JP2015086341A - Photocurable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fast-curing type photocurable composition that can be cured in a short time even with a small integrated quantity of light and has excellent workability and storage stability.SOLUTION: A photocurable composition comprises (A) a crosslinkable silicon group-containing organic polymer, and (B) an organic silicon compound that generates a silanol group by light. Preferably, the photocurable composition further comprises (C) a curing catalyst.

Description

  The present invention relates to a photocurable composition, and more particularly, to a photocurable composition that is fast-curing even with a low integrated light quantity and can be cured in a short time.

  An organic polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a silicon-containing group that can be crosslinked by forming a siloxane bond (hereinafter also referred to as “crosslinkable silicon group”) is obtained at room temperature. It is also known that the rubber has a property that it can be cross-linked by formation of a siloxane bond accompanied by hydrolysis reaction of a cross-linkable silicon group due to moisture or the like to obtain a rubber-like cured product. Among these polymers having a crosslinkable silicon group, organic polymers whose main chain skeleton is a polyoxyalkylene polymer or a (meth) acrylate polymer are used for sealing materials, adhesives, paints, etc. Widely used.

  The curable composition used for sealing materials, adhesives, paints, etc. and the rubber-like cured product obtained by curing have various properties such as curability, adhesiveness, storage stability, mechanical properties such as modulus, strength, and elongation. Properties are required, and many studies have been made on organic polymers containing crosslinkable silicon groups. In recent years, rapid curing is required in various fields such as an electronic component / electronic device assembling field, but in the case of a moisture-curing adhesive, there is a problem that a bonding time after application is shortened.

  On the other hand, as a photocrosslinkable composition using an organic polymer containing a crosslinkable silicon group, Patent Document 1 discloses a polymer having two or more hydrolyzable silyl groups in one molecule, and the polymer by light irradiation. A photocrosslinkable composition comprising a compound that crosslinks a compound, and a compound containing a compound that generates an acid or a base upon irradiation with light as a compound that crosslinks a polymer by light irradiation. The crosslinkable composition is illustrated (patent document 1, claims 1-3).

  However, in the composition described in Patent Document 1, when a photoacid generator is used as a compound that crosslinks a polymer by light irradiation, there is a problem that rust is generated, and a photobase is used as a compound that crosslinks a polymer by light irradiation. When the generating agent is used, there is a problem that the efficiency is low and the irradiation time and the curing require a long time.

JP 2001-172514 A

  An object of the present invention is to provide a fast-curing photocurable composition that can be cured in a short time even with a low integrated light amount and is excellent in workability and storage stability.

  In order to solve the above problems, the photocurable composition of the present invention contains (A) a crosslinkable silicon group-containing organic polymer, and (B) an organosilicon compound that generates a silanol group by light. Features.

The photocurable composition of the present invention preferably further comprises (C) a curing catalyst.
The (C) curing catalyst is preferably an organometallic compound.

  The photocurable composition of the present invention preferably further comprises (D) a photosensitizer.

  According to the present invention, it is a photocurable composition that does not cure when not irradiated with UV, and is cured by UV irradiation. It can be cured in a short time even with a low integrated light amount, has excellent storage stability, and is suitable. It is possible to provide a photocurable composition having fast curability while securing the bonding possible time. In addition, the photocurable composition of the present invention is not cured immediately after UV irradiation depending on the UV irradiation conditions, and can be cured after a certain period of time. When the photocurable composition is used as an adhesive, it can be adhered after being applied for a certain period of time after the adhesive is applied.

  Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.

  The photocurable composition of the present invention contains (A) a crosslinkable silicon group-containing organic polymer, and (B) an organosilicon compound that generates a silanol group by light.

  The (A) crosslinkable silicon group-containing organic polymer is not particularly limited as long as it is an organic polymer having a crosslinkable silicon group, but is an organic polymer in which the main chain is not polysiloxane, and other than polysiloxane. Those having the main chain skeleton are preferable in that they do not contain or generate a low-molecular cyclic siloxane that causes contact failure.

  Specifically, polyoxyalkylene heavy polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Copolymer; ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymer of butadiene and acrylonitrile and / or styrene, polybutadiene, isoprene or butadiene A copolymer of acrylonitrile and styrene, etc., a hydrocarbon polymer such as a hydrogenated polyolefin polymer obtained by hydrogenating these polyolefin polymers; a dibasic acid such as adipic acid and a glycol; Polyester polymers obtained by condensation or ring-opening polymerization of lactones; (meth) acrylic acid ester 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, styrene, etc .; graft polymers obtained by polymerizing vinyl monomers in the organic polymers; polysulfides Polymer: 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-aminolaurolacta by condensation polymerization A polyamide polymer such as nylon 12 by ring-opening polymerization of the above, a copolymer nylon having two or more components among the above-mentioned nylons; for example, a polycarbonate polymer produced by condensation polymerization of bisphenol A and carbonyl chloride, diallyl Examples thereof include phthalate polymers.

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

  The crosslinkable silicon group of the (A) organic polymer used in the present invention is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. As the crosslinkable silicon group, for example, a group represented by the following general formula (1) is preferable.

In the formula (1), R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon An aralkyl group of 7 to 20; a triorganosiloxy group represented by R ¹ ₃ SiO— (R ¹ is as defined above), or at least one hydrogen atom on the 1st to 3rd carbon atoms is halogenated , -OR ⁴¹ , -NR ⁴² R ⁴³ , -N = R ⁴⁴ , -SR ⁴⁵ (R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁵ are each a hydrogen atom or a substituted or unsubstituted carbon atom having 1 to 20 carbon atoms. A hydrogen group, R ⁴⁴ is a divalent substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.), A C 1 substituted with a perfluoroalkyl group having 1 to 20 carbon atoms, or a cyano group -20 hydrocarbon groups and when two or more R ¹ are present They may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2, respectively. Further, p in the following general formula (2) need not be the same. p shows the integer of 0-19. However, a + (sum of b) ≧ 1 is satisfied.

  The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and a + (sum of b) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different. The number of silicon atoms forming the crosslinkable silicon group may be one or two or more, but in the case of silicon atoms linked by a siloxane bond or the like, there may be about 20 silicon atoms.

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

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

Specific examples of R ¹ include alkyl groups such as methyl and ethyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups, and R ¹ ₃ SiO—. And triorganosiloxy group. Of these, a methyl group is preferred.

  It does not specifically limit as a hydrolysable group shown by said X, What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable, and an alkoxy group, an amide group, and an aminooxy group are more preferable. An alkoxy group is particularly preferred from the viewpoint of mild hydrolysis and easy handling. Among the alkoxy groups, those having a smaller number of carbon atoms have higher reactivity, and the reactivity increases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group. Although it can be selected according to the purpose and use, a methoxy group or an ethoxy group is usually used.

Specific examples of the crosslinkable silicon group include trialkoxysilyl groups [—Si (OR) ₃ ] such as trimethoxysilyl group and triethoxysilyl group, dialkoxy such as methyldimethoxysilyl group and methyldiethoxysilyl group. silyl groups [-SiR ¹ (OR) _2] can be mentioned, trimethoxysilyl group is more preferable. Here, R is an alkyl group such as a methyl group or an ethyl group.

