating aminosilane does not proceed.

  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 and the adhesiveness of the obtained cured product tends to be good.

  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.

  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 EG), 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 (C) base proliferating aminosilane used in the present invention is a base proliferating amine compound and a compound having a crosslinkable silicon group at an amine residue (a compound which forms an amine compound having a crosslinkable silicon group when it is decomposed) Can be illustrated. As such a compound, 9-fluorenyl methyl ester of a carbamic acid having a crosslinkable silicon group (C ₁₃ H ₉ CH ₂ OCON R ¹⁰ R ¹¹ , wherein R ¹⁰ and R ^{11 each} represent a hydrogen atom or a hydrocarbon group) It is an organic group, and at least one of R ¹⁰ and R ¹¹ is an organic group such as a hydrocarbon group having a crosslinkable silicon group), 2-arylsulfonyl ethyl ester of a carbamic acid having a crosslinkable silicon group (ArSO ₂ CH ₂ CH ₂ OCONR ¹⁰ R ¹¹ , wherein Ar is an aromatic group which may have a substituent, R ¹⁰ and R ¹¹ are as defined above, and 3-nitropentane-carbamic acid having a crosslinkable silicon group 2-yl ester _{(CH 3 CH 2 CH (NO} 2) CH (CH 3) OCONR 10 R 11, wherein, R ^10, R ¹¹ are as defined above), and the like.

The crosslinkable silicon group in the carbamic acid having a crosslinkable silicon group is the same as the crosslinkable silicon group in (A). Specific examples of the carbamic acid having a crosslinkable silicon group are 3-trimethoxysilylpropylcarbamic acid ((CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOOH) and 3-triethoxysilylpropylcarbamic acid ((C ₂ H ₅₎ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOOH) can be mentioned.

  A specific example of a 9-fluorenyl methyl ester of carbamic acid having a crosslinkable silicon group and a method for producing the same are described in Patent Document 2, and (3-aminopropyl) methyldialkoxysilane or (3-aminopropyl) tri Compounds prepared by the condensation reaction of alkoxysilanes with chloroformic acid 9-fluorenyl methyl ester, or alternatively, (3-isocyanatopropyl) methyldialkoxysilane or (3-isocyanatopropyl) trialkoxysilane with 9-fluorene Mention may be made of the compounds which are also produced by addition reactions with nylmethyl alcohol. In addition, 2-arylsulfonyl ethyl ester of carbamic acid having a crosslinkable silicon group and 3-nitropentane-2-yl ester of carbamic acid having a crosslinkable silicon group are also 9-fluorenylmethyl of carbamic acid having a crosslinkable silicon group It can be obtained by a method similar to that of the ester.

  The photocurable composition of the present invention is a silicon compound having (D) (D1) Si-F bond, and / or (D2) boron trifluoride, a complex of boron trifluoride, a fluorinating agent and a polyvalent fluoro It is preferred to use 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 (D).

  In the present invention, the silicon compound having (D1) Si-F bond acts as a curing catalyst for the compound having (A) crosslinkable silicon group. As the silicon compound having the (D1) 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 (D1) Si-F bond is a compound having a fluorosilyl group represented by the following formula (8) such as fluorosilanes represented by the following formula (7) (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 (7)
(In the formula (7), each R ⁸⁰ independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ⁹⁰ SiO— (wherein each R ⁹⁰ 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 (8)
(In formula (8), R ⁸⁰ and d are respectively the same as formula (7), X ′ is 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 (7) include known fluorosilanes represented by the formula (7), 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 (8), as the hydrolyzable group represented by X ′ in the formula (8), 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 (8) is, for example, an alkyl group such as a methyl group or an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, 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 above formula (8) 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 (8), 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 (7), 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 .; 8) High-molecular compounds such as fluorinated polysiloxanes having a fluorosilyl group shown by 8) are mentioned, and fluorosilanes shown by the above-mentioned formula (7), or by a formula (8) at the end of the main chain or side chain Preferred are polymers having a fluorosilyl group.