  Further, the crosslinkable silicon group may be used alone or in combination of two or more. The crosslinkable silicon group can be present in the main chain, the side chain, or both.

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

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

  In order to obtain a rubber-like cured product having high strength, high elongation, and low elastic modulus, the average number of crosslinkable silicon groups contained in the organic polymer is 0.8 or more in one molecule of the polymer. Is 1.0 or more, more preferably 1.1 to 5. If the number of crosslinkable silicon groups contained in the molecule is less than 0.8 on average, the curability becomes insufficient and it becomes difficult to develop good rubber elastic behavior. The crosslinkable silicon group may be at the end of the main chain or the side chain of the organic polymer molecular chain, or at both ends. 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 is increased, so that the strength and elongation are high. It becomes easy to obtain a rubber-like cured product exhibiting a low elastic modulus.

The polyoxyalkylene polymer is essentially a polymer having a repeating unit represented by the following general formula (4).
-R ² -O- ··· (4)
In the general formula (4), R ² is a linear or branched alkylene group having 1 to 14 carbon atoms, 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) include
_{-CH 2 O -, - CH 2} CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H 5) O -, - CH 2 C (CH 3) 2 O-, _{-CH 2 CH 2 CH 2 CH 2} O-
Etc. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, when used as a sealant or the like, a polymer comprising a propylene oxide polymer as a main component is preferable because it is amorphous or has a relatively low viscosity.

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

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

  The introduction of a crosslinkable silicon group into a polyoxyalkylene polymer can be performed on a polyoxyalkylene polymer having a functional group such as an unsaturated group, a hydroxyl group, an epoxy group or an isocyanate group in the molecule. The reaction can be carried out by reacting a compound having a reactive functional group and a crosslinkable silicon group (hereinafter referred to as a polymer reaction method).

  As a specific example of the polymer reaction method, a hydrosilane or mercapto compound obtained by allowing a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to act on an unsaturated group-containing polyoxyalkylene polymer to form a crosslinkable silicon group The method of obtaining the polyoxyalkylene type polymer which has this can be mention | raise | lifted. An unsaturated group-containing polyoxyalkylene polymer is obtained by reacting an organic polymer having a functional group such as a hydroxyl group with an organic compound having an active group and an unsaturated group that are reactive with the functional group, A polyoxyalkylene polymer containing can be obtained.

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

  Specific examples of the polyoxyalkylene polymer having a crosslinkable silicon group include JP-B Nos. 45-36319, 46-12154, JP-A Nos. 50-156599, 54-6096, and 55-13767. No. 57-164123, JP-B No. 3-2450, JP-A No. 2005-213446, No. 2005-306891, International Publication No. WO2007-040143, US Pat. No. 3,632,557, No. 4,345,053, The ones proposed in the publications such as 4,960,844 can be listed.

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

  The saturated hydrocarbon polymer is a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring, and the polymer constituting the skeleton thereof is (1) ethylene, propylene, 1-butene, isobutylene, etc. (2) Diene compounds such as butadiene and isoprene are homopolymerized, or copolymerized with the olefin compounds. After that, it can be obtained by a method such as hydrogenation. However, isobutylene polymers and hydrogenated polybutadiene polymers are easy to introduce functional groups at the terminals, control the molecular weight, and the number of terminal functional groups. Therefore, an isobutylene polymer is particularly preferable.

  Those whose main chain skeleton is a saturated hydrocarbon polymer have characteristics of excellent heat resistance, weather resistance, durability, and moisture barrier properties.

  In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, or may be a copolymer with other monomers, but the repeating unit derived from isobutylene is 50 from the viewpoint of rubber properties. Those containing at least mass% are preferred, those containing at least 80 mass% are more preferred, and those containing from 90 to 99 mass% are particularly preferred.

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

  Examples of the method for producing a saturated hydrocarbon polymer having a crosslinkable silicon group include, for example, Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, Japanese Patent Publication No. 63-254149, Japanese Patent Publication No. 64-22904, Although described in each specification of Kaihei 1-197509, Japanese Patent Publication No. 2539445, Japanese Patent Publication No. 2873395, and Japanese Patent Application Laid-Open No. 7-53882, it is not particularly limited thereto.

  The above saturated hydrocarbon polymer 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 (meth) 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, tetramethylpiperidinyl (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, etc. Alicyclic (meth) acrylic acid ester monomers; phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, parac Milphenoxyethylene glycol (meth) acrylate, hydroxyethylated o-phenylphenol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxydiethyl Aromatic (meth) acrylic acid ester monomers such as ethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and phenylthioethyl (meth) acrylate; 2-methoxy (meth) acrylate, (meth) acrylic acid (Meth) acrylate 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 monomers such as tildimethoxymethylsilane and methacryloyloxymethyldiethoxymethylsilane; (meth) acrylic acid derivatives such as ethylene oxide adducts of (meth) acrylic acid; (meth) acrylic Trifluoromethyl methyl acid, 2-trifluoromethyl ethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl (meth) acrylate, (meth ) Perfluoroethyl acrylate, trifluoromethyl (meth) acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, (meth) 2-perfluorohexylethyl acrylate , Fluorine-containing (meth) acrylate monomers such as 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate.

  In the (meth) acrylic acid ester polymer, other monomers such as vinyl monomers can be copolymerized together with the (meth) acrylic acid ester monomer. Examples of the vinyl monomer include styrene monomers such as styrene, vinyl toluene, α-methyl styrene, 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 and dialkyl esters of maleic acid; fumaric acid, monoalkyl 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, cyclohexyl Maleimide monomers such as maleimide; Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, cinnamon Examples thereof include vinyl esters such as vinyl acid; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol.

  These may be used alone or a plurality of these may be copolymerized. Especially, the polymer which consists of a styrene-type monomer and a (meth) acrylic-acid type monomer from the physical property of a product etc. is preferable. More preferred is a (meth) acrylic polymer comprising an acrylate monomer and a methacrylic acid ester monomer, and particularly preferred is an acrylic polymer comprising an acrylate monomer. More preferably, it is a (meth) acrylic acid ester polymer using one or two or more (meth) acrylic acid alkyl ester monomers and optionally using other (meth) acrylic monomers as well. By using the group-containing (meth) acrylic acid ester monomer together, the number of silicon groups in the (meth) acrylic acid ester polymer (A) can be controlled. A methacrylic acid ester polymer composed of a methacrylic acid ester monomer is particularly preferred because of its good adhesiveness. Moreover, when performing viscosity reduction, a softness | flexibility provision, and tackiness provision, it is suitable to use an acrylate ester monomer timely. In the present specification, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  In applications such as general construction, a butyl acrylate monomer is more preferred from the viewpoint that physical properties such as low viscosity of the blend, low modulus of the cured product, high elongation, weather resistance, and heat resistance are required. On the other hand, in applications that require oil resistance, such as automobile applications, copolymers based on ethyl acrylate are more preferred. This polymer mainly composed of ethyl acrylate is excellent in oil resistance but tends to be slightly inferior in low temperature characteristics (cold resistance). Therefore, in order to improve the low temperature characteristics, a part of ethyl acrylate is converted into butyl acrylate. It is also possible to replace it. However, as the ratio of butyl acrylate is increased, its good oil resistance is impaired. Therefore, for applications requiring oil resistance, the ratio is preferably 40% or less, and more preferably 30% or less. More preferably. It is also preferred to use 2-methoxyethyl acrylate or 2-ethoxyethyl acrylate in which oxygen is introduced into the side chain alkyl group in order to improve the low temperature characteristics without impairing oil resistance. However, since heat resistance tends to be inferior due to the introduction of an alkoxy group having an ether bond in the side chain, when heat resistance is required, the ratio is preferably 40% or less. In accordance with various uses and required purposes, it is possible to obtain suitable polymers by changing the ratio in consideration of required physical properties such as oil resistance, heat resistance and low temperature characteristics. For example, although not limited, examples of excellent physical property balance such as oil resistance, heat resistance, and low temperature characteristics include ethyl acrylate / butyl acrylate / -2-methoxyethyl acrylate (40-50 / 20 by mass ratio). To 30/30 to 20). In the present invention, these preferable monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, it is preferable that these preferable monomers are contained in a mass ratio of 40% or more. .

  In the present invention, the method for obtaining the (meth) acrylic acid ester polymer is not particularly limited, and known polymerization methods (for example, JP-A-63-112642, JP-A-2007-230947, JP-A-2001-40037). And a synthesis method described in JP-A-2003-313397), and a radical polymerization method using a radical polymerization reaction is preferable. As the radical polymerization method, a radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator or a reactive silyl group is introduced at a controlled position such as a terminal. Possible controlled radical polymerization methods are mentioned. However, a polymer obtained by a normal free radical polymerization method using an azo compound or a peroxide as a polymerization initiator has a problem that the molecular weight distribution is generally as large as 2 or more and the viscosity is increased. Yes. Therefore, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio. It is preferable to use a controlled radical polymerization method.

  Controlled radical polymerization methods include free radical polymerization methods and living radical polymerization methods using chain transfer agents having specific functional groups, such as atom transfer radical polymerization (ATRP), addition-cleavage transfer. Living radical polymerization methods such as a reaction (Reversible Addition-Fragmentation chain Transfer; RAFT) polymerization method (JP-A Nos. 2005-232419 and 2006-291073) are more preferable. A reaction using a thiol compound having a crosslinkable silicon group and a reaction using a thiol compound having a crosslinkable silicon group and a metallocene compound (Japanese Patent Laid-Open No. 2001-40037) are also suitable.

In atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position), or a halogenated sulfone. It is preferable that a dil compound or the like is used as an initiator. In order to obtain a vinyl polymer having at least two alkenyl groups capable of hydrosilylation in one molecule, an organic halide having two or more starting points or a halogenated sulfonyl compound is used as an initiator. It is preferable to use as.
There is no restriction | limiting in particular as a (meth) acrylic-type monomer and vinyl-type monomer used in atom transfer radical polymerization, All the (meth) acrylic-type monomers and vinyl-type monomer which were illustrated can be used suitably.

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

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

A method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group is disclosed in JP-A-59-122541. Although proposed in Japanese Laid-Open Patent Publication No. 63-112642, Japanese Laid-Open Patent Publication No. 6-172631, and Japanese Laid-Open Patent Publication No. 11-116763, the invention is not particularly limited thereto. Preferable specific examples include a crosslinkable silicon group and a molecular chain substantially having the following general formula (5):
^{_{-CH 2 -C (R 3) (}} COOR 4) - ··· (5)
(Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group having 1 to 8 carbon atoms), and a (meth) acrylate monomer unit represented by the following general formula (6):
—CH ₂ —C (R ³ ) (COOR ⁵ ) — (6)
(Wherein R ³ is the same as described above, and R ⁵ represents an alkyl group having 10 or more carbon atoms) A copolymer composed of a (meth) acrylic acid ester monomer unit is represented by a crosslinkable silicon group. It is a method of blending and producing a polyoxyalkylene polymer.

R ^{4 in the} general formula (5) is, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a 2-ethylhexyl group, etc. More preferably, 1-2 alkyl groups are mentioned. The alkyl group of R ⁴ may alone, or may be a mixture of two or more.

R ^{5 in the} general formula (6) is, for example, a long-chain alkyl having 10 or more carbon atoms such as lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group, etc., usually 10-30, preferably 10-20. Group. Incidentally, as with the alkyl group for R ⁵ is a R ^4, alone may or may be a mixture of two or more.

  The molecular chain of the (meth) acrylic acid ester-based copolymer is substantially composed of monomer units of the formulas (5) and (6), and the term “substantially” here refers to the copolymer. It means that the total of the monomer units of the formula (5) and the formula (6) present therein exceeds 50% by mass. The total of the monomer units of the formula (5) and the formula (6) is preferably 70% by mass or more. The abundance ratio of the monomer unit of the formula (5) and the monomer unit of the formula (6) is preferably 95: 5 to 40:60, more preferably 90:10 to 60:40 in terms of mass ratio.

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

  Having a crosslinkable silicon group used in a method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group (meta ) As an acrylate polymer, for example, it has a crosslinkable silicon group described in JP-A No. 63-112642, and the molecular chain substantially has (a1) an alkyl group having 1 to 8 carbon atoms (meta (Meth) acrylic acid ester-based copolymers containing an acrylic acid alkyl ester monomer unit and (a2) a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 10 or more carbon atoms These (meth) acrylic acid ester copolymers can also be used.

The molecular chain of the acrylic copolymer preferably contains a total of 50% by mass or more of the monomer unit (a1) and the monomer unit (a2). It is more preferable that the total of the monomer units is 70% by mass or more. The abundance ratio of (a1) to (a2) is preferably (a1) / (a2) = 90/10 to 20/80, more preferably 70/30 to 30/70 in terms of mass ratio. When the mass ratio of (a1) / (a2) is in the range of 90/10 to 20/80, the transparency can be improved.
The acrylic copolymer may contain monomer units other than (a1) and (a2). As the monomer unit other than (a1) and (a2), for example, the other monomer units described above in the description of the (meth) acrylic acid ester-based copolymer can be used in the same manner.

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

  Organic polymers formed by blending a saturated hydrocarbon polymer having a crosslinkable silicon group and a (meth) acrylic acid ester copolymer having a crosslinkable silicon group are disclosed in JP-A-1-168774 and JP-A-2000-. Although it is proposed in Japanese Patent No. 186176, etc., it is not particularly limited thereto.

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

  When two or more kinds of polymers are blended and used, a saturated hydrocarbon polymer having a crosslinkable silicon group and / or a crosslink with respect to 100 parts by mass of the polyoxyalkylene polymer having a crosslinkable silicon group. It is preferable to use 10-200 mass parts of (meth) acrylic acid ester-type polymer which has a crystalline silicon group, and it is more preferable to use 20-80 mass parts.