The fluorosilanes represented by the formula (7) and the compound having a fluorosilyl group represented by the formula (8) may use commercially available reagents or may be synthesized from starting compounds. The synthesis method is not particularly limited, but a compound having a crosslinkable silicon group represented by the following formula (9) and a fluorinating agent are known methods (for example, Organometallics 1996, p. 15, 2478 (Ishikawa et al.), Etc. The compound obtained by making it react using (iii) is used suitably.
-SiR ⁸⁰ _3-q X ' _q (9)
(In formula (9), R ⁸⁰ and X ′ are respectively the same as formula (8), and q is any of 1 to 3.)

  As a crosslinkable silicon group shown by said Formula (9), halo silyl groups, such as an alkoxy silyl group, a siloxane bond, a chloro silyl group, a 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 (8) is preferable. Examples Although fluoro silyl group is incorporated in the main chain of the _{polymer, -Si (CH 3) F -} , - Si (C 6 H 5) F -, - SiF 2 -, and the like ≡SiF .

  The fluorinated polymer is a single polymer 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 of 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 (9) 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.

  Although the compounding ratio of the (D1) Si-F bond-containing silicon compound is not particularly limited, when using a polymer compound having a number average molecular weight of 3000 or more such as a fluorinated polymer, it has (A) a crosslinkable silicon group 0.01-80 mass parts is preferable with respect to 100 mass parts of compounds, 0.01-30 mass parts is more preferable, 0.05-20 mass parts is further more preferable. Low molecular weight compound having a fluorosilyl group having a number average molecular weight of less than 3,000 (for example, fluorosilanes represented by the formula (7), low molecular weight organosilicon compounds having a fluorosilyl group represented by the formula (8), 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 (D2) 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.

  Although the compounding ratio of the (D2) fluorine-based compound is not particularly limited, it is 0.001 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. 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.

  When using one or more selected from the group consisting of the silicon compound having the (D1) Si-F bond, which is the component (D), and the (D2) fluorine-based compound in the photocurable composition of the present invention, Either (D1) or (D2) may be used alone, or both may be used in combination. Among these, it is particularly preferable to use a silicon compound having a (D1) Si-F bond.

  The photocurable composition of the present invention may further contain a silane coupling agent, and in particular, epoxy group-containing silanes are preferred.

  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.

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

  In the curable composition of the present invention, in addition to the (B) photobase generator, by light, at least one amino group selected from the group consisting of a primary amino group and a secondary amino group is formed. It may further contain a crosslinkable silicon group-containing compound. 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 photocurable composition of the present invention may, if necessary, be a photosensitizer, an extender, a plasticizer, a water absorbent, a curing catalyst, a physical property modifier to improve tensile properties, a reinforcing agent, a colorant, Various additives such as flame retardants, anti-sagging agents, antioxidants, anti-aging agents, ultraviolet light absorbers, solvents, perfumes, pigments, dyes and the like may be added.

  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.

  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 glycerin monooleyl ester, and dioctyl adipate. And aliphatic dibasic acid esters, polypropylene glycols and the like. These may be used alone or in combination of two or more.

  As the water absorbent, the above-mentioned silane coupling agent and silicate are 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 (D) act as a curing catalyst. Therefore, when using a curing catalyst other than the component (B) and the component (D) 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 are added. 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 Synthesis of Polyoxyalkylene-Based Polymer A1 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 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 A1 having a group was obtained.

  As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A1 having a trimethoxysilyl group at the 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 2 Synthesis of Polyoxyalkylene-Based Polymer A2 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 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 A2 having a group was obtained.

  As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A2 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 3 Synthesis of (Meth) acrylic Polymer A3 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 A3 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 4 Synthesis of Base-Proliferating Aminosilane According to Example 3 of Patent Document 2, 9-fluorenylmethyl alcohol (C ₁₃ H ₉ CH ₂ OH) and 3-isocyanatopropyltriethoxysilane (ONCCH ₂ CH ₂ CH) _{2 Si (OC 2 H 5)} 3) as a base proliferating aminosilane compound is reacted with N- (3- triethoxysilylpropyl) carbamate 9-fluorenylmethyl ester _{(C 13 H 9 CH 2 OCONHCH} 2 CH 2 CH ₂ Si (OC ₂ H ₅ ) ₃ ) was obtained.

Synthesis Example 5 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 ̃).