  Although the compounding quantity of (A) crosslinkable silicon group containing organic polymer in the photocurable composition of this invention does not have a restriction | limiting in particular, 20 mass%-99 mass% in conversion of solid content may be contained in a composition. Preferably, 50 mass% to 95 mass% is contained, more preferably 70 mass% to 95 mass%.

  The (B) organosilicon compound that generates a silanol group by light may be any compound as long as it generates a silanol group by light. For example, an SiTQ group (T is O or S, Q Represents an optical functional group), and an organosilicon compound represented by the following formula (I) is more preferable.

In the formula (I), R ^{11 to} R ¹³ may be the same or different, and are each a hydrogen atom, a halogen atom, a vinyl group, an allyl group, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms. Represents an alkoxy group having 1 to 10 carbon atoms, an unsubstituted or substituted aryl group, an aryloxy group, and a siloxy group, Q represents a photofunctional group, m, n, and r are 0 ≦ m, n, r ≦ 3, An integer satisfying the condition of 1 ≦ m + n + r ≦ 3 is represented.

  In the formula (I), examples of the halogen atom include a chlorine atom and a bromine atom. Examples of the unsubstituted or substituted alkyl group having 1 to 10 carbon atoms (or 1 to 5 carbon atoms) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a tert-butyl group, and an n-pentyl group. Chloromethyl group, chloroethyl group, fluoromethyl group, cyanomethyl group and the like. As a C1-C10 (or C1-C5) alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, n-butoxy group etc. are mentioned, for example. Examples of the unsubstituted or substituted aryl group include a phenyl group, a p-methoxyphenyl group, a p-chlorophenyl group, and a p-trifluoromethylphenyl group. Examples of the aryloxy group include a phenoxy group.

  The organosilicon compound may be a compound having a Si—O—Q group in the above formula (I) as a terminal group and a main chain composed of a group represented by the following formula (II).

In the formula (II), t represents 0 or an integer of 1 or more, R ¹¹ and R ¹² have the same meaning as described above, Z and Y may be the same or different, and each represents oxygen. Represents an atom, an alkylene group, an aryldiyl group, or the like;

Examples of the photofunctional group include a known group that decomposes by light, and are not particularly limited. For example, an o-nitrobenzyl group represented by the following formula (III), a benzyl group represented by the following formula (IV), A coumarin derivative residue represented by the following formula (V), a benzoylphenylmethyl group represented by the following formula (VI), an oxime residue represented by the following formula (VII), a ketone group represented by the following formula (VIII), An imide group represented by the formula (IX), a trans-o-coumaric acid derivative residue represented by the following formula (X), an —OR ¹⁴ group (that is, the compound represented by the formula (I) is an organic compound having a peroxysilyl group. .R ¹⁴ of the silicon compound is a hydrogen atom, an alkyl group or an aryl group, a substituted or unsubstituted 1 to 10 carbon atoms.) or a substituted these groups were can be mentioned, o- nitrobenzyl group Preferred. Further, groups in the photofunctional group may be bonded to each other to form a cyclic structure.

(In the formula (III), R ²¹ and R ²² may be the same or different and each represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or a substituted phenyl group. , R ^{23 to} R ²⁶ may be the same or different and are each a hydrogen atom, a nitro group, a cyano group, a hydroxy group, a mercapto group, a halogen atom, an acetyl group, an allyl group, or an alkyl group having 1 to 5 carbon atoms. A group, an alkoxy group having 1 to 5 carbon atoms, an unsubstituted or substituted aryl group, and an aryloxy group, and any of R ^{21 to} R ²⁶ may be bonded to each other to form a cyclic structure, and k is 1 or 2 and k is 2, the plurality of R ²¹ and R ²² may be the same or different.)

(In the formula (IV), R ¹⁰¹ and R ¹⁰² may be the same or different and each represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or a substituted phenyl group. R ^{103 to} R ¹⁰⁷ may be the same or different and are each a hydrogen atom, a nitro group, a cyano group, a hydroxy group, a mercapto group, a halogen atom, an acetyl group, an allyl group, or an alkyl having 1 to 5 carbon atoms. Group, an alkoxy group having 1 to 5 carbon atoms, an unsubstituted or substituted aryl group, and an aryloxy group, and any of R ^{101 to} R ¹⁰⁷ may be bonded to each other to form a cyclic structure.)

(In the formula (V), R ¹¹¹ and R ¹¹² may be the same or different and each represents a hydrogen atom or a substituent, and R ^{113 to} R ¹¹⁷ may be the same or different. well, each represent a hydrogen atom or a substituent, may form two or more ring structure by bonding with the R ¹¹³ ~R ^117.)

(In the formula (VI), R ³⁰ represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, a phenyl group or a substituted phenyl group, and R ^{31 to} R ⁴⁰ may be the same or different. Each may be a hydrogen atom, nitro group, cyano group, hydroxy group, mercapto group, halogen atom, acetyl group, allyl group, alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, unsubstituted or substituted. An aryl group or an aryloxy group is shown, and any of R ^{30 to} R ⁴⁰ may be bonded to each other to form a cyclic structure.)

(In the formula (VII), R ⁴¹ represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, a phenyl group or a substituted phenyl group, and R ^{42 to} R ⁴⁶ may be the same or different. Each may be a hydrogen atom, nitro group, cyano group, hydroxy group, mercapto group, halogen atom, acetyl group, allyl group, alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, unsubstituted or substituted. An aryl group or an aryloxy group is shown, and any of R ^{41 to} R ⁴⁶ may be bonded to each other to form a cyclic structure.)

(In the formula (VIII), R ⁵⁰ and R ⁵¹ may be the same or different and each represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or a substituted phenyl group. R ^{52 to} R ⁵⁶ may be the same or different and are each a hydrogen atom, a nitro group, a cyano group, a hydroxy group, a mercapto group, a halogen atom, an acetyl group, an allyl group, or an alkyl having 1 to 5 carbon atoms. Group, an alkoxy group having 1 to 5 carbon atoms, an unsubstituted or substituted aryl group, and an aryloxy group, and any of R ^{51 to} R ⁵⁶ may be bonded to each other to form a cyclic structure.)

(In the formula (IX), R ^{61 to} R ⁶⁴ may be the same or different and are each a hydrogen atom, a nitro group, a cyano group, a hydroxy group, a mercapto group, a halogen atom, an acetyl group, an allyl group, An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an unsubstituted or substituted aryl group, and an aryloxy group, and any one of R ^{61 to} R ⁶⁴ is bonded to each other to form a cyclic structure; May be good.)

(In the formula (X), R ^{71 to} R ⁷⁷ may be the same or different, and each is a hydrogen atom, nitro group, cyano group, hydroxy group, mercapto group, halogen atom, acetyl group, allyl group, An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an unsubstituted or substituted aryl group, and an aryloxy group, and any of R ^{71 to} R ⁷⁷ are bonded to each other to form a cyclic structure; May be good.)

  In the organosilicon compound having the SiTQ group, examples of the residue excluding the TQ group include a triphenylsilyl group, a t-butylmethylphenylsilyl group, a diphenylmethylsilyl group, a dimethylphenylsilyl group, and tri (2-chloroethyl). ) Silyl group, tri (p-trifluoromethylphenyl) silyl group, triethylsilyl group, trimethylsilyl group, silyl group such as vinylmethylphenylsilyl group, 2-chloroethylphenylsilylidene group, t-butylphenylsilylidene group, Diethylsilylidene group, diphenylsilylidene group, dimethylsilylidene group, vinylphenylsilylidene group, methylphenylsilylidene group, 1,1,3,3,5,5-hexaphenyltrisiloxane-1,5-diyl group 1,1,3,3,5,5-hexamethyltrichiro Silylidene groups such as sun-1,5-diyl group, 1,1,3,3-tetraphenylsiloxane-1,3-diyl group, 1,4-phenylenedimethylsilyl group, 1,4-xylylenedimethylsilyl group , Phenylsilylidine groups, methylsilyridine groups, ethylsilyridine groups, vinylsilyridine groups, t-butylsilyridine groups, and the like.

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

  Examples of the -OQ group in which the photofunctional group Q is a benzyl group represented by the formula (IV) include 3,5-dimethoxybenzyloxy group and [1- (3,5-dimethoxyphenyl) -1-methylethyl ] Oxy group, 9-anthrylmethyloxy group, 9-phananthrylmethyloxy group, 1-pyrenylmethyloxy group, [1- (anthraquinone-2-yl) ethyl] oxy group, 9-phenylxanthene-9- Examples thereof include benzyloxy groups such as an yloxy group.

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

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

  Examples of the —OQ group in which the photofunctional group Q is an oxime residue represented by the formula (VII) include N- (1-phenylethylidene) aminooxy group, diphenylmethylideneaminooxy group, and di (4-methoxy). And oximeoxy groups such as phenyl) methylideneaminooxy group.

  Examples of the —OQ group in which the photofunctional group Q is an imide group represented by the formula (IX) include imideoxy groups such as a phthalimidooxy group and a succinimideoxy group.

  Examples of the -OQ group in which the photofunctional group Q is a trans-o-coumaric acid derivative residue represented by the formula (X) include (E) -2- (2-hydroxyphenyl) ethenylcarbonyloxy group, (E) -2- (2-hydroxyphenyl) -1-propenylcarbonyloxy group, (E) -2- (2-hydroxyphenyl) -1-propenylcarbonyloxy group, (E) -2- (2-hydroxy Phenyl) -2-phenylethenylcarbonyloxy group, (E) -2- (2-hydroxy-4,5-methylenedioxyphenyl) ethenylcarbonyloxy group, (E) -2- (2-hydroxy-4) , 5-Dimethoxyphenyl) -1-propenylcarbonyloxy group, (E) -2- (2-hydroxy-5-nitrophenyl) -1-propenylcarbonyloxy group (E) -2- (1-hydroxy-2-anthryl) -1- trans-O- coumaric acid residue such as propenyloxy carbonyloxy group.

  Specific examples of the organosilicon compound in which Q in the formula (I) is an o-nitrobenzyl group represented by the above formula (III) include, for example, trimethyl (o-nitrobenzyloxy) silane, dimethylphenyl (o- Nitrobenzyloxy) silane, diphenylmethyl (o-nitrobenzyloxy) silane, triphenyl (o-nitrobenzyloxy) silane, vinylmethylphenyl (o-nitrobenzyloxy) silane, t-butylmethylphenyl (o-nitrobenzyl) Oxy) silane, triethyl (o-nitrobenzyloxy) silane, tri (2-chloroethyl) -o-nitrobenzyloxysilane, tri (p-trifluoromethylphenyl) -o-nitrobenzyloxysilane, trimethyl [α- ( o-nitrophenyl) -o-nitrobenzyloxy] Orchid, dimethylphenyl [α- (o-nitrophenyl) -o-nitrobenzyloxy] silane, methylphenyldi [α- (o-nitrophenyl) -o-nitrobenzyloxy] silane, triphenyl (α-ethyl- o-nitrobenzyloxy) silane, trimethyl (3-methyl-2-nitrobenzyloxy) silane, dimethylphenyl (3,4,5-trimethoxy-2-nitrobenzyloxy) silane, triphenyl (4,5,6- Trimethoxy-2-nitrobenzyloxy) silane, diphenylmethyl (5-methyl-4-methoxy-2-nitrobenzyloxy) silane, triphenyl (4,5-dimethyl-2-nitrobenzyloxy) silane, vinylmethylphenyl ( 4,5-dichloro-2-nitrobenzyloxy) silane, triphenyl ( 2,6-dinitrobenzyloxy) silane, diphenylmethyl (2,4-dinitrobenzyloxy) silane, triphenyl (3-methoxy-2-nitrobenzyloxy) silane, vinylmethylphenyl (3,4-dimethoxy-2-) Dinitrobenzyloxy) silane, dimethyldi (o-nitrobenzyloxy) silane, vinylphenyldi (o-nitrobenzyloxy) silane, t-butylphenyldi (o-nitrobenzyloxy) silane, diethyldi (o-nitrobenzyloxy) Silane, 2-chloroethylphenyldi (o-nitrobenzyloxy) silane, diphenyldi (o-nitrobenzyloxy) silane, diphenyldi (3-methoxy-2-nitrobenzyloxy) silane, diphenyldi (3,4- Dimethoxy-2-nitrobenzyloxy ) Silane, diphenyldi (2,6-dinitrobenzyloxy) silane, diphenyldi (2,4-dinitrobenzyloxy) silane, methyltri (o-nitrobenzyloxy) silane, phenyltri (o-nitrobenzyloxy) silane, p-bis (o-nitrobenzyloxydimethylsilyl) benzene, 1,1,3,3-tetraphenyl-1,3-di (o-nitrobenzyloxy) siloxane, 1,1,3,3,5,5 -Hexaphenyl-1,5-di (o-nitrobenzyloxy) siloxane, silicon compound produced | generated by reaction of SiCl containing silicone resin and o-nitrobenzyl alcohol, etc. are mentioned.

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

  The photocurable composition of the present invention preferably further comprises (C) a curing catalyst. As the curing catalyst, known curing catalysts can be widely used, and are not particularly limited. Examples thereof include organometallic compounds and amines, and organometallic compounds are preferable.

  Examples of the organometallic compound include metal atoms such as titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, aluminum, zirconium, alkoxy groups, substituted or unsubstituted phenoxy groups, acyloxy groups, A complex in which an organic group such as a β-diketonato group or an o-carbonylphenolate group is bonded is preferable, and an organic aluminum compound is more preferable because the photocuring rate is effectively increased.

  In the organic group, examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group, and a gentoxy group. Examples of the substituted or unsubstituted phenoxy group include a phenoxy group, an o-methylphenoxy group, an o-methoxyphenoxy group, a p-nitrophenoxy group, and a 2,4-dimethylphenoxy group. Examples of the acyloxy group include an acetate group, a propionate group, an iopropionate group, a butyrate group, a stearato group, an ethylacetoacetate group, a propylacetoacetate group, a butylacetoacetate group, a diethylmalolato group, and a dibivaloylmethanato group. Is mentioned. Examples of the β-diketonato group include acetylacetonato group, trifluoroacetylacetonato group, hexafluoroacetylacetonato group,

Etc. Examples of the o-carbonylphenolate group include a salicylaldehyde group.