(Example 1, Example 2)
(A) Organic polymer having a crosslinkable silicon group in its molecule, (D) fluorine-based compound in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet and water-cooled condenser at the blending ratio shown in Table 1 A tin-based curing catalyst and an aminosilane compound were added and stirred. Also, 5 parts by mass of (B) photo base generator, (C) base proliferating aminosilane, and propylene carbonate solvent are placed in another 100 mL eggplant flask, stirred and dissolved, and 300 mL of the entire solution is weighed out. The mixture was charged into a flask and stirred under reduced pressure to obtain a photocurable composition. The adhesive strength of this photocurable composition, tack free time without light irradiation and tack free time after light irradiation were measured. The tack free time when light is not irradiated is for evaluating the storage stability of the composition, and the tack free time after light irradiation is for evaluating the curing rate. Details of the measurement method are shown below.

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) Tin-based catalyst, manufactured by Nitto Kasei Co., Ltd., trade name "Neostan U830".

1) Adhesion evaluation A photocurable composition is applied to an adherend (aluminum (alumite sulfate treated)) using a glass rod so as to have a thickness of 100 μm, and UV irradiation (irradiation conditions: LED 365 nm lamp, illuminance: 1000 mW / cm ² and integrated light quantity: 1000 mJ / cm ² ) were performed. Immediately after the irradiation, the adherend (aluminum (alumite sulfate treated)) was bonded in an area of 25 mm × 25 mm, pressed with an eyeball clip, and cured for 7 days in an environment of 23 ° C. and 50% RH. After the curing, the adhesive strength was measured at a test speed of 50 mm / min according to the tensile shear adhesive strength test method of JIS K 6850 rigid adherend. The results are shown in Table 1.

2) Evaluation of stability of non-irradiated photocurable composition The photocurable composition is poured into a cylindrical container (polypropylene) having a diameter of 20 mm and a height of 7 mm so that the thickness is 7 mm, and 23 ° C. in a dark room. The time until the surface was not sticky by finger touch in an environment of 50% RH was measured. The longer the time it takes to cure and become non-greasy, the better the stability.

3) Evaluation of usable time after light irradiation Pour the photocurable composition into a cylindrical container (polypropylene) 20 mm in diameter and 7 mm in height so that the thickness is 7 mm, UV irradiation (irradiation conditions: LED 365 nm lamp, illuminance) 1000 mW / cm ² and integrated light quantity: 1000 mJ / cm ² ) were performed. Thereafter, in a dark room under an environment of 23 ° C. and 50% RH, a time (tack free time) until the surface was not sticky by finger touch was measured every 30 seconds. The longer the tack free time, the longer the pot life after light irradiation. However, if it is too long, the curing time of the composition becomes long, so the amount of catalyst and light irradiation time can be changed to adjust the pot life according to the purpose.

(Comparative example 1-3)
A composition was prepared and measured in the same manner as in Example 1 except that the composition was changed as shown in Table 1. The results are shown in Table 1.

  As shown in Table 1, the photocurable composition of the present invention exhibits excellent adhesion performance and has sufficient tack free time before light irradiation and tack free time after light irradiation. It is clear that the quality is excellent.

Claims (4)

(A) an organic polymer having a crosslinkable silicon group,
(B) a photobase generator and
(C) 9-fluorenyl methyl ester of carbamic acid having a crosslinkable silicon group, 2-arylsulfonyl ethyl ester of carbamic acid having a crosslinkable silicon group, or carbamine having a crosslinkable silicon group as base proliferating aminosilane 3-nitropentan-2-yl ester of acid ,
The photocurable composition characterized by including .   Furthermore, a group consisting of (D) (D1) a silicon compound having a Si—F bond, and / or (D2) boron trifluoride, a complex of boron trifluoride, a fluorinating agent and an alkali metal salt of a polyvalent fluoro compound The photocurable composition according to claim 1, comprising one or more fluorine-based compounds selected from   The photocurable composition according to claim 1 or 2, wherein the (B) photobase generator is a photolatable tertiary amine.   The organic polymer having the crosslinkable silicon group (A) is at least one selected from the group consisting of a crosslinkable silicon group-containing polyoxyalkylene polymer and a crosslinkable silicon group-containing (meth) acrylic polymer The photocurable composition according to any one of claims 1 to 3, characterized in that