  Examples of the organoaluminum compound include trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, trisphenoxyaluminum, trisparamethylphenoxyaluminum, isopropoxydiethoxyaluminum, trisbutoxyaluminum, trisacetoxyaluminum, trisstearatoaluminum. , Trisbutyrate aluminum, trispropionate aluminum, trisisopropionate aluminum, trisacetylacetonatoaluminum, tristrifluoroacetylacetonatoaluminum, trishexafluoroacetylacetonatoaluminum, trisethylacetoacetoaluminum, tris (n-propyl Acetoacetato) aluminum, tris (i o-propylacetoacetate) aluminum, tris (n-butylacetoacetate) aluminum, trissalicylaldehyde aluminum, trisdiethylmalonatoaluminum, trispropylacetoacetiumaluminum, trisbutylacetoacetoaluminum, trisdipivalo Ilmethanato aluminum, diacetylacetonatodipivaloylmethanato aluminum,

Etc. These may be used alone or in combination of two or more.

  The blending ratio of the (C) curing catalyst is not particularly limited, but is preferably 0.01 to 30.00 parts by mass with respect to 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer. 20.00 mass parts is more preferable, and 1.00-10.00 mass parts is further more preferable. These curing catalysts may be used alone or in combination of two or more.

  The photocurable composition of the present invention preferably further comprises (D) a photosensitizer. Examples of the (D) photosensitizer include 9,10-dibutoxyanthracene, anthracene, perylene, coronene, tetracene, benzanthracene, phenothiazine, flavin, acridine, ketocoumarin, benzophenone, acetophenone, or 2-chlorothioxanthone, Examples include thioxanthone derivatives such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and isopropylthioxanthone.

  The blending ratio of the (D) photosensitizer is not particularly limited, but is preferably 0.001 to 30.00 parts by mass with respect to 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer. 01-20.00 mass parts is more preferable, and 0.1-10.00 mass parts is further more preferable. These photosensitizers may be used independently and may use 2 or more types together.

  The photocurable composition of the present invention preferably further comprises (E) a silane coupling agent. Examples of the (E) silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, and N- (β-aminoethyl) -γ-aminopropyl. Amino such as trimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane Group-containing silanes; N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl)- Ketimine type silanes such as 1-propanamine; γ-glycidoxypropyltrimethoxysilane, γ-group Epoxy group-containing silanes such as lysidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercapto Mercapto group-containing silanes such as propylmethyldimethoxysilane; Vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane; Chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane; Isocyanate-containing silanes such as γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropylmethyldimethoxysilane; Alkyl silanes such as siltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane; phenyl group-containing silanes such as phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, etc. However, it is not limited to these. Further, modified amino group-containing silanes modified by reacting the amino group-containing silanes with an epoxy group-containing compound, an isocyanate group-containing compound, and a (meth) acryloyl group-containing compound containing the silanes. It may be used.

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

  In the photocurable composition of the present invention, a bulking agent, a plasticizer, a moisture absorbent, a physical property modifier that improves tensile properties, a reinforcing agent, a colorant, a flame retardant, an anti-sagging agent, an oxidation, if necessary. Various additives such as an inhibitor, an antioxidant, an ultraviolet absorber, a solvent, a fragrance, a pigment, and a dye may be added.

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

  Examples of the plasticizer include phosphoric esters such as tributyl phosphate and tricresyl phosphate, phthalic esters such as dioctyl phthalate, aliphatic monobasic esters such as glycerol monooleate, dioctyl adipate, and the like. And aliphatic dibasic acid esters such as polypropylene glycols. These may be used alone or in combination of two or more.

  As the moisture absorbent, the silane coupling agent and silicate described above are suitable. The silicate is not particularly limited, and examples thereof include tetraalkoxysilane or a partial hydrolysis condensate thereof. More specifically, tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, Tetraalkoxysilanes (tetraalkyl silicates) such as methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, And those partial hydrolysis-condensation products are mentioned.

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

  In the case of irradiating active energy rays at the time of curing, as the active energy rays, in addition to electromagnetic waves such as ultraviolet rays, visible rays and infrared rays, X rays and γ rays, electron beams, proton rays, neutron rays, etc. can be used. Curing by ultraviolet ray or electron beam irradiation is preferred, and curing by ultraviolet ray irradiation is more preferred from the viewpoints of curing speed, availability and price of the irradiation device, easiness of handling under sunlight or general illumination, and the like. The active energy ray source is not particularly limited, but may be, for example, a high pressure mercury lamp, a low pressure mercury lamp, an electron beam irradiation device, a halogen lamp, a light emitting diode, a semiconductor laser, or a metal halide depending on the nature of the photobase generator used. It is done.

For The irradiation energy such as ultraviolet, preferably ^{10~20,000mJ / cm 2, 50~10,000mJ / cm} 2 is more preferable. If it is less than 10 mJ / cm ² , the curability may be insufficient. If it is greater than 20,000 mJ / cm ² , it will not only waste time and cost, but also damage the substrate. May end up.

  The method for producing the photocurable composition of the present invention is not particularly limited. For example, a predetermined amount of the components (A) and (B) is blended, and if necessary, other blending substances are blended to deaerate. It can be produced by stirring. There is no restriction | limiting in particular in the mixing | blending order of component (A), (B) and another compounding substance, What is necessary is just to determine suitably.

  The photocurable composition of the present invention is a fast curable photocurable composition excellent in workability and storage stability, and is particularly useful as an adhesive / adhesive composition. It can be suitably used as an adhesive material, coating material, potting material, paint, putty material, primer and the like. The photocurable composition of the present invention includes, for example, a coating agent used for moisture-proofing and insulation of a mounted circuit board and the like, a coating for solar power generation panels and the outer peripheral portion of the panel, and the like; , Architectural and industrial sealing agents such as vehicle sealing agents; Electrical and electronic component materials such as solar cell backside sealing agents; Electrical insulating materials such as insulation coating materials for electric wires and cables; Adhesives; Adhesives; Elastic bonding Agent: It can be suitably used for applications such as contact adhesives. Moreover, the coating method of the photocurable composition of the present invention is not particularly limited, but coating methods such as screen printing, stencil printing, roll printing, flexographic printing, spin coating, and roll coating are preferably used.

  The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

The number average molecular weight in the synthesis examples, examples and comparative examples was measured according to the following method.
1) Measurement of number average molecular weight It measured on the following conditions by the gel permeation chromatography (GPC). In the present invention, the maximum frequency molecular weight measured by GPC under the measurement conditions and converted with standard polyethylene glycol is referred to as the number average molecular weight.
THF solvent measuring device / analyzer: Alliance (manufactured by Waters), 2410 type differential refraction detector (manufactured by Waters), 996 type multi-wavelength detector (manufactured by Waters), Millenium data processing device (manufactured by Waters)
Column: Plgel GUARD + 5 μmMixed-C × 3 (50 × 7.5 mm, 300 × 7.5 mm: manufactured by Polymer Lab)
・ Flow rate: 1 mL / min ・ Converted polymer: Polyethylene glycol ・ Measurement temperature: 40 ° C.
FT-NMR measuring apparatus: JNM-ECA500 (500 MHz) manufactured by JEOL Ltd.
FT-IR measuring device: FT-IR460Plus manufactured by JASCO Corporation

(Synthesis example 1) Synthesis | combination of the organosilicon compound which produces | generates the silanol group by light 5.19g of o-nitrobenzyl alcohol was measured to the flask provided with the stirring apparatus, the nitrogen gas inlet tube, the thermometer, and the reflux condenser. Then 70 ml of THF was injected with a syringe. Further, 4.03 g of triethylamine was weighed out and added to the flask with a syringe. In another container, 10.0 g of triphenylchlorosilane was weighed and 70 ml of THF was added to dissolve the triphenylchlorosilane. After dissolution of triphenylchlorosilane, the entire amount was taken into a syringe and placed in a flask containing o-nitrobenzyl alcohol. Stirring was carried out at 50 ° C. for 3 hours, and the completion of the reaction was confirmed by TLC. Subsequently, vacuum filtration was performed using a Kiriyama funnel and filter paper to remove salt in the system. The solvent was removed by stirring under reduced pressure to obtain 15.86 g of a solid. The obtained solid was recrystallized with ethyl acetate to obtain crystal B (organosilicon compound B1 which generates a silanol group by light represented by the following formula (X)). The obtained crystal B was identified by H-NMR measurement. (8.12 (s, 1H) 7.58 (t, 1H) 7.54 (dd, 6H) 7.45 (m, 2H) 7.36 (m, 9H) 5.05 (s, 2H))

(Synthesis example 2) Oxyalkylene polymer Propylene oxide in the presence of a zinc hexacyanocobaltate-glyme complex catalyst using ethylene glycol as an initiator in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. The polyoxypropylene triol having a molecular weight of 24,000 and a molecular weight distribution of 1.3 obtained by reacting was obtained. A methanol solution of sodium methoxide is added to the obtained polyoxypropylene triol, methanol is distilled off under heating and reduced pressure, and the terminal hydroxyl group of the polyoxypropylene triol is converted to sodium alkoxide to obtain a polyoxyalkylene polymer M1. It was.

  Next, the polyoxyalkylene polymer M1 was reacted with allyl chloride to remove unreacted allyl chloride and purified to obtain a polyoxyalkylene polymer having an allyl group at the terminal. This polyoxyalkylene polymer having an allyl group at the end is reacted with trimethoxysilane, which is a silicon hydride compound, by adding 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt%, and 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 by GPC, the peak top molecular weight was 25,000 and the molecular weight distribution was 1.3. According to H ¹ -NMR measurement, the number of terminal trimethoxysilyl groups was 1.7 per molecule.

(Synthesis example 3) Oxyalkylene polymer Propylene oxide in the presence of a zinc hexacyanocobaltate-glyme complex catalyst using ethylene glycol as an initiator in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. A polyoxypropylene triol having a molecular weight of 11000 and a molecular weight distribution of 1.3 obtained by reacting was obtained. A methanol solution of sodium methoxide is added to the obtained polyoxypropylene triol, methanol is distilled off under heating and reduced pressure, and the terminal hydroxyl group of the polyoxypropylene triol is converted to sodium alkoxide to obtain a polyoxyalkylene polymer M2. It was.

  Next, the polyoxyalkylene polymer M2 was reacted with allyl chloride to remove unreacted allyl chloride and purified to obtain a polyoxyalkylene polymer having an allyl group at the terminal. This polyoxyalkylene polymer having an allyl group at the end is reacted with trimethoxysilane, which is a silicon hydride compound, by adding 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt%, and 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 by GPC, the peak top molecular weight was 12,000 and the molecular weight distribution was 1.3. According to H ¹ -NMR measurement, the number of terminal trimethoxysilyl groups was 1.7 per molecule.

(Synthesis example 4) Vinyl polymer 40.00 g of ethyl acetate, 70.00 g of methyl methacrylate, 2-ethylhexyl methacrylate (Tokyo Kasei Kogyo Co., Ltd.) in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. 30.00 g (made by Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (trade name: KBM503, made by Shin-Etsu Chemical Co., Ltd.) 12.00 g, and titanocene dicylide 0.10 g as a metal catalyst were charged in the flask. The contents of the flask were heated to 80 ° C. while introducing nitrogen gas. Next, 4.30 g of 3-mercaptopropyltrimethoxysilane sufficiently substituted with nitrogen gas was added all at once to the flask with stirring. After adding 4.30 g of 3-mercaptopropyltrimethoxysilane, heating and cooling were performed for 4 hours so that the temperature of the contents in the stirring flask could be maintained at 80 ° C. Further, 4.30 g of 3-mercaptopropyltrimethoxysilane sufficiently substituted with nitrogen gas was added to the flask over 5 minutes with stirring. After the additional addition of 4.30 g of 3-mercaptopropyltrimethoxysilane, the reaction was carried out for 4 hours while further cooling and heating so that the temperature of the contents in the stirring flask could be maintained at 90 ° C. . After a total of 8 hours and 5 minutes of reaction, the temperature of the reaction product was returned to room temperature, 20.00 g of a benzoquinone solution (95% THF solution) was added to the reaction product to stop the polymerization, and a vinyl system having a trimethoxysilyl group A polymer A3 was obtained. The peak top molecular weight was 4000, and the molecular weight distribution was 2.4. The number of trimethoxysilyl groups contained by H ¹ -NMR measurement was 2.00 per molecule.

Example 1
As shown in Table 1, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube, and a water-cooled condenser, 60 g of the polymer A1 obtained in Synthesis Example 2 and the weight obtained in Synthesis Example 3 were used. 20 g of polymer A2, 20 g of polymer A3 obtained in Synthesis Example 4, 5 g of 3-aminopropyltrimethoxysilane, 4 g of aluminum bisethylacetoacetate / monoacetylacetonate, 30 g of THF in another 100 mL eggplant flask Then, 8 g of the organosilicon compound B1 obtained in Synthesis Example 1 and 2 g of 2,4-diethylthioxanthen-9-one were added, stirred and dissolved. The entire amount of this solution was put into a 300 mL flask that had been weighed out earlier and stirred under reduced pressure to obtain a photocurable composition.

In Table 1, the compounding quantity of each compounding substance is shown by g, the polymers A1 to A3 are the polymers A1 to A3 obtained in Synthesis Examples 2 to 4, respectively, and the organosilicon compound B1 is obtained in Synthesis Example 1. Crystal B (organosilicon compound B1), and details of each compounding substance are as follows.
Organometallic compound C1: Aluminum bisethylacetoacetate / monoacetylacetonate: manufactured by Kawaken Fine Chemical Co., Ltd.
Organometallic compound C2: Aluminum alkyl acetoacetate / diisopropylate: manufactured by Kawaken Fine Chemical Co., Ltd.
Photosensitizer D1: 2,4-diethylthioxanthen-9-one, manufactured by Tokyo Chemical Industry Co., Ltd.
3-aminopropyltrimethoxysilane: manufactured by Shin-Etsu Chemical Co., Ltd.
X12-812H: trade name, ketimine silane, manufactured by Shin-Etsu Chemical Co., Ltd.
Vinyltrimethoxysilane: manufactured by Shin-Etsu Chemical Co., Ltd.
Solvent: Tetrahydrofuran, manufactured by Tokyo Chemical Industry Co., Ltd.

1) UV irradiation test A photocurable composition was applied on a stainless steel plate (25 mm × 100 mm × 1.5 mm) to a thickness of about 50 μm, and UV irradiation [irradiation conditions: metal halide lamp (illuminance 50 mW / cm ² ), integrated light quantity: 200 mJ / cm ² ]. Immediately after UV irradiation, according to JIS A 1439 5.19 tack-free test, finger touch drying time (tack-free time: TFT) was measured in an environment of 23 ° C. and RH 50%, and the curability was evaluated. Moreover, the color of the photocurable composition before and after UV irradiation was confirmed visually. The results are shown in Table 2.
Moreover, after confirming the presence or absence of tack immediately after UV irradiation, if not cured, UV irradiation was performed again and repeated until tack free. Table 2 shows the number of UV irradiations until tack-free expression.

2) Measurement of pot life On a stainless steel plate (25 mm x 100 mm x 1.5 mm), a photocurable composition is applied to a thickness of about 50 µm, and left in a dark room at 23 ° C RH 50% to avoid exposure to light. Therefore, the time to tack free was measured and used as the pot life. The results are shown in Table 2.

(Example 2)
As shown in Table 1, 60 g of the polymer A1 obtained in Synthesis Example 2 was obtained in Synthesis Example 3 in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. 20 g of polymer A2, 20 g of polymer A3 obtained in Synthesis Example 4, 5 g of X12-812H, 4 g of aluminum bisethyl acetoacetate / monoacetylacetonate, 30 g of THF in another 100 ml eggplant flask, synthesis example 8 g of the organosilicon compound B1 obtained in 1 and 2 g of 2,4-diethylthioxanthen-9-one were added, stirred and dissolved. The total amount of this solution was put into a 300 ml flask that had been weighed out earlier and stirred under reduced pressure to prepare a photocurable composition. The same measurement as Example 1 was performed with respect to the obtained photocurable composition. The results are shown in Table 2.

(Example 3)
As shown in Table 1, 60 g of the polymer A1 obtained in Synthesis Example 2 was obtained in Synthesis Example 3 in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. 20 g of polymer A2, 20 g of polymer A3 obtained in Synthesis Example 4, 5 g of vinyltrimethoxysilane, 4 g of aluminum bisethylacetoacetate / monoacetylacetonate, 30 g of THF in another 100 ml eggplant flask 8 g of the organosilicon compound B1 obtained in Example 1 and 2 g of 2,4-diethylthioxanthen-9-one were added, stirred and dissolved. The total amount of this solution was put into a 300 ml flask that had been weighed out earlier and stirred under reduced pressure to prepare a photocurable composition. The same measurement as Example 1 was performed with respect to the obtained photocurable composition. The results are shown in Table 2.

Example 4
As shown in Table 1, 60 g of the polymer A1 obtained in Synthesis Example 2 was obtained in Synthesis Example 3 in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. 20 g of polymer A2, 20 g of polymer A3 obtained in Synthesis Example 4, 5 g of 3-aminopropyltrimethoxysilane, 4 g of aluminum alkyl acetoacetate diisopropylate, 30 g of THF in another 100 ml eggplant flask, 8 g of the organosilicon compound B1 obtained in Synthesis Example 1 and 2 g of 2,4-diethylthioxanthen-9-one were added, stirred and dissolved. The total amount of this solution was put into a 300 ml flask that had been weighed out earlier and stirred under reduced pressure to prepare a photocurable composition. The same measurement as Example 1 was performed with respect to the obtained photocurable composition. The results are shown in Table 2.

(Example 5)
As shown in Table 1, 60 g of the polymer A1 obtained in Synthesis Example 2 was obtained in Synthesis Example 3 in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. 20 g of polymer A2, 20 g of polymer A3 obtained in Synthesis Example 4, 5 g of 3-aminopropyltrimethoxysilane, 4 g of aluminum bisethylacetoacetate / monoacetylacetonate, and THF in another 100 ml eggplant flask 30 g and 8 g of the organosilicon compound B1 obtained in Synthesis Example 1 were added, stirred and dissolved. The total amount of this solution was put into a 300 ml flask that had been weighed out earlier and stirred under reduced pressure to prepare a photocurable composition. The same measurement as Example 1 was performed with respect to the obtained photocurable composition. The results are shown in Table 2.

(Example 6)
As shown in Table 1, 60 g of the polymer A1 obtained in Synthesis Example 2 was obtained in Synthesis Example 3 in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. 20 g of polymer A2, 20 g of polymer A3 obtained in Synthesis Example 4, 5 g of 3-aminopropyltrimethoxysilane, 30 g of THF in another 100 ml eggplant flask, and organosilicon compound B1 obtained in Synthesis Example 1 2 g of 8 g of 2,4-diethylthioxanthen-9-one was added, stirred and dissolved. The total amount of this solution was put into a 300 ml flask that had been weighed out earlier and stirred under reduced pressure to prepare a photocurable composition. The same measurement as Example 1 was performed with respect to the obtained photocurable composition. The results are shown in Table 2.

(Comparative Example 1)
As shown in Table 1, 60 g of the polymer A1 obtained in Synthesis Example 2 was obtained in Synthesis Example 3 in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. 20 g of the polymer A2, 20 g of the polymer A3 obtained in Synthesis Example 4, 5 g of 3-aminopropyltrimethoxysilane, 4 g of aluminum bisethylacetoacetate / monoacetylacetonate, and 30 g of THF were added and stirred under reduced pressure. A composition was prepared. The measurement similar to Example 1 was performed with respect to the obtained composition. The results are shown in Table 2.

  As shown in Table 2, the photocurable composition of the present invention is a photocurable composition that has an appropriate pot life without being cured when not irradiated with UV, and is rapidly cured by UV irradiation. Curing was possible in a short time even with a low integrated light intensity. Further, it was not possible to cure immediately after UV irradiation depending on the UV irradiation conditions, and it was possible to cure after a certain period of time.

Claims (4)

(A) a crosslinkable silicon group-containing organic polymer, and (B) an organosilicon compound that generates a silanol group by light,
A photocurable composition comprising:   The photocurable composition according to claim 1, further comprising (C) a curing catalyst.   The photocurable composition according to claim 2, wherein the (C) curing catalyst is an organometallic compound.   (D) The photocurable composition according to any one of claims 1 to 3, further comprising a photosensitizer.